JP2007291372A - Curable composition, optical film using the curable composition, polarizing plate using the optical film, and image display device - Google Patents

Abstract

The present invention relates to a curable composition capable of improving the slipperiness of a material with little bleeding, aging or high temperature conditions, transfer of a silicone component to a contact medium, performance deterioration associated with these, and contamination of a production line. To provide things. Also, to provide a coating type optical film which is excellent in antifouling property, scratch resistance and adhesion and suitable for mass production.
(A) a copolymer having a specific proportion of structural units containing a polysiloxane structure in the main chain or side chain, and a polymer unit based on a hydroxyl group-containing monomer, and (B) a polysiloxane structure. A fluorine-containing copolymer having a specific unit of structural units contained in the main chain or side chain and having a polymer unit based on a hydroxyl group-containing monomer, (C) a curing agent capable of reacting with a hydroxyl group, and (D) a curing catalyst , (E) an organosilane compound, a composition containing at least one of a hydrolyzate of the organosilane compound and a partial condensate thereof, (F) inorganic fine particles, and (G) a polymerization initiator in a specific ratio A curable composition.
[Selection] Figure 1

Description

  The present invention relates to a curable composition, an optical film using the curable composition, a polarizing plate using the optical film, and an image display device using the optical film or the polarizing plate on the outermost surface of a display.

  In general, an antireflection film is used for an image display device such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), a liquid crystal display (LCD), etc. In order to prevent reflection of images and images, it is arranged on the outermost surface of the display so as to reduce the reflectance by using the principle of optical interference.

  Such an antireflection film can be generally produced by forming a low refractive index layer having an appropriate thickness on a support or a high refractive index layer formed thereon. As a material for the low refractive index layer, a material having a refractive index as low as possible is desired from the viewpoint of antireflection performance, and at the same time it is used for the outermost surface of the display, so it has high antifouling properties, scratch resistance, and adhesion to the lower layer. Sex is required.

  As a polymer for forming a low refractive index layer, it is well known that a low refractive index fluorine-containing polymer is cured, and various curing methods are known, for example, having a hydroxyl group or the like. It has been generally performed to cure polymers with various curing agents (Patent Documents 1 to 3). However, it was not sufficient in terms of film hardness, and an improvement was desired.

  As means for lowering the refractive index of the material, there are also means for lowering the density (introducing voids) in addition to (1) means for introducing fluorine atoms, as in Patent Documents 1 to 3 above. Both have the problem that the film strength is impaired and the scratch resistance is lowered.

  As a means for greatly improving antifouling properties and scratch resistance while maintaining a low refractive index, imparting slipperiness to the surface is effective. Techniques such as introduction of fluorine and introduction of silicon are effective for imparting slipperiness. In particular, by adding a small amount of a silicone compound to a low refractive index material, the effect of developing slipperiness, the effect of improving antifouling properties, and the effect of improving scratch resistance are remarkably exhibited. However, there are various problems such as compatibility with low refractive index layer materials, bleeding out over time or at high temperatures, transfer of silicone components to contact media, performance degradation associated with these, and contamination of production lines. It was.

  Particularly in an antireflection film, generation of haze due to insufficient compatibility is a serious problem because optical performance deteriorates. Further, when the film after the application of the low refractive index layer is wound, a silicone compound may adhere to the back surface of the film, which is a serious problem because it hinders subsequent processing steps. That is, there is a demand for a technique in which only the siloxane sites are effectively segregated on the surface and the remaining sites bonded to silicon are effectively anchored in the low refractive index layer coating.

To solve this problem, a fluorine-containing olefin copolymer in which a polysiloxane block copolymer component is introduced using a silicone-based macroazo initiator, and a technique for applying the fluorine-containing olefin copolymer to an antireflection film (Patent Document) 4-7) have been proposed. Although these technologies are extremely effective in terms of suppressing bleed-out and transfer of the silicone component to the contact medium and improving the uniformity of the coating, the antifouling effect and the scratch resistance improvement effect For example, it does not reach the addition of silicone compounds.
Sho 57-34107 Sho 61-275311 JP-A-8-92323 JP-A-11-189621 Japanese Patent Laid-Open No. 11-228631 JP 2000-17028 A JP 2000-313709 A

  From the above background, bleed-out of materials is improved while suppressing bleed out over time or high temperature conditions, transfer of silicone components to contact media, performance degradation associated with these, and contamination of production lines. Therefore, development of a technique capable of improving antifouling / dustproofing and scratch resistance has been demanded.

  The object of the present invention is to improve the slipperiness of the material, firstly, bleed out under aging or high temperature conditions, transfer of silicone component to contact medium, performance degradation associated with these, and contamination of the production line are few. And secondly, bleeding out under time or high temperature conditions, transfer of the silicone component to the contact medium, performance degradation associated therewith, contamination of the production line, etc. Is to provide a coating type optical film that is excellent in antifouling property, scratch resistance, and adhesion and suitable for mass production. Third, such an optical film is used as a protective film for a polarizing film. There is to provide the used polarizing plate. Fourthly, by using such an optical film or polarizing plate on the outermost surface, an image display device having excellent antifouling property and scratch resistance on the surface is provided. Especially That.

[1] 0.1 to 40 parts by mass of the following component (A), 10 to 100 parts by mass of (B) to (E), and 0 to 100 parts by mass of (F) to (G) Curable composition:
(A) The structural unit containing the polysiloxane structure represented by the following general formula (1) in the main chain or side chain is 40 (%) or more and 100 (%) in mass fraction with respect to all the structural units in the component (A). A copolymer having a polymerization unit based on a hydroxyl group-containing monomer,
(B) The structural unit containing the polysiloxane structure represented by the following general formula (1) in the main chain or side chain is 0 (%) or more and 20 (% by mass fraction with respect to all the structural units in the component (B). ) A fluorine-containing copolymer having a polymerization unit based on a hydroxyl group-containing monomer,
(C) a curing agent capable of reacting with a hydroxyl group,
(D) a curing catalyst,
(E) 0-100 parts by mass of a composition containing at least one of an organosilane compound, a hydrolyzate of the organosilane compound and a partial condensate thereof,
(F) inorganic fine particles,
(G) A polymerization initiator.

General formula (1):

(In the general formula (1), R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group. P represents an integer of 10 to 500.)
[2] The curable composition according to 1 above, wherein the (A) copolymer is a copolymer represented by the following general formula (2).

General formula (2):

(In the general formula (2), X represents a structural unit containing the polysiloxane structure represented by the general formula (1) in the main chain or side chain. Y represents a polymerized unit based on any vinyl monomer, R ²¹ represents a hydrogen atom or a methyl group, L ²¹ represents a single bond or a divalent linking group, and y and z are composed of all structural units. This represents the molar fraction (%) of each structural unit when the remaining structural unit excluding the unit X is 100 (%), and represents a value satisfying 0 ≦ y <100 and 0 <z ≦ 100. Represents the mass fraction of the structural unit X with respect to all structural units, and satisfies the relationship of 40 ≦ x <100.)
[3] The curable composition according to 1 above, wherein the (A) copolymer is a copolymer represented by the following general formula (3).

General formula (3):

(In General Formula (3), Rf ¹¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ¹² represents a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 30 carbon atoms, and ether. B may represent a polymerized unit based on a hydroxyl group-containing monomer, A represents a polymerized unit based on any vinyl monomer, and may be a single species or a plurality of species. S represents a structural unit containing the polysiloxane structure represented by the general formula (1) in the main chain or side chain, and may be composed of a single species or a plurality of species. Represents the mole fraction (%) of each structural unit when the remaining structural unit excluding the structural unit S from the structural unit is 100 (%), 0 ≦ a ≦ 90, 0 ≦ b ≦ 70, 0 ≦ c Represents a value satisfying ≦ 50, 0 <d, where e is the total structural unit of the structural unit S Against represents the mass fraction (percent) satisfy the relation 40 ≦ e <100.)
[4] The curable composition according to any one of 1 to 3, wherein the (B) fluorine-containing copolymer is a fluorine-containing copolymer represented by the following general formula (4).

General formula (4):

(In the general formula (4), Rf ¹¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ¹² represents a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 30 carbon atoms, and ether. B may represent a polymerized unit based on a hydroxyl group-containing monomer, A represents a polymerized unit based on any vinyl monomer, and may be a single species or a plurality of species. S represents a structural unit containing the polysiloxane structure represented by the general formula (1) in the main chain or side chain, and may be composed of a single species or a plurality of species. Represents the mole fraction (%) of each structural unit when the remaining structural unit excluding the structural unit S from the structural unit is 100 (%), 0 ≦ a ≦ 90, 0 ≦ b ≦ 70, 0 ≦ c Represents a value satisfying ≦ 50, 0 <d, where e is the total structural unit of the structural unit S Represents against mass fraction (percent) satisfy the relation of 0 ≦ e ≦ 20.)
[5] In the general formula (3), the molar fraction (%) of the polymerized unit B based on the hydroxyl group-containing monomer when the remaining structural unit excluding the structural unit S from all structural units is 100 (%). 4. The fluorine-containing copolymer according to 3 above, wherein d is 20 ≦ d ≦ 60.
[6] In the general formula (4), the molar fraction (%) of the polymerized unit B based on the hydroxyl group-containing monomer when the remaining structural unit excluding the structural unit S from all the structural units is 100 (%). 6. The fluorine-containing copolymer according to 4 or 5 above, wherein d is 20 ≦ d ≦ 50.
[7] The above (1) to (6), wherein the curing agent capable of reacting with the hydroxyl group (C) is a compound having two or more carbon atoms adjacent to a nitrogen atom and substituted with an alkoxy group in one molecule. The curable composition in any one.
[8] The curable composition according to any one of 1 to 7, wherein the (D) curing catalyst is a thermal acid generator.
[9] The curable composition according to any one of 1 to 8, wherein the (E) organosilane compound is represented by the following general formula (5).

General formula (5):

(In the general formula (5), R ³² represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom. U ³¹ represents a single bond, an ester group, an amide group or an ether. L ³¹ represents a divalent linking chain, m 2 represents 0 or 1. m 2 is preferably 0. R ³⁰ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. when the .X ³¹ to represent a substituted aryl group .X ³¹ representing a hydroxyl group or a hydrolyzable group there are a plurality, the plurality of X ³¹ may be different even in respectively the same)
[10] The curable composition according to any one of 1 to 9, wherein the inorganic fine particles (F) are silica fine particles.
[11] The curable composition as described in 10 above, wherein the silica fine particles are hollow silica fine particles having an average particle diameter of 30 nm to 150 nm.
[12] The curable composition according to any one of 1 to 11, wherein the (G) polymerization initiator is a heat and / or ionizing radiation curable initiator.
[13] An optical film having a functional layer formed by curing the curable composition according to any one of 1 to 12 above.
[14] The optical film as described in 13 above, wherein the functional layer is a low refractive index layer, and the optical film has an antireflection function and / or an antiglare function due to optical interference.
[15] A polarizing plate in which the optical film described in 13 or 14 is used for one of the two protective films of the polarizing film in the polarizing plate.
[16] An image display device in which the optical film described in 13 or 14 or the polarizing plate described in 15 is used on the outermost surface of the display.

  The curable composition used in the present invention forms a film having excellent strength and bleed-out under aging or high-temperature conditions, little transfer of the silicone component to the contact medium, and slipperiness. Further, by controlling the ratio of the component (A) and the components (B) to (E), the introduction amount of the silicone component can be controlled as desired without impairing the uniformity of the film. The optical film having a functional layer obtained by curing this composition has excellent bleeding resistance and scratch resistance as well as bleed out under time or high temperature conditions, little transfer of the silicone component to the contact medium. Excellent adhesion to the lower layer. A polarizing plate and a liquid crystal display device using this optical film have an excellent effect of having high antifouling properties, scratch resistance, and adhesion. In addition to these properties, an optical film provided with an antireflection function using this composition as a composition for a low refractive index layer has a lower reflectance. A polarizing plate device and a liquid crystal display device using this optical film are Furthermore, it has an excellent feature that the reflection of external light is sufficiently prevented.

  In this specification, the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”.

1. [Layer structure of optical film]
The optical film of the present invention comprises 0.1 to 40 parts by mass of the following component (A), 10 to 100 parts by mass of (B) to (E), and 0 to (F) of (F). It has a functional layer formed by coating and curing a curable composition containing 100 parts by mass.
(A) The structural unit containing the polysiloxane structure represented by the following general formula (1) in the main chain or side chain is 40 (%) or more and 100 (%) in mass fraction with respect to all the structural units in the component (A). A copolymer having a polymerization unit based on a hydroxyl group-containing monomer,
(B) The structural unit containing the polysiloxane structure represented by the following general formula (1) in the main chain or side chain is 0 (%) or more and 20 (% by mass fraction with respect to all the structural units in the component (B). ) A fluorine-containing copolymer having a polymerization unit based on a hydroxyl group-containing monomer,
(C) a curing agent capable of reacting with a hydroxyl group,
(D) a curing catalyst,
(E) 0-100 parts by mass of a composition containing at least one of an organosilane compound, a hydrolyzate of the organosilane compound and a partial condensate thereof,
(F) inorganic fine particles,
(G) A polymerization initiator.

General formula (1):

In general formula (1), R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group. p represents an integer of 10 to 500.

  Although it is preferable that the optical film of this invention has a functional layer obtained by hardening the curable composition of this invention as an outermost surface layer, it is not limited. As the functional layer obtained by curing the curable composition of the present invention, a low refractive index layer, an antifouling layer, a transparent conductive layer, a hard coat layer, an antiglare layer and the like are preferable, and a low refractive index layer is particularly preferable. preferable. By using the functional layer obtained by curing the curable composition of the present invention as the low refractive index layer, an antireflection function can be imparted to the optical film due to the effect of optical interference. The optical film of the present invention may have a single layer structure or a multilayer structure, but is preferably in the form of a multilayer structure. It is preferable that a functional layer is formed on a transparent support in advance to form an optical film and then disposed in the image display device. Hereinafter, the antireflection film which is a preferred embodiment of the optical film of the present invention will be further described as an example.

  The antireflection film of the present invention has a hard coat layer as necessary on a support, and the refractive index, film thickness, number of layers, layer order, etc. so that the reflectance is reduced by optical interference thereon. In consideration of the above, those laminated are preferable. In the simplest configuration, the low-reflective antireflection film has a configuration in which only a low refractive index layer is coated on a support. In order to further reduce the reflectance, the antireflection layer is preferably composed of a high refractive index layer having a higher refractive index than that of the support and a low refractive index layer having a lower refractive index than that of the support. Examples of the configuration of the antireflection film of the present invention include two layers of a high refractive index layer / low refractive index layer from the support side, and three layers having different refractive indexes, a medium refractive index layer (base material or hard coat layer). In which the refractive index is higher and the refractive index is lower than that of the high-refractive-index layer) / high-refractive-index layer / low-refractive-index layer. Has also been proposed.

The example of the preferable layer structure of the antireflection film of this invention is shown below.
-Support / low refractive index layer,
・ Support / Antistatic layer / Low refractive index layer,
・ Support / antiglare layer / low refractive index layer,
Support / antiglare layer / antistatic layer / low refractive index layer,
Support / antistatic layer / antiglare layer / low refractive index layer,
・ Support / hard coat layer / low refractive index layer,
Support / hard coat layer / antiglare layer / low refractive index layer,
Support / hard coat layer / antiglare layer / antistatic layer / low refractive index layer,
Support / hard coat layer / antistatic layer / antiglare layer / low refractive index layer,
Support / hard coat layer / high refractive index layer / low refractive index layer,
Support / hard coat layer / antistatic layer / high refractive index layer / low refractive index layer,
Support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Support / antiglare layer / high refractive index layer / low refractive index layer,
Support / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Support / antistatic layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Support / antistatic layer / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / support / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / support / antiglare layer / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer.

  As long as the reflectance can be reduced by optical interference, it is not limited to these layer configurations. The high refractive index layer may be a light diffusing layer having no antiglare property. The antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (for example, ATO, ITO), and can be provided by coating or atmospheric pressure plasma treatment.

  Hereinafter, a basic configuration of an antireflection film suitable as an embodiment of the present invention will be described with reference to the drawings.

  The cross-sectional view schematically shown in FIG. 1A is an example of the antireflection film of the present invention. The antireflection film 1a has a layer structure in the order of a transparent support 2, a hard coat layer 3, a high refractive index layer 4, and a low refractive index layer 5 obtained by curing the curable composition of the present invention. The refractive index of the high refractive index layer 4 is preferably in the range of 1.50 to 2.00, and the refractive index of the low refractive index layer 5 is preferably in the range of 1.30 to 1.45.

  In the present invention, the hard coat layer may be provided separately from the high refractive index layer as described above, or may be a high refractive index hard coat layer having the function of the high refractive index layer. The hard coat layer may be a single layer or may be composed of a plurality of layers, for example, 2 to 4 layers. Further, the hard coat layer may be omitted. Accordingly, the hard coat layer shown in FIG. 1 is not essential, but it is preferable that any of these hard coat layers is applied to impart film strength. The low refractive index layer is coated on the outermost layer.

The cross-sectional view schematically shown in FIG. 1B is another example of the antireflection film of the present invention. The antireflection film 1b includes a transparent support 2, a hard coat layer 3, a medium refractive index layer 6, a high refractive index layer 4, and a low refractive index layer (outermost layer) obtained by curing the curable composition of the present invention. It has a 5 layer structure. The transparent support 2, the medium refractive index layer 6, the high refractive index layer 4, and the low refractive index layer 5 have refractive indexes that satisfy the following relationship.
The refractive index of the high refractive index layer> The refractive index of the medium refractive index layer> The refractive index of the transparent support> The refractive index of the low refractive index layer

In the layer structure as shown in FIG. 1B, as described in JP-A-59-50401, the medium refractive index layer is represented by the following mathematical formula (1), and the high refractive index layer is represented by the following mathematical formula (2). It is preferable that the low refractive index layer satisfies the following formula (3) in that an antireflection film having more excellent antireflection performance can be produced.
Formula (1): (hλ / 4) × 0.7 <n ₁ d ₁ <(hλ / 4) × 1.3
Formula (2): (iλ / 4) × 0.7 <n ₂ d ₂ <(iλ / 4) × 1.3
Formula (3): (jλ / 4) × 0.7 <n ₃ d ₃ <(jλ / 4) × 1.3

In formulas (1) to (3), h is a positive integer (generally 1, 2 or 3), i is a positive integer (typically 1, 2 or 3), and j is a positive odd number (generally 1). ). n ₁ , n ₂ and n ₃ are the refractive indexes of the medium refractive index layer, the high refractive index layer and the low refractive index layer, respectively, and d ₁ , d ₂ and d ₃ are the medium refractive index layer, the high refractive index layer and the high refractive index layer, respectively. It is the layer thickness (nm) of the refractive index layer and the low refractive index layer. λ is the wavelength (nm) of visible light, and is a value in the range of 380 to 680 nm.

In the layer configuration as shown in FIG. 1B, the medium refractive index layer is represented by the following mathematical formula (1-1), the high refractive index layer is represented by the following mathematical formula (2-1), and the low refractive index layer is represented by the following mathematical formula (3-1). It is particularly preferable that each of these is satisfied. Here, λ is 500 nm, h is 1, i is 2, and j is 1.
Formula (1-1): (hλ / 4) × 0.80 <n ₁ d ₁ <(hλ / 4) × 1.00
Formula (2-1): (iλ / 4) × 0.75 <n ₂ d ₂ <(iλ / 4) × 0.95
Formula (3-1): (jλ / 4) × 0.95 <n ₃ d ₃ <(jλ / 4) × 1.05

  The high refractive index, medium refractive index, and low refractive index described herein refer to the relative refractive index between layers. Moreover, in FIG.1 (b), the high refractive index layer is used as a light interference layer, and the antireflection film which has the very outstanding antireflection performance can be produced.

2. [Low refractive index layer]
The low refractive index layer in the antireflection film of the present invention will be described below.
The refractive index of the low refractive index layer of the antireflection film of the present invention is 1.20 to 1.49, preferably 1.30 to 1.45. Further, the low refractive index layer preferably satisfies the following mathematical formula (3) from the viewpoint of reducing the reflectance.
Formula (3): (jλ / 4) × 0.7 <n ₃ d ₃ <(jλ / 4) × 1.3

In the formula, j, n ₃ , d ₃ and λ are as described above, and λ is a value in the range of 380 to 680 nm.
In addition, satisfy | filling said numerical formula (3-2) means that j (positive odd number, usually 1) which satisfy | fills numerical formula (3-2) exists in the said wavelength range.

  The thickness of the low refractive index layer is preferably 50 to 200 nm, and more preferably 70 to 100 nm. The dynamic friction coefficient of the cured low refractive index layer surface is preferably 0.03 to 0.30, and the contact angle with water is preferably 85 to 120 degrees. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The specific strength of the low refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test under a 500 g load.

2- (1). [Material for low refractive index layer]
The low refractive index layer of the curable composition of the present invention comprises 0.1 to 40 parts by mass of the following component (A) for the purpose of improving the scratch resistance by imparting slipperiness and improving the antifouling property. B) to (E) are combined to form a curable composition containing 10 to 100 parts by mass, and (F) to (G) and 0 to 100 parts by mass.
(A) The structural unit containing the polysiloxane structure represented by the following general formula (1) in the main chain or side chain is 40 (%) or more and 100 (%) in mass fraction with respect to all the structural units in the component (A). A copolymer having a polymerization unit based on a hydroxyl group-containing monomer,
(B) The structural unit containing the polysiloxane structure represented by the following general formula (1) in the main chain or side chain is 0 (%) or more and 20 (% by mass fraction with respect to all the structural units in the component (B). ) A fluorine-containing copolymer having a polymerization unit based on a hydroxyl group-containing monomer,
(C) a curing agent capable of reacting with a hydroxyl group,
(D) a curing catalyst,
(E) 0-100 parts by mass of a composition containing at least one of an organosilane compound, a hydrolyzate of the organosilane compound and a partial condensate thereof,
(F) inorganic fine particles,
(G) A polymerization initiator.

General formula (1):

(In the general formula (1), R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group. P represents an integer of 10 to 500.)

2- (1) -1. {(A): The structural unit containing the polysiloxane structure represented by the following general formula (1) in the main chain or the side chain is contained in the mass component with respect to all the structural units in the component (A). Copolymer having a polymer unit based on a hydroxyl group-containing monomer and having a percentage of 40% or more and less than 100%}
The copolymer (A) is a copolymer having a polymer unit based on a hydroxyl group-containing monomer. The copolymer (A) is more likely to segregate on the surface of the coating film because the ratio of “structural unit containing a polysiloxane structure in the main chain or side chain” is larger than that of the fluorine-containing copolymer (B). Furthermore, since the polysiloxane structural unit has antifouling and dustproof performance, the amount of the copolymer (A) added is adjusted, and the distribution of the polysiloxane structural unit in the coating film is controlled to control the slip of the material. It is possible to adjust the performance, antifouling performance, dustproof performance, scratch resistance, etc. Furthermore, by making the hydroxyl group of the copolymer (A) into a specific range, effective crosslinking to the fluorinated copolymer (B) becomes possible, bleeding out under time or high temperature conditions, It is possible to suppress the transfer of the silicone component, the performance deterioration associated therewith, the contamination of the production line, and the like. The copolymer (A) is excellent in compatibility with the fluorine-containing copolymer (B) by containing a polymer unit based on a vinyl monomer and / or a polymer unit containing a fluorine atom in the polymer. The effect that it is excellent in is obtained.

  Hereinafter, in the copolymer (A), “a structural unit containing a polysiloxane structure in the main chain or side chain” is referred to as “polysiloxane component”, “a polymerization unit based on a hydroxyl group-containing monomer” is referred to as “hydroxyl group-containing polymerization unit”, and There is something to say.

General formula (1):

In general formula (1), R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group.

The alkyl group which may have a substituent preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, a trifluoromethyl group, and an ethyl group. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.
p represents an integer of 10 to 500, preferably 50 to 300, and particularly preferably 100 to 250.

  The copolymer (A) is preferably a copolymer (A-1) having a structure represented by the general formula (2).

General formula (2):

In general formula (2), X represents a structural unit containing a polysiloxane structure in the main chain or side chain.
Y represents a polymerization unit based on an arbitrary vinyl monomer, and may be composed of a single species or a plurality of species. That is, it may be derived from a single vinyl monomer or may be derived from a plurality of vinyl monomers.
R ²¹ represents a hydrogen atom or a methyl group, and L ²¹ represents a single bond or a divalent linking group.
y and z represent the mole fraction (%) of each structural unit when the remaining structural unit excluding the structural unit X from all structural units is 100 (%), and 0 ≦ y <100, 0 <z It represents a value satisfying ≦ 100. x represents a mass fraction of the structural unit X with respect to all the structural components, and satisfies the relationship of 40 ≦ x <100.
Hereinafter, the “structural unit” constituting the copolymer (A-1) may be referred to as “structural component”.

  The copolymer (A-1) used by this invention contains a hydroxyl-containing structural unit in a side chain. By having a specific range amount of the hydroxyl group, it is possible to effectively crosslink, bleed out over time or under high temperature conditions, transfer of the silicone component to the contact medium, performance deterioration associated with these, contamination of the production line, etc. The effect of suppressing is obtained.

  Hereinafter, a suitable polymerization unit (hydroxyl group-containing structural unit (Z)) represented by the following general formula (2-Z) of the copolymer (A-1) used in the present invention will be described.

General formula (2-Z):

In the general formula (2-Z), R ²¹ represents a hydrogen atom or a methyl group. L ²¹ represents a single bond or a divalent linking group, and examples of the divalent linking group include —O—, —CO—, —NH—, —CO—NH—, —COO—, and —O—COO—. , A substituted or unsubstituted alkylene group, an arylene group, a heterocyclic group, and a combination thereof, among which a combination of —COO— and an alkylene group is preferable.

  Hereinafter, although the preferable example of the polymerization unit represented by the said general formula (2-Z) is shown, this invention is not limited to this.

  The copolymer (A-1) used in the present invention represented by the general formula (2) has adhesion to a substrate, solubility in a solvent, compatibility with other coating liquid compositions, and transparency. In addition to those described above from various viewpoints such as properties, other constituent components (Y) may be included, and examples of monomers constituting such polymerized units include methyl acrylate, ethyl acrylate, and n-butyl acrylate. , Isobutyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, stearyl methacrylate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, styrene, α-methyl styrene, acrylonitrile, methacrylonitrile, etc. Can be mentioned

  The copolymer (A-1) used by this invention contains the structural component which contains a polysiloxane structure in a principal chain or a side chain. By having the polysiloxane component, the amount of the copolymer (A-1) added is adjusted as appropriate, and the distribution of the polysiloxane component in the coating film is controlled, thereby making the material slippery, antifouling performance, and dustproof. It becomes possible to adjust the performance and scratch resistance. A plurality of polysiloxane components may be combined depending on the purpose.

The component (X) containing a polysiloxane structure in the main chain or side chain in the copolymer (A-1) represented by the general formula (2) will be described below.

  As a method for synthesizing a copolymer containing a constituent component having a polysiloxane structure in the main chain, several methods have been conventionally proposed.

  For example, J. et al. C. Saam et al., “Macromolecules”, Vol. 3, page 1 (1970), reported that a styrene-dimethylsiloxane block copolymer was obtained by an anionic polymerization method (this method is hereinafter referred to as an anionic polymerization method). .

  In addition, in “Makromol. Chem., Rapid Commun.”, Vol. 5, page 559 (1984), a vinyl acetate-dimethylsiloxane block copolymer is obtained by a coupling reaction between prepolymers having functional groups. (This method is hereinafter referred to as a prepolymer method).

  Furthermore, Hiroshi Inoue et al. In “Science of Polymer Science Proceedings”, 34, 293 (1984), methyl methacrylate-dimethylsiloxane block copolymer by radical polymerization with azo group-containing polysiloxane amide having radical polymerization initiation ability. It has been reported that a coalescence was obtained (this method is hereinafter referred to as a polymer initiator method).

  However, in the above anionic polymerization method and prepolymer method, vinyl group monomers that can be applied to the reaction are limited, and the reaction process can be multistage or the reaction conditions can be difficult to use industrially. . In order to produce a block copolymer industrially, it can be synthesized using radical polymerization, can be applied to many vinyl monomers, and preferably has few reaction steps.

  From the above viewpoint, the copolymer (A-1) used in the present invention is preferably produced by a polymer initiator method. Such a polymer initiator is, for example, a polysiloxane compound having a radical-generating group such as an azo group or a peroxy group. Such an initiator can be synthesized as described in, for example, Japanese Patent Publication No. 6-104711 and Japanese Patent Laid-Open No. 6-93100.

(Preferred examples of polymer initiator)
Examples of preferred polymer initiators are shown below, but the present invention is not limited thereto.

  The side chain polysiloxane partial structure will be described. The polysiloxane partial structure generally has a repeating siloxane moiety represented by the following general formula (11).

General formula (11):

In the general formula (11), R ²¹ and R ²² may be the same or different and each represents an alkyl group or an aryl group which may have a substituent. The alkyl group which may have a substituent preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, a trifluoromethyl group, and an ethyl group. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.
p1 represents an integer of 10 to 500, preferably 10 to 350, and particularly preferably 10 to 250.

  A copolymer having a polysiloxane structure represented by the general formula (11) in the side chain is, for example, “JA Appl. Polym. Sci.”, 2000, p. 78 (1955), as disclosed in JP-A-56-28219, etc., a reactive group having reactivity with a polymer having a reactive group such as an epoxy group, a hydroxyl group, a carboxyl, or an acid anhydride group. Polysiloxane [for example, “Silaplane” series {manufactured by Chisso Corporation, etc.] having a polymer at one end (for example, an amino group, a mercapto group, a carboxyl group, a hydroxyl group, etc. with respect to an epoxy group or an acid anhydride group) is a polymer. It can be synthesized by a method of introducing by reaction; a method of polymerizing a polysiloxane-containing silicon macromer, and both methods can be preferably used. In the present invention, a method of introducing by polymerization of silicon macromer is more preferable.

  Although the preferable example of the polymerization unit which is useful for this invention and contains a polysiloxane site | part in a side chain is shown below, this invention is not limited to these.

Other than the above, as the polymerized unit containing a siloxane moiety repeatedly in the side chain, as described above, a polysiloxane having a reactive group at one end with respect to a reactive group possessed by another polymerized unit. What is formed by carrying out a polymer reaction can also be used, and the following can be illustrated as such commercially available polysiloxane.
SS- (36): “Silaplane FM-0711” {manufactured by Chisso Corporation}
SS- (37): “Silaplane FM-0721” (same as above)
SS- (38): “Silaplane FM-0725” (same as above)

From the above viewpoints, the copolymer (A-1) in the present invention includes, in addition to the siloxane component (X), the hydroxyl group-containing structural unit (Z) represented by the general formula (2-Z), and an arbitrary one. The form consisting of the structural unit (Y) is preferred.

  The molar fraction (%) of each component when the remaining component excluding the siloxane component (X) from all the components is 100 (%) has a relationship of 0 ≦ y <100 and 0 <z ≦ 100. Selected to meet. X representing the mass fraction (%) of the siloxane component (X) with respect to all components satisfies the relationship of 40 ≦ x <100.

  In the copolymer (A-1) in the present invention, the siloxane component (X) is an essential component for imparting sufficient scratch resistance to the material, and for imparting transparency and antifouling durability. X representing a mass fraction (%) with respect to all components of (X) is preferably 50 ≦ x <100, and more preferably 60 ≦ x <95.

  In the copolymer (A-1), the hydroxyl group-containing structural unit (Z) is a unit containing a hydroxyl group that is a crosslinking group for preventing transfer. The range of the preferred molar fraction (%) z of the hydroxyl group-containing component (Z) when the remaining component excluding component X from all components is 100 (%) is 0 <z ≦ 100. More preferably, 20 <z ≦ 100.

  In the copolymer (A-1), the structural unit (Y) other than the siloxane component (X) and the hydroxyl group-containing structural unit (Z) is adhesive to the substrate, soluble in the solvent, and other coating solutions. You may introduce | transduce suitably, in order to provide various performances, such as compatibility with a composition and transparency. The range of the preferred molar fraction (%) y of the constituent component (Y) when the remaining constituent component excluding the constituent component X from all the constituent components is 100 (%) is 0 ≦ y ≦ 80, and more Preferably 0 ≦ y ≦ 60.

  Table 1 shows specific examples of the copolymer (A-1) particularly useful in the present invention, but the present invention is not limited thereto. In Table 1, x is a mass fraction (%) with respect to all components of the siloxane component (X), and y and z are 100% (%) of the remaining components obtained by removing the component X from all components. ) Is the molar fraction (%) of the constituent components (Y) and (Z).

In addition, the abbreviation in a table | surface represents the following.
The mass average molecular weight (Mw) of t-BuMA: t-butyl methacrylate MMA: methyl methacrylate copolymer (A-1) is preferably 10 ³ to 10 ⁶ , more preferably 5 × 10 ^{3 to} 5 ×. 10 ⁵ , particularly preferably 10 ⁴ to 10 ⁵ .

  Preferable examples of the copolymer (A) include a copolymer (A-2) having a structure represented by the general formula (3) in addition to the copolymer (A-1).

一般式（３）中、Ｒｆ¹¹は炭素数１〜５のペルフルオロアルキル基を表し、Ｒｆ¹²は炭素数１〜３０の直鎖、分岐又は脂環構造を有する含フッ素アルキル基を表し、エーテル結合を有していてもよい。
Ｂは水酸基含有モノマーに基づく重合単位を表す。
Ａは任意のビニルモノマーに基づく重合単位を表し、単一種であっても複数種で構成されていてもよい。すなわち単一のビニルモノマーから誘導されていても、複数のビニルモノマーから誘導されていてもよい。
Ｓは前記一般式（１）で表されるポリシロキサン構造を主鎖または側鎖に含む構成単位
を表し、単一種であっても複数種で構成されていてもよい。
ａ〜ｄは、全構成単位から構成単位Ｓを除いた残りの構成単位を１００（％）としたときの各構成単位のモル分率（％）を表し、０≦ａ≦９０、０≦ｂ≦７０、０≦ｃ≦５０、０＜ｄ、を満たす値を表す。ｅは構成単位Ｓの、全構成単位に対する質量分率（％）を表し、４０≦ｅ＜１００の関係を満たす。
以下、共重合体（Ａ−２）を構成する「構成単位」を「構成成分」ということがある。 General formula (3):

In the general formula (3), Rf ¹¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ¹² represents a fluorine-containing alkyl group having a straight-chain, branched or alicyclic structure having from 1 to 30 carbon atoms, an ether bond You may have.
B represents a polymerized unit based on a hydroxyl group-containing monomer.
A represents a polymerization unit based on an arbitrary vinyl monomer, and may be a single type or a plurality of types. That is, it may be derived from a single vinyl monomer or may be derived from a plurality of vinyl monomers.
S represents a structural unit containing the polysiloxane structure represented by the general formula (1) in the main chain or side chain, and may be composed of a single species or a plurality of species.
a to d represent the mole fraction (%) of each structural unit when the remaining structural unit excluding the structural unit S from the total structural unit is 100 (%), and 0 ≦ a ≦ 90, 0 ≦ b It represents a value satisfying ≦ 70, 0 ≦ c ≦ 50, and 0 <d. e represents the mass fraction (%) of the structural unit S relative to all the structural units, and satisfies the relationship of 40 ≦ e <100.
Hereinafter, the “constituent unit” constituting the copolymer (A-2) may be referred to as “constituent component”.

The polymer unit having Rf ¹¹ and the polymer unit having Rf ¹² are both polymer units based on a fluorine-containing vinyl monomer. Specific examples of the fluorine-containing vinyl monomer include fluoroolefins (for example, fluoroethylene, vinylidene fluoride). , Tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, etc.), perfluoro (alkyl vinyl ethers) {eg, perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether)}, perfluoro (alkoxyalkyl vinyl ether) s {For example, perfluoro (propoxypropyl vinyl ether)}. These may be used alone or in combination of two or more.

  From the viewpoint of refractive index, solubility, transparency, availability, etc., hexafluoropropylene alone or a combination of hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) is particularly preferable.

  In the general formula (3), A represents a polymerization unit based on an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component based on a monomer copolymerizable with hexafluoropropylene. It can be appropriately selected from various viewpoints such as adhesion to the material, Tg of the polymer (contributing to film hardness), solubility in a solvent, transparency, slipperiness, and dust / stain resistance. A plurality of these vinyl monomers may be combined depending on the purpose.

  The vinyl monomer unit that can be used as A is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylates (methyl acrylate, methyl acrylate, ethyl acrylate) , 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethyl) Styrene, p-methoxystyrene, etc.), fluorine-containing vinyl ethers, vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, cinnamic acid) Nyl), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, Nt-butylacrylamide, N-cyclohexylacrylamide, etc.), Examples include methacrylamides (N, N-dimethylmethacrylamide) and acrylonitrile.

  Of the vinyl monomers that can be used in combination, vinyl ethers or fluorine-containing vinyl ethers are preferably introduced from the viewpoint of further lowering the refractive index.

  The copolymer (A-2) represented by the general formula (3) has a polymer unit (hydroxyl group-containing polymer unit) based on the hydroxyl group-containing monomer represented by B in the general formula (3) as a constituent component. . By having an appropriate amount of the hydroxyl group, it is possible to effectively crosslink, bleed out over time or at high temperature, transfer of the silicone component to the contact medium, performance deterioration associated with these, contamination of the production line, etc. The effect of suppressing is acquired. The hydroxyl group-containing polymer unit B is not particularly limited, but is preferably a polymer unit based on a hydroxyl group-containing vinyl monomer from the viewpoint of polymerization. As the hydroxyl group-containing vinyl monomer, any vinyl ethers, (meth) acrylates, styrenes and the like can be used as long as they are copolymerizable with the above-described fluorine-containing monomer polymerization unit. For example, when perfluoroolefin (such as hexafluoropropylene) is used as the fluorine-containing monomer, it is preferable to use a hydroxyl group-containing vinyl ether having good copolymerization properties, specifically 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether. , 6-hydroxyhexyl vinyl ether, 8-hydroxyoctyl vinyl ether, diethylene glycol vinyl ether, triethylene glycol vinyl ether, 4- (hydroxymethyl) cyclohexyl methyl vinyl ether, and the like are suitable. These hydroxyl group-containing vinyl ethers may be introduced singly or in combination of two or more.

  Furthermore, the copolymer (A-2) represented by the general formula (3) includes an essential component represented by S in the general formula (3) and containing a polysiloxane structure in the main chain or side chain. As a constituent. By having the polysiloxane component, the amount of the copolymer (A-1) added is adjusted as appropriate, and the distribution of the polysiloxane component in the coating film is controlled, thereby making the material slippery, antifouling performance, and dustproof. It becomes possible to adjust the performance and scratch resistance. The polysiloxane component S may be a combination of a plurality of types depending on the purpose.

“a”, “b”, “c”, and “d” represent mol% of each constituent component, and represent values satisfying 0 ≦ a ≦ 90, 0 ≦ b ≦ 70, 0 ≦ c ≦ 50, and 0 <d.
Preferably, 30 ≦ a + b ≦ 90, 5 ≦ a ≦ 90, 0 ≦ b ≦ 70, 0 ≦ c ≦ 50, 10 ≦ d, and more preferably 35 ≦ a + b ≦ 70, 30 ≦ a ≦ 60. 0 ≦ b ≦ 30, 0 ≦ c ≦ 40, 20 ≦ d ≦ 60, particularly preferably 40 ≦ a + b ≦ 60, 40 ≦ a ≦ 55, 0 ≦ b ≦ 20, 0 ≦ c ≦ 30, This is the case of 25 ≦ d ≦ 60.

  E represents the mass% of the component S containing a polysiloxane structure in the main chain or side chain, and represents a range satisfying 40 ≦ e <100. The case is preferably 60 ≦ e <95, and particularly preferably 70 ≦ e <90.

The mass average molecular weight (Mw) of the copolymer (A-2) represented by the general formula (3) is preferably 10 ³ to 10 ⁶ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁵ . Yes, particularly preferably 10 ⁴ to 10 ⁵ .

A particularly preferred form of the copolymer (A-2) used in the present invention includes a copolymer (A-2 ′) represented by the general formula (3 ′). In general formula (3 ′), Rf ¹¹ , Rf ¹² , A, a, b, c, d, and e have the same meaning as in general formula (3), and the preferred ranges are also the same.

General formula (3 ′):

In the general formula (3 ′), L ³¹ represents a divalent linking group, preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, It may have a branched structure, may have a ring structure, and may have a heteroatom selected from O, N, and S.

Preferred examples of the linking group L ³¹ include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O — **, * _{- (CH 2) 6 -O -} **, * - (CH 2) 2 -O- (CH 2) 2 -O - **, - CONH- (CH 2) 3 -O - **, * - CH ₂ CH (OH) CH ₂ —O— *, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (* represents a linking site on the polymer main chain side, and ** represents a linking site on the hydroxyl side. For example).

(Preferred examples of each polymerization unit)
Although the preferable example of each polymerization unit in the copolymer (A-2 ') used for this invention shown by the said general formula (3') is shown below sequentially, this invention is not limited to these. .

  In the following, the fluorine-containing component represented by the general formula (Q) in the copolymer (A-2 ′) represented by the general formula (3 ′) and preferred examples thereof are shown. It is not limited to.

General formula (Q):

In the general formula (Q), Rf ¹¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms.

  In the following, the fluorine-containing component represented by the general formula (N) in the copolymer (A-2 ′) represented by the general formula (3 ′) and preferred examples thereof are shown. It is not limited to.

Formula (N):

In the general formula (N), Rf ¹² represents a fluorine-containing alkyl group having a straight-chain, branched or alicyclic structure having from 1 to 30 carbon atoms, which may have an ether bond.

  Although the preferable example of the polymerization unit A based on the arbitrary vinyl monomers in the copolymer (A-2 ') represented by the said general formula (3') below is shown, this invention is not limited to these.

  Although the hydroxyl-containing component represented by general formula (H) in the copolymer (A-2 ') represented by the said general formula (3') below and its preferable example are shown, this invention is these. It is not limited to.

Formula (H):

In the general formula (H), L ³¹ represents a divalent linking group, preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, and is branched even if it is linear. It may have a structure, may have a ring structure, and may have a hetero atom selected from O, N, and S.

  The component S containing a polysiloxane structure in the main chain or side chain in the copolymer (A-2 ′) represented by the general formula (3 ′) will be described below.

  As a method for synthesizing a copolymer containing a constituent component having a polysiloxane structure in the main chain, several methods have been conventionally proposed.

  For example, J. et al. C. Saam et al., “Macromolecules”, Vol. 3, page 1 (1970), reported that a styrene-dimethylsiloxane block copolymer was obtained by an anionic polymerization method (this method is hereinafter referred to as an anionic polymerization method). .

  In addition, in “Makromol. Chem., Rapid Commun.”, Vol. 5, page 559 (1984), a vinyl acetate-dimethylsiloxane block copolymer is obtained by a coupling reaction between prepolymers having functional groups. (This method is hereinafter referred to as a prepolymer method).

  Furthermore, Hiroshi Inoue et al. In “Science of Polymer Science Proceedings”, 34, 293 (1984), methyl methacrylate-dimethylsiloxane block copolymer by radical polymerization with azo group-containing polysiloxane amide having radical polymerization initiation ability. It has been reported that a coalescence was obtained (this method is hereinafter referred to as a polymer initiator method).

  However, in the anionic polymerization method and the prepolymer method, vinyl group monomers that can be applied to the reaction are limited, and the reaction process becomes multi-stage and the reaction conditions become difficult to use industrially. Yes. In order to produce a block copolymer industrially, it can be synthesized using radical polymerization, can be applied to many vinyl monomers, and preferably has few reaction steps.

  From the above viewpoints, the copolymers (A-2) and (A-3) used in the present invention are preferably produced by a polymer initiator method. Such a polymer initiator is, for example, a polysiloxane compound having a radical-generating group such as an azo group or a peroxy group. Such an initiator can be synthesized as described in, for example, Japanese Patent Publication No. 6-104711 and Japanese Patent Laid-Open No. 6-93100.

(Preferred examples of polymer initiator)
Preferred examples of such polymer initiators include polymer initiators S- (1) to S- (35) described in relation to the copolymer (A-1). In addition, this invention is not limited at all by these.

  The side chain polysiloxane partial structure will be described. The polysiloxane partial structure generally has a repeating siloxane moiety represented by the following general formula (11).

General formula (11):

In the general formula (11), R ²¹ and R ²² may be the same or different and each represents an alkyl group or an aryl group which may have a substituent. The alkyl group which may have a substituent preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, a trifluoromethyl group, and an ethyl group. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.
p1 represents an integer of 10 to 500, preferably 10 to 350, and particularly preferably 10 to 250.

  A copolymer having a polysiloxane structure represented by the general formula (11) in the side chain is, for example, “JA Appl. Polym. Sci.”, 2000, p. 78 (1955), as disclosed in JP-A-56-28219, etc., a reactive group having reactivity with a polymer having a reactive group such as an epoxy group, a hydroxyl group, a carboxyl, or an acid anhydride group. Polysiloxane [for example, “Silaplane” series {manufactured by Chisso Corporation, etc.] having a polymer at one end (for example, an amino group, a mercapto group, a carboxyl group, a hydroxyl group, etc. with respect to an epoxy group or an acid anhydride group) is a polymer. It can be synthesized by a method of introducing by reaction; a method of polymerizing a polysiloxane-containing silicon macromer, and both methods can be preferably used. In the present invention, a method of introducing by polymerization of silicon macromer is more preferable.

  Preferable examples of the polymer units containing a polysiloxane moiety in the side chain useful in the present invention include polymer units SS- (1) to SS- (38) described in relation to the copolymer (A-1). Is mentioned. The present invention is not limited to these.

  Specific examples of copolymers (A-2) and (A-2 ′) useful in the present invention are shown in Table 2, but the present invention is not limited thereto.

In addition, the abbreviation in a table | surface represents the following.
Q: Polymerized unit represented by the above general formula (Q) N: Polymerized unit represented by the above general formula (N) M1: Polymerized unit A based on any vinyl monomer
H: Polymer unit represented by the general formula (H) S: Component S containing a polysiloxane structure in the main chain or side chain
a: Mole fraction (%) of polymerized units Q when the remaining constituents excluding constituent S from all constituents are taken as 100 (%)
b: mole fraction (%) of polymerized units N when the remaining constituents excluding constituent S from all constituents are taken as 100 (%)
c: Mole fraction (%) of polymerized units M1 when the remaining constituents excluding constituent S from all constituents are taken as 100 (%)
d: mole fraction (%) of polymerized units H when the remaining constituents excluding constituent S from all constituents are taken as 100 (%)
e: Mass fraction (%) of component S relative to all components
Mw: mass average molecular weight

(Synthesis of copolymer (A))
The copolymer (A) represented by the general formulas (2) and (3) used in the present invention can be synthesized by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. Can be done by. Moreover, it is compoundable by well-known operations, such as a batch type, a semi-continuous type, and a continuous type.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are, for example, the revised version of Tsuruta Junji “Polymer Synthesis Method” (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masato Kinoshita, “Experimental Methods for Polymer Synthesis” It is described in pp. 47-154 published in 1972.

  Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable. Solvents used in the solution polymerization method are, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, Each of various organic solvents such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol may be used alone or as a mixture of two or more kinds, or as a mixed solvent with water. Good.

  The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc., and can be from 0 ° C. or lower to 100 ° C. or higher, but it is preferable to perform the polymerization in the range of 50 to 100 ° C. .

  The reaction pressure can be appropriately selected, but is usually 0.01 to 10 MPa, preferably 0.05 to 5 MPa, more preferably about 0.1 to 2 MPa. The reaction time is about 5 to 30 hours.

  When introducing a polysiloxane moiety using a polymer initiator, other radical initiators can be used in combination as required.

  Examples of the radical initiator that can be used in combination include diacyl peroxides such as acetyl peroxide and benzoyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; hydroperoxides such as hydrogen peroxide, t-butyl hydroperoxide and cumene hydroperoxide; Dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide and dilauroyl peroxide; peroxy esters such as t-butyl peroxyacetate and t-butyl peroxypivalate; azobisisobutyronitrile and azobisisovalero Azo compounds such as nitrile; persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate; perfluoroethyl iodide, perfluoropropyl iodide Zido, perfluorobutyl iodide, (perfluorobutyl) ethyl iodide, perfluorohexyl iodide, 2- (perfluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluorodecyl iodide, 2, -(Perfluorodecyl) ethyl iodide, heptafluoro-2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5-methylhexyl iodide, 2- (perfluoro-5-methylhexyl) ethyl iodide, perfluoro-7-methyl Octyl iodide, 2- (perfluoro-7-methyloctyl) ethyl iodide, perfluoro-9-methyldecyl iodide, 2- (perfluoro-9-methylde L) Ethyl iodide, 2,2,3,3-tetrafluoropropyl iodide, 1H, 1H, 5H-octafluoropentyl iodide, 1H, 1H, 7H-dodecafluoroheptyl iodide, tetrafluoro-1,2-diiodoethane And iodine-containing fluorine compounds such as octafluoro-1,4-diiodobutane and dodecafluoro-1,6-diiodohexane.

  The iodine-containing fluorine compound can be used alone or in combination with the organic peroxide, azo compound or persulfate.

  The radical polymerization initiator may be used in combination with an inorganic reducing agent such as sodium hydrogen sulfite and sodium pyrosulfite, and an organic reducing agent such as cobalt naphthenate and dimethylaniline, as necessary.

  The obtained polymer can be used as it is for the application of the present invention, or can be purified by reprecipitation or liquid separation operation.

  As the reprecipitation solvent for the obtained polymer, water, isopropanol, hexane, methanol, and a mixed solvent thereof are preferable.

2- (1) -2. {(B): The structural unit containing the polysiloxane structure represented by the following general formula (1) in the main chain or the side chain is contained in the component (B) by mass A fluorine-containing copolymer having a polymerization unit based on a hydroxyl group-containing monomer and having a percentage of 0% to 20%

The copolymer (B) is a fluorine-containing copolymer having a polymer unit based on a hydroxyl group-containing monomer. The fluorine-containing copolymer (B) has a high fluorine atom content in the molecule, and the effect of lowering the refractive index of the coating film is obtained. Furthermore, the fluorine-containing copolymer (B) is excellent in compatibility with the copolymer (A), and the effect that it is excellent in surface shape is obtained.
Hereinafter, in the copolymer (B), “a structural unit containing a polysiloxane structure in the main chain or side chain” is referred to as “polysiloxane component”, “a polymerization unit based on a hydroxyl group-containing monomer” is referred to as “hydroxyl group-containing polymerization unit”, and There is something to say.

General formula (1):

In general formula (1), R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group.

The alkyl group which may have a substituent preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, a trifluoromethyl group, and an ethyl group. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.
p represents an integer of 10 to 500, preferably 50 to 300, and particularly preferably 100 to 250.

  The fluorine content of the fluorine-containing copolymer (B) is preferably 30% by mass or more, and more preferably 40 to 60% by mass.

  The fluorine-containing copolymer (B) preferably has a structure represented by the general formula (4).

General formula (4):

In the general formula (4), Rf ¹¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ¹² represents a fluorine-containing alkyl group having a straight-chain, branched or alicyclic structure having from 1 to 30 carbon atoms, an ether bond You may have.
B represents a polymerized unit based on a hydroxyl group-containing monomer.
A represents a polymerized unit based on a hydroxyl group-containing monomer. A represents a polymerization unit based on an arbitrary vinyl monomer, and may be a single type or a plurality of types. That is, it may be derived from a single vinyl monomer or may be derived from a plurality of vinyl monomers.
S represents a constituent component containing the polysiloxane structure represented by the general formula (1) in the main chain or side chain, and may be a single type or a plurality of types.
a to d represent the mole fraction (%) of each structural unit when the remaining structural unit excluding the structural unit S from the total structural unit is 100 (%), and 0 ≦ a ≦ 90, 0 ≦ b It represents a value satisfying ≦ 70, 0 ≦ c ≦ 50, and 0 <d. e represents the mass fraction (%) of the structural unit S relative to all the structural units, and satisfies the relationship of 0 ≦ e ≦ 20.
Hereinafter, the “constituent unit” constituting the fluorinated copolymer (B) may be referred to as “constituent component”.

The polymer unit having Rf ¹¹ and the polymer unit having Rf ¹² are both polymer units based on a fluorine-containing vinyl monomer. Specific examples of the fluorine-containing vinyl monomer include fluoroolefins (for example, fluoroethylene, vinylidene fluoride). , Tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, etc.), perfluoro (alkyl vinyl ethers) {eg, perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether)}, perfluoro (alkoxyalkyl vinyl ether) s {For example, perfluoro (propoxypropyl vinyl ether)}. These may be used alone or in combination of two or more.

  From the viewpoint of refractive index, solubility, transparency, availability, etc., hexafluoropropylene alone or a combination of hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) is particularly preferable.

  In the general formula (4), A represents a polymer unit based on an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component based on a monomer copolymerizable with hexafluoropropylene. It can be appropriately selected from various viewpoints such as adhesion to the material, Tg of the polymer (contributing to film hardness), solubility in a solvent, transparency, slipperiness, and dust / stain resistance. A plurality of these vinyl monomers may be combined depending on the purpose.

  The vinyl monomer unit that can be used as A is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylates (methyl acrylate, methyl acrylate, ethyl acrylate) , 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethyl) Styrene, p-methoxystyrene, etc.), fluorine-containing vinyl ethers, vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, cinnamic acid) Nyl), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, Nt-butylacrylamide, N-cyclohexylacrylamide, etc.), Examples include methacrylamides (N, N-dimethylmethacrylamide) and acrylonitrile.

  Of the vinyl monomers that can be used in combination, vinyl ethers or fluorine-containing vinyl ethers are preferably introduced from the viewpoint of further lowering the refractive index.

  The copolymer represented by the general formula (4) has a polymer unit (hydroxyl group-containing polymer unit) based on the hydroxyl group-containing monomer represented by B in the general formula (4) as a constituent component. Since the hydroxyl group has a function of reacting with the crosslinking agent and curing, the higher the hydroxyl group content, the better the anchoring function to the low refractive index layer film. The hydroxyl group-containing polymer unit B is not particularly limited, but is preferably a polymer unit based on a hydroxyl group-containing vinyl monomer from the viewpoint of polymerization. As the hydroxyl group-containing vinyl monomer, any vinyl ethers, (meth) acrylates, styrenes and the like can be used as long as they are copolymerizable with the above-described fluorine-containing monomer polymerization unit. For example, when perfluoroolefin (such as hexafluoropropylene) is used as the fluorine-containing monomer, it is preferable to use a hydroxyl group-containing vinyl ether having good copolymerization properties, specifically 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether. , 6-hydroxyhexyl vinyl ether, 8-hydroxyoctyl vinyl ether, diethylene glycol vinyl ether, triethylene glycol vinyl ether, 4- (hydroxymethyl) cyclohexyl methyl vinyl ether, and the like are suitable. These hydroxyl group-containing vinyl ethers may be introduced singly or in combination of two or more.

  Furthermore, the copolymer represented by the general formula (4) has, as an optional constituent, a constituent component represented by S in the general formula (4) that includes a polysiloxane structure in the main chain or side chain. The S component is not particularly limited as long as it is a constituent component containing a polysiloxane structure, and can be appropriately selected from the viewpoint of antifouling properties, scratch resistance, suitability for saponification, and the like. A plurality of types of S component may be combined depending on the purpose.

“a”, “b”, “c”, and “d” represent mol% of each constituent component, and represent values satisfying 0 ≦ a ≦ 90, 0 ≦ b ≦ 70, 0 ≦ c ≦ 50, and 0 <d.
Preferably, 30 ≦ a + b ≦ 90, 5 ≦ a ≦ 90, 0 ≦ b ≦ 70, 0 ≦ c ≦ 50, 10 ≦ d, and more preferably 35 ≦ a + b ≦ 70, 30 ≦ a ≦ 60. 0 ≦ b ≦ 30, 0 ≦ c ≦ 40, 20 ≦ d ≦ 60, particularly preferably 40 ≦ a + b ≦ 60, 40 ≦ a ≦ 55, 0 ≦ b ≦ 20, 0 ≦ c ≦ 30, This is the case of 20 ≦ d ≦ 50.

  E represents the mass% of the component S containing a polysiloxane structure in the main chain or side chain, and represents a range satisfying 0 ≦ e ≦ 20. Preferred is the case of 0 ≦ e ≦ 10, more preferred is the case of 0 ≦ e ≦ 5, and particularly preferred is the case of 0 ≦ e ≦ 3.

The mass average molecular weight (Mw) of the fluorine-containing copolymer represented by the general formula (4) is preferably 10 ³ to 10 ⁶ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁵ , particularly The case of 10 ⁴ to 10 ⁵ is preferred.

A particularly preferred form of the fluorinated copolymer used in the present invention is a copolymer represented by the general formula (4 ′). In the general formula (4 ′), Rf ¹¹ , Rf ¹² , A, a, b, c, d, and e have the same meaning as in the general formula (4), and the preferred range is also the same.

General formula (4 ′):

In General Formula (4 ′), L ³¹ represents a divalent linking group, preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, It may have a branched structure, may have a ring structure, and may have a heteroatom selected from O, N, and S.

Preferred examples of the linking group L ³¹ include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O — **, * _{- (CH 2) 6 -O -} **, * - (CH 2) 2 -O- (CH 2) 2 -O - **, - CONH- (CH 2) 3 -O - **, * - CH ₂ CH (OH) CH ₂ —O— *, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (* represents a linking site on the polymer main chain side, and ** represents a linking site on the hydroxyl side. For example).

(Preferred examples of each polymerization unit)
Although the preferable example of each polymerization unit in the fluorine-containing copolymer (B) used for this invention shown by the said general formula (4 ') is shown below sequentially, this invention is not limited to these.

  Examples of the fluorine-containing component represented by the general formula (Q) in the fluorine-containing copolymer (B) represented by the general formula (4 ′) and preferred examples thereof include the copolymer (A). Fluorine-containing components Q-1) to Q-4) described in relation to this can be mentioned. The present invention is not limited to these.

General formula (Q):

In the general formula (Q), Rf ¹¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms.

  Examples of the fluorine-containing component represented by the general formula (N) in the fluorine-containing copolymer (B) represented by the general formula (4 ′) and preferred examples thereof include the copolymer (A). Fluorine-containing components N-1) to N-6) described in relation to them. The present invention is not limited to these.

Formula (N):

In the general formula (N), Rf ¹² represents a fluorine-containing alkyl group having a straight-chain, branched or alicyclic structure having from 1 to 30 carbon atoms, which may have an ether bond.

  Preferred examples of the polymer unit A based on an arbitrary vinyl monomer in the fluorine-containing copolymer (B) represented by the general formula (4 ′) are described in relation to the copolymer (A). And polymerized units M1- (1) to M1- (51). The present invention is not limited to these.

  In the fluorine-containing copolymer (B) represented by the general formula (4 ′), the hydroxyl group-containing component represented by the general formula (H), and preferred examples thereof include the copolymer (A). Examples of the polymerized units H-1) to H-4) described above are mentioned. The present invention is not limited to these.

Formula (H):

In the general formula (H), L ³¹ represents a divalent linking group, preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, and is branched even if it is linear. It may have a structure, may have a ring structure, and may have a hetero atom selected from O, N, and S.

  The component S containing a polysiloxane structure in the main chain or side chain in the fluorine-containing copolymer (B) represented by the general formula (4 ′) will be described below.

  As a method for synthesizing a copolymer containing a constituent component having a polysiloxane structure in the main chain, several methods have been conventionally proposed.

  For example, J. et al. C. Saam et al., “Macromolecules”, Vol. 3, page 1 (1970), reported that a styrene-dimethylsiloxane block copolymer was obtained by an anionic polymerization method (this method is hereinafter referred to as an anionic polymerization method). .

  In addition, in “Makromol. Chem., Rapid Commun.”, Vol. 5, page 559 (1984), a vinyl acetate-dimethylsiloxane block copolymer is obtained by a coupling reaction between prepolymers having functional groups. (This method is hereinafter referred to as a prepolymer method).

  Furthermore, Hiroshi Inoue et al. In “Science of Polymer Science Proceedings”, 34, 293 (1984), methyl methacrylate-dimethylsiloxane block copolymer by radical polymerization with azo group-containing polysiloxane amide having radical polymerization initiation ability. It has been reported that a coalescence was obtained (this method is hereinafter referred to as a polymer initiator method).

  However, in the anionic polymerization method and the prepolymer method, vinyl group monomers that can be applied to the reaction are limited, and the reaction process becomes multi-stage and the reaction conditions become difficult to use industrially. Yes. In order to produce a block copolymer industrially, it can be synthesized using radical polymerization, can be applied to many vinyl monomers, and preferably has few reaction steps.

  From the above viewpoint, it is preferable that the fluorine-containing copolymer (B) used in the present invention is produced by a polymer initiator method. Such a polymer initiator is, for example, a polysiloxane compound having a radical-generating group such as an azo group or a peroxy group. Such an initiator can be synthesized as described in, for example, Japanese Patent Publication No. 6-104711 and Japanese Patent Laid-Open No. 6-93100.

(Preferred examples of polymer initiator)
Preferred examples of such polymer initiators include polymer initiators S- (1) to S- (35) described in relation to the copolymer (A). In addition, this invention is not limited at all by these.

  The side chain polysiloxane partial structure will be described. The polysiloxane partial structure generally has a repeating siloxane moiety represented by the following general formula (11).

General formula (11):

In the general formula (11), R ²¹ and R ²² may be the same or different and each represents an alkyl group or an aryl group which may have a substituent. The alkyl group which may have a substituent preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, a trifluoromethyl group, and an ethyl group. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.
p1 represents an integer of 10 to 500, preferably 10 to 350, and particularly preferably 10 to 250.

  The fluorine-containing copolymer having a polysiloxane structure represented by the general formula (11) in the side chain is, for example, “JA Appl. Polym. Sci.”, 2000, p. 78 (1955), as disclosed in JP-A-56-28219, etc., a reactive group having reactivity with a polymer having a reactive group such as an epoxy group, a hydroxyl group, a carboxyl, or an acid anhydride group. Polysiloxane [for example, “Silaplane” series {manufactured by Chisso Corporation, etc.] having a polymer at one end (for example, an amino group, a mercapto group, a carboxyl group, a hydroxyl group, etc. with respect to an epoxy group or an acid anhydride group) is a polymer. It can be synthesized by a method of introducing by reaction; a method of polymerizing a polysiloxane-containing silicon macromer, and both methods can be preferably used. In the present invention, a method of introducing by polymerization of silicon macromer is more preferable.

  Preferable examples of polymerized units containing a polysiloxane moiety in the side chain useful for the present invention include polymerized units SS- (1) to SS- (38) described in relation to the copolymer (A). It is done. The present invention is not limited to these.

  Specific examples of the fluorine-containing copolymer (B) useful in the present invention are shown in Table 3, but the present invention is not limited thereto.

In addition, the abbreviation in a table | surface represents the following.
Q: Polymerized unit represented by the above general formula (Q) N: Polymerized unit represented by the above general formula (N) M1: Polymerized unit A based on any vinyl monomer
H: Polymer unit represented by the general formula (H) S: Component S containing a polysiloxane structure in the main chain or side chain
a: Mole fraction (%) of polymerized units Q when the remaining constituents excluding constituent S from all constituents are taken as 100 (%)
b: mole fraction (%) of polymerized units N when the remaining constituents excluding constituent S from all constituents are taken as 100 (%)
c: Mole fraction (%) of polymerized units M1 when the remaining constituents excluding constituent S from all constituents are taken as 100 (%)
d: mole fraction (%) of polymerized units H when the remaining constituents excluding constituent S from all constituents are taken as 100 (%)
e: Mass fraction (%) of component S relative to all components
Mw: mass average molecular weight

(Synthesis of fluorinated copolymer (B))
The fluorine-containing copolymer represented by the general formula (4) used in the present invention can be synthesized by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. . Moreover, it is compoundable by well-known operations, such as a batch type, a semi-continuous type, and a continuous type.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are, for example, the revised version of Tsuruta Junji “Polymer Synthesis Method” (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masato Kinoshita, “Experimental Methods for Polymer Synthesis” It is described in pp. 47-154 published in 1972.

  Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable. Solvents used in the solution polymerization method are, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, Each of various organic solvents such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol may be used alone or as a mixture of two or more kinds, or as a mixed solvent with water. Good.

  The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc., and can be from 0 ° C. or lower to 100 ° C. or higher, but it is preferable to perform the polymerization in the range of 50 to 100 ° C. .

  The reaction pressure can be appropriately selected, but is usually 0.01 to 10 MPa, preferably 0.05 to 5 MPa, more preferably about 0.1 to 2 MPa. The reaction time is about 5 to 30 hours.

  When introducing a polysiloxane moiety using a polymer initiator, other radical initiators can be used in combination as required.

Examples of radical initiators that can be used in combination include diacyl peroxides such as acetyl peroxide and benzoyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; hydroperoxides such as hydrogen peroxide, t-butyl hydroperoxide and cumene hydroperoxide; Dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, dilauroyl peroxide; t-
Peroxyesters such as butylperoxyacetate and t-butylperoxypivalate; azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile; persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate Perfluoroethyl iodide, perfluoropropyl iodide, perfluorobutyl iodide, (perfluorobutyl) ethyl iodide, perfluorohexyl iodide, 2- (perfluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ) Ethyl iodide, perfluorodecyl iodide, 2- (perfluorodecyl) ethyl iodide, heptafluoro-2-iodopropane, perfluoro-3-methylbutyl iodide, Rufluoro-5-methylhexyl iodide, 2- (perfluoro-5-methylhexyl) ethyl iodide, perfluoro-7-methyloctyl iodide, 2- (perfluoro-7-methyloctyl) ethyl iodide, perfluoro-9-methyldecyl iodide 2- (perfluoro-9-methyldecyl) ethyl iodide, 2,2,3,3-tetrafluoropropyl iodide, 1H, 1H, 5H-octafluoropentyl iodide, 1H, 1H, 7H-dodecafluoroheptyl iodide, Mention may be made of iodine-containing fluorine compounds such as tetrafluoro-1,2-diiodoethane, octafluoro-1,4-diiodobutane, dodecafluoro-1,6-diiodohexane.

  The iodine-containing fluorine compound can be used alone or in combination with the organic peroxide, azo compound or persulfate.

  The radical polymerization initiator may be used in combination with an inorganic reducing agent such as sodium hydrogen sulfite and sodium pyrosulfite, and an organic reducing agent such as cobalt naphthenate and dimethylaniline, as necessary.

  The obtained polymer can be used as it is for the application of the present invention, or can be purified by reprecipitation or liquid separation operation.

  As the reprecipitation solvent for the obtained polymer, water, isopropanol, hexane, methanol, and a mixed solvent thereof are preferable.

Among the components of the curable composition of the present invention,
(A) The structural unit containing the polysiloxane structure represented by the following general formula (1) in the main chain or side chain is 40 (%) or more and 100 (%) in mass fraction with respect to all the structural units in the component (A). A copolymer having a polymerization unit based on a hydroxyl group-containing monomer,
(B) The structural unit containing the polysiloxane structure represented by the following general formula (1) in the main chain or side chain is 0 (%) or more and 20 (% by mass fraction with respect to all the structural units in the component (B). ) A fluorine-containing copolymer having a polymerization unit based on a hydroxyl group-containing monomer,
The blending ratio of the silicone component in the copolymer (A) and the fluorine-containing copolymer (B) is 0.1 to 40% by mass based on the total solid mass of the curable composition. It is preferable to mix | blend so that it may become, and it is still more preferable to mix | blend so that it may become 1-15 mass%. If it is 40% by mass or less, the scratch resistance is sufficient and the surface state does not deteriorate. Moreover, if it is 0.1 mass% or more, required antifouling performance can be obtained.

General formula (1):

In general formula (1), R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group. p represents an integer of 10 to 500.

2- (1) -3. {(C) Curing agent capable of reacting with hydroxyl group}
The curable composition for the low refractive index layer used in the antireflection film of the present invention is a compound that can react with the hydroxyl group of the copolymer (A) and the hydroxyl group of the fluorinated copolymer (B) (C ) Contains a curing agent. The curing agent preferably has two or more sites that react with a hydroxyl group, and more preferably has four or more sites. The structure of the curing agent is not particularly limited as long as it has the above number of functional groups capable of reacting with hydroxyl groups. For example, polyisocyanates, partial condensates of isocyanate compounds, multimers, polyhydric alcohols, low molecular weight polyester films And the like, block polyisocyanate compounds in which isocyanate groups are blocked with a blocking agent such as phenol, aminoplasts, polybasic acids or anhydrides thereof.

(Aminoplasts)
Among them, in the present invention, aminoplasts that undergo a crosslinking reaction with a hydroxyl group-containing compound under acidic conditions are preferable from the viewpoints of both the stability during storage and the activity of the crosslinking reaction, and the strength of the formed film. Aminoplasts are adjacent to the amino group capable of reacting with the hydroxyl group present in the copolymer (A) and the fluorine-containing copolymer (B), that is, a hydroxyalkylamino group or an alkoxyalkylamino group, or a nitrogen atom, and It is a compound containing a carbon atom substituted with an alkoxy group. A compound having two or more carbon atoms adjacent to a nitrogen atom and substituted with an alkoxy group is preferable. Specific examples include melamine compounds, urea compounds, benzoguanamine compounds, glycoluril compounds, and the like.

  The melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples include melamine, alkylated melamine, methylol melamine, and alkoxylated methyl melamine. . In particular, methylolated melamine and alkoxylated methyl melamine obtained by reacting melamine and formaldehyde under basic conditions and derivatives thereof are preferable, and alkoxylated methyl melamine is particularly preferable in view of storage stability. There are no particular restrictions on methylolated melamine and alkoxylated methylmelamine. For example, various resins obtained by the method described in Plastic Materials Course [8] Urea Melamine Resin (Nikkan Kogyo Shimbun) can be used. is there.

  In addition to urea, polymethylolated urea and derivatives thereof, alkoxylated methylurea, and compounds having a glycoluril skeleton and a 2-imidazolidinone skeleton having a cyclic urea structure are also preferable as the urea compound. As for the amino compounds such as the urea derivatives, various resins described in the above-mentioned “Yurea / Melamine resin” can be used.

  The amino compound used in the production of the curable composition used in the present invention is particularly preferably a melamine compound or a glycoluril compound from the viewpoint of compatibility with the fluorine-containing copolymer and the polysiloxane structure-containing copolymer. In view of reactivity, alkoxylated methylated melamine compounds or glycoluril compounds are preferred. Among them, the crosslinking agent is preferably a compound containing a nitrogen atom in the molecule and two or more carbon atoms substituted with an alkoxy group adjacent to the nitrogen atom. Particularly preferred compounds are compounds represented by the following structural formulas (H-1) and (H-2), and partial condensates thereof. In the formula, R represents an alkyl group having 1 to 6 carbon atoms or a hydroxyl group.

Structural formulas (H-1) and (H-2):

Among the curable compositions of the present invention,
(A) The structural unit containing the polysiloxane structure represented by the following general formula (1) in the main chain or side chain is 40 (%) or more and 100 (%) in mass fraction with respect to all the structural units in the component (A). A copolymer having a polymerization unit based on a hydroxyl group-containing monomer,
(B) The structural unit containing the polysiloxane structure represented by the following general formula (1) in the main chain or side chain is 0 (%) or more and 20 (% by mass fraction with respect to all the structural units in the component (B). ) A fluorine-containing copolymer having a polymerization unit based on a hydroxyl group-containing monomer,
(C) a curing agent capable of reacting with a hydroxyl group,
The blending ratio of (C) the solid content mass of the curing agent capable of reacting with a hydroxyl group is 1 to 100 mass% with respect to the sum of the solid mass of the copolymer (A) and the fluorinated copolymer (B). It is preferable to mix | blend so that it may become, it is still more preferable to mix | blend so that it may become 5-60 mass%, and it is especially preferable to mix | blend so that it may become 10-30 mass%. If it is 100% by mass or less, the reflectance due to the increase in the refractive index of the coating film does not deteriorate, and if it is 1% by mass or more, the necessary hardness can be obtained and the scratch resistance is sufficient. .

Of the curable composition of the present invention,
The total solid content of the copolymer (A), the fluorinated copolymer (B), and the curing agent (C) is 1 to 100% by mass based on the solid content of the curable composition. It is preferable to add 10 to 80% by mass.

General formula (1):

In general formula (1), R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group. p represents an integer of 10 to 500.

2- (1) -4. {(D) Curing catalyst}
When the curable composition for the low refractive index layer used in the antireflection film of the present invention reacts with the hydroxyl groups of the copolymer (A), the fluorinated copolymer (B), and the curing agent (C). Contains an acidic substance (acid catalyst) that serves as a catalyst. Curing is accelerated by the acid catalyst. In order to achieve both storage stability and curing activity, it is more preferable to add a compound that generates an acidic substance by heating (thermal acid generator) and / or a compound that generates acid by light irradiation (photosensitive acid generator). preferable.

(Thermal acid generator)
The thermal acid generator that can be blended in the curable composition used in the present invention, when heating and curing the coating film of the curable composition, makes the heating conditions milder. It is a substance that can be improved. In this system, since curing is accelerated by an acid, it is preferable to add an acidic substance to the curable composition. On the other hand, when a normal acid is added, a crosslinking reaction proceeds even in the coating solution, which causes failure (unevenness, repelling, etc.). Therefore, in order to achieve both storage stability and curing activity in a thermosetting system, it is more preferable to add a compound that generates an acid by heating (thermal acid generator) as a curing catalyst.

  Specific examples of the thermal acid generator include various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid and maleic acid, and various aromatic carboxylic acids such as benzoic acid and phthalic acid. Acids and salts thereof, aromatic sulfonic acids and ammonium salts thereof, various amine salts and various metal salts, phosphonic acids and salts thereof, organic acids and salts thereof, inorganic acids such as sulfuric acid and phosphoric acid and salts thereof, organic acids Examples thereof include phosphoric acid esters. The thermal acid generator is preferably a salt composed of an acid and an organic base. Among these, from the viewpoint of compatibility with the polymer, a salt composed of an organic acid and an organic base is more preferable, an aliphatic sulfonic acid, an aromatic sulfonic acid, and / or a salt composed of a phosphonic acid and an organic base is more preferable. Most preferred is a salt comprising an acid and / or an aromatic sulfonic acid and an organic base.

  Preferred aliphatic sulfonic acids and / or aromatic sulfonic acids include p-toluenesulfonic acid (PTS), benzenesulfonic acid (BS), p-dodecylbenzenesulfonic acid (DBS), p-chlorobenzenesulfonic acid (CBS), 1,4-naphthalenedisulfonic acid (NDS), methanesulfonic acid (MsOH), nonafluorobutane-1-sulfonic acid (NFBS), and the like can be mentioned, and any of them can be preferably used (the abbreviations in parentheses).

  The curing catalyst varies greatly depending on the basicity and boiling point of the organic base combined with the acid. The curing catalyst preferably used in the present invention is described below from each viewpoint.

  The lower the basicity of the organic base, the higher the acid generation efficiency during heating, which is preferable from the viewpoint of curing activity. However, if the basicity is too low, the storage stability becomes insufficient. Therefore, it is preferable to use an organic base having an appropriate basicity. When expressed using pKa of a conjugate acid as a basic index, the pKa of the organic base used in the present invention is preferably 5.0 to 11.0, and more preferably 6.0 to 10.5. 6.5 to 10.0 is more preferable. The value of pKa of organic base in aqueous solution is described in Chemical Handbook Fundamentals (5th revised edition, edited by The Chemical Society of Japan, Maruzen, 2004) Volume II, pages II-334 to 340. An organic base having an appropriate pKa can be selected. In addition, a compound that can be presumed to have a pKa that is structurally appropriate even if not described in this document can be preferably used. Table 3 shows compounds having an appropriate pKa described in the literature, but compounds that can be preferably used in the present invention are not limited thereto.

  The lower the boiling point of the organic base, the higher the acid generation efficiency during heating, which is preferable from the viewpoint of curing activity. Therefore, it is preferable to use an organic base having an appropriate boiling point. The boiling point of the base is preferably 120 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower.

Examples of the organic base that can be preferably used in the present invention include, but are not limited to, the following compounds. Figures in parentheses indicate boiling points.
b-3: pyridine (115 ° C), b-14: N-methylmorpholine (115 ° C), b-20: diallylmethylamine (111 ° C), b-19: triethylamine (88.8 ° C), b-21 : T-butylmethylamine (67-69 ° C), b-22: dimethylisopropylamine (66 ° C), b-23: diethylmethylamine (63-65 ° C), b-24: dimethylethylamine (36-38 ° C) ), B-18: trimethylamine (3-5 ° C.).

  When used as a thermal acid generator, a salt composed of the acid and the organic base may be isolated and used, or the acid and the organic base may be mixed to form a salt in the solution, and the solution may be used. Further, only one kind of acid or organic base may be used, or a plurality of kinds may be mixed and used. When the acid and the organic base are mixed and used, it is preferable that the equivalent ratio of the acid and the organic base is 1: 0.9 to 1.5, preferably 1: 0.95 to 1.3. Is more preferable, and 1: 1.0 to 1.1 is preferable.

  The use ratio of the thermal acid generator is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the fluorinated copolymer (B) and the copolymer (A) in the curable composition. More preferably, it is 0.1-5 mass parts. If this ratio is below the said upper limit, it is preferable, without the storage stability of a curable composition being inferior.

(Photosensitive acid generator)
In the present invention, in addition to the thermal acid generator described above, a compound that generates an acid upon irradiation with light, that is, a photosensitive acid generator may be further added. The photoacid generator that can be used in the present invention is described in detail below.
Examples of the acid generator include a photoinitiator for photocationic polymerization, a photodecolorant for dyes, a photochromic agent, a known acid generator used in a microresist, and the like, a known compound, and a mixture thereof. Is mentioned. The photosensitive acid generator is a substance that imparts photosensitivity to the coating film of the curable composition and enables the coating film to be photocured by, for example, irradiation with radiation such as light. Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, iminium salt, arsonium salt, selenonium salt, pyridinium salt; (2) β Sulfone compounds such as ketoesters and β-sulfonylsulfones and their α-diazo compounds; (3) sulfonic acid esters such as alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters and iminosulfonates; and (4) sulfones. Imide compounds; (5) Diazomethane compounds; and the like, and can be used as appropriate. Of these, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of photosensitivity at the start of photopolymerization, material stability of the compound, and the like. Examples thereof include compounds described in paragraph numbers [0058] to [0059] of JP-A-2002-29162.

  The photosensitive acid generator can be used alone or in combination of two or more, and can also be used in combination with the thermal acid generator. The proportion of the photosensitive acid generator used is preferably 0 to 20 parts by mass, more preferably 100 parts by mass in total of the fluorinated copolymer (B) and the copolymer (A) in the curable composition. Is 0.1 to 10 parts by mass. If the ratio of the photosensitive acid generator is less than or equal to the upper limit, it is preferable because the resulting cured film has excellent strength and good transparency.

The photosensitive acid generator can be used for layers other than the above-described low refractive index layer, for example, a hard coat layer, and the use ratio thereof is preferably 100 parts by weight of the curable resin composition for forming the hard coat layer. Is 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.
In addition, as specific compounds and methods of use, for example, the contents described in JP-A-2005-43876 can be used.

2- (1) -5. {(E) Organosilane compound or hydrolyzate and / or partial condensate of the organosilane compound}
As the curable composition of the present invention, in addition to the copolymer (A) and the fluorine-containing copolymer (B), (E) an organosilane compound or a hydrolyzate of the organosilane compound and / or a partial condensation thereof. It is preferable to use a composition composed of a product (hereinafter also referred to as “sol component”). As the organosilane compound, an organosilane represented by the following general formula (5-0) produced in the presence of at least one of an acid catalyst and a metal chelate compound is preferably used. Next, this organosilane compound will be described in detail.

Formula (5-0): (R ³⁰ ) _m1 -Si (X ³¹ ) _4-m1

In General Formula (5-0), R ³⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, hexyl group, t-butyl group, s-butyl group, hexyl group, decyl group, hexadecyl group and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.

X ³¹ represents a hydroxyl group or a hydrolyzable group. As the hydrolyzable group, for example, an alkoxy group (an alkoxy group having 1 to 5 carbon atoms is preferable. For example, a methoxy group, an ethoxy group, etc.), a halogen atom (eg, Cl, Br, I, etc.), and an R ³² COO group ( R ³² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (for example, CH ₃ COO group, C ₂ H ₅ COO group, etc.), preferably an alkoxy group, particularly preferably a methoxy group or an ethoxy group. It is.

m1 represents an integer of 1 to 3. When R ³⁰ or X ³¹ there are a plurality, a plurality of R ³⁰ or X ³¹ may be different even in the same, respectively. m1 is preferably 1 or 2, particularly preferably 1.

The substituent contained in R ³⁰ is not particularly limited, but is a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl group, ethyl group, i-propyl group, propyl group, t-butyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), aromatic heterocyclic group (furyl group, pyrazolyl group, pyridyl group, etc.), alkoxy group (methoxy group, ethoxy group) Group, i-propoxy group, hexyloxy group etc.), aryloxy group (phenoxy group etc.), alkylthio group (methylthio group, ethylthio group etc.), arylthio group (phenylthio group etc.), alkenyl group (vinyl group, 1-propenyl) Group), acyloxy group (acetoxy group, acryloyloxy group, methacryloyloxy group, etc.), alkoxycarbonyl (Methoxycarbonyl group, ethoxycarbonyl group etc.), aryloxycarbonyl group (phenoxycarbonyl group etc.), carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-methyl-N-octylcarbamoyl) Group), an acylamino group (acetylamino group, benzoylamino group, acrylamino group, methacrylamino group, etc.) and the like, and these substituents may be further substituted. In the present specification, even if a hydrogen atom is replaced by a single atom, it is treated as a substituent for convenience.

When there are a plurality of R ^{30 s} , at least one is preferably a substituted alkyl group or a substituted aryl group. Among these, the substituted alkyl group or substituted aryl group preferably further has a vinyl polymerizable group. In this case, the compound represented by the general formula (5-0) is a vinyl polymer represented by the following general formula (5). It can be expressed as an organosilane compound having a functional substituent.
General formula (5):

In the general formula (5), R ³² represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. R ³² is preferably a hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom, more preferably a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom or a chlorine atom, And a methyl group are particularly preferred.

U ³¹ represents a single bond, an ester group, an amide group, an ether group or a urea group. Single bonds, ester groups and amide groups are preferred, single bonds and ester groups are more preferred, and ester groups are particularly preferred.

L ³¹ is a divalent linking chain, specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and a linking group (eg, ether group, ester group, amide group) inside. A substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group having a linking group therein, among which a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted carbon number An arylene group having 6 to 20 carbon atoms and an alkylene group having 3 to 10 carbon atoms having a linking group therein are preferred, and an unsubstituted alkylene group, an unsubstituted arylene group, and an alkylene group having an ether linking group or an ester linking group therein. More preferably, an unsubstituted alkylene group and an alkylene group having an ether linking group or an ester linking group therein are particularly preferable. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

m2 represents 0 or 1. When X ³¹ there are a plurality, the plurality of X ³¹ may be different even in respectively the same. m2 is preferably 0.
R ³⁰ has the same meaning as R ^{30 in} formula (5-0), preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
X ³¹ has the same meaning as X ^{31 in} formula (5-0), preferably a halogen, a hydroxyl group, or an unsubstituted alkoxy group, more preferably a chlorine, a hydroxyl group, or an unsubstituted alkoxy group having 1 to 6 carbon atoms, A hydroxyl group and an alkoxy group having 1 to 3 carbon atoms are more preferable, and a methoxy group is particularly preferable.

As the organosilane compound used in the present invention, those represented by the following general formula (5-2) are also preferred.
Formula ^{_{(5-2) :( R f 31 -L}} 32) m3 -Si (R 33) 4-m3

In the general formula (5-2), R _f ³¹ represents a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated aromatic group having 6 to 14 carbon atoms. R _f ³¹ is preferably a linear, branched or cyclic fluoroalkyl group having 3 to 10 carbon atoms, and more preferably a linear fluoroalkyl group having 4 to 8 carbon atoms. L ³² represents a divalent linking group having 10 or less carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms. The alkylene group is a linear or branched, substituted or unsubstituted alkylene group which may have a linking group (for example, ether, ester, amide) inside. The alkylene group may have a substituent, and preferable substituents in that case include a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group. R ³³ represents a hydroxyl group or a hydrolyzable group, preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom. m3 represents an integer of 1 to 3.

  Next, among the fluorine-containing organosilane compounds represented by the general formula (5-2), the fluorine-containing organosilane compounds represented by the following general formula (5-3) are preferable.

Formula _{(5-3): C n F 2n} + 1 - (CH 2) t6 -Si (R 34) 3

In the general formula (5-3), n represents an integer of 1 to 10, and t6 represents an integer of 1 to 5. R ³⁴ represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom. n is preferably 4 to 10, t6 is preferably 1 to 3, and R ³⁴ is preferably a methoxy group, an ethoxy group, or a chlorine atom.

  Two or more compounds of the general formulas (5-0), (5), (5-2), and (5-3) may be used in combination. Specific examples of the compounds represented by the general formulas (5-0), (5), (5-2), and (5-3) are shown below, but the present invention is not limited thereto.

  Among these specific examples, (OS-1), (OS-2), (OS-56), (OS-57) and the like are particularly preferable. Moreover, the compounds of A, B, and C described in Reference Examples of Japanese Patent No. 3474330 are also preferable.

  The hydrolyzate and / or partial condensate of the organosilane compound is generally produced by treating the organosilane compound in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples thereof include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; metal chelate compounds having a metal such as Zr, Ti or Al as a central metal. In the present invention, it is preferable to use a metal chelate compound, an acid catalyst of inorganic acids and organic acids. Inorganic acids are preferably hydrochloric acid and sulfuric acid, and organic acids are preferably those having an acid dissociation constant (pKa value (25 ° C.)) of 4.5 or less in water, and further, acid dissociation constants in hydrochloric acid, sulfuric acid and water. Is preferably an organic acid having an acid dissociation constant of 2.5 or less in hydrochloric acid, sulfuric acid or water, more preferably an organic acid having an acid dissociation constant of 2.5 or less in water. Specifically, methanesulfonic acid, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

As the metal chelate compound, (wherein, R ³ represents an alkyl group having 1 to 10 carbon atoms) Formula R ³ OH alcohol and R ⁴ COCH ₂ COR ⁵ (formula represented by, R ⁴ is the number of carbon atoms 1 to 10 alkyl groups, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or a compound represented by an alkoxy group having 1 to 10 carbon atoms), and is selected from Zr, Ti, and Al. Any metal having a central metal as the metal can be used without any particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has the general formula Zr (OR ³ ) _p1 (R ⁴ COCHCOR ⁵ ) _p2 , Ti (OR ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 , and Al (OR ³ ) _r1 (R ⁴ Those selected from the group of compounds represented by COCHCOR ⁵ ) _r2 are preferred and serve to promote the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.
R ³ and R ⁴ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ⁵ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. In addition, p1 in the metal chelate compound,
p2, q1, q2, r1, and r2 represent integers determined to be p1 + p2 = 4, q1 + q2 = 4, and r1 + r2 = 3, respectively.

Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.
Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

  Moreover, it is preferable that a β-diketone compound and / or a β-ketoester compound is further added to the curable composition of the present invention. This will be further described below.

The β-diketone compound and / or β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ⁵ is used in the present invention, and is used as a stability improver for the curable composition used in the present invention. It works. Here, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. That is, by coordinating with a metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound by these metal chelate compounds is performed. It is considered that the promoting action is suppressed and the storage stability of the resulting composition is improved. R ⁴ and R ⁵ constituting the β- diketone compound and / or β- ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and / or β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-sec-butyl, acetoacetic acid-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane -Dione, 5-methyl-hexane-dione and the like can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and / or β-ketoester compounds may be used alone or in combination of two or more. In the present invention, the β-diketone compound and / or β-ketoester compound is preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. If it is less than 2 mol, the storage stability of the resulting composition may be inferior, which is not preferable.

  The organosilane compound may be added directly to the curable composition, but the organosilane compound is previously treated in the presence of a catalyst to prepare a hydrolyzate and / or partial condensate of the organosilane compound, It is preferable to adjust the curable composition using the obtained reaction solution (sol solution). In the present invention, the silane composition first contains a hydrolyzate and / or partial condensate of the organosilane compound and a metal chelate compound. It is preferable to prepare a composition and apply a solution obtained by adding a β-diketone compound and / or a β-ketoester compound to the curable composition.

The use ratio of the sol component (E) is preferably 0 to 100 parts by mass, more preferably 5 to 50 parts by mass, with respect to 100 parts by mass in total of the copolymer (A) and the fluorine-containing copolymer (B). Parts, particularly preferably 10 to 35 parts by mass.
As the curable composition of the present invention, a curable composition comprising the sol component (E) as a main component is formed without using a fluorinated copolymer (B) and a curing agent (C) capable of reacting with a hydroxyl group. However, it is preferable to use a fluorinated copolymer (B) and a curing agent (C) capable of reacting with a hydroxyl group from the viewpoint of compatibility.
At this time, the use ratio of the sol component (E) is preferably 1 to 1000 parts by weight, more preferably 7 to 100 parts by weight, and particularly preferably 10 to 50 parts by weight with respect to 1 part by weight of the copolymer (A). Part by mass.

2- (1) -6. {(F) inorganic fine particles}
The curable composition of the present invention includes a copolymer (A), a fluorinated copolymer (B), and a (C) curing agent, as well as physical properties such as hardness, optical properties such as reflectance and scattering properties. (F) Inorganic fine particles are added to improve characteristics and the like.
Examples of the inorganic fine particles include oxides of at least one metal selected from silicon, zirconium, titanium, aluminum, indium, zinc, tin, and antimony. Specific _{examples, ZrO 2, TiO 2, Al} 2 O 3, In 2 O 3, ZnO, SnO 2, Sb 2 O 3, ITO , and the like. Others include BaSO ₄ , CaCO ₃ , talc and kaolin.

  The particle diameter of the inorganic particles used in the present invention is preferably as fine as possible in the dispersion medium, and the mass average diameter is 1 to 200 nm. Preferably it is 5-150 nm, More preferably, it is 10-100 nm, Most preferably, it is 10-80 nm. A film that does not impair the transparency can be formed by refining the inorganic particles to 100 nm or less. The particle diameter of the inorganic particles can be measured by a light scattering method or an electron micrograph.

The specific surface area of the inorganic particles is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

The inorganic particles used in the present invention are preferably added to a coating solution for a layer used as a dispersion in a dispersion medium.
As the dispersion medium for the inorganic particles, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of dispersion media include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methyl) Carboxymethyl-2-propanol) are included. Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferred.
Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  The inorganic particles are dispersed using a disperser. Examples of dispersers include sand grinder mills (eg, pinned bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

The inorganic fine particles (F) to be contained in the low refractive index layer desirably have a low refractive index, and examples thereof include fine particles of magnesium fluoride and silica. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.
The average particle diameter of the silica fine particles is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
Here, the average particle diameter of the inorganic particles is measured by a Coulter counter.

  If the particle size of the silica fine particles is too small, the effect of improving the scratch resistance is reduced. If it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.

Further, at least one kind of silica fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (referred to as “small size particle size silica particles”) is used as silica fine particles having the above particle size (“large size particles”). It is preferably used in combination with “silica fine particles having a diameter”.
Since the fine silica particles having a small particle size can exist in the gaps between the fine silica particles having a large particle size, they can contribute as a retaining agent for the fine silica particles having a large particle size.
When the low refractive index layer is 100 nm, the average particle size of the silica fine particles having a small size is preferably from 1 nm to 20 nm, more preferably from 5 nm to 15 nm, and particularly preferably from 10 nm to 15 nm. Use of such silica fine particles is preferable in terms of raw material costs and a retaining agent effect.

The coating amount of the low refractive index particles is preferably ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated.

(Hollow silica particles)
For the purpose of further reducing the refractive index, it is preferable to use hollow silica fine particles.

The hollow silica fine particles preferably have a refractive index of 1.15 to 1.40, more preferably 1.17 to 1.35, and most preferably 1.17 to 1.30. The refractive index here represents the refractive index of the whole particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, when the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x
Is represented by the following formula (VIII).

(Formula VIII)
^{x = (4πa 3/3)} / (4πb 3/3) × 100

  The porosity x is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%. If hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. From the viewpoint of scratch resistance, the low refractive index is less than 1.15. Rate particles are not preferred.

  A method for producing hollow silica is described in, for example, Japanese Patent Application Laid-Open Nos. 2001-233611 and 2002-79616. In particular, particles having cavities inside the shell and having fine pores in the shell are particularly preferred. The refractive index of these hollow silica particles can be calculated by the method described in JP-A-2002-79616.

The coating amount of the hollow silica is preferably from ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of lowering the refractive index and the effect of improving the scratch resistance will be reduced.
The average particle diameter of the hollow silica is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the hollow silica is preferably 30 nm to 150 nm, more preferably 35 nm to 100 nm, and still more preferably 40 nm to 65 nm.
If the particle size of the silica particles is too small, the proportion of cavities will decrease and a decrease in refractive index cannot be expected. Getting worse. The silica fine particles may be either crystalline or amorphous, and monodisperse particles are preferred. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.
Further, two or more kinds of hollow silica having different particle average particle sizes can be used in combination. Here, the average particle diameter of the hollow silica can be determined from an electron micrograph.
The specific surface area of the hollow silica in the present invention is preferably from 20 to 300 m ² / g, more preferably 30~120m ² / g, most preferably 40~90m ² / g. The surface area can be obtained by the BET method using nitrogen.

  In the present invention, silica particles having no voids can be used in combination with hollow silica. The preferred particle size of silica without voids is 30 nm to 150 nm, more preferably 35 nm to 100 nm, and most preferably 40 nm to 80 nm.

(Surface treatment agent)
Inorganic particles used in the present invention are dispersed in a dispersion liquid or coating liquid, or are used in plasma discharge treatment or corona discharge treatment in order to stabilize dispersion, or to improve affinity and binding properties with a binder component. A physical surface treatment, a chemical surface treatment with a surfactant, a coupling agent or the like may be performed.

The surface treatment can be performed using a surface treatment agent of an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include inorganic compounds containing cobalt (CoO ₂ , Co ₂ O ₃ , Co ₃ O _4, etc.), inorganic compounds containing aluminum (Al ₂ O ₃ , Al (OH) _{3, etc.} Etc.), inorganic compounds containing zirconium (ZrO ₂ , Zr (OH) ₄ etc.), inorganic compounds containing silicon (SiO ₂ etc.), inorganic compounds containing iron (Fe ₂ O ₃ etc.), etc. .
Inorganic compounds containing cobalt, inorganic compounds containing aluminum, and inorganic compounds containing zirconium are particularly preferred, and inorganic compounds containing cobalt, Al (OH) ₃ , and Zr (OH) ₄ are most preferred.
Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. In particular, the surface treatment is preferably performed with at least one of a silane coupling agent (organosilane compound), a partial hydrolyzate thereof, and a condensate thereof.

Examples of titanate coupling agents include metal alkoxides such as tetramethoxy titanium, tetraethoxy titanium, and throat tetraisopropoxy titanium, and preneact (KR-TTS, KR-46B, KR-55, KR-41B, etc .; Ajinomoto Co., Inc. ))).
Examples of the organic compound used for the surface treatment include polyols, alkanolamines, and other organic compounds having an anionic group, and particularly preferable are organic compounds having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. is there. Stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid and the like can be preferably used.
The organic compound used for the surface treatment preferably further has a crosslinked or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acrylic groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, cationic polymerizable groups (Epoxy groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like can be mentioned, and groups having an ethylenically unsaturated group are preferred.

  Two or more kinds of these surface treatments can be used in combination, and it is particularly preferable to use an inorganic compound containing aluminum and an inorganic compound containing zirconium.

When the inorganic particles are silica, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
The above coupling agent is used as a surface treatment agent for the inorganic filler of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, and is added as an additive during the preparation of the layer coating solution. It is preferable to make it contain in a layer.
The silica fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.
Specific examples of the surface treatment agent and the surface treatment catalyst that can be preferably used in the present invention include organosilane compounds and catalysts described in International Publication No. 2004/017105 pamphlet.

(Dispersant)
Various dispersants can be used for dispersing the particles used in the present invention.
The dispersant preferably further contains a crosslinkable or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acryloyl groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, and cationic polymerizable groups (epoxies). Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, and functional groups having an ethylenically unsaturated group are preferred.

It is preferable to use a dispersant having an anionic group for the dispersion of inorganic particles, particularly for the dispersion of inorganic particles containing TiO ₂ as a main component, more preferably having an anionic group and a crosslinkable or polymerizable functional group, It is particularly preferable that the dispersant has the cross-linked or polymerizable functional group in the side chain.

  As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (sulfo), a phosphoric acid group (phosphono), a sulfonamide group, or a salt thereof is effective, and in particular, a carboxyl group, a sulfonic acid group, A phosphoric acid group or a salt thereof is preferable, and a carboxyl group and a phosphoric acid group are particularly preferable. The number of anionic groups contained in the dispersing agent per molecule may be plural, but is preferably 2 or more on average, more preferably 5 or more, Particularly preferred is 10 or more. Moreover, the anionic group contained in a dispersing agent may contain multiple types in 1 molecule.

In the dispersant having an anionic group in the side chain, the composition of the anionic group-containing repeating unit is in the range of 10 ^{−4 to} 100 mol%, preferably 1 to 50 mol%, particularly preferably 5 in the total repeating units. ˜20 mol%.

  The dispersant preferably further contains a crosslinkable or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acryloyl groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, and cationic polymerizable groups (epoxies). Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, and functional groups having an ethylenically unsaturated group are preferred.

  The average number of cross-linkable or polymerizable functional groups contained in the dispersant per molecule is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the crosslinking or polymerizable functional group contained in the dispersant may contain a plurality of types in one molecule.

In the preferred dispersant for use in the present invention, examples of the repeating unit having an ethylenically unsaturated group in the side chain include poly-1,2-butadiene and poly-1,2-isoprene structures or (meth) acrylic acid. An ester or amide repeating unit to which a specific residue (the R group of —COOR or —CONHR) is bonded can be used. Examples of the specific residue (R _{group), - (CH 2) n} -CR 21 = CR 22 R 23, - (CH 2 O) n-CH 2 CR 21 = CR 22 R 23, - (CH _{2 CH 2 O) n-CH} 2 CR 21 = CR 22 R 23, - (CH 2) n-NH-CO-O-CH 2 CR 21 = CR 22 R 23, - (CH 2) n-O-CO —CR ²¹ ═CR ²² R ²³ and — (CH ₂ CH ₂ O) ₂ —X (R ^{21 to} R ²³ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an alkoxy group. R ²¹ and R ²² or R ²³ may be bonded to each other to form a ring, n is an integer of 1 to 10, and X is a dicyclopentadienyl residue. There are). Specific examples of R of the ester residue include —CH ₂ CH═CH ₂ (corresponding to an allyl (meth) acrylate polymer described in JP-A No. 64-17047), —CH ₂ CH ₂ O—CH ₂ CH _{= CH 2, -CH 2 CH 2} OCOCH = CH 2, -CH 2 CH 2 OCOC (CH 3) = CH 2, -CH 2 C (CH 3) = CH 2, -CH 2 CH = CH-C 6 H ₅ , —CH ₂ CH ₂ OCOCH═CH—C ₆ H ₅ , —CH ₂ CH ₂ —NHCOO—CH ₂ CH═CH ₂ and —CH ₂ CH ₂ O—X (X is a dicyclopentadienyl residue) Is included. Specific examples of R of the amide residue include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ —Y (Y is a 1-cyclohexenyl residue) and —CH ₂ CH ₂ —OCO—CH═CH ₂ , _{-CH 2 CH 2 -OCO-C (} CH 3) = CH 2 are included.

  In the dispersant having an ethylenically unsaturated group, a free radical (a polymerization initiation radical or a growth radical of a polymerization process of a polymerizable compound) is added to the unsaturated bond group, and the polymer compound is directly or between molecules. Addition polymerization is carried out through the polymerization chain, and a crosslink is formed between the molecules to cure. Alternatively, atoms in the molecule (for example, hydrogen atoms on carbon atoms adjacent to the unsaturated bond group) are extracted by free radicals to form polymer radicals that are bonded together to form a bridge between the molecules. Harden.

  The weight average molecular weight (Mw) of the dispersant having an anionic group and a crosslinkable or polymerizable functional group and having the crosslinkable or polymerizable functional group in the side chain is not particularly limited, but is preferably 1000 or more. . The more preferable mass average molecular weight (Mw) of the dispersant is 2000 to 1000000, more preferably 5000 to 200000, and particularly preferably 10000 to 100000.

  The cross-linkable or polymerizable functional group-containing unit may constitute all repeating units other than the anionic group-containing repeating unit, preferably 5 to 50 mol% of the total cross-linking or repeating unit, particularly Preferably it is 5-30 mol%.

  The dispersant may be a copolymer with an appropriate monomer other than a monomer having a crosslinking or polymerizable functional group or an anionic group. Although it does not specifically limit regarding a copolymerization component, It selects from various viewpoints, such as dispersion stability, compatibility with another monomer component, and the intensity | strength of a formed film. Preferable examples include methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene and the like.

  The form of the dispersant is not particularly limited, but is preferably a block copolymer or a random copolymer, and particularly preferably a random copolymer from the viewpoint of cost and ease of synthesis.

  The amount of the dispersant used relative to the inorganic particles is preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 30% by mass, and most preferably 5 to 20% by mass. Two or more dispersants may be used in combination.

2- (1) -7. {(G) polymerization initiator}
In addition to the copolymer (A), the fluorine-containing copolymer (B), and the (C) curing agent, it is preferable to add (G) a polymerization initiator to the curable composition of the present invention. (G) If a polymerization initiator is normally used, it will not be specifically limited but can be used. (G) The polymerization initiator is preferably a heat and / or ionizing radiation curable initiator.

  The SP values of “(G) polymerization initiator” and “(E) organosilane compound or hydrolyzate and / or partial condensate thereof of the present invention” used in the present invention are (B) hydroxyl group. A thing larger than SP value of a containing fluorine-containing compound is preferable. Due to this SP value difference, the SP value of the (B) hydroxyl group-containing fluorine-containing compound is likely to be localized on the upper part (outermost surface side) of the low refractive index layer, while adding “(G) polymerization initiator”, and “(E) Organosilane compound or hydrolyzate and / or partial condensate thereof is easily localized in the lower part of the low refractive index layer (on the side opposite to the outermost surface), and polymerization is facilitated. It is considered to proceed efficiently. These are preferable because the transfer of the silicone component to the contact medium and the contamination of the production line can be sufficiently suppressed.

(SP value)
The SP value of a compound is a solubility parameter and is a numerical value of how easily it is soluble in a solvent. It is synonymous with the polarity often used in organic compounds. The greater the SP value, the greater the polarity. Represents that. As the SP value, a value calculated by the Fedors method can be used.

  The polymerization initiator may have any structure of the polymerization initiator skeleton shown below. A compound in which the curable site of the organosilane compound is linked and bonded in the molecule to these polymerization initiators can also be used as the polymerization initiator, and the same effect can be obtained if the SP value of the linked and bonded compound is larger than that of the binder polymer. Have As will be described later, a compound in which the curable sites of the monomer containing an ethylenically unsaturated group are linked and bonded in the molecule can also be used as a polymerization initiator, and the SP value of the linked and bonded compound is larger than that of the binder polymer. Have the same effect.

(Ionizing radiation curable polymerization initiator skeleton)
The ionizing radiation curable polymerization initiator skeleton is a compound similar to a commonly used photo radical polymerization initiator, and has an initiator skeleton showing a value larger than the SP value of the fluorinated copolymer (B). Is preferred.

  Examples of photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (JP-A-2001-139663, etc.), 2, 3 -Dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.

  Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t- Butyl-dichloroacetophenone is included.

  Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether It is. Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4′-dimethylaminobenzophenone (Michler's ketone), 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and the like are included.

  Examples of the borate salt are described in Japanese Patent Nos. 2764769 and 2002-116539, and Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”. And the organic borate compounds described. For example, the compounds described in JP-A-2002-116539, paragraph numbers [0022] to [0027] can be mentioned. Examples of other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Specific examples include organoboron transition metal coordination complexes and the like, and specific examples include ion complexes with cationic dyes.

Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Examples of active esters include IRGACURE OXE01 (1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] manufactured by Ciba Specialty Chemicals), sulfonate esters, cyclic Active ester compounds and the like are included.
Specifically, Examples 1 to 21 described in JP-A 2000-80068 are particularly preferable.
Examples of the onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.

Specific examples of the active halogens include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-5-27830, M.M. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry”, Vol. 1 (No. 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group: s-triazine compounds. More preferred are s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring. Specific examples include S-triazine and oxathiazole compounds, such as 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl). -4,6-bis (trichloromethyl) -s-triazine, 2- (p-styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-Br-4-di (ethyl) Acetate) amino) phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-trihalomethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole. Specifically, p.14 to p30 in JP-A-58-15503, p6-p10 in JP-A-55-77742, and p287 in JP-B-60-27673. 1-No. 8, No. pp. 443 to p444 of JP-A-60-239736. 1-No. 17, No. 4,701,399. Compounds such as 1-19 are particularly preferred.
Examples of inorganic complexes include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.
Examples of coumarins include 3-ketocoumarin.

These initiators may be used alone or in combination.
“Latest UV Curing Technology”, Technical Information Association, 1991, p. 159, and “UV curing system” written by Kayo Kiyomi, 1989, General Technology Center, p. Various examples are also described in 65-148 and are useful in the present invention.

  Commercially available photo radical polymerization initiators include KAYACURE (DETX-S, BP-100, BDKM, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd. MCA, etc.), Irgacure (651, 184, 500, 819, 907, 369, 1173, 1870, 2959, 4265, 4263, etc.) manufactured by Ciba Specialty Chemicals, Ltd., Esacure (KIP100F, KB1, manufactured by Sartomer) EB3, BP, X33, KT046, KT37, KIP150, TZT) and the like and combinations thereof are preferred examples.

  It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.

(Photosensitizer)
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.
Examples of commercially available photosensitizers include KAYACURE (DMBI, EPA) manufactured by Nippon Kayaku Co., Ltd.

(Thermal radical initiator skeleton)
The thermal radical initiator skeleton is also a compound similar to a commonly used thermal radical polymerization initiator, and preferably has an initiator skeleton showing a value larger than the SP value of the fluorinated copolymer (B).

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Diazo compounds such as ammonium sulfate, potassium persulfate and the like, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile), etc. And diazoaminobenzene, p-nitrobenzenediazonium and the like.

These initiators may be used alone or in combination.
Specific examples of initiators that can be preferably used in the present invention and their SP values (calculated by the Fedors method) are shown below, but are not limited thereto.

  A monomer containing an ethylenically unsaturated group and a self-polymerization initiating compound in which the polymerization initiation site is linked and bonded in the molecule can also be suitably used as the polymerization initiator in the present invention. Such compounds are exemplified below.

  Further, specific compounds of the initiator that can be used in the present invention are shown below.

  (G) Although there is no restriction | limiting in particular in the usage-amount of a polymerization initiator, with respect to a total of 100 mass parts of solid content mass of the copolymer (A) used together and a fluorine-containing copolymer (B), it is 0. It is preferably used in the range of 1 to 20 parts by mass, more preferably 1 to 10 parts by mass.

  These polymerization initiator compounds may be used alone or in combination of two or more with other photosensitizers. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.

2- (1) -8. {Other additives}
The curable composition that is the coating liquid composition for the low refractive index layer in the present invention comprises (A) the structural unit containing the polysiloxane structure represented by the general formula (1) in the main chain or the side chain, A copolymer having a mass fraction of 40% or more and less than 100% with respect to all the structural units in the component (A) and having a polymer unit based on a hydroxyl group-containing monomer,
(B) The structural unit containing the polysiloxane structure represented by the general formula (1) in the main chain or the side chain is 0 (%) or more and 20 (% by mass fraction with respect to all the structural units in the component (B). ) A fluorine-containing copolymer having a polymerization unit based on a hydroxyl group-containing monomer,
(C) a curing agent capable of reacting with a hydroxyl group,
(D) a curing catalyst,
(E) 0-100 parts by mass of a composition containing at least one of an organosilane compound, a hydrolyzate of the organosilane compound and a partial condensate thereof,
(F) inorganic fine particles,
(G) a polymerization initiator,
Is dissolved in a suitable solvent. It can also be prepared by adding various additives to the components (A) to (G) and dissolving them in a suitable solvent. At this time, the concentration of the solid content is appropriately selected depending on the application, but is generally about 0.01 to 60% by mass, preferably 0.5 to 50% by mass, particularly preferably 1 to 20% by mass. %.

  From the viewpoint of interfacial adhesion between the lower refractive index layer and the lower layer that is in direct contact, a curing agent such as a polyfunctional (meth) acrylate compound, polyfunctional epoxy compound, polyisocyanate compound, aminoplast, polybasic acid, or an anhydride thereof. Can also be added in small amounts. When adding these, it is preferable to set it as the range of 30 mass% or less with respect to the total solid of a low refractive index layer film | membrane, It is more preferable to set it as the range of 20 mass% or less, The range of 10 mass% or less It is particularly preferable that

(Dustproofing agent, antistatic agent, etc.)
The curable composition for forming the low refractive index layer is further provided with a dust-proofing agent such as a known cationic surfactant or polyoxyalkylene-based compound for the purpose of imparting properties such as dust resistance and antistatic property, and antistatic property. An agent or the like can also be added as appropriate. As for these dustproof agent and antistatic agent, the structural unit may be included in the silicone-based compound or the fluorine-based compound as a part of the function.

  When these are added as additives, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferably 0.1 to 5% by mass.

  Examples of preferred compounds include “Megafac F-150” (trade name) manufactured by Dainippon Ink & Chemicals, Inc., “SH-3748” (trade name) manufactured by Toray Dow Corning Co., Ltd. However, it is not limited to these.

(Surfactant)
In the curable composition for forming the low refractive index layer, in order to ensure surface uniformity such as coating unevenness, drying unevenness, point defects, etc., either a fluorine-based surfactant or a silicone-based surfactant, or both Can also be added as appropriate. In particular, a fluorine-based surfactant can be preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects appears at a smaller addition amount. Productivity can be improved by giving high-speed coating suitability while improving surface uniformity.

  Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following monomer (i): An acrylic resin, a methacrylic resin, and a vinyl monomer copolymerizable with the acrylic resin, the methacrylic resin characterized by containing a corresponding repeating unit, or a repeating unit corresponding to the monomer (ii) below: Copolymers are useful.

(I) Fluoroaliphatic group-containing monomer represented by the following general formula

General formula

In the general formula A, R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, m is an integer of 1-6, and n is an integer of 2-4. To express. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.

(Ii) A monomer represented by the following general formula (b) that can be copolymerized with the monomer (i)

General formula

In the general formula B, R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically Specifically, it represents a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. Y is an oxygen atom, -N (H) -, and -N (CH ₃₎ - are preferred.
R ¹⁴ represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. Examples of the substituent for the alkyl group of R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a nitro group, and a cyano group. , Amino groups and the like, but not limited thereto. Examples of the linear, branched or cyclic alkyl group having 4 to 20 carbon atoms include a butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group which may be linear or branched. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., and monocyclic cycloalkyl groups such as cyclohexyl group, cycloheptyl group and bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, A polycyclic cycloalkyl group such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, or the like is preferably used.

  The amount of the fluoroaliphatic group-containing monomer represented by the general formula (a) used in the fluoropolymer used in the present invention is 10 mol% or more based on each monomer of the fluoropolymer, preferably Is 15 to 70 mol%, more preferably in the range of 20 to 60 mol%.

The preferred weight average molecular weight of the fluoropolymer used in the present invention is preferably 3000 to 100,000, more preferably 5,000 to 80,000.
Furthermore, the preferable addition amount of the fluoropolymer used in the present invention is in the range of 0.001 to 5% by mass, preferably in the range of 0.005 to 3% by mass, and more preferably, with respect to the coating solution. It is the range of 0.01-1 mass%. If the addition amount of the fluorine-based polymer is less than 0.001% by mass, the effect is insufficient, and if it exceeds 5% by mass, the coating film may not be sufficiently dried or the performance as a coating film (for example, reflectance) Adversely affect the scratch resistance).

(Thickener)
A thickener may be used in the curable composition for forming the low refractive index layer in order to adjust the viscosity of the coating solution.
The term “thickener” as used herein means that the viscosity of the liquid is increased by adding it, and preferably 0.05 to 50 cP (mPa · m) as the magnitude of increase in the viscosity of the coating liquid when added. sec), more preferably 0.10 to 20 cP (mPa · sec), and most preferably 0.10 to 10 cP (mPa · sec).

Examples of such thickeners include, but are not limited to:
Poly-ε-caprolactone poly-ε-caprolactone diol poly-ε-caprolactone triol polyvinyl acetate poly (ethylene adipate)
Poly (1,4-butylene adipate)
Poly (1,4-butylene glutarate)
Poly (1,4-butylene succinate)
Poly (1,4-butylene terephthalate)
polyethylene terephthalate)
Poly (2-methyl-1,3-propylene adipate)
Poly (2-methyl-1,3-propylene glutarate)
Poly (neopentyl glycol adipate)
Poly (neopentyl glycol sebacate)
Poly (1,3-propylene adipate)
Poly (1,3-propylene glutarate)
Polyvinyl butyral Polyvinyl formal Polyvinyl acetal Polyvinyl propanal Polyvinyl hexanal Polyvinyl pyrrolidone Polyacrylic acid ester Polymethacrylic acid ester Cellulose acetate Cellulose propionate Cellulose acetate butyrate

  In addition, smectite, fluorine tetrasilicon mica, bentonite, silica, montmorillonite and sodium polyacrylate described in JP-A-8-325491, ethyl cellulose, polyacrylic acid, organic clay described in JP-A-10-219136, Known viscosity modifiers and thixotropic agents can be used.

(Conductive particles)
Various conductive particles can be used in the curable composition for forming the low refractive index layer in order to impart conductivity.
The conductive particles are preferably formed from a metal oxide or nitride. Examples of metal oxides or nitrides include tin oxide, indium oxide, zinc oxide and titanium nitride. Tin oxide and indium oxide are particularly preferred. The conductive inorganic particles are mainly composed of oxides or nitrides of these metals, and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and halogen atoms are included. In order to increase the conductivity of tin oxide and indium oxide, it is preferable to add Sb, P, B, Nb, In, V and a halogen atom. Particularly preferred are tin oxide containing Sb (ATO) and indium oxide containing Sn (ITO). The proportion of Sb in ATO is 3-20% by mass
It is preferable that The ratio of Sn in ITO is preferably 5 to 20% by mass.

The average particle diameter of the primary particles of the conductive inorganic particles is preferably 1 to 150 nm, more preferably 5 to 100 nm, and most preferably 5 to 70 nm. The average particle diameter of the conductive inorganic particles in the antistatic layer to be formed is 1 to 200 nm, preferably 5 to 150 nm, more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the conductive inorganic particles is an average diameter weighted by the mass of the particles and can be measured by a light scattering method or an electron micrograph.
The specific surface area of the conductive inorganic particles is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

The conductive inorganic particles may be surface treated. The surface treatment is performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina and silica. Silica treatment is particularly preferred. Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. Two or more kinds of surface treatments may be performed in combination.
The shape of the conductive inorganic particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape.

Two or more kinds of conductive particles may be used in a specific layer or as a film.
The proportion of the conductive inorganic particles in the antistatic layer is preferably 20 to 90% by mass, preferably 25 to 85% by mass, and more preferably 30 to 80% by mass.

  The conductive inorganic particles can be used in the state of a dispersion.

(Solvent for coating low refractive index layer)
In the present invention, as the solvent used in the coating liquid composition for forming the low refractive index layer, each component can be dissolved or dispersed, and it is easy to form a uniform surface in the coating process and the drying process. Various solvents selected from the viewpoints of ensuring storage stability and having an appropriate saturated vapor pressure can be used.
Two or more kinds of solvents can be mixed and used. In particular, from the viewpoint of drying load, it is preferable that a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature as a main component and a small amount of solvent having a boiling point of 100 ° C. or higher for adjusting the drying speed.

Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichloroethylene (87.2 ° C) Hydrogens, diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), ethers such as tetrahydrofuran (66 ° C), ethyl formate (54.2 ° C), Esters such as methyl acetate (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.), acetone (56.1 ° C.), 2-butanone (methyl ethyl) Ketones such as Luketone, 79.6 ° C, methanol (64.5 ° C), ethanol (78.3 ° C), 2-propanol (82.4 ° C), 1-propanol (97.2 ° C), etc. Alcohols, cyano compounds such as acetonitrile (81.6 ° C.), propionitrile (97.4 ° C.), carbon disulfide (46.2 ° C.), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point of 100 ° C. or more include, for example, octane (125.7 ° C.), toluene (110.6 ° C.), xylene (138 ° C.), tetrachloroethylene (121.2 ° C.), and chlorobenzene (131.7 ° C.). , Dioxane (101.3 ° C.), dibutyl ether (142.4 ° C.), isobutyl acetate (118 ° C.), cyclohexanone (155.7 ° C.), 2-methyl-4-pentanone {same as methyl isobutyl ketone (MIBK), 115.9 ° C.}, 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

  Moreover, although the density | concentration of solid content is suitably selected according to a use, generally it is about 0.01-60 mass%, Preferably it is 0.5-50 mass%, Most preferably, it is 1% -20 mass. %.

The film thickness of the low refractive index layer is preferably 5 nm to 10 μm, more preferably 10 nm to 1 μm, and most preferably 30 nm to 500 nm.
The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less.

  Other low refractive index layer forming compositions include various resins, coupling agents, anti-coloring agents, coloring agents (pigments, dyes), antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, and adhesion imparting. An agent, a polymerization inhibitor, an antioxidant, a surface modifier, and the like may be appropriately added as necessary.

3. [Layers other than low refractive index layer]
The layers other than the low refractive index layer in the antireflection film of the present invention will be described below.

3- (1). [Anti-glare layer]
The antiglare layer is formed for the purpose of contributing to the film an antiglare property due to surface scattering defined in the present invention, and preferably a hard coat property for improving the scratch resistance of the film.

As a method of forming the antiglare property, a method of laminating and forming a mat-shaped shaping film having fine irregularities on the surface as described in JP-A-6-16851, as described in JP-A-2000-206317 A method of forming by curing shrinkage of an ionizing radiation curable resin due to a difference in the amount of ionizing radiation applied, and by reducing the mass ratio of a good solvent to a light transmitting resin by drying as described in JP-A No. 2000-338310. A method of solidifying the light-sensitive fine particles and the translucent resin while gelling to form unevenness on the coating film surface, a method of imparting surface unevenness by external pressure as described in JP-A-2000-275404, etc. These known methods can be used.
The antiglare layer that can be used in the present invention preferably contains a binder capable of imparting hard coat properties, translucent particles for imparting antiglare properties, and a solvent as essential components. It is preferable that irregularities on the surface be formed by the protrusions of the protrusions themselves or protrusions formed by an aggregate of a plurality of particles.
The antiglare layer formed by dispersing the matte particles is composed of a binder and translucent particles dispersed in the binder. The antiglare layer having antiglare properties preferably has both antiglare properties and hard coat properties.

As specific examples of the mat particles, inorganic particles such as silica particles and TiO ₂ particles; resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles are preferable. Can be mentioned. Of these, crosslinked styrene particles, crosslinked acrylic particles, and silica particles are preferred.
The shape of the mat particles can be either spherical or irregular.

  The particle size distribution of the matte particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

  The internal haze and surface haze of the present invention can be achieved by adjusting the refractive index of the translucent resin in accordance with the refractive index of each translucent particle selected from these particles. Specifically, a translucent resin (having a refractive index after curing of 1.55 to 1.70) mainly composed of a trifunctional or higher functional (meth) acrylate monomer preferably used in the antiglare layer of the present invention described later. And a combination of translucent particles and / or benzoguanamine particles made of a crosslinked poly (meth) acrylate polymer having a styrene content of 50 to 100% by mass, particularly the translucent resin and styrene content of 50 to 100. A combination with translucent particles (having a refractive index of 1.54 to 1.59) made of a crosslinked poly (styrene-acrylate) copolymer having a mass% is particularly preferred.

The translucent particles are preferably blended in the formed antiglare layer so as to be contained in an amount of 3 to 30% by mass in the total solid content of the antiglare layer. More preferably, it is 5-20 mass%. If it is less than 3% by mass, the antiglare property is insufficient, and if it exceeds 30% by mass, problems such as image blur, surface turbidity and glare occur.
The density of the translucent particles is preferably 10 to 1000 mg / m ² , more preferably 1
It is a 00~700mg / m ^2.

The absolute value of the difference between the refractive index of the translucent resin and the refractive index of the translucent particles is preferably 0.04 or less. The absolute value of the difference between the refractive index of the translucent resin and the refractive index of the translucent particles is preferably 0.001 to 0.030, more preferably 0.001 to 0.020, and still more preferably 0.001. ~ 0.015. If this difference exceeds 0.040, problems such as film character blur, dark room contrast reduction, and surface turbidity occur.
Here, the refractive index of the translucent resin can be quantitatively evaluated by directly measuring it with an Abbe refractometer or by measuring a spectral reflection spectrum or a spectral ellipsometry. The refractive index of the light-transmitting particles is measured by measuring the turbidity by equally dispersing the light-transmitting particles in the solvent in which the refractive index is changed by changing the mixing ratio of two kinds of solvents having different refractive indexes. It is measured by measuring the refractive index of the solvent when the turbidity is minimized with an Abbe refractometer.

  Two or more kinds of mat particles having different particle diameters may be used in combination. It is possible to impart anti-glare properties with mat particles having a larger particle size and to impart other optical characteristics with mat particles having a smaller particle size. For example, when an anti-glare antireflection film is attached to a high-definition display of 133 ppi or higher, a problem in display image quality called “glare” may occur. “Glitter” is derived from the fact that pixels are enlarged or reduced due to unevenness present on the surface of the antiglare and antireflection antireflection film, resulting in loss of luminance uniformity, but particles smaller than mat particles that impart antiglare properties. It can be greatly improved by using mat particles having a diameter different from that of the binder.

  The film thickness of the antiglare layer is preferably 1 to 10 μm, and more preferably 1.2 to 8 μm. If it is too thin, the hard property is insufficient, and if it is too thick, curling and brittleness may be deteriorated and workability may be lowered.

  On the other hand, the center line average roughness (Ra) of the antiglare layer is preferably in the range of 0.10 to 0.40 μm. If it exceeds 0.40 μm, problems such as glare and whitening of the surface when external light is reflected occur. Further, it is preferable that the value of the transmitted image definition is 5 to 60%.

  The strength of the antiglare layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test.

3- (2). [Hard coat layer]
The film of the present invention can be provided with a hard coat layer in addition to the antiglare layer in order to impart the physical strength of the film.
Preferably, a low refractive index layer is provided thereon, and more preferably, an intermediate refractive index layer and a high refractive index layer are provided between the hard coat layer and the low refractive index layer to constitute an antireflection film.
The hard coat layer may be composed of two or more layers.

  The refractive index of the hard coat layer in the present invention is preferably in the range of 1.48 to 2.00, more preferably 1.52 to 1, from the optical design for obtaining an antireflection film. .90, more preferably 1.55 to 1.80. In the present invention, since there is at least one low refractive index layer on the hard coat layer, if the refractive index is too small, the antireflection property is lowered, and if it is too large, the color of the reflected light tends to be strong. is there.

From the viewpoint of imparting sufficient durability and impact resistance to the film, the thickness of the hard coat layer is usually about 0.5 μm to 50 μm, preferably 1 μm to 20 μm, more preferably 2 μm. 10 μm, most preferably 3 μm to 7 μm.
Further, the strength of the hard coat layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test.
Furthermore, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. For example, it may be formed by coating a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a transparent support and subjecting the polyfunctional monomer or polyfunctional oligomer to a crosslinking reaction or a polymerization reaction. it can.
The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

  The hard coat layer contains matte particles having an average particle diameter of 1.0 to 10.0 μm, preferably 1.5 to 7.0 μm, such as inorganic compound particles or resin particles, for the purpose of imparting internal scattering properties. May be.

  For the purpose of controlling the refractive index of the hard coat layer, a high refractive index monomer, inorganic particles, or both can be added to the binder of the hard coat layer. In addition to the effect of controlling the refractive index, the inorganic particles also have the effect of suppressing cure shrinkage due to the crosslinking reaction. In the present invention, a polymer formed by polymerizing the polyfunctional monomer and / or the high refractive index monomer after the hard coat layer is formed, and the inorganic particles dispersed therein are referred to as a binder.

  For the purpose of maintaining the sharpness of the image, it is preferable to adjust the sharpness of the transmitted image in addition to adjusting the uneven shape of the surface. The clearness of the transmitted image of the clear antireflection film is preferably 60% or more. The transmitted image clarity is generally an index indicating the degree of blurring of an image reflected through a film, and the larger this value, the clearer and better the image viewed through the film. The transmitted image definition is preferably 70% or more, and more preferably 80% or more.

3- (3). [High refractive index layer, middle refractive index layer]
The film of the present invention can be provided with a high refractive index layer and a medium refractive index layer to enhance antireflection properties.
In the following specification, the high refractive index layer and the medium refractive index layer may be collectively referred to as a high refractive index layer. In the present invention, “high”, “medium”, and “low” in the high refractive index layer, the medium refractive index layer, and the low refractive index layer represent the relative refractive index relationship between the layers. In terms of the relationship with the transparent support, the refractive index preferably satisfies the relationship of transparent support> low refractive index layer, high refractive index layer> transparent support.
In the present specification, the high refractive index layer, the middle refractive index layer, and the low refractive index layer may be collectively referred to as an antireflection layer.

  When an antireflection film is prepared by coating a medium refractive index layer, a high refractive index layer, and a low refractive index layer in order from the support, the refractive index of the high refractive index layer is 1.60 to 2.40. It is preferable that it is 1.60 to 2.00. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The medium refractive index layer preferably has a refractive index of 1.55 to 1.80, and the low refractive index layer preferably has a refractive index of 1.30 to 1.45.

The inorganic particles mainly composed of TiO ₂ used for the high refractive index layer and the medium refractive index layer are used for forming the high refractive index layer and the medium refractive index layer in the state of dispersion.
In the dispersion of the inorganic particles, the inorganic particles are dispersed in a dispersion medium in the presence of a dispersant.

  The high refractive index layer and the medium refractive index layer used in the present invention are preferably used in a dispersion liquid in which inorganic particles are dispersed in a dispersion medium, preferably a binder precursor necessary for matrix formation (for example, an ionizing radiation curable composition described later). Polyfunctional monomer, polyfunctional oligomer, etc.), photopolymerization initiator, etc. are added to form a coating composition for forming a high refractive index layer and a medium refractive index layer, and a high refractive index layer and a medium refractive index layer are formed on a transparent support. It is preferable that the coating composition is applied and cured by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer).

Furthermore, it is preferable to cause the binder of the high refractive index layer and the medium refractive index layer to undergo a crosslinking reaction or a polymerization reaction with the dispersant simultaneously with or after the coating of the layer.
The binder of the high refractive index layer and the medium refractive index layer produced in this way is, for example, the above-mentioned preferred dispersant and ionizing radiation curable polyfunctional monomer or polyfunctional oligomer are crosslinked or polymerized to form a binder. The anionic group of the dispersant is incorporated. Furthermore, the binder of the high refractive index layer and the medium refractive index layer has a function in which the anionic group maintains the dispersion state of the inorganic particles, and the crosslinked or polymerized structure imparts a film forming ability to the binder and contains inorganic particles. To improve the physical strength, chemical resistance and weather resistance of the high refractive index layer and medium refractive index layer.

  The binder of the high refractive index layer is added in an amount of 5 to 80% by mass based on the solid content of the coating composition of the layer.

The content of the inorganic particles in the high refractive index layer is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and particularly preferably 15 to 75% by mass with respect to the mass of the high refractive index layer. . Two or more inorganic particles may be used in combination in the high refractive index layer.
When the low refractive index layer is provided on the high refractive index layer, the refractive index of the high refractive index layer is preferably higher than the refractive index of the transparent support.
The high refractive index layer contains an ionizing radiation curable compound containing an aromatic ring, an ionizing radiation curable compound containing a halogenated element other than fluorine (for example, Br, I, Cl, etc.), and atoms such as S, N, P, etc. A binder obtained by a crosslinking or polymerization reaction such as an ionizing radiation curable compound can also be preferably used.

  The film thickness of the high refractive index layer can be appropriately designed depending on the application. When using a high refractive index layer as an optical interference layer described later, the thickness is preferably 30 to 200 nm, more preferably 50 to 170 nm, and particularly preferably 60 to 150 nm.

The haze of the high refractive index layer is preferably as low as possible when it does not contain particles that impart an antiglare function. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
The high refractive index layer is preferably constructed directly on the transparent support or via another layer.

3- (4). [Antistatic layer, conductive layer]
In the present invention, it is preferable to provide an antistatic layer from the viewpoint of preventing static electricity on the film surface. The antistatic layer can be formed by, for example, applying a conductive coating solution containing conductive fine particles and a reactive curable resin, or depositing or sputtering a metal or metal oxide that forms a transparent film. Conventionally known methods such as a method of forming a conductive thin film can be listed. The conductive layer can be formed directly on the support or via a primer layer that strengthens adhesion to the support. Further, the antistatic layer can be used as a part of the antireflection film. In this case, when used in a layer close to the outermost layer, sufficient antistatic properties can be obtained even if the film is thin.

The thickness of the antistatic layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and even more preferably from 0.05 to 5 μm. The surface resistance of the antistatic layer is preferably from 10 ⁵ ~10 ¹² Ω / sq, more preferably from 10 ⁵ ~10 ⁹ Ω / sq, most be 10 ⁵ ~10 ⁸ Ω / sq preferable. The surface resistance of the antistatic layer can be measured by a four probe method.

The antistatic layer is preferably substantially transparent. Specifically, the haze of the antistatic layer is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and most preferably 1% or less. . The transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more.
The antistatic layer of the present invention has excellent strength, and the specific antistatic layer has a pencil hardness of 1 kg, preferably H or higher, more preferably 2H or higher, more preferably 3H or higher. Is more preferable, and 4H or more is most preferable.

3- (5). [Anti-fouling layer]
An antifouling layer can be provided on the outermost surface of the present invention. The antifouling layer lowers the surface energy of the antireflection layer and makes it difficult to attach hydrophilic or lipophilic stains.
The antifouling layer can be formed using a fluorine-containing polymer or an antifouling agent.
The thickness of the antifouling layer is preferably 2 to 100 nm, and more preferably 5 to 30 nm.

3- (6). [Interference unevenness (rainbow unevenness) prevention layer]
When there is a substantial refractive index difference (refractive index difference of 0.03 or more) between the transparent support and the hard coat layer, or between the transparent support and the antiglare layer, the transparent support / hard coat layer or the transparent support / Reflected light is generated at the antiglare interface. This reflected light interferes with the reflected light on the surface of the antireflection layer, and may cause interference unevenness due to subtle film thickness unevenness of the hard coat layer (or antiglare layer). In order to prevent such interference unevenness, for example, an interference having an intermediate refractive index n _P between the transparent support and the hard coat layer (or antiglare layer) and a film thickness d _P satisfying the following equation: An unevenness prevention layer can also be provided.

Formula (dp):
d _P = (2N−1) × λ / (4n _P )

  However, λ is a wavelength of visible light and any value in the range of 450 to 650 nm, and N represents a natural number.

  Moreover, when bonding an antireflection film to an image display etc., an adhesive layer (or adhesive layer) may be laminated | stacked on the side which has not laminated | stacked the antireflection layer of a transparent support body. In such an embodiment, when there is a substantial refractive index difference (0.03 or more) between the transparent support and the pressure-sensitive adhesive layer (or adhesive layer), the transparent support / pressure-sensitive adhesive layer (or adhesive layer) The reflected light interferes with the reflected light on the surface of the antireflection layer, and the interference unevenness due to the film thickness unevenness of the support or the hard coat layer may occur as described above. For the purpose of preventing such interference unevenness, an interference unevenness preventing layer similar to the above can be provided on the side of the transparent support on which the antireflection layer is not laminated.

  Such an interference non-uniformity prevention layer is described in detail in Japanese Patent Application Laid-Open No. 2004-345333, and the interference non-uniformity prevention layer introduced here can also be used in the present invention.

3- (7). [Adhesive layer]
An easy-adhesion layer can be coated on the film of the present invention. An easy-adhesion layer means the layer which provides the function which makes it easy to adhere | attach a protective film for polarizing plates, its adjacent layer, or a hard-coat layer and a support body, for example.
Examples of the easy adhesion treatment include a treatment of providing an easy adhesion layer on a transparent plastic film with an easy adhesive composed of polyester, acrylic acid ester, polyurethane, polyethyleneimine, silane coupling agent and the like.
Examples of the easy-adhesion layer preferably used in the present technology include a layer containing a polymer compound having a -COOM (M represents a hydrogen atom or a cation) group, and a more preferable embodiment is a film substrate. A layer containing a polymer compound having a —COOM group is provided on the side, and a layer containing a hydrophilic polymer compound as a main component is provided on the polarizing film side adjacent to the layer. Examples of the polymer compound having -COOM group herein include styrene-maleic acid copolymer having -COOM group, vinyl acetate-maleic acid copolymer having -COOM group, and vinyl acetate-maleic acid-maleic anhydride. For example, it is preferable to use a vinyl acetate-maleic acid copolymer having a —COOM group. These polymer compounds are used alone or in combination of two or more, and the preferred mass average molecular weight is preferably about 500 to 500,000. Particularly preferred examples of the polymer compound having a —COOM group include those described in JP-A-6-094915 and JP-A-7-333436.

The hydrophilic polymer compound is preferably a hydrophilic cellulose derivative (eg, methyl cellulose, carboxymethyl cellulose, hydroxy cellulose, etc.), a polyvinyl alcohol derivative (eg, polyvinyl alcohol, vinyl acetate-vinyl alcohol copolymer, polyvinyl acetal, polyvinyl formal). , Polyvinyl benzal, etc.), natural polymer compounds (eg, gelatin, casein, gum arabic, etc.), hydrophilic polyester derivatives (eg, partially sulfonated polyethylene terephthalate), hydrophilic polyvinyl derivatives (eg, poly -N-vinylpyrrolidone, polyacrylamide, polyvinylindazole, polyvinylpyrazole and the like), and may be used alone or in combination of two or more.
The thickness of the easy adhesion layer is preferably in the range of 0.05 to 1.0 μm. If it is thinner than 0.05 μm, it is difficult to obtain sufficient adhesiveness, and if it is thicker than 1.0 μm, the effect of adhesiveness is saturated.

3- (8). [Anti-curl layer]
The film of the present technology can be anti-curled. The anti-curl processing is to give the function of trying to curl with the surface to which it is applied inside, but by applying this processing, some surface processing is performed on one side of the transparent resin film and both sides are processed. When surface treatments of different degrees and types are applied, it functions to prevent curling with the surface facing inward.
The anti-curl layer may be provided on the side opposite to the side having the anti-glare layer or anti-reflection layer of the base material, or for example, an easy-adhesion layer may be coated on one side of the transparent resin film, and the anti-curl processing is performed on the opposite side The mode which coats is mentioned.

  Specific examples of the anti-curl processing include solvent coating, and a method of applying a solvent and a transparent resin layer such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate. The method using a solvent is specifically performed by applying a composition containing a solvent for dissolving or swelling a cellulose acylate film used as a protective film for a polarizing plate. Accordingly, the coating solution for the layer having a function of preventing curling preferably contains a ketone-based or ester-based organic solvent. Examples of preferred ketone-based organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl lactate, acetyl acetone, diacetone alcohol, isophorone, ethyl-n-butyl ketone, diisopropyl ketone, diethyl ketone, di-n-propyl ketone, Examples thereof include methylcyclohexanone, methyl-n-butyl ketone, methyl-n-propyl ketone, methyl-n-hexyl ketone, methyl-n-heptyl ketone, etc. Examples of preferable ester organic solvents include methyl acetate, ethyl acetate, acetic acid Examples include butyl, methyl lactate, and ethyl lactate. However, as a solvent to be used, in addition to a solvent mixture to be dissolved and / or a solvent to be swollen, it may further contain a solvent that does not dissolve, and a composition in which these are mixed at an appropriate ratio depending on the degree of curl of the transparent resin film and the type of resin. This is done using the product and the coating amount. In addition, the anti-curl function is exhibited even if transparent hard processing or antistatic processing is applied.

3- (9). [Water absorption layer]
A water absorbent can be used in the film of the present invention. The water absorbent can be selected from compounds having a water absorption function, mainly alkaline earth metals. Examples thereof include BaO, SrO, CaO, and MgO. Further, it can be selected from metal elements such as Ti, Mg, Ba, and Ca. The particle size of these absorbent particles is preferably 100 nm or less, and more preferably 50 nm or less.
The layer containing these water absorbents may be prepared by using a vacuum deposition method or the like as in the above-described barrier layer, or nanoparticles may be prepared by various methods. The thickness of the layer is preferably 1 to 100 nm, and more preferably 1 to 10 nm. The layer containing the water absorbent is between the support and the laminate (a laminate of the barrier layer and the organic layer), between the uppermost layer of the laminate, between the laminates, or in the organic layer or barrier layer in the laminate. It may be added. When added to the barrier layer, a co-evaporation method is preferably used.

3- (10). [Primer layer / inorganic thin film layer]
In the film of the present invention, gas barrier properties can be enhanced by installing a known primer layer or inorganic thin film layer between the support and the laminate.
As the primer layer, for example, an acrylic resin, an epoxy resin, a urethane resin, a silicone resin, or the like can be used. In the present invention, an organic-inorganic hybrid layer is used as the primer layer, an inorganic vapor deposition layer or a sol is used as the inorganic thin film layer. -A dense inorganic coating thin film by a gel method is preferred. As an inorganic vapor deposition layer, vapor deposition layers, such as a silica, a zirconia, an alumina, are preferable. The inorganic vapor deposition layer can be formed by a vacuum vapor deposition method, a sputtering method, or the like.

4. [Support]
The support for the film of the present invention is not particularly limited, such as a transparent resin film, a transparent resin plate, a transparent resin sheet, and transparent glass. Transparent resin films include cellulose acylate films (for example, cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film), polyethylene terephthalate film, polyethersulfone. Films, polyacrylic resin films, polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth) acrylonitrile films, and the like can be used.

4- (1). [Cellulose acylate film]
Among them, a cellulose acylate film having high transparency, optically low birefringence, easy production, and generally used as a protective film for a polarizing plate is preferable, and a cellulose triacetate film is particularly preferable. The thickness of the transparent support is usually about 25 μm to 1000 μm.

In the present invention, it is preferable to use cellulose acetate having an acetylation degree of 59.0 to 61.5% for the cellulose acylate film.
The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like).
The viscosity average degree of polymerization (DP) of cellulose acylate is preferably 250 or more, and more preferably 290 or more.
In addition, the cellulose acylate used in the present invention has a Mw / Mn (Mw is mass average molecular weight, Mn is number average molecular weight) value by gel permeation chromatography close to 1.0, in other words, a molecular weight distribution. Narrow is preferred. The specific value of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and most preferably 1.4 to 1.6. preferable.

In general, the 2, 3, and 6 hydroxyl groups of cellulose acylate are not evenly distributed by 1/3 of the total substitution degree, and the substitution degree of the 6-position hydroxyl group tends to be small. In the present invention, it is preferable that the substitution degree of the 6-position hydroxyl group of cellulose acylate is larger than that of the 2- and 3-positions.
The hydroxyl group at the 6-position with respect to the total degree of substitution is preferably substituted with an acyl group of 32% or more, more preferably 33% or more, and particularly preferably 34% or more. Furthermore, the substitution degree of the 6-position acyl group of cellulose acylate is preferably 0.88 or more. The 6-position hydroxyl group may be substituted with a propionyl group, butyroyl group, valeroyl group, benzoyl group, acryloyl group or the like, which is an acyl group having 3 or more carbon atoms, in addition to the acetyl group. The degree of substitution at each position can be determined by NMR.
In the present invention, as cellulose acylate, paragraphs “0043” to “0044” [Example] [Synthesis Example 1], paragraphs “0048” to “0049” [Synthesis Example 2], paragraph “ Cellulose acetate obtained by the method described in “0051” to “0052” [Synthesis Example 3] can be used.

4- (2). [Polyethylene terephthalate film]
In the present invention, the polyethylene terephthalate film is also preferably used because it is excellent in transparency, mechanical strength, flatness, chemical resistance and moisture resistance, and is inexpensive.
In order to further improve the adhesion strength between the transparent plastic film and the hard coat layer provided thereon, the transparent plastic film is more preferably subjected to an easy adhesion treatment.
Examples of commercially available PET films with an easily adhesive layer for optics include Toyobo Co., Ltd. Cosmo Shine A4100 and A4300.

5). 〔Production method〕
Although the film of this invention can be formed with the following method, it is not restrict | limited to this method.

5- (1). [Adjustment of coating solution]

(Preparation)
First, a coating solution containing components for forming each layer is prepared. In that case, the raise of the moisture content in a coating liquid can be suppressed by suppressing the volatilization amount of a solvent to the minimum. The moisture content in the coating solution is preferably 5% or less, more preferably 2% or less. The suppression of the volatilization amount of the solvent is achieved by improving the sealing property at the time of stirring after putting each material into the tank, minimizing the air contact area of the coating liquid at the time of liquid transfer operation, and the like. Moreover, you may provide the means to reduce the moisture content in a coating liquid during application | coating, or before and behind that.

(Coating liquid properties)
In the coating method of the present invention, the upper limit speed at which coating is possible is greatly affected by the liquid physical properties, so it is necessary to control the liquid physical properties, particularly the viscosity and surface tension at the moment of coating.
The viscosity is preferably 2.0 [mPa · sec] or less, more preferably 1.5 [mPa · sec] or less, and most preferably 1.0 [mPa · sec] or less. Since there are some coating solutions whose viscosity changes depending on the shear rate, the above value indicates the viscosity at the shear rate at the moment of coating. When a thixotropic agent is added to the coating solution and the coating solution is subjected to high shear, the viscosity is low, and when the coating solution is hardly sheared, if the viscosity is high, unevenness during drying is less likely to occur.
Moreover, although it is not a liquid physical property, the quantity of the coating liquid apply | coated to a transparent support body also affects the upper limit speed | rate which can be apply | coated. The amount of the coating solution applied to the transparent support is preferably 2.0 to 5.0 [ml / m ² ]. Increasing the amount of the coating liquid applied to the transparent support is preferable because the upper limit of the application rate can be increased, but if the amount of the coating liquid applied to the transparent support is increased too much, the load on drying increases. It is preferable to determine the optimal amount of coating liquid to be applied to the transparent support depending on the liquid formulation and process conditions.
The surface tension is preferably in the range of 15 to 36 [mN / m]. It is preferable to reduce the surface tension by adding a leveling agent or the like because unevenness during drying is suppressed. On the other hand, if the surface tension is too low, the upper limit speed at which coating can be performed is reduced. Therefore, a range of 17 [mN / m] to 32 [mN / m] is more preferable, and 19 [mN / m] to 26 [mN / m]. mN / m] is more preferable.

(filtration)
The coating solution used for coating is preferably filtered before coating. As a filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within a range in which components in the coating solution are not removed. For filtration, a filter having an absolute filtration accuracy of 0.1 to 10 μm is used, and a filter having an absolute filtration accuracy of 0.1 to 5 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 1.5 MPa or less, more preferably 1.0 MPa or less, and further preferably 0.2 MPa or less.
The filtration filter member is not particularly limited as long as it does not affect the coating solution. Specifically, the same thing as the filter member of the wet dispersion of an inorganic compound mentioned above is mentioned.
It is also preferable to ultrasonically disperse the filtered coating solution immediately before coating to assist defoaming and dispersion holding of the dispersion.

5- (2). [Processing before coating]
The support used in the present invention is preferably subjected to a surface treatment before coating. Specific examples include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment, and ultraviolet irradiation treatment. In addition, as described in JP-A-7-333433, it is preferable to provide an undercoat layer.

Furthermore, as a dust removing method used in the dust removing step as a pre-process for application, a method of pressing a nonwoven fabric, a blade or the like on the film surface described in JP-A-59-150571, JP-A-10-309553 A method of blowing the air with high cleanliness described at a high speed to peel off the deposits from the film surface and sucking it with a suction port close to it, blowing compressed air that is ultrasonically vibrated as described in JP-A-7-333613 Examples thereof include a dry dust removing method such as a method for peeling and sucking adhered substances (manufactured by Shinkosha, New Ultra Cleaner, etc.).
In addition, a method of introducing a film into a cleaning tank and peeling off deposits with an ultrasonic vibrator, supplying a cleaning liquid to the film described in Japanese Patent Publication No. 49-13020, and then blowing and sucking high-speed air As described in JP-A-2001-38306, a wet dust removal method such as a method in which a web is continuously rubbed with a roll wetted with liquid and then the liquid is sprayed onto the rubbed surface for cleaning. Can do. Among such dust removal methods, a method using ultrasonic dust removal or a method using wet dust removal is particularly preferable in terms of dust removal effect.
In addition, it is particularly preferable to remove static electricity on the film support before performing such a dust removal step from the viewpoint of increasing dust removal efficiency and suppressing adhesion of dust. As such a static elimination method, a corona discharge ionizer, a light irradiation ionizer such as UV or soft X-ray, or the like can be used. The charged voltage of the film support before and after dust removal and coating is desirably 1000 V or less, preferably 300 V or less, and particularly preferably 100 V or less.

From the viewpoint of maintaining the flatness of the film, the temperature of the cellulose acylate film in these treatments is preferably Tg or less, specifically 150 ° C. or less.
When the cellulose acylate film is adhered to the polarizing film as in the case of using the film of the present invention as a protective film for a polarizing plate, from the viewpoint of adhesiveness to the polarizing film, acid treatment or alkali treatment, that is, cellulose acylate. It is particularly preferred to carry out a saponification treatment on the rate.
From the viewpoint of adhesiveness and the like, the surface energy of the cellulose acylate film is preferably 55 mN / m or more, more preferably 60 mN / m or more and 75 mN / m or less, and it can be adjusted by the surface treatment. .

5- (3). [Application]
Each layer of the film of the present invention can be formed by the following coating method, but is not limited to this method.
Dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method and extrusion coating method (die coating method) (see US Pat. No. 2,681,294), micro gravure coating method, etc. Known methods are used, and among them, the micro gravure coating method and the die coating method are preferable.

  The micro gravure coating method used in the present invention is a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm and engraved with a gravure pattern on the entire circumference, below the support and in the transport direction of the support. The gravure roll is rotated in reverse with respect to the gravure roll, the excess coating liquid is scraped off from the surface of the gravure roll by a doctor blade, and a fixed amount of the coating liquid is removed from the support in a position where the upper surface of the support is in a free state. The coating method is characterized in that the coating liquid is transferred onto the lower surface for coating. A roll-shaped transparent support is continuously unwound, and at least one layer of at least one of a hard coat layer or a low refractive index layer containing a fluorine-containing olefin-based polymer is formed on one side of the unwound support. It can be applied by a gravure coating method.

  As coating conditions by the micro gravure coating method, the number of gravure patterns imprinted on the gravure roll is preferably 50 to 800 lines / inch, more preferably 100 to 300 lines / inch, and the depth of the gravure pattern is 1 to 600 μm. Is preferable, 5 to 200 μm is more preferable, the rotation speed of the gravure roll is preferably 3 to 800 rpm, more preferably 5 to 200 rpm, and the conveyance speed of the support is 0.5 to 100 m / min. It is preferably 1 to 50 m / min.

In order to supply the film of the present invention with high productivity, an extrusion method (die coating method) is preferably used. In particular, a die coater that can be preferably used in a region with a small amount of wet coating (20 cc / m ² or less) such as a hard coat layer or an antireflection layer will be described below.

(Die coater configuration)
FIG. 2 is a sectional view of a coater using a slot die embodying the present invention. The coater 10 is applied to the web W supported by the backup roll 11 and continuously applied from the slot die 13 as a bead 14a to form a coating film 14b on the web W.

  Inside the slot die 13, a pocket 15 and a slot 16 are formed. The cross section of the pocket 15 is configured by a curve and a straight line. For example, the pocket 15 may be substantially circular as shown in FIG. 2 or may be semicircular. The pocket 15 is a liquid storage space for the coating liquid extended in the width direction of the slot die 13 with its cross-sectional shape, and the length of the effective extension is generally equal to or slightly longer than the coating width. The supply of the coating liquid 14 to the pocket 15 is performed from the side surface of the slot die 13 or from the center of the surface opposite to the slot opening 16a. The pocket 15 is provided with a stopper that prevents the coating liquid 14 from leaking out.

  The slot 16 is a flow path of the coating liquid 14 from the pocket 15 to the web W, and has a cross-sectional shape in the width direction of the slot die 13 similarly to the pocket 15, and the opening 16a located on the web side is generally Using a width regulating plate (not shown), the width is adjusted to be approximately the same as the coating width. The angle between the slot tip of the slot 16 and the tangent in the web running direction of the backup roll 11 is preferably 30 ° or more and 90 ° or less.

  The tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is tapered, and the tip is a flat portion 18 called a land. In the land 18, the upstream side in the traveling direction of the web W with respect to the slot 16 is referred to as an upstream lip land 18 a and the downstream side is referred to as a downstream lip land 18 b.

FIG. 3 shows a cross-sectional shape of the slot die 13 used for manufacturing the antireflection film of the present invention in comparison with the conventional one, (A) shows the slot die 13 according to the present invention, (B) A conventional slot die 30 is shown. In the conventional slot die 30, the distance between the upstream lip land 31a and the web of the downstream lip land 31b is equal. Reference numeral 32 denotes a pocket, and 33 denotes a slot. On the other hand, in the slot die 13 of the present invention, the downstream side lip land length I _LO is shortened, whereby the wet film thickness of 20 μm or less can be applied with high accuracy.

The land length I _UP of the upstream lip land 18a is not particularly limited, but is preferably used in the range of 500 μm to 1 mm. The land length I _LO of the downstream lip land 18b is not less than 30 μm and not more than 100 μm, preferably not less than 30 μm and not more than 80 μm, more preferably not less than 30 μm and not more than 60 μm. If the land length I _LO of the downstream lip is shorter than 30 μm, the edge or land of the tip lip is likely to be chipped, streaks are likely to occur in the coating film, and consequently application is impossible. In addition, it becomes difficult to set the position of the wetting line on the downstream side, and there is a problem that the coating liquid tends to spread on the downstream side. It has been conventionally known that this spreading of the coating liquid on the downstream side means non-uniform wetting lines and leads to a problem of causing a defective shape such as a streak on the coating surface. On the other hand, when the land length I _LO of the downstream lip is longer than 100 μm, the bead itself cannot be formed, so that it is impossible to apply the thin layer.

Further, the downstream lip land 18b has an overbite shape closer to the web W than the upstream lip land 18a. Therefore, the degree of decompression can be lowered, and a bead suitable for thin film coating can be formed. The difference in distance between the downstream side lip land 18b and the web W of the upstream side lip land 18a (hereinafter referred to as overbit length LO) is preferably 30 μm or more and 120 μm or less, more preferably 30 μm or more and 100 μm or less, and most preferably 30 μm. It is 80 μm or less. When the slot die 13 has an overbite shape, the gap _GL between the tip lip 17 and the web W indicates the gap between the downstream lip land 18b and the web W.

FIG. 4 is a perspective view showing a slot die and its periphery in a coating process in which the present invention is implemented.
On the opposite side of the web W in the direction of travel, a decompression chamber 40 is installed at a position where it does not come into contact with the bead 14a so that sufficient decompression can be adjusted. The decompression chamber 40 includes a back plate 40a and a side plate 40b for maintaining its operating efficiency, and there are gaps G _B and G between the back plate 40a and the web W and between the side plate 40b and the web W, respectively. _S exists.

5- (4). [Dry]
The film of the present invention is preferably applied on a support directly or via another layer and then conveyed by a web to a heated zone to dry the solvent.
Various knowledges can be used as a method for drying the solvent. Specific examples include JP-A Nos. 2001-286817, 2001-314798, 2003-126768, 2003-315505, and 2004-34002.
The temperature of the drying zone is preferably 25 ° C. to 140 ° C., the first half of the drying zone is preferably a relatively low temperature, and the latter half is preferably a relatively high temperature. However, it is preferably below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize. For example, some of the commercially available photo radical generators used in combination with ultraviolet curable resins volatilize around several tens of percent within a few minutes in warm air at 120 ° C. Some acrylate monomers and the like undergo volatilization in warm air at 100 ° C. In such a case, it is preferable that it is below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize as described above.

Moreover, the dry wind after apply | coating the coating composition of each layer on a support body has the wind speed of the coating-film surface of 0.1-2 m / sec while the solid content concentration of the said coating composition is 1-50%. It is preferable to be in the range in order to prevent drying unevenness.
Moreover, after apply | coating the coating composition of each layer on a support body, the temperature difference of the conveyance roll which contacts the surface opposite to the coating surface of a support body in a drying zone, and a support body is 0 to 20 degreeC or less. Then, the drying nonuniformity by the heat transfer nonuniformity on a conveyance roll can be prevented, and it is preferable.

5- (5). [Curing]
After drying the solvent, the film of the present invention can be passed through a zone where the coating film is cured by ionizing radiation and / or heat on the web to cure the coating film.

It is preferable that the film of the present invention is first heated at a temperature of 70 ° C. or higher and 130 ° C. or lower for 5 to 20 minutes, and then cured by an active energy ray typified by ultraviolet rays.
The temperature of thermosetting is preferably 70 ° C. or higher and 120 ° C. or lower, and most preferably 80 ° C. or higher and 115 ° C. or lower.
The ionizing radiation species in the present invention is not particularly limited, and is appropriately selected from ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays and the like according to the type of curable composition forming the film. Although it can be selected, ultraviolet rays and electron beams are preferred, and ultraviolet rays are particularly preferred because they are easy to handle and high energy can be easily obtained.
As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Among these, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be preferably used.

  Moreover, an electron beam can be used similarly. As an electron beam, 50 to 1000 keV, preferably 100 to 100, emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. An electron beam having an energy of 300 keV can be given.

Irradiation conditions vary depending on each lamp, but the irradiation light quantity is preferably 10 mJ / cm ² or more, more preferably 50 mJ / cm ^{2 to} 10000 mJ / cm ² , and particularly preferably 50 mJ / cm ^{2 to} 2000 mJ / cm ^2. It is. At that time, the irradiation distribution in the width direction of the web is preferably 50 to 100%, more preferably 80 to 100%, including both ends with respect to the central maximum irradiation.

In the present invention, at least one layer laminated on the support is irradiated with ionizing radiation and heated to a film surface temperature of 60 ° C. or more for 0.5 seconds or more from the start of irradiation with ionizing radiation, with an oxygen concentration of 10 volumes. It is preferable to cure by the step of irradiating ionizing radiation in an atmosphere of less than or equal to%.
It is also preferable to heat in an atmosphere having an oxygen concentration of 3% by volume or less simultaneously and / or continuously with ionizing radiation irradiation.
In particular, it is preferable that the low refractive index layer which is the outermost layer and has a small film thickness is cured by this method. The curing reaction is accelerated by heat, and a film having excellent physical strength and chemical resistance can be formed.

  The time for irradiating with ionizing radiation is preferably 0.7 seconds or longer and 60 seconds or shorter, and more preferably 0.7 seconds or longer and 10 seconds or shorter. If it is 0.5 seconds or less, the curing reaction cannot be completed, and sufficient curing cannot be performed. Also, maintaining low oxygen conditions for a long time is not preferable because the equipment becomes large and a large amount of inert gas is required.

  The oxygen concentration is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound in an atmosphere of 6% by volume or less, more preferably 4% by volume or less, particularly preferably 2% by volume of oxygen. Hereinafter, it is most preferably 1% by volume or less. In order to reduce the oxygen concentration more than necessary, a large amount of inert gas such as nitrogen is required, which is not preferable from the viewpoint of production cost.

As a method of reducing the oxygen concentration to 10% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

By supplying inert gas to the ionizing radiation irradiation chamber and slightly blowing it out to the web entrance side of the irradiation chamber, the entrained air accompanying the web transfer can be eliminated, and the oxygen concentration in the reaction chamber can be effectively reduced. It is possible to efficiently reduce the substantial oxygen concentration on the extreme surface where the inhibition of curing due to is large. The direction of the inert gas flow on the web entrance side of the irradiation chamber can be controlled by adjusting the balance between the supply and exhaust of the irradiation chamber.
Direct blowing of an inert gas onto the web surface is also preferably used as a method for removing the carried air.

  Further, by providing a front chamber in front of the reaction chamber and excluding oxygen on the web surface in advance, the curing can proceed more efficiently. Further, the side surface constituting the web entrance side of the ionizing radiation reaction chamber or the front chamber is preferably 0.2 to 15 mm in gap with the web surface in order to use the inert gas efficiently, more preferably, 0.1%. The thickness is preferably 2 to 10 mm, and most preferably 0.2 to 5 mm. However, in order to continuously manufacture the web, it is necessary to join and connect the webs, and a method of sticking with a joining tape or the like is widely used for joining. For this reason, if the gap between the entrance surface of the ionizing radiation reaction chamber or the front chamber and the web is too narrow, there arises a problem that the joining member such as the joining tape is caught. For this reason, in order to narrow the gap, it is preferable to make at least a part of the entrance surface of the ionizing radiation reaction chamber or the front chamber movable, and to widen the gap by the junction thickness when the junction enters. In order to realize this, the entrance surface of the ionizing radiation reaction chamber or the front chamber is made movable in the forward and backward direction, and when the joint passes, the gap is moved back and forth to widen the gap, It is possible to move the chamber entrance surface vertically with respect to the web surface and move up and down to widen the gap as the joint passes.

  In curing, the film surface is preferably heated at 60 ° C. or higher and 170 ° C. or lower. Below 60 ° C., there is little curing by heating, and at 170 ° C. or higher, problems such as deformation of the substrate occur. A more preferable temperature is 60 ° C to 100 ° C. The film surface refers to the film surface temperature of the layer to be cured. The time for the film to reach the temperature is preferably 0.1 second or more and 300 seconds or less from the start of UV irradiation, and more preferably 10 seconds or less. If the time for maintaining the temperature of the film surface in the above temperature range is too short, the reaction of the curable composition that forms the film cannot be accelerated, and conversely, if it is too long, the optical performance of the film deteriorates and the equipment is large. Manufacturing problems such as

  There is no particular limitation on the heating method, but a method of heating a roll to contact the film, a method of spraying heated nitrogen, irradiation with far infrared rays or infrared rays is preferable. A method of heating a rotating metal roll described in Japanese Patent No. 2523574 by flowing a medium such as hot water, steam or oil can also be used. As a heating means, a dielectric heating roll or the like may be used.

  The ultraviolet irradiation may be performed every time one layer is provided for each of a plurality of constituent layers, or may be performed after lamination. Or you may irradiate combining these. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers.

In the present invention, at least one layer laminated on the support can be cured by multiple times of ionizing radiation. In this case, it is preferable that at least two ionizing radiations are performed in a continuous reaction chamber in which the oxygen concentration does not exceed 3% by volume. By performing multiple times of ionizing radiation irradiation in the same low oxygen concentration reaction chamber, the reaction time required for curing can be effectively ensured.
In particular, when the production rate is increased for high productivity, ionizing radiation irradiation is required multiple times to ensure the energy of ionizing radiation necessary for the curing reaction.

  Further, when the curing rate (100-residual functional group content) is a certain value of less than 100%, the lower layer has a curing rate of the upper layer when a layer is provided thereon and cured by ionizing radiation and / or heat. When the height is higher than before, the adhesion between the lower layer and the upper layer is improved, which is preferable.

5- (6). [Handling]
In order to continuously produce the film of the present invention, a process of continuously feeding a roll-shaped support film, a process of applying and drying a coating liquid, a process of curing a coating film, and a support film having a cured layer The step of winding is performed.
The film support is continuously sent out from the roll-shaped film support to the clean room. In the clean room, the static electricity charged on the film support is removed by an electrostatic charge-off device, and then the film support adheres on the film support. Remove the foreign material that has been removed with a dust remover. Subsequently, the coating liquid is applied onto the film support in the application section installed in the clean room, and the applied film support is sent to the drying chamber and dried.
The film support having the dried coating layer is fed from the drying chamber to the curing chamber, and the monomer contained in the coating layer is polymerized and cured. Further, the film support having the cured layer is sent to the curing unit to complete the curing, and the film support having the layer having been completely cured is wound up into a roll shape.

The above steps may be performed every time each layer is formed, or a plurality of coating parts-drying chambers-curing parts may be provided to continuously form each layer.
In order to create the film of the present invention, as described above, the coating step in the coating unit and the drying step performed in the drying chamber are performed in a highly clean air atmosphere simultaneously with the microfiltration operation of the coating solution, and It is preferable that dust and dust on the film are sufficiently removed before application. The air cleanliness of the coating process and the drying process is desirably class 10 (353 particles / 0.5 m or more / (cubic meter) or less) based on the standard of air cleanliness in the US Federal Standard 209E. Preferably it is class 1 (35.5 particles / (cubic meter) or less) having a particle size of 0.5 μm or more. Moreover, it is more preferable that the degree of air cleanliness is high also in the feeding and winding parts other than the coating-drying process.

5- (7). [Saponification treatment]
When creating a polarizing plate using the film of the present invention as one of the surface protective films of two polarizing films, the adhesiveness on the adhesive surface is achieved by hydrophilizing the surface to be bonded to the polarizing film. It is preferable to improve.

a. Method of immersing in alkaline solution This is a method of saponifying all surfaces that are reactive with alkali on the entire surface of the film by immersing the film in an alkaline solution under appropriate conditions, and no special equipment is required. From the viewpoint of cost. The alkaline liquid is preferably a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 mol / L, particularly preferably 1 to 2 mol / L. The liquid temperature of a preferable alkali liquid is 30-75 degreeC, Most preferably, it is 40-60 degreeC.
The combination of the saponification conditions is preferably a combination of relatively mild conditions, but can be set according to the material and composition of the film and the target contact angle.
After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by immersing in a dilute acid so that the alkaline component does not remain in the film.

By saponification treatment, the surface opposite to the surface having the coating layer is hydrophilized. The protective film for polarizing plate is used by adhering the hydrophilic surface of the transparent support to the polarizing film.
The hydrophilized surface is effective for improving the adhesiveness with the adhesive layer mainly composed of polyvinyl alcohol.
In the saponification treatment, the lower the contact angle with respect to the surface of the transparent support opposite to the side having the coating layer, the better from the viewpoint of adhesion to the polarizing film, while the dipping method simultaneously has the coating layer. Since it is damaged by alkali from the surface to the inside, it is important to set the minimum reaction conditions. When the contact angle to water of the transparent support on the opposite surface is used as an index of damage to each layer due to alkali, particularly when the transparent support is triacetylcellulose, preferably 10 to 50 degrees, more preferably Is 30 to 50 degrees, more preferably 40 to 50 degrees. If it is 50 degrees or less, a problem does not arise in adhesiveness with a polarizing film, and it is preferable. On the other hand, if it is 10 degree | times or more, there is little damage which a film receives and it is preferable, without impairing physical strength.

b. Method of applying alkaline solution As a means of avoiding damage to each film in the above-mentioned immersion method, an alkali solution is applied, heated, washed with water, and dried only on the surface opposite to the surface having the coating layer under appropriate conditions. A liquid coating method is preferably used. The application in this case means that an alkaline solution or the like is brought into contact only with the surface to be saponified, and in addition to the application, it may be carried out by spraying or contacting a belt containing the solution. Including. By adopting these methods, a separate facility and process for applying an alkaline solution are required. It is inferior to the dipping method. On the other hand, since the alkali solution contacts only the surface to be saponified, the opposite surface can have a layer using a material that is weak against the alkali solution. For example, vapor deposition films and sol-gel films have various effects such as corrosion, dissolution, and peeling due to alkali solution, so it is not desirable to use the immersion method. Is possible.

  A. B. In any of these saponification methods, since each layer can be formed after being unwound from a roll-shaped support, it may be performed by a series of operations in addition to the film manufacturing process. Furthermore, the polarizing plate can be produced more efficiently than the same operation with a single wafer by continuously performing the pasting step with the polarizing plate made of the unwound support.

c. Method of saponification by protecting with a laminate film b. Similarly, when the coating layer is insufficient in resistance to the alkaline solution, after the final layer is formed, the laminate film is bonded to the surface on which the final layer is formed and then immersed in the alkaline solution. Only the triacetyl cellulose surface opposite to the formed surface can be made hydrophilic, and then the laminate film can be peeled off. Even in this method, the hydrophilic treatment necessary for the polarizing plate protective film can be applied only to the surface opposite to the surface on which the final layer of the triacetyl cellulose film is formed without damaging the coating layer. B. Compared with this method, the laminate film is generated as waste, but there is an advantage that a device for applying a special alkaline solution is unnecessary.

d. Method of immersing in alkaline solution after forming up to middle layer Although resistant to alkaline solution up to lower layer, but insufficient resistance to alkaline solution of upper layer, dip into alkaline solution after forming up to lower layer to make both sides hydrophilic The upper layer can also be formed after processing. Although the manufacturing process is complicated, for example, in a film composed of an antiglare layer and a low refractive index layer of a fluorine-containing sol-gel film, when there is a hydrophilic group, the interlayer adhesion between the antiglare layer and the low refractive index layer is improved. There are advantages to doing.

e. Method of forming a coating layer on a saponified triacetyl cellulose film A saponification of a triacetyl cellulose film by immersing it in an alkaline solution in advance and applying the coating layer directly on one side or via another layer It may be formed. In the case of saponification by dipping in an alkaline solution, the interlayer adhesion with the triacetyl cellulose surface hydrophilized by saponification may deteriorate. In such a case, after saponification, only the surface on which the coating layer is to be formed is treated by corona discharge, glow discharge or the like to remove the hydrophilic surface and then form the coating layer. Further, when the coating layer has a hydrophilic group, the interlayer adhesion may be good.

5- (8). [Preparation of polarizing film]
The film of the present invention can be used as a protective film disposed on one side or both sides of a polarizing film, and can be used as a polarizing plate.
As one protective film, the film of the present invention may be used, and as the other protective film, a normal cellulose acetate film may be used, but it is produced by the above-mentioned solution casting method and has a stretch ratio of 10 to 100%. It is preferable to use a cellulose acetate film stretched in the width direction in the form of a roll film.
Furthermore, in the polarizing plate of the present invention, it is preferable that one side is an antireflection film, whereas the other protective film is an optical compensation film having an optically anisotropic layer made of a liquid crystalline compound.

Examples of the polarizing film include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. The iodine polarizing film and the dye polarizing film are generally produced using a polyvinyl alcohol film.
The transparent support of the antireflection film and the slow axis of the cellulose acetate film and the transmission axis of the polarizing film are arranged so as to be substantially parallel.

The moisture permeability of the protective film is important for the productivity of the polarizing plate. The polarizing film and the protective film are bonded together with an aqueous adhesive, and the adhesive solvent is dried by diffusing in the protective film. The higher the moisture permeability of the protective film, the faster the drying and the higher the productivity. However, if the protective film is too high, moisture will enter the polarizing film depending on the usage environment (high humidity) of the liquid crystal display device. Polarization ability decreases.
The moisture permeability of the protective film is determined by the thickness, free volume, hydrophilicity / hydrophobicity, etc. of the transparent support or polymer film (and polymerizable liquid crystal compound).
When using the film of the present invention as a protective film of a polarizing plate, the moisture permeability is preferably from 100~1000g / m ² · 24hrs, and more preferably a 300~700g / m ² · 24hrs.
In the case of film formation, the thickness of the transparent support can be adjusted by lip flow rate and line speed, or stretching and compression. Since the moisture permeability varies depending on the main material to be used, it is possible to make a preferable range by adjusting the thickness.
In the case of film formation, the free volume of the transparent support can be adjusted by the drying temperature and time.
Also in this case, moisture permeability varies depending on the main material to be used, so that a preferable range can be obtained by adjusting the free volume.
The hydrophilicity / hydrophobicity of the transparent support can be adjusted by an additive. The moisture permeability can be increased by adding a hydrophilic additive to the free volume, and conversely, the moisture permeability can be lowered by adding a hydrophobic additive.
By independently controlling the moisture permeability, a polarizing plate having an optical compensation ability can be manufactured at low cost with high productivity.

As the polarizing film, a known polarizing film or a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.
That is, a polarizing film stretched by applying tension while holding both ends of a continuously supplied polymer film by a holding means, stretched at least 1.1 to 20.0 times in the film width direction, The progress of the film is such that the difference between the moving speeds in the longitudinal direction of the holding device is within 3%, and the angle formed by the film moving direction at the exit of the step of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. The film can be produced by a stretching method in which the direction is bent while holding both ends of the film. In particular, those inclined by 45 ° are preferably used from the viewpoint of productivity.

The method for stretching the polymer film is described in detail in paragraphs 0020 to 0030 of JP-A-2002-86554.
Of the two protective films of the polarizer, the film other than the antireflection film is preferably an optical compensation film having an optical compensation layer comprising an optically anisotropic layer. The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen.
A known film can be used as the optical compensation film, but the optical compensation film described in JP-A-2001-100042 is preferable in terms of widening the viewing angle.

6). [Usage form of the present invention]
The film of the present invention is used for an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). The optical filter according to the present invention can be used on a known display such as a plasma display panel (PDP) or a cathode ray tube display (CRT).

6- (1). [Liquid crystal display device]
The film and polarizing plate of the present invention can be advantageously used for an image display device such as a liquid crystal display device, and is preferably used for the outermost layer of the display.
The liquid crystal display device has a liquid crystal cell and two polarizing plates arranged on both sides thereof, and the liquid crystal cell carries a liquid crystal between two electrode substrates. Furthermore, one optically anisotropic layer may be disposed between the liquid crystal cell and one polarizing plate, or two optically anisotropic layers may be disposed between the liquid crystal cell and both polarizing plates.

  The liquid crystal cell is preferably in TN mode, VA mode, OCB mode, IPS mode or ECB mode.

(TN mode)
In the TN mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and are twisted and aligned at 60 to 120 °.
The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents.

(VA mode)
In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.
The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). (2) Liquid crystal cell (SID97, Digest of Tech. Papers (Proceedings) 28 (1997) 845, in which the VA mode is made into a multi-domain (MVA mode) in order to expand the viewing angle. (3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary Collection 58- 59 (described in 1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).

(OCB mode)
The OCB mode liquid crystal cell is a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in substantially opposite directions (symmetrically) at the upper and lower portions of the liquid crystal cell. US Pat. No. 4,583,825, This is disclosed in each publication of Japanese Patent No. 5410422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. Therefore, this liquid crystal mode is called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

(IPS mode)
The IPS mode liquid crystal cell is a type in which a nematic liquid crystal is switched by applying a lateral electric field. IDRC (Asia Display '95), pages 577-580 and pages 707-710.

(ECB mode)
In the ECB mode liquid crystal cell, rod-like liquid crystalline molecules are substantially horizontally aligned when no voltage is applied. The ECB mode is one of the liquid crystal display modes having the simplest structure, and is described in detail in, for example, Japanese Patent Application Laid-Open No. 5-203946.

6- (2). [Displays other than liquid crystal display devices]
(PDP)
A plasma display panel (PDP) is generally composed of a gas, a glass substrate, an electrode, an electrode lead material, a thick film printing material, and a phosphor. Two glass substrates are a front glass substrate and a rear glass substrate. An electrode and an insulating layer are formed on the two glass substrates. A phosphor layer is further formed on the rear glass substrate. Two glass substrates are assembled and gas is sealed between them.
Plasma display panels (PDP) are already commercially available. The plasma display panel is described in JP-A-5-205643 and JP-A-9-306366.

The front plate may be disposed on the front surface of the plasma display panel. The front plate preferably has sufficient strength to protect the plasma display panel. The front plate can be used with a gap from the plasma display panel, or can be used by directly pasting the front plate to the plasma display body.
In an image display device such as a plasma display panel, an optical filter can be directly attached to the display surface. When a front plate is provided in front of the display, an optical filter can be attached to the front side (outside) or the back side (display side) of the front plate.

(Touch panel)
The film of the present invention can be applied to touch panels described in JP-A-5-127822 and JP-A-2002-48913.

(Organic EL device)
The film of the present invention can be used as a protective film for organic EL elements and the like.
When the film of the present invention is used for an organic EL device or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP-A-2001-192653, JP-A-2001-335776, JP-A-2001-247859, JP-A-2001-181616, JP-A-2001-181617, JP-A-2002-181816, JP-A-2002-181617, JP-A-2002-056776, etc. The contents described in each publication can be applied. Japanese Patent Laid-Open No. 2001-14829
No. 1, JP-A No. 2001-221916, and JP-A No. 2001-231443 are preferably used in combination with the contents described in the respective publications.

7). [Various characteristic values]
Various measurement methods and preferred characteristic values relating to the present invention are shown below.
7- (1). [Reflectance]
The specular reflectivity and color are measured by attaching an adapter “ARV-474” to a spectrophotometer “V-550” (manufactured by JASCO Corporation), and an incident angle of 5 ° in the wavelength region of 380 to 780 nm. By measuring the specular reflectance at an exit angle of -5 °, the average reflectance of 450 to 650 nm is calculated, and the antireflection property can be evaluated.
It is preferable that the antiglare antireflection film of the present invention has a specular reflectance of 5.0% or less and a transmittance of 90% or more because reflection of external light can be suppressed and visibility is improved. The specular reflectance is particularly preferably 3.0% or less, and most preferably 2.0% or less.

7- (2). [Color]
Antireflection performance polarizing plate of the present invention, the CIE standard illuminant D _65, with respect to the incident angle of 5 ° incident light at 780nm region from the wavelength 380 nm, the specular reflected light color, i.e. CIE1976L ^* a ^* b ^* By obtaining the L ^* , a ^* , and b ^* values of the color space, the color can be evaluated.
The L ^* , a ^* , and b ^* values are preferably in the ranges of 3 ≦ L ^* ≦ 20, −7 ≦ a ^* ≦ 7, and −10 ≦ b ^* ≦ 10, respectively. By setting it within this range, the color of reflected light from red purple to blue purple, which has been a problem with conventional polarizing plates, is reduced, and 3 ≦ L ^* ≦ 10, 0 ≦ a ^* ≦ 5, and − 7 ≦ b ^* ≦ 0 is greatly reduced, and when applied to a liquid crystal display device, when applied to a liquid crystal display device, such as indoor fluorescent light, the color tone when a little bright external light is reflected. Neutral, don't mind. Specifically, if a ^* ≦ 7, the reddishness will not be too strong, and if a ^* ≧ −7, the cyanishness will not be too strong. If b ^* ≧ −7, the bluish color does not become too strong, and if b ^* ≦ 0, the yellowish color does not become too strong.

Furthermore, the color uniformity of the reflected light is a change in color according to the following formula from a ^* b ^* on the L ^* a ^* b ^* chromaticity diagram obtained from the reflection spectrum of the reflected light from 380 nm to 680 nm. Can be obtained as a rate.

Where a ^* _max and a ^* _min are the maximum and minimum values of a ^* values, respectively; b ^* _max and b ^* _min are the maximum and minimum values of b ^* values, respectively; a ^* _av and b ^* _av Are average values of a ^* and b ^* values, respectively. The color change rate is preferably 30% or less, more preferably 20% or less, and most preferably 8% or less.

In the film of the present invention, ΔE _w which is a change in color before and after the weather resistance test is preferably 15 or less, more preferably 10 or less, and most preferably 5 or less. In this range, it is possible to achieve both low reflection and reduction of the color of the reflected light. For example, when applied to the outermost surface of an image display device, there is a slight amount of high-brightness external light such as an indoor fluorescent lamp. The color tone when it is reflected is neutral, and the quality of the displayed image is good, which is preferable.

The color change ΔE _w can be obtained according to the following formula (22).

Formula (22): ΔE _w = [(ΔL _w ) ² + (Δa _w ) ² + (Δb _w ) ² ] ^1/2

Here, ΔL _w , Δa _w , and Δb _w are amounts of change of the L ^* value, the a ^* value, and the b ^* value before and after the weather resistance test.

7- (3). [Transparent image definition]
The transmitted image definition can be measured according to JIS-K7105 using an optical comb having a slit width of 0.5 mm with an image clarity measuring instrument (ICM-2D type) manufactured by Suga Test Instruments Co., Ltd.

  The transmission image definition of the film of the present invention is preferably 60% or more. The transmitted image clarity is generally an index indicating the degree of blurring of an image reflected through a film, and the larger this value, the clearer and better the image viewed through the film. It is preferable that the transparent image of the film of the present invention is 5% to 30%, since sufficient antiglare property and improvement in image blur and dark room contrast are compatible.

7- (4). [Surface roughness]
Centerline average roughness (Ra) can be measured according to JIS-B0601.
The antireflection film of the present invention has a surface roughness of 0.08 to 0.30 μm in center line average roughness, 10 times the average roughness Rz is 10 times or less of Ra, and an average mountain valley distance Sm of 1 to 100 μm. The standard deviation of the height of the convex part from the deepest part of the concavo-convex part is 0.5 μm or less, the standard deviation of the average mountain-valley distance Sm with respect to the center line is 20 μm or less, and the surface with the inclination angle of 0 to 5 degrees is 10% or more. Such a design is preferable because sufficient anti-glare properties and a visually uniform matte feeling can be achieved. If Ra is less than 0.08, sufficient antiglare property cannot be obtained, and if it exceeds 0.30, problems such as glare and surface whitening when external light is reflected occur.

7- (5). [Haze]
The haze of the film of the present invention is the haze value defined in JIS-K7105. Based on the measurement method defined in JIS-K7361-1, a turbidimeter “NDH-” manufactured by Nippon Denshoku Industries Co., Ltd. 1001DP "is automatically measured as haze = (diffused light / total transmitted light) × 100 (%).

The surface haze and internal haze can be measured by the following procedure.
(1) The total haze value (H) of the film is measured according to JIS-K7136.
(2) A few drops of silicone oil are added to the front and back surfaces of the low refractive index layer side of the film, and sandwiched from the front and back using two 1 mm thick glass plates (micro slide glass product number S 9111, manufactured by MATSANAMI), Two glass plates and a film are optically closely adhered to each other, and the haze is measured in a state where surface haze is removed, and only the silicone oil is sandwiched between two separately measured glass plates to subtract the measured haze. The calculated value is calculated as the internal haze (Hi) of the film.
(3) A value obtained by subtracting the internal haze (Hi) calculated in (2) from the total haze (H) measured in (1) above is calculated as the surface haze (Hs) of the film.

7- (6). [Abrasion resistance]

7- (6) -1. {Steel Wool Scratch Resistance Evaluation}
By using a rubbing tester and carrying out a rubbing test under the following conditions, it can be used as an index of scratch resistance.
-Evaluation environmental conditions: 25 ° C., 60% RH,
・ Rubbing material: Steel wool (Nippon Steel Wool Co., Ltd., gelled No. 0000). Wrap around the tip (1cm x 1cm) of the scraper of the tester that comes into contact with the sample, and fix the band.
・ Moving distance (one way): 13cm,
・ Rubbing speed: 13cm / second,
Load: 500 g / cm ² and 200 g / cm ²
-Tip contact area: 1 cm x 1 cm, rubbing frequency: 10 reciprocations.
An oil-based black ink is applied to the back side of the rubbed sample, and the scratches on the rubbed portion are visually observed with reflected light, or evaluated by the difference in the amount of reflection from other than the rubbed portion.

7- (6) -2. {Eraser scuff resistance evaluation}
By using a rubbing tester and carrying out a rubbing test under the following conditions, it can be used as an index of scratch resistance.
・ Evaluation environmental conditions: 25 ° C., 60% RH,
・ Rubbing material: Plastic eraser (MONO manufactured by Dragonfly Pencil Co., Ltd.). Used by fixing to the tip (1cm x 1cm) of the scraper of the tester that comes into contact with the sample.
・ Travel distance (one way): 4cm
・ Rubbing speed: 2cm / second,
・ Load: 500 g / cm ²
-Tip contact area: 1 cm x 1 cm,
・ Number of rubbing: 100 round trips.
Oily black ink is applied to the back side of the rubbed sample, and the scratches on the rubbed portion are visually observed with reflected light, or evaluated by the difference in the amount of reflected light from other than the rubbed portion.

7- (6) -3. {Taper test}
In the Taber test according to JIS-K5400, the scratch resistance can be evaluated from the wear amount of the test piece before and after the test.
The smaller the amount of wear, the better.

7- (7). [Hardness]
7- (7) -1. {Pencil hardness}
The strength of the film of the present invention can be evaluated by a pencil hardness test according to JIS-K5400.
The pencil hardness is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher.

7- (7) -2. {Surface elastic modulus}
The surface elastic modulus in the present invention is a value determined using a micro surface hardness tester (manufactured by Fisher Instruments: Fisherscope H100VP-HCU). Specifically, using a diamond pyramid indenter (tip-to-face angle: 136 °), the indentation depth is measured under an appropriate test load within a range where the indentation depth does not exceed 1 μm. This is the elastic modulus obtained from the change in load and displacement over time.
Further, the surface hardness can be obtained as a universal hardness by using the above-mentioned micro surface hardness tester. The universal hardness is a value obtained by measuring the indentation depth of a quadrangular pyramid indenter under a test load and dividing the test load by the surface area of the indent calculated from the geometric shape of the indent generated by the test load. It is known that there is a positive correlation between the surface elastic modulus and the universal hardness.

The universal hardness of the crosslinkable polymer defined in the present invention is determined by the following measurement procedure using a microhardness meter H100 manufactured by Fischer Instruments Co., Ltd. with respect to the crosslinkable polymer film having a thickness of about 20 to 30 μm cured on a glass plate. The universal hardness (N / mm ² ).
Appropriate bar coater is selected so that the film thickness after curing of a coating solution with a solid content of about 25% containing the necessary catalyst, crosslinking agent, polymerization initiator, etc. in addition to the crosslinkable polymer is about 20-30 μm. TOSHINRIKO. CO. Made of LTD (26 mm × 76 mm × 1.2 mm) coated on a polished glass slide plate. In the case where the crosslinkable polymer is thermosetting, a thermosetting condition for sufficiently curing the film is obtained in advance (for example, 125 ° C. for 10 minutes), and when the crosslinkable polymer is ionizing radiation curable, the film is similarly formed. The curing conditions for sufficient curing are obtained in advance (as an example, the oxygen concentration is 12 ppm, the UV irradiation amount is 750 mJ / cm ² ). Recess area for each film F when the load is continuously increased from 0 to 4 mN for each film, and the conical diamond indenter is pushed in with the maximum 1/10 film thickness not affected by the glass plate hardness of the substrate. Universal hardness is calculated from N = 6 measurement average value of F / A determined from A (mm ² ).
The surface hardness can be determined by nanoindentation described in JP-A No. 2004-354828. In this case, the hardness is preferably 2 GPa to 4 GPa, and the nanoindentation elastic modulus is preferably 10 GPa to 30 GPa.

7- (8). [Anti-fouling test]
7- (8) -1. {Magic wiping off}
The film is fixed on the glass surface with an adhesive, and a circle with a diameter of 5 mm is written three times with a pen tip (thin) of black magic “Mckey extra fine (product name: made by ZEBRA)” at 25 ° C. and 60 RH%. After 5 seconds, wipe it back and forth 20 times with a load that dents the bundle of Bencot (Brand name, Asahi Kasei Co., Ltd.) folded into 10 sheets. The writing and wiping are repeated under the above conditions until after the magic does not disappear by wiping, and the antifouling property can be evaluated by the number of times of wiping.
The number of times until it no longer disappears is preferably 5 times or more, and more preferably 10 times or more.

  For Black Magic, Magic Ink No. 700 (M700-T1 black) Using an ultra-fine sample, draw a circle with a diameter of 1 cm on the sample, paint it, rub it with Bencott (Asahi Kasei Co., Ltd.) after standing for 24 hours, and evaluate whether the magic can be wiped off. .

7- (9). [Contact angle]
Using a contact angle meter [“CA-X” type contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.], using a pure water as a liquid in a dry state (20 ° C./65% RH), a diameter of 1.0 mm A droplet was made on the needle tip and brought into contact with the surface of the film to form a droplet on the film. The angle formed between the tangent to the liquid surface and the film surface at the point where the film and the liquid are in contact with each other is defined as the contact angle.
The contact angle of the film of the present invention is preferably 94 degrees or more with respect to pure water. It is more preferably 97 degrees or more, and most preferably 101 degrees or more.

7- (10). [Surface free energy]
The surface energy can be obtained by a contact angle method, a wet heat method, and an adsorption method as described in “Basics and Applications of Wetting”, Realize, Inc., 1989.12.10. In the case of the film of the present invention, it is preferable to use a contact angle method.
Specifically, two kinds of solutions having known surface energies are dropped on a cellulose acylate film, and at the intersection of the surface of the droplet and the surface of the film, the angle formed between the tangent line drawn on the droplet and the film surface, The surface angle of the film can be calculated by defining the angle containing the droplet as the contact angle.

The surface free energy (γs ^v : unit, mN / m) of the film of the present invention is D.I. K. Owens: J.M. Appl. Polym. Sci. , 13, 1741 (1969) with reference to the following simultaneous equations a and b from the contact angles θ _H2O and θ _{CH2I2 of} pure water H2O and methylene iodide CH2I2 experimentally determined on the antireflection film. It represents the surface tension of the antireflection film as defined gamma] s ^d and gamma] s ^h sum represented by the value gamma] s ^v of ^{(= γs d + γs h)} . The smaller this γs ^v and the lower the surface free energy, the higher the surface repellency and the more generally the antifouling property.
a. 1 + cos θ _H2O =
2√γs ^d (√γ _H2O ^d / γ _H2O ^v ) + 2√γs ^h (√γ _H2O ^h / γ _H2O ^v )
b. 1 + cos θ _CH2I2 =
2√γs ^d (√γ _CH2I2 ^d / γ _CH2I2 ^v ) + 2√γs ^h (√γ _CH2I2 ^h / γ _CH2I2 ^v )
γ _H2O ^d = 21.8, γ _H2O ^h = 51.0, γ _H2O ^v = 72.8,
γ _CH2I2 ^d = 49.5, _γCH2I2 ^h = 1.3, _γCH2I2 ^v = 50.8
In the contact angle measurement, after the film was conditioned for 1 hour or more at 25 ° C. and 60%, 2 μl of the droplet was formed into a film using an automatic contact angle meter CA-V150 manufactured by Kyowa Interface Science Co., Ltd. The contact angle was determined 30 seconds after dropping.

  The surface free energy of the film of the present invention is preferably 25 mN / m or less, and particularly preferably 20 mN / m or less.

7- (11). [Curl]
The curl is measured using the curl measurement template of Method A in “Measuring Method of Curling of Photographic Film” of JIS-K7619-1988.
The measurement conditions are 25 ° C., relative humidity 60%, and humidity control time 10 hours.
The film according to the present invention preferably has a value when curl is expressed by the following mathematical formula in a range of minus 15 to plus 15, more preferably in a range of minus 12 to plus 12, more preferably minus 10. ~ Plus 10. In this case, the measurement direction of the curl in the sample is measured in the conveyance direction of the base material in the case of application in a web form.
(Formula) Curl = 1 / R R is the radius of curvature (m)
This is an important characteristic for preventing cracks and film peeling during film production, processing, and market handling. It is preferable that the curl value is in the above range and the curl is small.
Here, “curl plus” means a curl in which the coating side of the film is inside the curve, and “minus” means a curl in which the coating side is outside the curve.

  In the film according to the present invention, the absolute value of the difference between the curl values when the relative humidity is changed to 80% and 10% based on the curl measurement method is preferably 24 to 0, and preferably 15 to 0. Is more preferable, and 8 to 0 is most preferable. This is a property related to handling, peeling and cracking when films are attached under various humidity.

7- (12). [Adhesion evaluation]
The adhesion between the layers of the film or between the support and the coating layer can be evaluated by the following method.
Nitto Denko Co., Ltd. Polyester adhesive tape with 11 squares and 11 horizontal cuts at 1 mm intervals and a total of 100 squares on the surface of the coated layer. (NO.31B) is pressure-bonded, and the test for peeling off after leaving for 24 hours is repeated three times at the same place, and the presence or absence of peeling is visually observed.

  Of 100 squares, peeling is preferably within 10 mm, and more preferably within 2 mm.

7- (13). [Brittleness test (cracking resistance)]
Crack resistance is an important characteristic for preventing crack defects by handling such as film application, processing, cutting, adhesive application, and application to various objects.
A film sample is cut into 35 mm x 140 mm, left to stand for 2 hours at a temperature of 25 ° C and a relative humidity of 60%, and then the curvature diameter at which cracks start to occur when rolled into a cylinder is measured to evaluate surface cracks. can do.

  The crack resistance of the film of the present invention is preferably 50 mm or less, more preferably 40 mm or less, and most preferably 30 mm or less, when the film is rolled with the coating layer side facing outward. About the crack of an edge part, it is preferable that there is no crack or the length of a crack is less than 1 mm on average.

7- (14). [Dust removability]
The film of the present invention can be attached to a monitor, dust (futon, clothes fiber waste) can be sprinkled on the monitor surface, the dust can be wiped off with a cleaning cloth, and the dust removal property can be evaluated.
It is preferable to remove completely by wiping 6 times, and it is more preferable to remove dust completely by wiping within 3 times.

7- (15). [Performance of liquid crystal display]
Below, the evaluation method of a characteristic when the film of this invention is used on a display apparatus, and a preferable condition are described.
The polarizing plate on the viewing side provided in the liquid crystal display device (TH-15TA2, manufactured by Matsushita Electric Industrial Co., Ltd.) using a TN type liquid crystal cell is peeled off, and the film or polarizing plate of the present invention is used instead. It sticks through an adhesive so that the transmission side of a polarizing plate may correspond with the polarizing plate stuck on the product at the visual recognition side. In a 500 lux bright room, the liquid crystal display device is displayed in black, and the following various characteristics can be evaluated visually from various viewing angles.

7- (15) -1. {Evaluation of image unevenness and color}
Using the created liquid crystal display device, unevenness and color change during black display (L1) are visually evaluated by a plurality of observers.
It is preferable that three people or less can recognize the unevenness, left-right color change, color change due to temperature and humidity, and white blur, and more preferably no one can recognize it.
In addition, reflection of external light is performed using a fluorescent lamp, and a change in reflection can be relatively evaluated visually.

7- (15) -2. {Light leakage of black display}
The light leakage rate of black display in the azimuth direction 45 ° and polar angle direction 70 ° from the front of the liquid crystal display device is measured. The light leakage rate is preferably 0.4% or less, and more preferably 0.1% or less.

7- (15) -3. {Contrast and viewing angle}
Contrast and viewing angle are measured using a measuring instrument ("EZ-Contrast 160D" manufactured by ELDIM). The contrast ratio and the viewing angle in the left-right direction (direction perpendicular to the rubbing direction of the cell) (angle range in which the contrast ratio is 10 or more) Can be checked.

8). 〔Example〕
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto. In the following Examples and Synthesis Examples,% represents mass% unless otherwise specified.

Example 1-1. <Preparation of antireflection film>

[Synthesis of copolymer (A) and fluorine-containing copolymer (B)]
Synthesis Example 1-1: Synthesis of (T-1) A 100 mL stainless steel autoclave with a stirrer was charged with 40 ml of ethyl acetate, 3.0 g of hydroxyethyl vinyl ether (HEVE) and 0.35 g of dilauroyl peroxide. Was degassed and replaced with nitrogen gas. Further, 3.9 g of hexafluoropropylene (HFP) and 25.0 g of a polymer initiator “VPS-1001” {manufactured by Wako Pure Chemical Industries, Ltd.} having a polysiloxane structure of the above structural formula {S- (1)} It was introduced into an autoclave and heated up to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 5.4 kg / cm ² . The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 3.2 kg / cm ² , the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large excess of hexane, and the precipitated polymer was taken out by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer, thereby obtaining 25.0 g of copolymer (T-1). The number average molecular weight of the obtained polymer was 25,000.

Synthesis Example 1-2: Synthesis of (T-2) to (T-11), (K-1) to (K-3) The molar fraction (mol%) and the mass average molecular weight of each component are the same as above. (T-2) to (T-) in the same manner as the synthesis of (T-1) in Synthesis Example 1 except that the blending amounts of the respective components were adjusted so as to be as shown in Tables 2 and 3 of Table 1. 11) and (K-1) to (K-3) were synthesized. The mole fraction (mol%) and the mass average molecular weight of each component are as shown in Tables 2 and 3 above.

Synthesis Example 1-3: Synthesis of p-toluenesulfonic acid salt 3.0 g of diethylmethylamine was dissolved in 30 cm ³ of 2-butanone, and 5.7 g of p-toluenesulfonic acid monohydrate was added little by little while stirring. . After further stirring for 1 hour, the solvent was distilled off under reduced pressure, and the resulting solid was recrystallized from acetone to obtain diethyl methylamine salt of p-toluenesulfonic acid.

(Preparation of sol solution a)
To a reactor equipped with a stirrer and a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxyaluminum ethyl acetoacetate are added and mixed. After that, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all. Sol solution a was adjusted with methyl ethyl ketone so that the solid content was 29%.

(Preparation of hollow silica dispersion A)
Hollow silica fine particle sol (Isopropyl alcohol silica sol, average particle diameter 40 nm, shell thickness 6 nm, silica concentration 20% by mass, silica particle refractive index 1.30, prepared by changing the size according to Preparation Example 4 of JP-A-2002-79616 ) After adding 500 parts to 30 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, Shin-Etsu Chemical Co., Ltd.), 2 parts of trimethylmethoxysilane, and 1.5 parts of diisopropoxyaluminum ethyl acetate, ion exchange was performed. Nine parts of water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added.
While adding cyclohexanone to 500 g of this dispersion so that the silica content was almost constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 20 kPa. There was no generation of foreign matter in the dispersion, and the viscosity when the solid content concentration was adjusted to 26% by mass with cyclohexanone was 10 mP at 25 ° C.
a · s. When the residual amount of isopropyl alcohol in the obtained dispersion A was analyzed by gas chromatography, it was 1.0%.

[Preparation of antireflection film]
[Preparation of coating solutions for low refractive index layers (LLL-1 to LLL-16)]
Each component shown in Table 5 was mixed and dissolved in MEK to prepare a coating solution for a low refractive index layer having a solid content of 8%. The values in parentheses in Table 5 represent the mass part of the solid content of each component.

In addition, the description in Table 5 represents the following.
・ Colloidal silica: “MEK-ST” manufactured by Nissan Chemical Industries, Ltd.
MEK-ST: Colloidal silica dispersion [average particle size 10-20 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.]
PTS triethylamine salt: p-toluenesulfonic acid triethylamine salt H-11 and H-21 each represents a compound having the following structure.
IC-1: represents a compound having the following structure.

[Preparation of coating solution for antiglare layer (HCL-1)]
"PET-30" 50.0g
"Irgacure 184" 2.0g
"SX-350" (30%) 1.5g
Cross-linked acrylic-styrene particles (30%) 13.9g
"Sol liquid a" 10.0g
Toluene 38.5g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating solution (HCL-1).

The compounds used are shown below.
"PET-30": mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate {manufactured by Nippon Kayaku Co., Ltd.}
"Irgacure 184": polymerization initiator {Ciba Specialty Chemicals Co., Ltd.},
“SX-350”: Cross-linked polystyrene particles having an average particle size of 3.5 μm {refractive index: 1.60, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion. Use after dispersion at 10,000 rpm for 20 minutes in a Polytron disperser},
Crosslinked acrylic-styrene particles: average particle size 3.5 μm {refractive index 1.55, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion. Use after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser}.

[Preparation of Antireflection Film Sample 101]
An 80 μm-thick triacetyl cellulose film “TAC-TD80U” (manufactured by FUJIFILM Corporation) is unwound in the form of a roll, and the hard coat layer coating solution (HCL-1) is directly applied to the 180-wire film. Using a micro gravure roll with a diameter of 50 mm and a doctor blade having a gravure pattern with a depth of 40 μm and a doctor blade, it was applied at a gravure roll rotational speed of 30 rpm and a conveying speed of 30 m / min, and dried at 60 ° C. for 150 seconds. Furthermore, using an “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of 0.1% by volume under a nitrogen purge, ultraviolet rays having an irradiance of 400 mW / cm ² and an irradiation amount of 100 mJ / cm ² are used. The coating layer was cured by irradiation to form a 6 μm thick layer and wound up. The surface roughness of the antiglare layer (HC-1) thus obtained was Ra = 0.18 μm, Rz = 1.40 μm, the surface haze was 12%, and the internal haze was 29%. .

On the antiglare layer thus obtained, the low refractive index layer coating liquid LLL-1 was used, and the low refractive index layer film thickness was adjusted to 95 nm. Produced. The coating solution was applied after mixing the components for 2 hours, the low refractive index layer was dried at 110 ° C. for 10 minutes, and the ultraviolet curing condition was nitrogen so that the atmosphere had an oxygen concentration of 0.01% by volume or less. While purging, a 240 W / cm “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.) was used to obtain an irradiance of 120 mW / cm ² and an irradiation amount of 240 mJ / cm ² .

[Preparation of antireflection films 102 to 116]
In the production of the antireflection film (101), instead of using the coating solution for low refractive index layer (LLL-1), it is the same as the antireflection film 101 except that (LLL-2) to (LLL-16) are used. Thus, antireflection films 102 to 116 were produced.

[Saponification treatment of antireflection film]
The obtained antireflection films 102 to 116 were treated and dried under the following saponification standard conditions.
Alkaline bath: 1.5 mol / dm ³ aqueous sodium hydroxide solution at 55 ° C. for 120 seconds.
First washing bath: tap water, 60 seconds.
Neutralization bath: 0.05 mol / dm ³ sulfuric acid, 30 ° C.-20 seconds.
Second washing bath: tap water, 60 seconds.
Drying: 120 ° C., 60 seconds.

[Evaluation of antireflection film]
The following evaluation was performed using the saponified antireflection films 102 to 116 thus obtained. The results obtained are shown in Table 6.

(Evaluation 1) Scratch resistance (1)-Steel wool resistance evaluation A rubbing test was performed using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH,
Rubbing material: Steel wool “No. 0000” {manufactured by Nippon Steel Wool Co., Ltd.} was wound around the tip (1 cm × 1 cm) of the rubbing of a tester that was in contact with the sample, and the band was fixed so as not to move. Then, the reciprocating rubbing motion under the following conditions was given.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / second,
Load: 200 g / cm ²
Tip contact area: 1 cm × 1 cm,
Number of rubs: 10 round trips.
Oily black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
○: Even when viewed very carefully, no scratches are visible.
○ △: Slightly weak scratches are visible when viewed very carefully.
Δ: A weak scratch is visible.
Δ ×: moderate scratches are visible.
X: There are scratches that can be seen at first glance.

(Evaluation 2) Scratch resistance (2) -Eraser scuff resistance evaluation A rubbing test was performed using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rubbing material: A plastic eraser {"MONO" manufactured by Dragonfly Pencil Co., Ltd.) was fixed to the tip (1 cm x 1 cm) of the scraper of the tester that was in contact with the sample.
Moving distance (one way): 4 cm, rubbing speed: 2 cm / sec, load: 500 g / cm ² , tip contact area: 1 cm × 1 cm,
Number of rubs: 100 round trips.
Oily black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
○: Even when viewed very carefully, no scratches are visible.
○ △: Slightly weak scratches are visible when viewed very carefully.
Δ: A weak scratch is visible.
Δ ×: moderate scratches are visible.
X: There are scratches that can be seen at first glance.
XX: Single-sided film is damaged.

(Evaluation 3) Evaluation of adhesion Using a sunshine weather meter (S-80, manufactured by Suga Test Instruments Co., Ltd.), each antireflection film sample after exposure for 200 hours was exposed to a sunshine carbon arc lamp, relative humidity 60%. The humidity was adjusted for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%. On the surface of each sample having the low refractive index layer, 11 vertical and 11 horizontal cuts were made with a cutter knife in a grid pattern, and a total of 100 square squares were carved, and Nitto Denko ( A polyester pressure-sensitive adhesive tape (No. 31B) manufactured by Co., Ltd. was attached. After 30 minutes, the tape was quickly peeled off in the vertical direction, and the number of squares peeled off was counted and evaluated according to the following four criteria. The same adhesion evaluation was performed 3 times and the average was taken.
A: No peeling was observed at 100 mm.
○: peeling of 1 to 2 mm was observed at 100 mm.
Δ: Peeling of 3 to 10 mm was observed at 100 mm (within tolerance).
X: Peeling of 11 mm or more was observed at 100 mm.

(Evaluation 4) “Magic ink” adhesion evaluation As an index of surface contamination resistance, the optical material was conditioned for 2 hours at a temperature of 25 ° C. and a humidity of 60% RH, and then “magic ink / for fine writing” on the sample surface. After marking with (product name), the state when it was immediately wiped 10 times with a cleaning cloth was observed, and “magic ink” adhesion was evaluated as follows.
A: The mark of “magic ink” can be completely wiped off.
○: A trace of “magic ink” is visible.
Δ: A trace of “magic ink” is visible.
X: Traces of “magic ink” are hardly wiped off.

(Evaluation 5) Transferability test of polymer component to non-contact catalyst 80 μm triacetyl cellulose film (TD80UF (trade name), manufactured by FUJIFILM Corporation) and the above sample are bonded to each other and a load of 5 kg / m ² (196 kPa) is applied. And then allowed to stand at 25 ° C. for 24 hours, the amount of Si transferred to the TAC base surface was measured using ESCA, and the area ratio of Si / C was used as an index. The (Si / C) value of the base surface before the transfer test was 0.

As is clear from this example, the antireflection films (101) to (107) and (109) to (116) of the present invention formed using the curable composition of the present invention are sufficiently tough films. It can be seen that it has strength and adhesion, and is excellent in antifouling properties and transferability. The antireflection film of the present invention has a high ratio of polysiloxane structure as the copolymer (A) to the fluorine-containing copolymer (B), and contains a hydroxyl group, and further uses a compound containing fluorine. Compared with the antireflection film (108) of the comparative example, it is excellent in antifouling durability, scratch resistance and adhesion. Furthermore, since the antireflection film of the present invention can arbitrarily control the silicone content in the curable composition by changing the amount of the copolymer (A), it can impart antifouling durability and scratch resistance. Easy to control.

Example 1-2. [Preparation of polarizing plate with antireflection film]
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. A saponified antireflection film was attached to one side of the polarizing film using a polyvinyl alcohol adhesive so that the support (triacetylcellulose) side of the antireflection film was the polarizing film side. A viewing angle widening film “Wide View Film SA12B” (manufactured by Fuji Film Co., Ltd.) having an optical compensation layer was saponified and attached to the other side of the polarizing film using a polyvinyl alcohol-based adhesive. In this way, a polarizing plate was produced. As a result of performing the evaluation according to Example 1 in this polarizing plate state, the same effect was obtained by using the low refractive index layer of the present invention.

Example 1-3.
It was confirmed that the TN, IPS, VA, and OCB mode transmission type liquid crystal display devices equipped with the produced polarizing plate of the present invention have excellent scratch resistance and antifouling properties.

Example 1-4.
When the antireflection film sample of Example 1-2 was bonded to the glass plate on the surface of the organic EL display device via an adhesive, reflection on the glass surface was suppressed, and a display device with high visibility was obtained. It was.

<Preparation of antireflection film>

[Preparation of curable composition]
[Synthesis of polysiloxane structure-containing copolymer]
Synthesis Example 2-1: Synthesis of (P-1) 10 g of methyl ethyl ketone was placed in a three-necked flask having an internal volume of 200 mL, and the temperature was raised to 80 ° C while stirring. After sufficiently substituting the inside of the flask with nitrogen, 10.0 g of polymer initiator “VPS-1001” {manufactured by Wako Pure Chemical Industries, Ltd.} having a polysiloxane structure of the structural formula {S- (1)} Then, a mixed solution of 0.5 g of hydroxyethyl methacrylate (HEMA) and 30 g of methyl ethyl ketone was added dropwise in 3 hours with a chemical pump while stirring. After dropping, the mixture was further stirred for 5 hours and cooled to room temperature. The polymerization solution was poured into a mixed solvent of water / methanol = 400 mL / 40 mL to precipitate a polymer, followed by vacuum drying at 50 ° C. to have 8.5 g of a polysiloxane structure and a hydroxyl group. The fluorine-free polysiloxane structure-containing copolymer (P-1) was obtained (Mw: 56000).

Synthesis Example 2-2: (P-2, Mw: 62000), (P-3, Mw: 48000), (P-5, Mw: 32000), (P-9, Mw: 78000), (P-17) , Mw: 65000), (P-19, Mw: 58000), (K-1), (K-2), (K-4), (K-5), (K-8) synthesis (P-2) In the same manner as in the synthesis of (P-1) in Synthesis Example 1, except that the blending amount of each component was adjusted so that the molar fraction of the unit was as shown in Tables 1 and 3. ), (P-3), (P-5), (P-9), (P-17), (P-19), (K-1), (K-2), (K-4), (K-5) and (K-8) were synthesized.

Synthesis Example 2-3: Synthesis of p-toluenesulfonate 3.0 g of diethylmethylamine was dissolved in 30 cm ³ of 2-butanone, and 5.7 g of p-toluenesulfonic acid monohydrate was added little by little while stirring. . After further stirring for 1 hour, the solvent was distilled off under reduced pressure, and the resulting solid was recrystallized from acetone to obtain diethyl methylamine salt of p-toluenesulfonic acid.

(Preparation of sol solution a)
To a reactor equipped with a stirrer and a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxyaluminum ethyl acetoacetate are added and mixed. After that, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all. Sol solution a was adjusted with methyl ethyl ketone so that the solid content was 29%.

(Preparation of hollow silica dispersion A)
Hollow silica fine particle sol (Isopropyl alcohol silica sol, average particle diameter 40 nm, shell thickness 6 nm, silica concentration 20% by mass, silica particle refractive index 1.30, prepared by changing the size according to Preparation Example 4 of JP-A-2002-79616 ) After adding 500 parts to 30 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, Shin-Etsu Chemical Co., Ltd.), 2 parts of trimethylmethoxysilane, and 1.5 parts of diisopropoxyaluminum ethyl acetate, ion exchange was performed. Nine parts of water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added.
While adding cyclohexanone to 500 g of this dispersion so that the silica content was almost constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 20 kPa. Foreign matter was not generated in the dispersion, and the viscosity when the solid content was adjusted to 26% by mass with cyclohexanone was 10 mPa · s at 25 ° C. When the residual amount of isopropyl alcohol in the obtained dispersion A was analyzed by gas chromatography, it was 1.0%.

[Preparation of antireflection film]
[Preparation of coating solutions for low refractive index layers (LLL-17 to LLL-46)]
Each component shown in Table 7 was mixed and dissolved in MEK to prepare a coating solution for a low refractive index layer having a solid content of 8%. The values in parentheses in Table 7 represent parts by mass of the solid content of each component.

In addition, the description in Table 7 represents the following.
・ Colloidal silica: “MEK-ST” manufactured by Nissan Chemical Industries, Ltd.
MEK-ST: Colloidal silica dispersion [average particle size 10-20 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.]
• CY303: “Cymel 303”, methylolated melamine manufactured by Nippon Cytec Industries, Ltd. • H-11, H-21: each represents a compound having the following structure.
PTS triethylamine salt: p-toluenesulfonic acid triethylamine salt IC-1 represents a compound having the following structure.

[Preparation of coating solution for low refractive index layer (LLL-47)]
5 parts by mass of copolymer (T-1), 1750 parts by mass of Colcoat N103X (manufactured by Colcoat Co., Ltd., number average molecular weight 950 in terms of ethylene glycol, solid content: 2% by mass) as a siloxane oligomer (corresponding to component (E)) And 230 parts by mass of hollow silica dispersion A (26% by mass) were added to prepare a coating solution LLL-47 for a low refractive index layer.

(Preparation of hard coat layer paint HC-1)
-Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.): 25.4 parts by mass-Methyl isobutyl ketone: 40.0 parts by mass-Propylene glycol: 6.3 parts by mass -Polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals): 1.3 parts by mass-5.2 parts by mass of silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)-Cellulose Acetate butyrate (CAB-531-1, manufactured by Eastman Chemical Co., Ltd., separation amount: 40,000): 0.50 parts by mass Cross-linked poly (acryl-styrene) particles (copolymerization composition ratio = 50/50, 30% methyl isobutyl ketone dispersion having a refractive index of 1.536 and an average particle size of 3.5 μm: 21.0 parts by mass

  After stirring the mixed solution, the mixture was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating material (HC-1).

[Preparation of Antireflection Film Sample 117]
An 80 μm-thick triacetyl cellulose film “TAC-TD80U” (manufactured by FUJIFILM Corporation) is unwound in the form of a roll, and the hard coat layer coating solution (HCL-1) is directly applied to the 180-wire film. Using a micro gravure roll with a diameter of 50 mm and a doctor blade having a gravure pattern with a depth of 40 μm and a doctor blade, it was applied at a gravure roll rotational speed of 30 rpm and a conveying speed of 30 m / min, and dried at 60 ° C. for 150 seconds. Furthermore, using an “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of 0.1% by volume under a nitrogen purge, ultraviolet rays having an irradiance of 400 mW / cm ² and an irradiation amount of 100 mJ / cm ² are used. The coating layer was cured by irradiation to form a 6 μm thick layer and wound up. The surface roughness of the antiglare layer (HC-1) thus obtained was Ra = 0.18 μm, Rz = 1.40 μm, the surface haze was 12%, and the internal haze was 29%. .

On the antiglare layer thus obtained, the low refractive index layer coating liquid LLL-17 was used, and the low refractive index layer film thickness was adjusted to 95 nm, whereby the antireflection film sample 117 was prepared. Produced. The coating solution was applied after mixing the components for 2 hours, the low refractive index layer was dried at 110 ° C. for 10 minutes, and the ultraviolet curing condition was nitrogen so that the atmosphere had an oxygen concentration of 0.01% by volume or less. While purging, a 240 W / cm “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.) was used to obtain an irradiance of 120 mW / cm ² and an irradiation amount of 240 mJ / cm ² .

[Preparation of antireflection films 118 to 147]
In the production of the antireflection film (117), in the same manner as the antireflection film 117 except that (LLL-18) to (LLL-47) are used instead of using the coating liquid for low refractive index layer (LLL-17). Thus, antireflection films 118 to 147 were produced.

[Saponification treatment of antireflection film]
The obtained antireflection films 118 to 146 were treated and dried under the following saponification standard conditions. The antireflection film 147 was not saponified.
(1) Alkaline bath: 1.5 mol / L sodium hydroxide aqueous solution, 55 ° C.-120 seconds (2) First washing bath: tap water, 60 seconds (3) Neutralization bath: 0.05 mol / L sulfuric acid, 30 ° C. -20 seconds (4) Second washing bath: tap water, 60 seconds (5) Drying: 120 ° C.-60 seconds

[Evaluation of antireflection film]
Using the saponified antireflective films 118 to 146 and the unsaponified antireflective film 147 thus obtained, the following evaluation was performed. Table 8 shows the obtained results.

(Evaluation 1) Scratch resistance-Steel wool resistance evaluation A rubbing test was performed using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH,
Rubbing material: Steel wool “No. 0000” {manufactured by Nippon Steel Wool Co., Ltd.} was wound around the tip (1 cm × 1 cm) of the rubbing of the tester that was in contact with the sample, and the band was fixed so as not to move. Then, the reciprocating rubbing motion under the following conditions was given.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / second,
Load: 100 g / cm ² ,
Tip contact area: 1 cm × 1 cm,
Number of rubs: 30 round trips.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
○: Even when viewed very carefully, no scratches are visible.
○ △: Slightly weak scratches are visible when viewed very carefully.
Δ: A weak scratch is visible.
Δ ×: moderate scratches are visible.
X: There are scratches that can be seen at first glance.

(Evaluation 2) Antifouling durability test A film is fixed on a glass surface with an adhesive, and a black magic “Mackey Extra Fine (trade name: manufactured by ZEBRA)” nib (fine) is used at 25 ° C. and 60 RH%. A circle of 5 mm in diameter is written three times and wiped back and forth 20 times with a load that causes the bundle of Bencot to be dented with Bencot (trade name, Asahi Kasei Co., Ltd.) folded in 10 sheets after 5 seconds. The writing and wiping are repeated under the above conditions until after the magic does not disappear by wiping, and the antifouling property can be evaluated by the number of times of wiping.
“◎” if the number of writing and wiping is 20 times or more until wiping off after magic, “◯” if it is 10 times or more, “△” if it is 5 times or more, “△” if it is less than 5 times Evaluated as “x”.

(Evaluation 3) Evaluation of adhesion Using a sunshine weather meter (S-80, manufactured by Suga Test Instruments Co., Ltd.), each antireflection film sample after exposure for 250 hours with a sunshine carbon arc lamp, relative humidity 55%. The humidity was adjusted for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%. On the surface of each sample having the low refractive index layer, 11 vertical and 11 horizontal cuts were made with a cutter knife in a grid pattern, and a total of 100 square squares were carved, and Nitto Denko ( A polyester pressure-sensitive adhesive tape (No. 31B) manufactured by Co., Ltd. was attached. After 30 minutes, the tape was quickly peeled off in the vertical direction, and the number of squares peeled off was counted and evaluated according to the following four criteria. The same adhesion evaluation was performed 3 times and the average was taken.
A: No peeling was observed at 100 mm.
○: peeling of 1 to 2 mm was observed at 100 mm.
Δ: Peeling of 3 to 10 mm was observed at 100 mm (within tolerance).
X: Peeling of 11 mm or more was observed at 100 mm.

(Evaluation 4) Transferability test of polymer component to non-contact catalyst 80 μm triacetyl cellulose film (TD80UF (trade name), manufactured by Fuji Film Co., Ltd.) and the above sample were bonded to each other and a load of ² kg / m ² (196 kPa) And left at 25 ° C. for 48 hours, the amount of Si transferred to the TAC base surface was measured using ESCA, and the area ratio of Si / C was used as an index. The (Si / C) value of the base surface before the transfer test was 0.

  As is clear from this example, the antireflection film of the present invention formed using the curable composition of the present invention has sufficiently strong film strength and adhesion, and is excellent in antifouling properties. I understand that. Since the antireflection film of the present invention uses a compound having a high polysiloxane structure ratio and a hydroxyl group as the copolymer (A) with respect to the fluorine-containing copolymer (B), a comparative example (film No. 124, 133) is superior in antifouling durability, scratch resistance and adhesion. Furthermore, since the antireflection film of the present invention can arbitrarily control the silicone content, the amount of the copolymer (A) added for imparting antifouling durability and scratch resistance can be freely set as necessary. Can be changed to

[Preparation of polarizing plate with optical film]
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. A saponified antireflection film was attached to one side of the polarizing film using a polyvinyl alcohol adhesive so that the support side (triacetyl cellulose) of the antireflection film was the polarizing film side. Further, the disc surface of the discotic structural unit is inclined with respect to the support surface, and the angle formed by the disc surface of the discotic structural unit and the support surface changes in the depth direction of the optically anisotropic layer. Wide-view film SA with an optically anisotropic layer, “Side view film SA” (manufactured by FUJIFILM Corporation), saponified, and attached to the other side of the polarizing film using a polyvinyl alcohol adhesive It was. In this way, a polarizing plate with an optical film was produced.

[Production of image display device]
The polarizing plate with an optical film was attached to the liquid crystal display surface of a personal computer “PC9821NS / 340W” obtained from NEC Corporation to prepare an image surface device sample.

  The polarizing plate with an optical film and the image display device produced as described above showed excellent scratch resistance, antifouling property and adhesion as compared with the comparative example, as in the case of the optical film attached thereto. .

FIG. 1 is a schematic cross-sectional view showing a layer structure when the antireflection film of the present invention is a composite film, where (a) shows a four-layer structure and (b) shows an example of a five-layer structure. It is sectional drawing of the coater 10 using the slot die 13 which implemented this invention. (A) shows the cross-sectional shape of the slot die 13 of the present invention, and (B) shows the cross-sectional shape of the conventional slot die 30. It is a perspective view which shows the slot die 13 of the application | coating process which implemented this invention, and its periphery.

Explanation of symbols

1a: Antireflection film 1b: Antireflection film 2: Transparent support 3: Hard coat layer 4: High refractive index layer 5: Low refractive index layer (outermost layer)
6: Medium refractive index

DESCRIPTION OF SYMBOLS 10 Coater 11 Backup roll 13 Slot die 14 Coating liquid 14a Bead 14b Coating film 15 Pocket 16 Slot 16a Slot opening 17 Tip lip 18 Land 18a Upstream lip land 18b Downstream lip land I _UP Land length of upstream lip land 18a I _LO Land length of downstream lip land 18b LO Over bit length (difference in distance between downstream lip land 18b and web W of upstream lip land 18a)
G _L Tip lip 17 and web W gap (downstream lip land 18b and web W gap)
30 and the gap G _S side plate 40b between the conventional slot-die 31a upstream lip land 31b downstream lip land 32 pocket 33 slot 40 vacuum chamber 40a back plate 40b side plate 40c screws W Web G _B back plate 40a and the web W Gap between webs W

Claims (16)

Curability containing 0.1 to 40 parts by mass of the following components (A), 10 to 100 parts by mass of (B) to (E), and 0 to 100 parts by mass of (F) to (G). Composition:
(A) The structural unit containing the polysiloxane structure represented by the following general formula (1) in the main chain or side chain is 40 (%) or more and 100 (%) in mass fraction with respect to all the structural units in the component (A). A copolymer having a polymerization unit based on a hydroxyl group-containing monomer,
(B) The structural unit containing the polysiloxane structure represented by the following general formula (1) in the main chain or side chain is 0 (%) or more and 20 (% by mass fraction with respect to all the structural units in the component (B). ) A fluorine-containing copolymer having a polymerization unit based on a hydroxyl group-containing monomer,
(C) a curing agent capable of reacting with a hydroxyl group,
(D) a curing catalyst,
(E) 0-100 parts by mass of a composition containing at least one of an organosilane compound, a hydrolyzate of the organosilane compound and a partial condensate thereof,
(F) inorganic fine particles,
(G) A polymerization initiator.
General formula (1):

(In the general formula (1), R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group. P represents an integer of 10 to 500.) The curable composition according to claim 1, wherein the (A) copolymer is a copolymer represented by the following general formula (2).
General formula (2):

(In the general formula (2), X represents a structural unit containing the polysiloxane structure represented by the general formula (1) in the main chain or side chain. Y represents a polymerized unit based on any vinyl monomer, R ²¹ represents a hydrogen atom or a methyl group, L ²¹ represents a single bond or a divalent linking group, and y and z are composed of all structural units. This represents the molar fraction (%) of each structural unit when the remaining structural unit excluding the unit X is 100 (%), and represents a value satisfying 0 ≦ y <100 and 0 <z ≦ 100. Represents the mass fraction of the structural unit X with respect to all structural units, and satisfies the relationship of 40 ≦ x <100.) The curable composition according to claim 1, wherein the copolymer (A) is a copolymer represented by the following general formula (3).
General formula (3):

(In General Formula (3), Rf ¹¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ¹² represents a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 30 carbon atoms, and ether. B may represent a polymerized unit based on a hydroxyl group-containing monomer, A represents a polymerized unit based on any vinyl monomer, and may be a single species or a plurality of species. S represents a structural unit containing the polysiloxane structure represented by the general formula (1) in the main chain or side chain, and may be composed of a single species or a plurality of species. Represents the mole fraction (%) of each structural unit when the remaining structural unit excluding the structural unit S from the structural unit is 100 (%), 0 ≦ a ≦ 90, 0 ≦ b ≦ 70, 0 ≦ c Represents a value satisfying ≦ 50, 0 <d, where e is the total structural unit of the structural unit S Against represents the mass fraction (percent) satisfy the relation 40 ≦ e <100.) The curable composition according to any one of claims 1 to 3, wherein the (B) fluorine-containing copolymer is a fluorine-containing copolymer represented by the following general formula (4).
General formula (4):

(In the general formula (4), Rf ¹¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ¹² represents a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 30 carbon atoms, and ether. B may represent a polymerized unit based on a hydroxyl group-containing monomer, A represents a polymerized unit based on any vinyl monomer, and may be a single species or a plurality of species. S represents a structural unit containing the polysiloxane structure represented by the general formula (1) in the main chain or side chain, and may be composed of a single species or a plurality of species. Represents the mole fraction (%) of each structural unit when the remaining structural unit excluding the structural unit S from the structural unit is 100 (%), 0 ≦ a ≦ 90, 0 ≦ b ≦ 70, 0 ≦ c Represents a value satisfying ≦ 50, 0 <d, where e is the total structural unit of the structural unit S Represents against mass fraction (percent) satisfy the relation of 0 ≦ e ≦ 20.)   In the general formula (3), the molar fraction (%) d of the polymerization unit B based on the hydroxyl group-containing monomer when the remaining structural unit excluding the structural unit S from all the structural units is 100 (%), The fluorine-containing copolymer according to claim 3, wherein 20 ≦ d ≦ 60.   In the general formula (4), the molar fraction (%) d of the polymerized unit B based on the hydroxyl group-containing monomer, when the remaining structural unit excluding the structural unit S from all the structural units is 100 (%), The fluorine-containing copolymer according to claim 4 or 5, wherein 20≤d≤50.   The curing agent capable of reacting with the (C) hydroxyl group is a compound having two or more carbon atoms adjacent to a nitrogen atom and substituted with an alkoxy group in one molecule. A curable composition according to any one of the above.   The curable composition according to any one of claims 1 to 7, wherein the (D) curing catalyst is a thermal acid generator. The curable composition according to any one of claims 1 to 8, wherein the (E) organosilane compound is represented by the following general formula (5).
General formula (5):

(In the general formula (5), R ³² represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom. U ³¹ represents a single bond, an ester group, an amide group or an ether. L ³¹ represents a divalent linking chain, m 2 represents 0 or 1. m 2 is preferably 0. R ³⁰ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. when the .X ³¹ to represent a substituted aryl group .X ³¹ representing a hydroxyl group or a hydrolyzable group there are a plurality, the plurality of X ³¹ may be different even in respectively the same)   The curable composition according to any one of claims 1 to 9, wherein the inorganic fine particles (F) are silica fine particles.   The curable composition according to claim 10, wherein the silica fine particles are hollow silica fine particles having an average particle diameter of 30 nm to 150 nm.   The curable composition according to any one of claims 1 to 11, wherein the polymerization initiator (G) is a heat and / or ionizing radiation curable initiator.   The optical film which has a functional layer formed by hardening the curable composition in any one of Claims 1-12.   The optical film according to claim 13, wherein the functional layer is a low refractive index layer, and the optical film has an antireflection function and / or an antiglare function due to optical interference.   The polarizing plate in which the optical film of Claim 13 or Claim 14 is used for one of the two protective films of the polarizing film in a polarizing plate.   An image display device in which the optical film according to claim 13 or claim 14 or the polarizing plate according to claim 15 is used on the outermost surface of the display.

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