JP2010079098A - Hard coat film, polarizing plate and image display apparatus - Google Patents

Abstract

To provide a hard coat film excellent in anti-blocking properties while maintaining the specularity of the surface of the hard coat film. Moreover, the polarizing plate using this hard coat film is provided. Furthermore, an image display device having the hard coat film or the polarizing plate is provided.
A hard coat film having at least one hard coat layer containing a binder and fine particles on a transparent support, the average film thickness of the hard coat layer being smaller than the average particle size of the fine particles, The average particle size is 3 μm or more and 15 μm or less, the average film thickness of the hard coat layer is 0.01 to 3.0 μm smaller than the average particle size of the fine particles, and the fine particles are contained in the total solid content forming the hard coat layer. Hard coat film containing 0.0001 to 0.01% by mass.
[Selection figure] None

Description

  The present invention relates to a hard coat film, a polarizing plate using the film, and an image display device using the film or the polarizing plate.

  2. Description of the Related Art In recent years, flat panel displays such as LCDs and PDPs are rapidly spreading as image display devices for TVs instead of CRTs which have been mainstream until now. Conventionally, a hard coat film is provided on the display surface in order to prevent scratches. In order to reduce reflection of external light, the hard coat film may be subjected to an anti-glare process to apply a matte paint to eliminate glare.

  However, when matte paint is applied, an anti-glare effect can be obtained, but the image on the display may be blurred, moire may occur between the pixels of the display, and the brightness at the center may be noticeable. .

  On the other hand, from the standpoint of emphasizing the transparency of the hard coat film, the surface is used as a mirror surface to eliminate light scattering and improve the visibility of the display.

  However, the film having a mirror surface has an extremely poor surface slipperiness and is likely to be blocked, and the resulting rolled roll is unsatisfactory and remains unblocked when unrolled. Sometimes.

  As a measure to prevent blocking, it is possible to wrap the tape on both sides of the film, or to provide unevenness called knurling, but improve the device, remove the tape in the next process, or place the unevenness It needs to be removed by slitting.

  Conventionally, it is known to impart anti-blocking properties by providing fine irregularities on the film surface (see, for example, Patent Document 1). However, if fine irregularities are given to the surface, the specularity of the surface is lost, and the visibility of the display may be lowered.

JP 2004-42653 A

  An object of the present invention is to provide a hard coat film excellent in antiblocking properties while maintaining the mirror surface property of the surface of the hard coat film. Another object of the present invention is to provide a polarizing plate using the hard coat film as a protective film for the polarizing film. Furthermore, the objective of this invention is providing the image display apparatus which has such a hard coat film or a polarizing plate (especially it is preferable that a hard coat film is located in the visual recognition side outermost surface).

  As a result of intensive studies to solve the above problems, the present inventors have found that the present invention can be achieved by the following means, and have completed the present invention.

(1) A hard coat film having at least one hard coat layer containing a binder and fine particles on a transparent support, the average film thickness of the hard coat layer being smaller than the average particle size of the fine particles, The particle diameter is 3 μm or more and 15 μm or less, the average film thickness of the hard coat layer is 0.01 to 3.0 μm smaller than the average particle diameter of the fine particles, and the fine particles are 0 with respect to the total solid content forming the hard coat layer. Hard coat film containing 0.0001 to 0.01% by mass.
(2) The hard coat film as described in 1 above, wherein the number of particles per 1 mm ^{2 of the} hard coat layer is in the range of 0.1 or more and 20 or less.
(3) The hard coat film as described in 1 or 2 above, wherein an average interval (Sm) of irregularities on the surface of the hard coat layer is 0.12 mm <Sm <0.8 mm.
(4) The hard coat film according to any one of the above 1 to 3, wherein the 10-point average roughness (Rz) of the hard coat layer surface is 0.1 μm <Rz <1.0 μm.
(5) A polarizing plate having a polarizing film and protective films on both sides of the polarizing film, wherein any one of the protective films is the hard coat film according to any one of 1 to 4 above. Board.
(6) The image display apparatus which has the hard coat film of any one of said 1-4, or the polarizing plate of said 5.

  According to the present invention, since the mirror surface of the hard coat film is not lost and the blocking phenomenon hardly occurs, the display has high visibility and various hard defects caused by the blocking phenomenon are not likely to occur. A film can be obtained.

  Further, by using the hard coat film of the present invention, it is possible to provide an image display device in which deterioration in image quality such as blurring of the screen or moire is suppressed even in a flat panel display with high definition pixels. it can.

  Hereinafter, the present invention will be described in detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . In the present specification, the description “(meth) acrylate” means “at least one of acrylate and methacrylate”. The same applies to “(meth) acrylic acid” and the like.

<Hard coat film>
[Configuration of hard coat film]
The hard coat film of the present invention is a hard coat film having at least one hard coat layer containing a binder and fine particles on a transparent support, and the average film thickness of the hard coat layer is larger than the average particle size of the fine particles. The average particle size of the fine particles is 3 μm or more and 15 μm or less, the average film thickness of the hard coat layer is 0.01 to 3.0 μm smaller than the average particle size of the fine particles, and the total solid content forming the hard coat layer is On the other hand, it is a hard coat film containing 0.0001 to 0.01% by mass of fine particles. The hard coat film of the present invention will be described with reference to FIG.

  FIG. 1 is a schematic cross-sectional view schematically showing a preferred embodiment of the hard coat film of the present invention. The hard coat film in FIG. 1 has a single hard coat layer 2 on a transparent support 1. The outermost layer preferably has a low refractive index layer 3 having a refractive index lower than that of the hard coat layer 2.

  Below, each structure of the hard coat film of this invention is explained in full detail.

[Hard coat layer]
In the present invention, when the average thickness of the hard coat layer, the average particle diameter of the fine particles, and the addition amount of the fine particles are in a specific relationship as in the present invention, the blocking phenomenon is maintained while maintaining the specularity of the hard coat layer surface. A suppressed hard coat film can be obtained.

  Although the average particle diameter of the fine particles contained in the hard coat layer depends on the film thickness of the hard coat layer, it is preferably 3 μm or more and 15 μm or less, and more preferably 5 μm or more and 10 μm or less. The average particle diameter of the fine particles is calculated from an average value of 100 particle diameters by observing the hard coat film with an optical microscope.

  The average thickness of the hard coat layer is preferably 0.01 to 3.0 [mu] m smaller than the average particle diameter of the fine particles, and more preferably 0.1 to 1.0 [mu] m smaller. The average film thickness of the hard coat layer can be calculated from an average value obtained by observing the cross section of the hard coat film with an electron microscope and measuring the film thickness at 10 random locations.

  The fine particles contained in the hard coat layer are preferably 0.0001 to 0.01% by mass with respect to the total solid content forming the hard coat layer.

The amount of particles per 1 mm ^{2 of the} hard coat layer is preferably in the range of 0.1 or more and 20 or less. The number of particles in 1 mm ^{2 of the} hard coat film can be calculated by taking 10 film surfaces at random with an optical microscope, counting the number of particles present in 1 mm ² at each location, and taking the average value. By setting the number of particles in 1 mm ^{2 of the} hard coat film within the above range, screen glare is less likely to occur when the hard coat film of the present invention is placed on the surface of the image display device.

  One convex portion of the hard coat layer is preferably substantially formed of 4 or less fine particles, and more preferably, the convex portion is substantially formed of one fine particle. Here, “substantially” means that 90% or more of the convex portions defined above satisfy a preferable mode.

  The average interval (Sm) of the unevenness of the hard coat film of the present invention is preferably 0.12 mm <Sm <0.8 mm, and more preferably 0.2 mm <Sm <0.5 mm.

  The ten-point average roughness (Rz) of the hard coat film of the present invention is preferably 0.1 μm <Rz <1.0 μm, more preferably 0.1 μm <Rz <0.5 μm, and 0.1 μm <Rz <. 0.35 μm is more preferable.

  The combination of Sm and Rz is most preferably in the following region. When the height (Rz) of the convex portion is small, the particle interval (Sm) is short when the height (Rz) of the convex portion is small, and when the height (Rz) of the convex portion is large, the particle interval (Sm) is wide. This area is most suitable for preventing blocking while maintaining the clearness of the surface.

0.12 mm <Sm <0.8 mm
0.1 μm <Rz <1.0 μm
Rz (μm)> 1.32 × Sm (mm) −0.2
Rz (μm) <1.32 × Sm (mm) +0.1

  Here, various surface roughnesses in the present invention can be measured according to JIS B 0601 (1994). For example, it can be measured using a surface roughness meter “Surf Coder SE3500” manufactured by Kosaka Laboratory.

  Ten-point average roughness (Rz) is extracted from the roughness curve by the reference length in the direction of the average line, and the average height (Yp) of the highest peak from the highest peak to the fifth peak is extracted from the average line of this extracted part. It is defined by the sum of the average value and the average value of the absolute values of the altitude (Yv) of the bottom valley from the lowest valley bottom to the fifth, and is represented by the following formula.

  In addition, the average interval (Sm) of the irregularities is extracted from the roughness curve by the reference length in the direction of the average line, and the sum of the average line lengths corresponding to one peak and one valley adjacent to it is obtained. The average value is expressed in millimeters (mm), and is expressed by the following formula.

  The various surface roughness parameters are measured according to JIS B 0601 (1994) under the following conditions.

(Fine particles)
The type of the fine particles is not particularly limited as long as it satisfies the above particle diameter and the value of the internal haze of the hard coat layer described later, but the convex portion is substantially formed of one fine particle. Therefore, it is preferable to select fine particles having good dispersibility.

  As fine particles having good dispersibility, translucent organic resin particles such as polymethyl methacrylate fine particles and polymethyl methacrylate / polystyrene copolymer fine particles are preferable. The proportion of polymethyl methacrylate in the copolymer fine particles is preferably 40% by mass or more and 100% by mass or less from the viewpoint of dispersibility.

  In the case of using the above fine particles, in order to prevent dispersion of particles in the binder or coating solution and to prevent sedimentation, inorganic fillers such as silica that do not cause visible light scattering, organic compounds (even monomers) A dispersing agent such as a polymer) may be added.

  In addition, when adding an inorganic filler, it is effective for the precipitation prevention of microparticles | fine-particles, so that the addition amount increases, However, It is preferable to use in the range which does not have a bad influence on the transparency of a coating film. Accordingly, it is preferable that an inorganic filler having a particle size of 0.5 μm or less is contained in an amount of about 1 to 30% by mass so as not to impair the transparency of the coating film with respect to the binder.

  The dispersant is preferably added in an amount of 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.5 to 10% by mass with respect to the fine particles. If the dispersing agent is 0.1% by mass or more, an effect of addition to the dispersion stability appears, and if it is 20% by mass, a component that does not contribute to the dispersion stability is increased and problems such as bleed out do not occur. .

  For dispersion stability and prevention of settling in the binder or coating solution, the surface of the fine particles used as an additive may be surface-treated. The type of the surface treatment agent is appropriately selected depending on the binder to be used and the solvent in the coating solution. As a surface treatment amount, it is preferable to add 0.1 to 30% by mass with respect to fine particles. More preferably, it is 1-25 mass%, Most preferably, it is 3-20 mass%. If it is 0.1% by mass or more, the amount of surface treatment for dispersion stability will not be insufficient, and if it is 30% by mass or less, components that do not contribute to the surface treatment increase and problems such as bleed out may occur. It is preferable because it is not present.

  In the present invention, the particle size distribution of the fine particles used is a monodisperse particle, that is, a particle having a uniform particle diameter, from the viewpoint of control of haze value and diffusibility, and uniformity of the coated surface. Is preferred. The CV value representing the uniformity of the particle diameter is preferably 0 to 10%, more preferably 0 to 8%, and still more preferably 0 to 5%. Further, when a particle having a particle size of 20% or more than the average particle size is defined as a coarse particle, the proportion of the coarse particle is preferably 1% or less of the total number of particles, more preferably 0.1% or less. Yes, more preferably 0.01% or less.

  Fine particles having such a particle size distribution are also effective means of classification after preparation or synthesis reaction, and particles having a desired distribution can be obtained by increasing the number of classifications or increasing the degree of classification. . It is preferable to use a method such as an air classification method, a centrifugal classification method, a sedimentation classification method, a filtration classification method, or an electrostatic classification method for classification. The average particle diameter of the fine particles is calculated from an average value of the observed 10 particle diameters by observing the fine particles with an electron microscope.

  Further, two or more kinds of fine particles having different average particle diameters may be used in combination in order to obtain necessary light scattering properties. In particular, by adding fine particles having an average particle size smaller than the average film thickness of the hard coat layer, it is possible to obtain a hard coat film having internal scattering properties while maintaining the specularity of the hard coat layer surface.

  Next, the internal haze in the present invention will be described in detail. The internal haze of the hard coat film of the present invention is preferably from 0.1% to 25% from the viewpoint that the glare of the liquid crystal panel does not occur and the contrast is not lowered, more preferably from 1% to 20%. Particularly preferably, the content is 3% to 15%.

  The measurement of internal noise can be performed as follows. Add two drops of silicone oil to the front and back surfaces of the hard coat film, and use two glass plates ("Microslide Glass Part No. S9111", manufactured by MATSANAMI) between the front and back of the glass to completely separate the two sheets of glass. The value obtained by measuring the haze according to JIS-K7136 with the plate and the obtained hard coat film adhered, and subtracting the haze measured by sandwiching only silicone oil between two separately measured glass plates. It can be calculated as the internal haze.

  The refractive index of the hard coat layer is preferably 1.45 to 1.60, more preferably 1.46 to 1.57, and particularly preferably 1.47 to 1.55.

(binder)
The binder of the hard coat layer in the present invention is preferably formed by curing at least one of a thermosetting compound and an ionizing radiation curable compound.

  The hard coat layer in the present invention is preferably a layer formed by a crosslinking reaction and / or a polymerization reaction of an ionizing radiation curable compound. That is, the binder is formed by applying 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 and / or a polymerization reaction. it can.

  The functional group of the ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer is preferably a light (ultraviolet ray), electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable. Examples of the photopolymerizable functional group include an ethylenically unsaturated polymerizable functional group such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group, and among them, a (meth) acryloyl group is preferable.

  Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include alkylenes such as neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and propylene glycol di (meth) acrylate. (Meth) acrylic acid diesters of glycol; of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate (Meth) acrylic acid diesters; of polyhydric alcohols such as pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate Of (meth) acrylic polyesters; 2,2-bis {4- (acryloxy / diethoxy) phenyl} propane, ethylene oxide or propylene oxide adducts such as 2-2-bis {4- (acryloxy / polypropoxy) phenyl} propane (Meth) acrylic acid diesters; Furthermore, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.

  Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, a polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferable. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexatriacrylate, etc. Is mentioned.

  As the polyfunctional monomer binder, monomers having different refractive indexes can be used to control the refractive index of each layer. Examples of particularly high refractive index monomers include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4'-methoxyphenyl thioether and the like. Further, for example, dendrimers described in JP-A-2005-76005 and JP-A-2005-36105 and norbornene ring-containing monomers as described in JP-A-2005-60425 can also be used. Two or more types of these multifunctional monomers and multifunctional oligomer binders used as binders may be used in combination.

  The refractive index of the hard coat layer can be quantitatively evaluated by directly measuring it with an Abbe refractometer or by measuring a spectral reflection spectrum or spectral ellipsometry. The refractive index of the fine particles was measured by measuring the turbidity by dispersing the same amount of the fine particles in the solvent in which the refractive index was changed by changing the mixing ratio of two kinds of solvents having different refractive indexes, and the turbidity was minimized. It can be measured by measuring the refractive index of the solvent at the time with an Abbe refractometer.

  Polymerization of the precursor of the binder having these ethylenically unsaturated groups can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator. In the polymerization reaction of the photopolymerizable polyfunctional monomer or polyfunctional oligomer, it is preferable to use a photopolymerization initiator. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.

  In the present invention, a polymer or a crosslinked polymer can be used in combination as a binder. The crosslinked polymer preferably has an anionic group. The polymer having a crosslinked anionic group has a structure in which the main chain of the polymer having an anionic group is crosslinked.

  Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.

For the purpose of controlling the refractive index of the hard coat layer, the binder of the hard coat layer has a high refractive index monomer or inorganic particles that do not cause visible light scattering such as ZrO ₂ , TiO _{2, and} SiO ₂ , that is, an average particle size. Inorganic particles of 100 nm or less, or both of them can be added. 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, after the hard coat layer is formed, a polymer formed by polymerizing the polyfunctional monomer and / or the high refractive index monomer and the inorganic particles dispersed therein are referred to as a binder.

[Low refractive index layer]
In the present invention, a low refractive index layer can be provided on the outer side than the hard coat layer, that is, on the side farther from the transparent support. By having a low refractive index layer, an antireflection function can be imparted to the hard coat film. The refractive index of the low refractive index layer is preferably set lower than the refractive index of the hard coat layer. When the refractive index difference between the low refractive index layer and the hard coat layer is too small, the antireflection property is lowered, and when it is too large, the color of the reflected light tends to be strong.

  The low refractive index layer can be formed using a low refractive index material. A low refractive index binder can be used as the low refractive index material. Further, the low refractive index layer can be formed by adding fine particles to the binder. Moreover, the composition for low refractive index layer formation can also contain the organosilane compound mentioned later.

  As the low refractive index binder, a fluorine-containing copolymer can be preferably used. The fluorinated copolymer preferably has a structural unit derived from a fluorinated vinyl monomer and a structural unit for imparting crosslinkability.

(Fluorine-containing copolymer)
Examples of the fluorinated vinyl monomer mainly constituting the fluorinated copolymer include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), a part of (meth) acrylic acid or a fully fluorinated alkyl. Ester derivatives {for example, “Biscoat 6FM” (trade name), Osaka Organic Chemical Industry Co., Ltd., “R-2020” (trade name), manufactured by Daikin Industries, Ltd., etc.}, fully or partially fluorinated vinyl ethers, etc. Of these, perfluoroolefins are preferable, and hexafluoropropylene is particularly preferable from the viewpoint of refractive index, solubility, transparency, availability, and the like.

  Increasing the composition ratio of these fluorinated vinyl monomers can lower the refractive index, but the film strength tends to decrease. In the present invention, the fluorine-containing vinyl monomer is preferably introduced so that the fluorine content of the copolymer is 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 30 to 50%. This is a case of mass%.

Examples of the structural unit for imparting crosslinking reactivity include units represented by the following (A), (B), and (C).
(A): a structural unit obtained by polymerization of a monomer having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate or glycidyl vinyl ether,
(B): a monomer having a carboxyl group, a hydroxy group, an amino group, a sulfo group or the like {for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether , Maleic acid, crotonic acid, etc.}
(C): A group having a crosslinkable functional group separately from a group that reacts with the functional groups (A) and (B) in the molecule and a structural unit of the above (A) and (B). Examples thereof include structural units obtained (for example, structural units that can be synthesized by a technique such as allowing acrylic acid chloride to act on a hydroxyl group).

In the structural unit (C), the crosslinkable functional group is preferably a photopolymerizable group. Examples of the photopolymerizable group include (meth) acryloyl group, alkenyl group, cinnamoyl group, cinnamylideneacetyl group, benzalacetophenone group, styrylpyridine group, α-phenylmaleimide group, phenylazide group, sulfonylazide group, Carbonyl azide group, diazo group, o-quinonediazide group, furylacryloyl group, coumarin group, pyrone group, anthracene group, benzophenone group, stilbene group, dithiocarbamate group, xanthate group, 1,2,3-thiadiazole group, cyclopropene group And azadioxabicyclo group. These may be not only one type but also two or more types. Of these, a (meth) acryloyl group and a cinnamoyl group are preferable, and a (meth) acryloyl group is particularly preferable.

Specific methods for preparing the photopolymerizable group-containing copolymer include, but are not limited to, the following methods.
a. A method of esterifying by reacting a (meth) acrylic acid chloride with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
b. A method of urethanization by reacting a (meth) acrylic acid ester containing an isocyanate group with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
c. A method of reacting (meth) acrylic acid with a crosslinkable functional group-containing copolymer containing an epoxy group,
d. A method in which a crosslinkable functional group-containing copolymer containing a carboxyl group is reacted with a containing (meth) acrylic acid ester containing an epoxy group for esterification.

  The amount of the photopolymerizable group introduced can be arbitrarily adjusted, and the carboxyl group, hydroxyl group, etc. can be controlled from the viewpoints of surface stability of the coating film, reduction of surface failure when coexisting with inorganic particles, and improvement of film strength. You may leave.

  In the present invention, the introduction amount of the structural unit for imparting crosslinkability in the copolymer is preferably 10 to 50 mol%, more preferably 15 to 45 mol%, particularly preferably 20 to 40 mol%. This is the case of mol%.

  In the copolymer useful for the low refractive index layer in the present invention, in addition to the repeating unit derived from the fluorine-containing vinyl monomer and the structural unit for imparting crosslinkability, adhesion to a substrate, polymer Tg (film) Other vinyl monomers can be appropriately copolymerized from various viewpoints such as solubility in solvents, transparency, slipperiness, dustproof / antifouling properties, etc. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the copolymer in total, and in the range of 0 to 40 mol%. Is more preferable, and the range of 0 to 30 mol% is particularly preferable.

  The vinyl monomer unit that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic) 2-ethylhexyl acid, 2-hydroxyethyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethylstyrene, p-methoxystyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate) , Vinyl propionate, vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, Nt-butylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile and the like.

  The fluorine-containing copolymer particularly useful in the present invention is a random copolymer of a perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing crosslinking reaction alone {a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group}. These cross-linking reactive group-containing polymer units preferably occupy 5 to 70 mol%, particularly preferably 30 to 60 mol%, of the total polymerized units of the polymer. Regarding preferred polymers, JP-A-2002-243907, JP-A-2002-372601, JP-A-2003-26732, JP-A-2003-222702, JP-A-2003-294911, JP-A-2003-329804, JP-A-2004. -4444 and JP-A-2004-45462.

  In addition, the fluorine-containing copolymer useful in the present invention preferably has a polysiloxane structure introduced for the purpose of imparting antifouling properties. The method for introducing the polysiloxane structure is not limited. For example, as described in JP-A-6-93100, JP-A-11-189621, JP-A-11-228631, and JP-A-2000-313709, silicone macroazo A method for introducing a polysiloxane block copolymer component using an initiator; a method for introducing a polysiloxane graft copolymer component using a silicone macromer as described in JP-A-2-251555 and JP-A-2-308806. Is preferred. Particularly preferred compounds include the polymers of Examples 1, 2, and 3 of JP-A-11-189621, and copolymers A-2 and A-3 of JP-A-2-251555. It is preferable that these polysiloxane components are 0.5-10 mass% in a polymer, Most preferably, it is 1-5 mass%.

  The preferred molecular weight of the copolymer that can be preferably used in the present invention is a mass average molecular weight of 5000 or more, preferably 10,000 to 500,000, and most preferably 15,000 to 200,000. By using polymers having different average molecular weights in combination, it is possible to improve the surface state of the coating film and the scratch resistance.

  As described in JP-A-10-25388 and JP-A-2000-17028, a curing agent having a polymerizable unsaturated group may be appropriately used in combination with the above copolymer. Further, as described in JP-A-2002-145952, combined use with a compound having a fluorine-containing polyfunctional polymerizable unsaturated group is also preferable. Examples of the compound having a polyfunctional polymerizable unsaturated group include the polyfunctional monomers described in the hard coat layer. These compounds are particularly preferred because they have a large combined effect for improving scratch resistance, particularly when a compound having a polymerizable unsaturated group is used in the copolymer body.

  The refractive index of the low refractive index layer is preferably 1.20 to 1.46, more preferably 1.25 to 1.42, and particularly preferably 1.30 to 1.38. The thickness of the low refractive index layer is preferably 50 to 150 nm, and more preferably 70 to 120 nm.

  The refractive index of the low refractive index layer is as described above, but the difference in refractive index between the low refractive index layer and the hard coat layer is preferably 0.01 or more and 0.30 or less, more preferably 0.05 or more and 0. The refractive index of the low refractive index layer is set lower than that of the hard coat layer.

(Fine particles)
Next, the fine particles used for the low refractive index layer in the present invention will be described.

The coated amount of the fine particles contained in the low refractive index layer is preferably from 1 to 100 mg / m ^2, more preferably 1 to 80 mg / m ^2, more preferably from 1~70mg / m ^2. If the coating amount of the fine particles is greater than or equal to the lower limit value, the effect of improving the scratch resistance is clearly manifested. If the coating amount is smaller than or equal to the upper limit value, fine irregularities are formed on the surface of the low refractive index layer, and the appearance and integrated reflectance This is preferable because there is no problem such as deterioration. Since the fine particles are contained in the low refractive index layer, the low refractive index is preferable.

  Specifically, the fine particles contained in the low refractive index layer are inorganic fine particles, hollow inorganic fine particles, or hollow organic resin fine particles, preferably having a low refractive index, particularly hollow inorganic fine particles. preferable. Examples of the inorganic fine particles include silica or hollow silica fine particles ((hollow) silica fine particles). The average particle size of such fine particles is preferably 30% or more and 100% or less of the thickness of the low refractive index layer, more preferably 30% or more and 80% or less, and further preferably 35% or more and 70% or less. That is, when the thickness of the low refractive index layer is 100 nm, the particle size of the fine particles is preferably 30 nm to 100 nm, more preferably 30 nm to 80 nm, and still more preferably 35 nm to 70 nm.

  In order to enhance the scratch resistance, it is preferable that the entire hard coat film contains the above-mentioned inorganic fine particles (the particle size of the fine particles is 30 nm or more and 100 nm or less). Silica fine particles (the particle size of the fine particles is preferably 30 nm or more and 100 nm or less) are preferably contained.

  If the (hollow) silica fine particles have a particle size equal to or larger than the above lower limit value, the effect of improving the scratch resistance appears clearly, and if the particle size is equal to or smaller than the upper limit value, fine irregularities can be formed on the surface of the low refractive index layer. This is preferable because defects such as deterioration in appearance and integrated reflectance do not occur.

  The (hollow) silica fine particles may be either crystalline or amorphous, and may be monodisperse particles, aggregated particles (in this case, the secondary particle diameter is 30% to 100% of the layer thickness of the low refractive index layer) It may be preferable). Two or more types of particles (types or particle sizes) may be used. The particle shape is most preferably a spherical diameter, but there is no problem even if it is indefinite.

In order to lower the refractive index of the low refractive index layer, it is particularly preferable to use hollow silica fine particles. The hollow silica fine particles have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1.35, and still more preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, the radius r _i of the cavity inside the particle, the radius of the outer shell of the particle is r _o, the porosity x is calculated by the following equation (1).

Equation (1): x = (4πr i 3/3) / (4πr o 3/3) × 100

  The porosity x is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%. If the 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 1.17. Rate particles are difficult. In addition, the refractive index of these hollow silica particles was measured with an Abbe refractometer {manufactured by Atago Co., Ltd.}.

  In the present invention, it is preferable to further reduce the surface free energy of the surface of the low refractive index layer from the viewpoint of improving the antifouling property. Specifically, it is preferable to use a fluorine-containing compound or a compound having a polysiloxane structure for the low refractive index layer.

  Examples of the additive having a polysiloxane structure include a reactive group-containing polysiloxane {for example, “KF-100T”, “X-22-169AS”, “KF-102”, “X-22-3701IE”, “X-22”. -164B "," X-22-5002 "," X-22-173B "," X-22-174D "," X-22-167B "," X-22-161AS "(product name), "AK-5", "AK-30", "AK-32" (trade name), manufactured by Toa Gosei Co., Ltd .; "Silaplane FM0725", "Silaplane FM0721" It is also preferable to add (trade name), manufactured by Chisso Corporation, etc.}. Moreover, the silicone type compound of Table 2 and Table 3 of Unexamined-Japanese-Patent No. 2003-112383 can also be used preferably. These polysiloxanes are preferably added in the range of 0.1 to 10% by mass of the total solid content of the low refractive index layer, particularly preferably 1 to 5% by mass.

[Other components contained in the composition for forming a hard coat layer and / or a low refractive index layer]
[Organosilane compound]
At least one of the layers constituting the hard coat film of the present invention is at least one component of a hydrolyzate of an organosilane compound and / or a partial condensate thereof, a so-called sol component (hereinafter sometimes referred to as such). From the viewpoint of scratch resistance. In particular, in a hard coat film having a low refractive index layer, it is particularly preferable to contain a sol component in the low refractive index layer in order to achieve both antireflection performance and scratch resistance. This sol component is condensed by a drying and heating process after coating to form a cured product, and becomes a part of the binder of the low refractive index layer. Moreover, when this hardened | cured material has a polymerizable unsaturated bond, the binder which has a three-dimensional structure is formed by irradiation of actinic light.

The organosilane compound is preferably represented by the following general formula (1).
Formula _{^{(1) :( R 11) m1}} -Si (X 11) 4-m1

In the general formula (1), R ¹¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. As an alkyl group, a C1-C30 alkyl group is preferable, More preferably, it is C1-C16, Most preferably, it is a C1-C6 thing. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.

X ¹¹ represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I And a group represented by R ¹² COO (R ¹² is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably Is an alkoxy group, particularly preferably a methoxy group or an ethoxy group. m1 represents the integer of 1-3, Preferably it is 1-2.

When X ¹¹ there are a plurality, it may be different even multiple X ¹¹ is the same, respectively. The substituent contained in R ¹¹ is not particularly limited, but a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy (phenoxy etc.) ), Alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxy) Carbonyl, etc.), aryloxy Carbonyl groups (such as phenoxycarbonyl), carbamoyl groups (such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl), acylamino groups (acetylamino, benzoylamino, acrylicamino, methacrylamino) Etc.), and these substituents may be further substituted. R ¹¹ is preferably a substituted alkyl group or a substituted aryl group.

  Moreover, the organosilane compound which has a vinyl polymerizable substituent represented by following General formula (2) is also preferable.

General formula (2):

In the general formula (2), R ²¹ 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. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom, and a chlorine atom are preferable, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom, and a chlorine atom are more preferable, and a hydrogen atom and a methyl group Is particularly preferred.

Y ²¹ represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**. Bonds and * -COO-** are more preferred, and * -COO-** is particularly preferred. * Represents a position bonded to ═C (R ²¹ ) —, and ** represents a position bonded to L ²¹ .

L ²¹ represents a divalent linking chain. Specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group having a linking group (for example, ether, ester, amide, etc.) inside, and a linking group inside. A substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an alkylene group having a linking group therein is preferred, an unsubstituted alkylene group, an unsubstituted arylene group Further, an alkylene group having an ether or ester linking group inside is more preferred, an unsubstituted alkylene group, and an alkylene group having an ether or ester linking group inside is particularly preferred. 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.

  a1 (represents a number satisfying the mathematical formula of a1 = 100−a2) and a2 represent a molar ratio, and a2 represents a number of 0 to 50. As for a2, the number of 0-40 is more preferable, and the number of 0-30 is especially preferable.

R ^{22 to} R ²⁵ are preferably a halogen atom, a hydroxyl group, an unsubstituted alkoxy group, or an unsubstituted alkyl group. R ^{22 to} R ²⁴ are more preferably a chlorine atom, a hydroxyl group, or an unsubstituted alkoxy group having 1 to 6 carbon atoms, more preferably a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and particularly preferably a hydroxyl group or a methoxy group. R ²⁵ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and an alkoxycarbonyl group as a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom, and a chlorine atom are preferable, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom, and a chlorine atom are more preferable, and a hydrogen atom and a methyl group Is particularly preferred. R ²⁶ has the same meaning as R ^{11 in} the general formula (1), more preferably a hydroxyl group or an unsubstituted alkyl group, still more preferably a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydroxyl group or a methyl group. preferable.

  Two or more compounds of the general formula (1) may be used in combination. The compound of the general formula (2) is synthesized using at least one kind of the compound of the general formula (1) as a starting material. Specific examples of the starting materials of the compound represented by the general formula (1) and the compound represented by the general formula (2) are shown below, but are not limited thereto.

  Of these, (M-1), (M-2), and (M-25) are particularly preferable as the organosilane containing a polymerizable group.

  In order to obtain the effects of the present invention, the content of the organosilane containing the vinyl polymerizable group in the hydrolyzate of organosilane and / or its partial condensate is preferably 30% by mass to 100% by mass, and 50 The mass% is more preferably 100% by mass, and more preferably 70% by mass to 95% by mass. If the content of the organosilane containing the vinyl polymerizable group is 30% by mass or more, a solid matter is generated in the coating liquid for forming the hard coat layer and / or the low refractive index layer, the liquid becomes cloudy, There are no inconveniences such as deterioration of life and difficulty in controlling molecular weight (increase in molecular weight), and performance when polymerizing treatment is performed due to low content of polymerizable groups (for example, antireflection film This is preferable because problems such as difficulty in improving scratch resistance do not occur.

  When synthesizing the compound represented by the general formula (2), (M-1) and (M-2) as organosilanes containing the vinyl polymerizable group, as organosilanes having no vinyl polymerizable group. One of each of (M-19) to (M-21) and (M-48) is preferably used in combination with the above amounts.

[Hydrolysates and partial condensates of organosilane compounds]
At least one of the hydrolyzate of organosilane and its partial condensate (also referred to as a sol component) preferably used in the present invention preferably suppresses volatility in order to stabilize the performance of the coated product. The volatilization amount per hour at 105 ° C. is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

The sol component preferably used in the present invention is prepared by hydrolysis and / or partial condensation of the organosilane. In the hydrolysis condensation reaction, 0.05 to 2.0 mol, preferably 0.1 to 1.0 mol of water is added to 1 mol of the hydrolyzable group (X ¹¹ ), and the catalyst used in the present invention. Is carried out by stirring at 25-100 ° C. in the presence of.

  In at least one of the hydrolyzate of organosilane and its partial condensate preferably used in the present invention, the weight average molecular weight of either the hydrolyzate of organosilane containing a vinyl polymerizable group or its partial condensate is the molecular weight. Is preferably from 450 to 20000, more preferably from 500 to 10000, still more preferably from 550 to 5000, and even more preferably from 600 to 3000.

  Of the components having a molecular weight of 300 or more in the hydrolyzate of organosilane and / or its partial condensate, the component having a molecular weight of more than 20000 is preferably 10% by mass or less, more preferably 5% by mass or less. More preferably, it is 3 mass% or less. If such a component is 10% by mass or less, transparency of a cured film obtained by curing such a curable composition containing a hydrolyzate of organosilane and / or a partial condensate thereof, and a substrate Is preferable because of its excellent adhesion.

  Here, the weight average molecular weight and molecular weight were measured using a TPCgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL {(trade name) manufactured by Tosoh Corporation} column using a GPC analyzer using a solvent tetrahydrofuran (THF), a differential refractometer. The molecular weight is expressed in terms of polystyrene by detection, and the content is the area% of the peak in the molecular weight range when the peak area of a component having a molecular weight of 300 or more is defined as 100%.

  The dispersity (weight average molecule / number average molecular weight) is preferably 3.0 to 1.1, more preferably 2.5 to 1.1, still more preferably 2.0 to 1.1, and 1.5 to 1. 1 is particularly preferred.

²⁹ Si-NMR analysis of the organosilane hydrolyzate and partial condensate preferably used in the present invention can confirm the state in which X ^{11 in the} general formula (1) is condensed in the form of —OSi. At this time, when three bonds of Si are condensed in the form of -OSi (T ₃ ), when two bonds of Si are condensed in the form of -OSi (T ₂ ), one bond of Si Is condensed in the form of -OSi (T ₁ ), and when Si is not condensed at all (T ₀ ), the condensation rate α is expressed by the following formula (2).

Formula (2): α = (1/3) (T ₃ × 3 + T ₂ × 2 + T ₁ × 1) / (T ₃ + T ₂ + T ₁ + T ₀ )

  The condensation rate α is preferably 0.2 to 0.95, more preferably 0.3 to 0.93, and particularly preferably 0.4 to 0.9. If the condensation rate α is 0.1 or more, hydrolysis and condensation sufficiently occur and the monomer component is reduced, so that curing proceeds sufficiently, and if it is 0.95 or less, hydrolysis and condensation proceed too much. Since inconvenience such as consumption of hydrolyzable groups does not occur, the interaction between the binder polymer, the resin substrate, the inorganic fine particles and the like is improved, and the effects using these are sufficiently exhibited.

  Next, the hydrolyzate and partial condensate of the organosilane compound preferably used in the present invention will be described in detail.

(catalyst)
The hydrolysis reaction of organosilane and the subsequent condensation reaction are generally carried out in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid; organic acids such as oxalic acid, acetic acid, butyric acid, maleic acid, citric acid, formic acid, methanesulfonic acid, toluenesulfonic acid; sodium hydroxide, potassium hydroxide, ammonia, etc. Inorganic bases; organic bases such as triethylamine and pyridine; metal alkoxides such as triisopropoxyaluminum, tetrabutoxyzirconium, tetrabutyltitanate and dibutyltin dilaurate; and metals such as Zr, Ti or Al as the central metal Metal chelate compounds and the like; Fluorine-containing compounds such as KF and NH ₄ F are mentioned. The said catalyst may be used independently and may use multiple types together.

(solvent)
The hydrolysis / condensation reaction of the organosilane can be carried out without a solvent or in a solvent, but it is preferable to use an organic solvent in order to mix the components uniformly. For example, alcohols, aromatic hydrocarbons, ethers , Ketones, esters and the like are preferred. The solvent is preferably one that dissolves the organosilane and the catalyst. In addition, the organic solvent is preferably used as a part of the coating solution in terms of the process, and is preferably one that does not impair the solubility or dispersibility when mixed with other materials such as a fluorinated copolymer.

  Among these, as alcohols, a monohydric alcohol or a dihydric alcohol can be mentioned, for example, As a monohydric alcohol, a C1-C8 saturated aliphatic alcohol is preferable. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

  Specific examples of aromatic hydrocarbons include benzene, toluene, xylene, etc .; specific examples of ethers include tetrahydrofuran, dioxane, etc .; specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl. Ketone, cyclohexanone, etc. Specific examples of esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate and the like.

  These organic solvents can also be used individually by 1 type or in mixture of 2 or more types. The concentration of the solid content in this reaction is not particularly limited, but is usually in the range of 1 to 100% by mass.

  The hydrolysis / condensation reaction of the organosilane is carried out by adding 0.05 to 2 mol, preferably 0.1 to 1 mol of water to 1 mol of the hydrolyzable group of the organosilane, and in the presence or absence of the above solvent. It is carried out by stirring at 25-100 ° C. in the presence and in the presence of a catalyst.

(Metal chelate compound)
In the present invention, a metal selected from Zr, Ti, or Al having a ligand represented by an alcohol represented by the following general formula (3-1) and a compound represented by the following general formula (3-2). It is preferable to carry out hydrolysis by stirring at 25 to 100 ° C. in the presence of at least one metal chelate compound having a central metal.

Formula (3-1): R ³¹ OH
Formula (3-2): R ³² COCH ₂ COR ³³

In the above formula, R ³¹ represents an alkyl group having 1 to 10 carbon atoms, R ³² represents an alkyl group having 1 to 10 carbon atoms, R ³³ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Indicates.

  In addition, when using a fluorine-containing compound as a catalyst, the fluorine-containing compound has the ability to completely proceed with hydrolysis and condensation, so the degree of polymerization can be determined by selecting the amount of water to be added, and any molecular weight can be set. Therefore, it is preferable. That is, in order to prepare an organosilane hydrolyzate / partial condensate having an average degree of polymerization M, (M-1) mol of water may be used with respect to M mol of hydrolyzable organosilane.

  The metal chelate compound has a ligand selected from the alcohol represented by the general formula (3-1) and the compound represented by the general formula (3-2), and a metal selected from Zr, Ti, and Al as a central metal. As long as it can be used, it can be suitably used without 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 is preferably selected from the group of compounds represented by the following general formulas (3-3) to (3-5), and is a hydrolyzate or partial condensate of the organosilane compound. It acts to promote the condensation reaction.

General formula (3-3): Zr (OR ³¹ ) _p1 (R ³² COCHCOR ³³ ) _p2 ,
Formula (3-4): Ti (OR ³¹ ) _q1 (R ³² COCHCOR ³³ ) _q2 ,
Formula (3-5): Al (OR ³¹ ) _r1 (R ³² COCHCOR ³³ ) _r2 .

In the above formula, R ³¹ and R ³² may be the same or different, and are an alkyl group having 1 to 10 carbon atoms, specifically an ethyl group, n-propyl group, i-propyl group, n-butyl group, s -Butyl group, t-butyl group, n-pentyl group, and the like. R ³³ 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, s-butoxy group, t-butoxy group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be p1 + p2 = 4, q1 + q2 = 4, and r1 + r2 = 3, respectively.

  Specific examples of these metal chelate compounds include tri-n-butoxyethyl acetoacetate 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 (acetylacetonato) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.

  Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) 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.

  The metal chelate compound is preferably used in a proportion of 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.5 to 10% by mass with respect to the organosilane compound. When the metal chelate compound is used within the above range, the condensation reaction of the organosilane compound is fast, the durability of the coating film is good, and the hydrolyzate and partial condensate of the organosilane compound and the metal chelate compound are contained. The storage stability of the composition is good.

(Β-diketone compound and β-ketoester compound)
In addition to the composition containing the sol component and the metal chelate compound, at least one of a β-diketone compound and a β-ketoester compound is preferably added to the coating liquid used in the present invention. This will be further described below.

What is used in the present invention is at least one of a β-diketone compound and a β-ketoester compound represented by the general formula R ³² COCH ₂ COR ³³ , and is used as a stability improver for the composition used in the present invention. It works. That is, by coordinating with a metal atom in the metal chelate compound (a compound of at least one of zirconium, titanium and aluminum compounds), condensation of hydrolyzate and partial condensate of organosilane compound by these metal chelate compounds It is considered that the action of accelerating the reaction is suppressed and the action of improving the storage stability of the resulting composition is achieved. R ³² and R ³³ constitute a β- diketone compound and β- ketoester compound are the same as R ³² and R ³³ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate- s-butyl, acetoacetate-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione , 5-methylhexane-dione and the like. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred.

  These β-diketone compounds and β-ketoester compounds may be used alone or in combination of two or more. In the present invention, the β-diketone compound and β-ketoester compound are preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. The storage stability of the composition obtained by using 2 mol or more can be improved, and it is preferable.

  The content of the hydrolyzate and partial condensate of the organosilane compound is preferably small for a low refractive index layer that is a relatively thin film and large for a hard coat layer that is a thick film. The content is preferably 0.1 to 50% by mass, and preferably 0.5 to 30% by mass based on the total solid content of the containing layer (added layer), considering the effect, refractive index, film shape / surface shape, and the like. More preferred is 1 to 15% by mass.

  When using the hydrolyzate and / or partial condensate of the organosilane compound containing the vinyl polymerizable group, it is preferable to use a photodegradable initiator in combination. As for these initiator skeletons, there are compounds exemplified in the section of the polymerization initiator described below.

[Polymerization initiator]
(Photopolymerization initiator)
Examples of photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (JP-A No. 2001-139663, etc.), 2, 3 -Dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borates, 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 ketone), 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and the like are included.

  Examples of borates include, for example, Japanese Patent Nos. 2764769 and 2002-116539, and “Rad Tech'98. Proceeding April” by Kunz, Martin et al., Pages 19-22 (1998, Chicago). ) And the like described in the organic borate. Examples thereof include compounds described in paragraph numbers [0022] to [0027] of JP-A-2002-116539. 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 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], sulfonic acid esters, cyclic active ester compounds, and the like. In particular, compounds 1 to 21 described in Examples in JP-A No. 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), U.S. Pat. 27830, M.M. P. Examples include compounds described in Hutt's “Jurnal of Heterocyclic Chemistry”, Volume 1 (No. 3) (1970), and particularly, 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, Nos. In p14 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, U.S. Pat. No. 4,701,399. Compounds such as 1-19 are particularly preferred.

  Specific examples of the active halogens are as follows.

Examples of inorganic complexes as photoradical polymerization initiators 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.

  Also, “Latest UV Curing Technology”, published by Technical Information Association, 1991, p. 159 and “UV Curing System” written by Kiyomi Kato, 1989, General Technology Center, p. Various examples are also described in 65-148 and are useful in the present invention.

  As a commercially available photo radical polymerization initiator, “Kayacure (DETX-S, BP-100, BDDK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC” manufactured by Nippon Kayaku Co., Ltd. , MCA, etc.) ”,“ Irgacure (651, 184, 500, 819, 907, 127, 369, 1173, 1870, 2959, 4265, 4263, etc.) ”manufactured by Ciba Specialty Chemicals, Inc., manufactured by Sartomer Preferred examples include "Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT)" and the like.

  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 “Kaya Cure (DMBI, EPA)” manufactured by Nippon Kayaku Co., Ltd.

(Thermal initiator)
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 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile) as azo compounds such as ammonium sulfate and potassium persulfate And diazoaminobenzene, p-nitrobenzenediazonium and the like.

[Crosslinking agent (crosslinkable compound)]
When the monomer or polymer binder constituting the hard coat layer and the low refractive index layer of the present invention alone does not have sufficient curability, the necessary curability can be imparted by blending a crosslinkable compound. it can. In particular, it is effective to contain it in the low refractive index layer. For example, when the polymer body contains a hydroxyl group, various amino compounds are preferably used as the curing agent. The amino compound used as the crosslinkable compound is, for example, a compound containing one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total, specifically, for example, a melamine compound, Examples include urea compounds, benzoguanamine compounds, glycoluril compounds, and the like.

  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, alkoxylated methyl melamine, and the like. However, it is preferable to have one or both of a methylol group and an alkoxylated methyl group in one molecule in total.

  Specifically, methylolated melamine, alkoxylated methylmelamine, or a derivative thereof obtained by reacting melamine and formaldehyde under basic conditions is preferable, and good storage stability is obtained particularly for the curable resin composition. Alkoxylated methyl melamine is preferable in that it can be obtained and good reactivity can be obtained. There are no particular restrictions on the methylolated melamine and the alkoxylated methylmelamine used as the crosslinkable compound. Various resinous materials can be used.

  In addition to urea, examples of the urea compound include polymethylolated urea, alkoxylated methylurea which is a derivative thereof, methylolated uron having a uron ring, and alkoxylated methyluron. And also about compounds, such as a urea derivative, the use of the various resinous materials described in said literature is possible.

(Curing catalyst)
In the film of the present invention, a curing catalyst that generates radicals and acids upon irradiation with ionizing radiation or heat can be used as a curing catalyst for promoting curing.

(Thermal acid generator)
As an example of the hard coat film of the present invention, by heating, the film can be cured by a crosslinking reaction between a hydroxyl group of the fluorinated copolymer and a curing agent capable of crosslinking with the hydroxyl group. In this system, since the curing is accelerated by acid, it is desirable to add an acidic substance to the curable resin composition. However, when a normal acid is added, the crosslinking reaction proceeds in the coating solution, and failure (unevenness, 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 as a curing catalyst.

  The curing catalyst is preferably a salt composed of an acid and an organic base. Examples of the acid include organic acids such as sulfonic acid, phosphonic acid, and carboxylic acid, and inorganic acids such as sulfuric acid and phosphoric acid. From the viewpoint of compatibility with the polymer, organic acids are more preferable, and sulfonic acid and phosphonic acid are more preferable. Sulphonic acid is most preferred. Preferred 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, 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.

  As the curing catalyst, the lower the basicity of the organic base combined with the acid, 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 pKa value of the organic base is described in II-334-340 of Volume 2 of the Chemical Handbook Basic Edition (5th revised edition, edited by The Chemical Society of Japan, Maruzen, 2004), Volume 2. Among them, 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 2 below 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 the following compounds, but are not limited thereto. 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 an acid catalyst, 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. Moreover, 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.

  Commercially available materials for the thermal acid generator include “Catalyst 4040”, “Catalyst 4050”, “Catalyst 600”, “Catalyst 602”, “Catalyst 500”, “Catalyst 296-9”. {Nippon Cytec Industries, Ltd.}, “NACURE series 155, 1051, 5076, 4054J” and its block type “NACURE series 2500, 5225, X49-110, 3525, 4167” (manufactured by King) Is mentioned.

  The use ratio of the thermal acid generator is preferably 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 3 parts per 100 parts by mass of the curable resin composition. The mass. When the addition amount is within this range, the storage stability of the curable resin composition is good and the scratch resistance of the coating film is also good.

{Photosensitive acid generator (photoacid generator)}
Furthermore, the photo-acid generator which can be used as a photoinitiator is explained in full detail.
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. Examples of the acid generator include organic halogenated compounds, disulfone compounds, onium compounds, etc. Among these, specific examples of organic halogen compounds and disulfone compounds are the same as those described for the compound that generates radicals. Things.

  Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts; (2) β-ketoesters, β-sulfonylsulfones and these. sulfone compounds such as α-diazo compounds; (3) sulfonic acid esters such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates; (4) sulfonimide compounds; and (5) diazomethane compounds. Can be mentioned.

  Examples of the onium compounds include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, and selenonium salts. 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 JP-A-2002-29162, paragraph numbers [0058] to [0059].

  The use ratio of the photosensitive acid generator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin composition.

  In addition, as specific compounds and methods of use, for example, the contents described in JP-A-2005-43876 can be used.

(Formation of a low refractive index layer)
In the hard coat film of the present invention, the low refractive index layer can be formed by coating, and an ultraviolet (UV) curing and / or a thermal curing as a film forming component in the coating liquid for forming the low refractive index layer. It is preferable to have at least one kind of translucent resin having a functional group capable of being used {as the translucent resin having a functional group capable of ultraviolet (UV) curing and / or heat curing, preferably the aforementioned fluorine-containing copolymer A coalescence or an organosilane compound}.

  In the hard coat film of the present invention, the coating liquid for forming the low refractive index layer contains at least two kinds of translucent resins as a film forming component, and at least one of the translucent resins is an ultraviolet ray. It is more preferable that at least one kind of translucent resin having a functional group capable of (UV) curing has a functional group capable of being thermally cured. In addition, it is more preferable that the coating liquid for forming the low refractive index layer contains at least one polymerization initiator and at least one thermosetting crosslinking agent. In addition, it is even more preferable that the low refractive index layer contains a curing catalyst that promotes thermal curing (the polymerization initiator, the crosslinking agent that can be thermally cured, and the curing catalyst that promotes thermal curing are described above. Can be preferably used).

  Further, in the hard coat film of the present invention, a translucent resin having at least an ultraviolet (UV) curable functional group contained in the coating solution for forming the low refractive index layer, and at least one polymerization initiator A value obtained by dividing the total weight by the total weight of the translucent resin having at least one thermosetting functional group and the weight of at least one crosslinkable thermosetting agent is 0.05 to 0.19. It is preferable in terms of scratch resistance and cost. More preferably, it is 0.10-0.19, More preferably, it is 0.15-0.19. If this value is 0.05 or more, it is preferable because scratch resistance is good, and if it is 0.20 or less, the ratio of the UV curing component becomes appropriate, so that the polymerization efficiency during UV curing is increased. Process conditions (nitrogen purge during UV curing, film surface temperature increase, etc.) are preferable because they become appropriate.

  The oxygen concentration during UV curing by nitrogen purge is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 100 ppm or less, and most preferably 50 ppm or less. The film surface temperature during UV curing is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and still more preferably 90 ° C. or higher. If the temperature is equal to or lower than the upper limit value, there is no inconvenience such as softening of the support and causing a handling (conveyance) defect. Therefore, the upper limit temperature is preferably determined within this range.

[Leveling agent]
It is preferable to use various leveling agents in the at least one hard coat layer of the present invention for the purpose of improving the surface condition (preventing unevenness). Furthermore, it is preferable to use various leveling agents for the purpose of preventing unevenness in the low refractive index layer of the present invention.

  Specifically, the leveling agent is preferably a fluorine-based leveling agent or a silicone-based leveling agent. In particular, it is more preferable to use both a fluorine-based leveling agent and a silicone-based leveling agent because of their high ability to prevent unevenness. Moreover, it is more preferable that a leveling agent is used for all layers. The leveling agent is preferably an oligomer or a polymer rather than a low molecular compound.

  When a leveling agent is added, the leveling agent quickly moves to the surface of the applied liquid film and becomes unevenly distributed, and even after the film is dried, the leveling agent is unevenly distributed on the surface, so the hard coat layer to which the leveling agent is added In addition, the surface energy of the film of the low refractive index layer is lowered by the leveling agent. Therefore, from the viewpoint of preventing unevenness of the hard coat layer, the surface energy of the hard coat layer is preferably low.

The surface energy of the hard coat layer (γs ^v : unit, mJ / m ² ) K. Owens, “J. Appl. Polym. Sci.”, Volume 13, p. 1741 (1969) can be obtained experimentally using pure water H ₂ O and methylene iodide CH ₂ I ₂ on the hard coat layer. At this time, each of the contact angle theta _{H2 O} of pure water and methylene iodide as theta _CH2I2, the following simultaneous equations (1), determine the gamma] s ^d and gamma] s ^h (2), the value gamma] s represented by the sum ^v (= γs ^d + γs ^h ) is defined as an energy conversion value of the surface tension of the hard coat layer (mN / m unit is mJ / m ² unit). The sample needs to be conditioned for a predetermined time or more under a predetermined temperature and humidity condition before measurement. In this case, the temperature is preferably in the range of 20 ° C. to 27 ° C., the humidity is preferably in the range of 50 to 65 RH%, and the humidity conditioning time is preferably 2 hours or more.

_{(1) 1 + cosθ H2O =} 2√γs d (√γ H2O d / γ H2O v) + 2√γs h (√γ H2O h / γ H2O v)
_{(2) 1 + cosθ CH2I2 =} 2√γs d (√γ CH2I2 d / γ CH2I2 v) + 2√γs h (√γ CH2I2 h / γ CH2I2 v)

Here, γ _H2O ^d = 21.8 °, γ _H2O ^h = 51.0 °, γ _H2O ^v = 72.8 °, γ _CH2I2 ^d =
49.5 °, γ _CH2I2 ^h = 1.3 °, and γ _CH2I2 ^v = 50.8 °.

The preferable surface energy of the hard coat layer is in the range of 45 mJ / m ² or less, more preferably in the range of ^{20 to} 45 mJ / m ² , and still more preferably in the range of 20 to 40 mJ / m ² . By setting the surface energy of the hard coat layer to 45 mJ / m ² or less, an effect that unevenness of the hard coat layer hardly occurs can be obtained. However, when an upper layer such as a low refractive index layer is further coated on the hard coat layer, the leveling agent is preferably one that elutes and moves to the upper layer. The surface energy of the hard coat layer after immersing and washing the hard coat layer with methyl ethyl ketone, methyl isobutyl ketone, toluene, cyclohexanone, etc.) is preferably rather high, and the surface energy is preferably 35 to 70 mJ / m ^2. .

  Below, a preferable fluorine-type leveling agent is demonstrated as a leveling agent of a hard-coat layer. The silicone leveling agent will be described later.

(Fluorine leveling agent)
As the fluorine-based leveling agent, a polymer having a fluoroaliphatic group is preferable, and a polymer of a repeating unit (polymerization unit) corresponding to the monomer (i) below, or a repeating unit corresponding to the monomer (i) below. A copolymer of an acrylic resin, a methacrylic resin, and a vinyl monomer copolymerizable therewith containing a (polymerized unit) and a repeating unit (polymerized unit) corresponding to the monomer (ii) below is useful. Such monomers include "Polymer Handbook 2nd ed." Brandrup, Wiley lnterscience (1975), Chapter 2, P.I. 1-483 can be used, for example, addition selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Examples thereof include a compound having one polymerizable unsaturated bond.

  (I) Fluoroaliphatic group-containing monomer represented by the following general formula (4-1)

Formula (4-1):

In the above general formula (4-1), R ⁴¹ represents a hydrogen atom, a halogen atom or a methyl group, preferably a hydrogen atom or a methyl group. Y ⁴¹ represents an oxygen atom, a sulfur atom or —N (R ⁴² ) —, more preferably an oxygen atom or —N (R ⁴² ) —, and still more preferably an oxygen atom. R ⁴² represents an alkyl group having 1 to 8 carbon hydrogen atom or a carbon atoms which may have a substituent, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group. R _f ⁴¹ represents —CF ₃ or —CF ₂ H.

M in the general formula (4-1) represents an integer of 1 to 6, more preferably 1 to 3, and still more preferably 1. n represents an integer of 1 to 11, more preferably 1 to 9, and still more preferably 1 to 6. R _f ⁴¹ is preferably —CF ₂ H.

  Further, in the (co) polymer having a fluoroaliphatic group, two or more kinds of polymer units derived from the fluoroaliphatic group-containing monomer represented by the general formula (4-1) are contained as constituent components. Also good.

  (Ii) Monomer represented by the following general formula (4-2) copolymerizable with the above (i)

Formula (4-2):

In the above general formula (4-2), R ⁴³ represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group. Y ⁴² represents an oxygen atom, a sulfur atom or -N (R ⁴⁵⁾ - represents a oxygen atom or -N (R ⁴⁵⁾ - is more preferably an oxygen atom. R ⁴⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a methyl group. R ⁴⁴ is a linear, branched or cyclic alkyl group having 1 to 60 carbon atoms which may have a substituent, or an aromatic group which may have a substituent (for example, phenyl group or naphthyl). Group). The alkyl group may include a poly (alkyleneoxy) group. Furthermore, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms is more preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is very preferable. The amount of the fluoroaliphatic group-containing monomer represented by the general formula (4-1) used for the production of a preferred (co) polymer having a fluoroaliphatic group is based on the total amount of the monomer of the copolymer. It is 10 mass% or more, Preferably it is 50 mass% or more, More preferably, it is 70-100 mass%, More preferably, it is the range of 80-100 mass%.

  Hereinafter, although the example of a specific structure of the (co) polymer which has a preferable fluoro aliphatic group is shown, it is not this limitation. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

  The amount of polymer units of the fluoroaliphatic group-containing monomer constituting the (co) polymer having a fluoroaliphatic group is preferably more than 10% by mass, more preferably 50 to 100% by mass, and hard coat From the viewpoint of preventing unevenness of the layer, it is most preferably 75 to 100% by mass, and when a low refractive index layer is applied on the hard coat layer, it is 50 to 75% by mass. Most preferred. (Described in all polymer units constituting a (co) polymer having a fluoroaliphatic group)

(Silicone leveling agent)
Next, the silicone leveling agent will be described.
Preferable examples of the silicone compound include those having a substituent at the end of the compound chain and / or the side chain, containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include polyether groups, alkyl groups, aryl groups, aryloxy groups, acryloyl groups, methacryloyl groups, vinyl groups, aryl groups, cinnamoyl groups, epoxy groups, oxetanyl groups, hydroxyl groups, fluoroalkyl groups, polyoxy groups. Examples thereof include an alkylene group, a carboxyl group, an amino group and the like.

  Although there is no restriction | limiting in particular in molecular weight, It is preferable that it is 100,000 or less, It is more preferable that it is 50,000 or less, It is especially preferable that it is 1000-30000, It is most preferable that it is 1000-20000.

  Although there is no restriction | limiting in particular in silicone atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.8 mass%, and 30.0-37.0. Most preferably, it is mass%.

  Examples of preferable silicone compounds include “X-22-174DX”, “X-22-2426”, “X-22-164B”, “X22-164C”, “X-” manufactured by Shin-Etsu Chemical Co., Ltd. 22-170DX "," X-22-176D "," X-22-1821 "(named above);" FM-0725 "," FM-7725 "," FM-4421 "manufactured by Chisso Corporation, “FM-5521”, “FM-6621”, “FM-1121” (named above); “DMS-U22”, “RMS-033”, “RMS-083”, “UMS-182” manufactured by Gelest, “DMS-H21”, “DMS-H31”, “HMS-301”, “FMS121”, “FMS123”, “FMS131”, “FMS141”, “FMS221” (named above); Toray Dow “SH200”, “DC11PA”, “SH28PA”, “ST80PA”, “ST86PA”, “ST97PA”, “SH550”, “SH710”, “L7604”, “FZ-2105”, “FZ2123” manufactured by Corning Co., Ltd. ”,“ FZ2162 ”,“ FZ-2191 ”,“ FZ2203 ”,“ FZ-2207 ”,“ FZ-3704 ”,“ FZ-3736 ”,“ FZ-3501 ”,“ FZ-3789 ”,“ L-77 ” ”,“ L-720 ”,“ L-7001 ”,“ L-7002 ”,“ L-7604 ”,“ Y-7006 ”,“ SS-2801 ”,“ SS-2802 ”,“ SS-2803 ”, "SS-2804", "SS-2805" (named above); "TSF400", "TSF401", "TSF410" manufactured by GE Toshiba Silicone Co., Ltd. TSF433 "," TSF4450 "," TSF4460 "(trade name); is are exemplified but not limited thereto such.

  The amount of the fluorine-containing leveling agent and silicone leveling agent added to the coating solution is preferably 0.001 to 1.0% by mass, more preferably 0.01% to 0.2% by mass. .

[Liquid solvent for low refractive index layer]
The coating liquid solvent for the low refractive index layer of the hard coat film of the present invention is a low boiling point solvent having a boiling point of 120 ° C. or lower, and 50 of the total mass of the coating liquid solvent for the low refractive index layer in order to suppress drying unevenness of the low refractive index layer. It is preferably contained in an amount of 100% by mass to 100% by mass, preferably 70% by mass to 100% by mass, and more preferably 90% by mass to 100% by mass. By changing the solvent composition of the low refractive index layer of the sample of the present invention described later as described above, this effect could be confirmed in the surface evaluation of the low refractive index layer. Specific examples of the coating solution solvent include methyl ethyl ketone, methyl isobutyl ketone, and toluene, which have good solubility of the fluorine-containing polymer in the low refractive index layer.

[Thickener for hard coat layer]
In the hard coat layer, a thickener may be used to adjust the viscosity of the coating solution.
By increasing the viscosity, the sedimentation of contained particles can be suppressed, and the effect of preventing unevenness can be expected. The term “thickener” as used herein means that the viscosity of the liquid is increased by adding it, and is preferably 0.05 to 50 cP as the magnitude of increase in the viscosity of the coating liquid by adding it. More preferably, it is 1-50 cP, Most preferably, it is 2-50 cP.

  It is preferable that the polymer used as the thickener does not substantially contain a fluorine atom and / or a silicon atom. Here, “substantially” means that the content of fluorine atoms and / or silicon atoms in the mass of the polymer is 0.1% by mass or less, preferably 0.01% by mass or less.

  Such a thickener is preferably a high molecular polymer, and specific examples include, but are not limited to, the following.

  Polymeric polymer thickener: polyacrylic acid ester, polymethacrylic acid ester, polyvinyl acetate, vinyl polypropionate, polyvinyl butyrate, polyvinyl butyral, polyvinyl formal, polyvinyl acetal, polyvinyl propanal, polyvinyl hexanal, polyvinyl pyrrolidone, cellulose Acetate, cellulose propionate, cellulose acetate butyrate.

  Of these, polymethacrylates (specifically, polymethyl methacrylate and polyethyl methacrylate), polyvinyl acetate, vinyl polypropionate, cellulose propionate, and cellulose acetate butyrate are particularly preferable. Further, those having a mass average molecular weight of 100,000 to 1,000,000 are preferable.

  In addition, smectite, tetrasilica mica, bentonite, silica, montmorillonite and sodium polyacrylate described in JP-A-8-325491, ethylcellulose, polyacrylic acid, organic clay described in JP-A-10-219136, etc. Well-known viscosity modifiers and thixotropic agents can be used.

(Transparent support)
A plastic film is preferably used as the transparent support of the hard coat film of the present invention. Examples of the polymer forming the plastic film include cellulose esters (for example, triacetyl cellulose, diacetyl cellulose, typically “TAC-TD80U”, “TD80UF”, etc., manufactured by Fuji Film Co., Ltd.), polyamides, polycarbonates, polyesters (for example, , Polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, norbornene resin {"Arton" (trade name), manufactured by JSR Corporation}, amorphous polyolefin {"ZEONEX" (trade name), ZEON CORPORATION Etc.}. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable. In addition, a cellulose acylate film substantially free of halogenated hydrocarbons such as dichloromethane and a method for producing the same are disclosed in JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001; (Abbreviated as No. 2001-1745), and the cellulose acylate described therein can also be preferably used in the present invention.

  The thickness of the transparent support is preferably from 20 to 200 μm, preferably from 30 to 100 μm, more preferably from 35 to 90 μm, most preferably from 40 to 40 μm, considering the need for thinning and handling (conveyability). 80 μm.

  The width of the transparent support can be arbitrarily selected, but usually 100 to 5000 mm is used from the viewpoint of increasing the size of the image display device, handling (conveyability), yield, and productivity. It is preferable that it is 800-3000 mm, and it is more preferable that it is 1000-2000 mm.

[Characteristics of hard coat film]
The total light transmittance of the hard coat film of the present invention is measured according to JIS K-7316. The total light transmittance is preferably 85% or more from the viewpoint of front contrast. More preferably, it is 90% or more, and particularly preferably 92% or more.

  The contact angle of the hard coat film surface of the present invention with respect to pure water measured in an environment of 25 ° C. and 60% RH is preferably 90 ° or more from the viewpoint of antifouling property. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more. Further, the change in the contact angle before and after the saponification treatment (described later) required for polarizing plate processing is preferably 5 ° or less, more preferably 3 ° or less, and most preferably 1 ° or less.

The vertical peel charge amount of the hard coat film of the present invention measured in an environment of 25 ° C. and 60% RH with respect to polyethylene terephthalate is −500 pc (picocoulomb) / cm ² to +500 pc / cm ² . This is preferable. ^{Preferably, -200pcc / cm 2 ~ + 200pcc} / cm 2, more preferably ^{-100pcc / cm 2 ~ + 100pcc /} cm 2.

  The vertical peel charge amount is as follows. The measurement sample is previously left in an environment of 25 ° C. and 60% RH for 2 hours or more. The measuring device comprises a head on which a measurement sample is placed and a counterpart film, and a head that can repeatedly press and peel the measurement sample from above. A polyethylene terephthalate is attached to the head. After neutralizing the measurement portion, the head is pressure-bonded to the measurement sample and repeatedly peeled off. The value of the charge amount at the first peeling and the fifth peeling is read and averaged. This is repeated for three samples by changing the sample, and the average of all is taken as the vertical peel charge amount.

  Further, in the case of a hard coat film in which at least one of the constituent materials of the low refractive index layer is made of a fluorine-containing material, the photoelectron spectrum intensity ratio F / C is 0 in order to fall within the preferred range of the vertical peeling charge amount. 0.5 to 5, preferably 0.5 to 3, and more preferably 0.5 to 2. Further, as the adjustment of the vertical peeling charge amount, it is preferable to contain silicone having high surface orientation like fluorine, and as a result, the photoelectron spectrum intensity ratio Si / C is 0.05 to 0.5, preferably 0.1 to 0.1. It is preferably 0.5, more preferably 0.2 to 0.5.

F / C (= F _1s / C _1s ) and Si / C (= Si _2p / C _1s ) are values measured below. Further, the photoelectron spectra of Si _2p , F _1s , and C _{1s on} the outermost surface of the hard coat film were measured using “ESCA-3400” (vacuum degree 1 × 10 ⁻⁵ Pa, X-ray source; target Mg, voltage 12 kV, manufactured by Shimadzu Corporation. The current was measured at 20 mA.

Further, in order to enhance the dust resistance, the surface resistance value of the hard coat film of the present invention is less than 1 × 10 ¹¹ Ω / □, preferably less than 1 × 10 ¹⁰ Ω / □, and more preferably 1 × 10 ⁹ Ω. It is better to make it less than / □. The method for measuring the surface resistance value will be described later.

[Antistatic layer]
The hard coat film of the present invention can be provided with an antistatic layer containing various conductive particles in order to impart conductivity.

(Conductive particles)
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 these metal oxides or nitrides, and may 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 (ATO) containing Sb and indium oxide (ITO) containing Sn. The ratio of Sb in ATO is preferably 3 to 20% by mass. 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 used for the antistatic layer 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 10 to 400 m ² / g, and 20 to ²
More preferably 00m is ² / g, and most preferably from 30 to 150 m ² / g.

  The conductive inorganic particles may be subjected to a surface treatment. 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 the organic compound 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 combination in the antistatic 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. In addition, the conductive inorganic particles can be used for forming an antistatic layer in a dispersion state.

  As a method for measuring the surface resistance value, the sample film is previously left in an environment of 25 ° C. and 60% RH for 2 hours or more. Thereafter, the surface resistance on the coating layer side was measured with a super insulation resistance / microammeter “TR8601” {manufactured by Advantest Co., Ltd.}.

  The dynamic friction coefficient of the hard coat film surface of the present invention is preferably 0.3 or less from the viewpoint of improving scratch resistance (preventing stress concentration). More preferably, it is 0.2 or less, more preferably 0.1 or less.

The method for measuring the dynamic friction coefficient is as follows.
The measurement sample is previously left in an environment of 25 ° C. and 60% RH for 2 hours or more. Thereafter, values measured with a “HEIDON-14” dynamic friction measuring instrument at a 5 mmφ stainless steel ball, a load of 100 g, and a speed of 60 cm / min were used.

  In the hard coat film of the present invention, when the average value of 5 ° regular reflectance in the wavelength region of 450 nm to 650 nm is A and the average value of the integrated reflectance is B, B is 3% or less, B− A is preferably 1.5% or less from the viewpoint of tightening black display in a bright room environment and improving bright room contrast. B is more preferably 2% or less, and further preferably 1% or less. Further, B-A is more preferably 1% or less, and further preferably 0.5% or less.

Measurement of the average value of the 5 ° regular reflectance and the integral reflectance is as follows.
The specular reflectivity is measured by attaching an adapter “ARV-474” to a spectrophotometer “V-550” [manufactured by JASCO Corporation], and an emission angle at an incident angle of 5 ° in a wavelength region of 380 to 780 nm. The specular reflectance at −5 ° was measured, and the average specular reflectance at 450 to 650 nm was calculated. The integral reflectance is measured by attaching an adapter “ILV-471” to a spectrophotometer “V-550” [manufactured by JASCO Corporation] and integrating reflection at an incident angle of 5 ° in a wavelength range of 380 to 780 nm. The rate was measured, and the average integrated reflectance of 450 to 650 nm was calculated.

  The surface strength of the hard coat film is preferably H or more, more preferably 2H or more, and most preferably 3H or more in the pencil hardness test. Furthermore, in the Taber test according to JIS K-5400, the smaller the wear amount of the test piece before and after the test, the better.

[Method for producing hard coat film]
The hard coat film of the present invention can be formed by the following method, but is not limited thereto.

[Adjustment of coating solution]
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 after that.

[filtration]
The coating solution used for coating is preferably filtered before coating. As the filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within the range in which the components in the coating solution are not removed. For filtration, a filter having an absolute filtration accuracy of 0.1 to 50 μm, and an absolute filtration accuracy of 0.1 to 40 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. Further, it is also preferable that the filtered coating solution is ultrasonically dispersed immediately before coating to assist defoaming and dispersion holding of the dispersion.

[Processing before coating]
The transparent support used in the present invention is preferably subjected to a heat treatment for correcting base deformation, or a surface treatment for improving coating properties and adhesion with a coating layer before coating. Specific methods for the surface treatment 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.

  Further, it is preferable to perform a dust removing step as a pre-process for coating, and as a dust removing method used therefor, a method of pressing a nonwoven fabric, a blade or the like against the film surface described in JP-A-59-150571; A method in which air with high cleanliness described in JP-A-10-309553 is sprayed at high speed to peel off deposits from the surface of the film and sucked by a suction port close thereto; ultrasonic vibration described in JP-A-7-333613 A dry dust removal method such as a method of blowing the compressed air to peel off the adhering matter and sucking it {manufactured by Shinko Co., Ltd., New Ultra Cleaner, etc.}; In addition, a method of introducing a film into a cleaning tank and peeling off the deposits with an ultrasonic vibrator; after supplying a cleaning solution to the film described in Japanese Patent Publication No. 49-13020, spraying and sucking high-speed air A method of performing; a wet dust removing method such as a method of spraying a liquid onto a rubbed surface after continuously rubbing a web with a roll wetted with a liquid as described in JP-A-2001-38306; It can also be used. Among such dust removal methods, a method using ultrasonic dust removal or a method using wet dust removal is particularly preferable in terms of the dust removal effect.

  In addition, it is particularly preferable to remove static electricity on the transparent support before performing such a dust removal step from the viewpoint of increasing dust removal efficiency and suppressing dust adhesion. 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 transparent support before and after dust removal and application 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, in these treatments, the temperature of the transparent support, such as a cellulose acylate film, is Tg or less of the polymer constituting the film, and 150 ° C. or less in the case of the cellulose acylate film. It is preferable.

  As in the case of using the hard coat film of the present invention as a protective film for a polarizing plate, when a cellulose acylate film, which is a preferred transparent support of the hard coat film, is adhered to a polarizing film, From the viewpoint of adhesiveness, it is particularly preferable to perform acid treatment or alkali treatment, that is, saponification treatment for cellulose acylate.

  From the viewpoint of adhesiveness and the like, the surface energy of the cellulose acylate film as the transparent support is preferably 55 mN / m or more, more preferably 60 mN / m or more and 75 mN / m or less. Can be adjusted.

[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) (US Pat. No. 2,681,294, International Publication No. 2005/123274) A known method such as a microgravure coating method is used, and among these, a microgravure coating method and a die coating method are preferable.

  The micro gravure coating method used in the present invention is a method in which a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm and having a gravure pattern engraved on the entire circumference is provided below the transparent support. The gravure roll is rotated in the reverse direction with respect to the conveying direction of the body, and the excess coating liquid is scraped off from the surface of the gravure roll by a doctor blade so that the lower surface of the support is in a position where the upper surface of the support is in a free state. In addition, a coating method is characterized in that a certain amount of coating solution is transferred and applied. A roll-shaped transparent support is continuously unwound, and at least one layer of at least one of a hard coat layer and a low-refractive index layer containing a fluorine-containing olefin 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 lines of the gravure pattern imprinted on the gravure roll is preferably 50 to 800 lines / in, more preferably 100 to 300 lines / in, and the depth of the gravure pattern is 1 to 600 μm, Furthermore, 5-200 micrometers is preferable, it is preferable that the rotation speed of a gravure roll is 3-800 rpm, Furthermore, it is preferable that it is 5-200 rpm, The conveyance speed of a transparent support body is 0.5-100 m / min, Furthermore, 1-50 m / Minutes are preferred.

  In order to supply the film of the present invention with high productivity, an extrusion method (die coating method) is preferably used. In particular, the extrusion method described in JP-A-2006-122889 can be applied particularly preferably.

  Since the die coating method is a pre-measuring method, it is easy to ensure a stable film thickness. This coating method can be applied at high speed and with good film thickness stability to a coating solution of a low coating amount. Although application is possible by other application methods, the dip coating method inevitably causes vibration of the application liquid in the liquid receiving tank, and stepped unevenness is likely to occur. In the reverse roll coating method, stepped unevenness is liable to occur due to roll eccentricity and deflection related to coating. Further, since these coating methods are post-measuring methods, it is not easy to ensure a stable film thickness. It is preferable from the viewpoint of productivity that the die coating method is applied at a rate of 25 m / min or more.

[Dry]
The film of the present invention is preferably applied on a transparent 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 knowledge includes description techniques such as JP 2001-286817 A, 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 at a relatively low temperature, and the latter half is preferably at a relatively high temperature. However, the temperature is preferably equal to or lower than the temperature at which components other than the solvent contained in the coating liquid composition of each layer start to volatilize. For example, some commercially available photo radical generators used in combination with ultraviolet curable resins may volatilize about several tens of percent within a few minutes in 120 ° C. warm air. Some bifunctional (meth) acrylic acid ester monomers, etc., undergo volatilization in hot 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 liquid of each layer start to volatilize as described above.

  Moreover, the drying wind after apply | coating the coating liquid of each layer on a transparent support body has a wind speed of the coating-film surface of 0.1-2 m / sec while the solid content concentration of this coating liquid is 1-50%. It is preferable to be in the range in order to prevent drying unevenness. Moreover, after apply | coating the coating liquid of each layer on a transparent support body, the temperature difference of a conveyance roll and support body which contacts the surface opposite to the application surface of this support body in a drying zone is 0 degreeC-20 degreeC. By making it within the range, the occurrence of drying unevenness due to heat transfer unevenness on the transport roll can be prevented, which is preferable.

[Curing]
The hard coat film of this invention can pass through the zone which hardens each coating film by ionizing radiation and / or heat as a web after drying of a solvent, and can harden a coating film. 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 easily obtain high energy.

  As the ultraviolet light source for photopolymerizing the ultraviolet curable 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 amount is preferably 10 mJ / cm ² or more, more preferably 50 to 10,000 mJ / cm ² , and particularly preferably 50 mJ / cm ^2.
˜2000 mJ / cm ² . 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 transparent support is irradiated with ionizing radiation and heated to a film surface temperature of 50 ° C. or more for 0.5 seconds or more from the start of ionizing radiation irradiation, and an oxygen concentration of 1000 ppm. Preferably, it is cured by a step of irradiating with ionizing radiation in an atmosphere of 500 ppm, more preferably 100 ppm, and most preferably 50 ppm or less.

  It is also preferable to heat in an atmosphere of low oxygen concentration 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 is thin 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.

  About the time which irradiates ionizing radiation, 0.5 second or more and 60 seconds or less are preferable, and 0.7 second or more and 10 seconds or less are more preferable. If the irradiation time is 0.5 seconds or more, the curing reaction can be completed and sufficient curing can be performed. In order to maintain the low oxygen condition for a long time, the irradiation time is preferably 60 seconds or less because the equipment is enlarged and a large amount of inert gas such as nitrogen is required.

  As a method of setting the oxygen concentration to 1000 ppm or less, it is preferable to replace the atmosphere with another gas, and particularly preferably to replace with nitrogen (nitrogen purge).

  By supplying the inert gas to the ionizing radiation irradiation chamber (also referred to as “reaction chamber”) where the curing reaction is performed by ionizing radiation, and by slightly blowing out to the web inlet side of the reaction chamber, it is accompanied by the web conveyance. It is possible to eliminate the carry-in air, effectively reduce the oxygen concentration in the reaction chamber, and to efficiently reduce the substantial oxygen concentration on the electrode surface where the inhibition of curing by oxygen is large. The direction of the inert gas flow on the web inlet side of the reaction chamber can be controlled by adjusting the balance between supply and exhaust of the reaction 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 be promoted more efficiently. Further, the side surface constituting the web entrance side of the ionizing radiation reaction chamber or the front chamber preferably has a gap with the web surface of 0.2 to 15 mm, more preferably, in order to use an inert gas efficiently. 0.2 to 10 mm, and most preferably 0.2 to 5 mm.

  However, in order to continuously manufacture the web, it is necessary to join the webs together, and a method of attaching with a joining tape or the like is widely used for joining, but the entrance surface of the ionizing radiation reaction chamber or the front chamber is used. If the gap of the web is too narrow, there arises a problem that a joining member such as a 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, it moves forward and backward to widen the gap, or the ionizing radiation reaction chamber or The entrance surface of the front chamber can be moved vertically with respect to the web surface, and when the joint passes, it can be moved up and down to widen the gap.

  The ultraviolet irradiation may be performed each time a plurality of layers constituting the hard coat film of the present invention are provided, or may be irradiated after lamination. Moreover, 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 transparent 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 1000 ppm. 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 curing rate of the lower layer is obtained when a layer is provided thereon and cured by ionizing radiation and / or heat. Is higher than before the upper layer is provided, and the adhesion between the lower layer and the upper layer is improved, which is preferable.

[handling]
In order to continuously produce the hard coat film of the present invention, a process of continuously feeding a roll-shaped transparent support film, a process of applying and drying a coating liquid, a process of curing a coating film, and a cured layer The step of winding up the support film having is performed.

The support is continuously sent out from the roll-shaped transparent support to the clean room. In the clean room, the static electricity charged on the support is removed by an electrostatic charge-removing device, and subsequently attached to the transparent support. Remove the foreign material that has been removed with a dust remover. Subsequently, the coating liquid is applied onto the support in the application section installed in the clean room, and the applied transparent support is sent to the drying chamber and dried.
The transparent 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 transparent support having the cured layer is sent to the curing unit to complete the curing, and the transparent support having the layer that has 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 produce the hard coat film of the present invention, as described above, simultaneously with the microfiltration operation of the coating solution, the coating process in the coating unit and the drying process performed in the drying chamber are performed in a high clean air atmosphere. And before application | coating is performed, it is preferable that the dust and dust on a transparent support film are fully removed. The air cleanliness of the coating process and the drying process is desirably class 10 (353 particles / m ³ or less of 0.5 μm or more) based on the standard of air cleanliness in US Federal Standard 209E, and more preferably. Is preferably class 1 (35.5 particles / m ³ or less of particles of 0.5 μm or more) 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.

[Saponification]
When producing a polarizing plate using the hard coat film of the present invention as one of the two surface protective films of the polarizing film, the adhesive surface can be obtained by hydrophilizing the surface to be bonded to the polarizing film. It is preferable to improve the adhesion in

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 above saponification conditions is preferably a combination of relatively mild conditions, but can be set depending on 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 water on the surface of the transparent support opposite to the side having the coating layer, the better from the viewpoint of adhesiveness to the polarizing film. Since it is damaged by alkali from the surface to the inside, it is important to set the reaction conditions to the minimum necessary. 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 °, more preferably Is 30 ° to 50 °, more preferably 40 ° to 50 °. If it is 50 degrees or less, a problem does not arise in adhesiveness with a polarizing film, and it is preferable. Moreover, if it is 10 degrees or more, since the damage which a film receives is not large, since physical strength is not impaired, it is preferable.

b. Method for applying alkaline solution As a means for avoiding damage to each film in the above-described immersion method, the alkaline solution is applied only on the surface opposite to the surface having the coating layer, heated, washed and dried under appropriate conditions. An alkaline solution coating method is preferably used. The application in this case means that an alkaline liquid or the like is brought into contact only with the surface to be saponified, and includes application by spraying, contact with a belt containing the liquid, or the like in addition to the application. .

  By adopting these methods, a separate facility and process for applying an alkaline solution are required, which is higher in cost than the immersion method (1). 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.

  In any of the saponification methods (a) and (b) above, since each layer can be formed by unwinding from a roll-shaped support, it may be carried out by a series of operations in addition to the film production process. . Furthermore, by similarly performing the bonding process of the unwound support and the polarizing plate continuously, it is possible to produce the polarizing plate more efficiently than when performing the same operation on a single wafer.

c. Method of saponification by protecting with a laminate film As in the case of (b) above, when the coated layer is insufficient in resistance to an alkaline solution, the laminate film is formed on the surface on which the final layer is formed after forming the final layer. It is also possible to use a method in which only the triacetyl cellulose surface opposite to the surface on which the final layer has been formed is made hydrophilic by dipping in an alkaline solution after bonding, and then the laminate film is peeled off. Even in this method, the hydrophilic treatment necessary for the polarizing plate protective film is applied only to the surface opposite to the surface on which the final layer is formed of the triacetyl cellulose film, which is a transparent support, without damaging the coating layer. Can be applied. Compared with the method (b) above, there is an advantage that a laminate film is generated as a waste, but an apparatus 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, both sides are hydrophilized by immersing in alkaline solution after forming up to lower layer However, the upper layer can be formed thereafter. Although the manufacturing process is complicated, for example, in the case of a film composed of a hard coat layer and a low refractive index layer of a fluorine-containing sol-gel film, when having a hydrophilic group, the layer between the hard coat layer and the low refractive index layer There is an advantage that adhesion is improved.

e. Method for forming a coating layer on a pre-saponified triacetyl cellulose film A triacetyl cellulose film, which is a transparent support, is saponified by dipping in an alkaline solution in advance, and either directly or on another surface. A coating layer may be formed via In the case of saponification by dipping in an alkaline solution, the interlayer adhesion between the triacetyl cellulose surface hydrophilized by saponification and the coating layer 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.

<Polarizing plate>
[Preparation of polarizing plate]
[Configuration of polarizing plate]
The hard coat film of this invention can be used for one or both of the protective film of the polarizing plate which consists of a polarizing film and the protective film arrange | positioned on the both sides.

  The hard coat film of the present invention is used as one protective film, and a normal cellulose acetate film may be used as the other protective film, but the other protective film is manufactured by a solution casting method, and It is preferable to use a cellulose acetate film stretched in the width direction in the form of a roll film at a stretch ratio of 10 to 100%.

  Furthermore, in the polarizing plate of the present invention, it is also preferable that one side is the hard coat film of the present invention, while the other protective film is an optical compensation film having an optically anisotropic layer made of a liquid crystalline compound. It is an aspect.

[Polarizing film]
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.

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, it stretches by applying tension while holding both ends of a polymer film such as a polyvinyl alcohol film continuously supplied by a holding means, and stretches at least 1.1 to 20.0 times in the film width direction. The difference between the longitudinal travel speeds of the holding devices at both ends of the film is within 3%, and the angle formed by the film traveling direction at the exit of the step of holding the film both ends and the substantial stretching direction of the film is inclined by 20 to 70 °. In addition, the film traveling direction can be produced by a stretching method in which the film is bent while both ends of the film are held. 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.

  In the present invention, the transparent support of the hard coat film or the slow axis of the cellulose acetate film and the transmission axis of the polarizing film are preferably arranged so as to be substantially parallel.

[Protective film]
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 a hard coat 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.

(Optical compensation film)
Of the two protective films of the polarizing film, a film other than the hard coat film of the present invention 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.

<Usage form of the present invention>
(Image display device)
The hard coat film of the present invention is used in 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 hard coat film 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).

[Liquid Crystal Display]
The hard coat film and polarizing plate of the present invention can be advantageously used in an image display device such as a liquid crystal display device, and is preferably used as the outermost layer of the display.

  In general, a 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.
In VA mode liquid crystal cell,
(1) In addition to a narrowly-defined VA mode liquid crystal cell (described in JP-A-2-176625) in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied. ,
(2) VA mode multi-domain (MVA mode) liquid crystal cell (SID97, Digest of Tech. Papers (Preliminary Book) 28 (1997) 845 described)
(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 (Procedures 58-59 (1998) ) Description) and
(4) Includes a SURVAVAL mode liquid crystal cell (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, No. 5,410,422. 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), p. 577-580 and p. 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.

[Image display devices 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, a hard coat film can be directly attached to the display surface. When a front plate is provided in front of the display, a hard coat film can be attached to the front side (outside) or back side (display side) of the front plate.

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

(Organic EL device)
The hard coat film of the present invention can be used as a substrate (base film) such as an organic EL element or a protective film.

  When the hard coat 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, 2001-335776, JP 2001-247859, JP 2001-181616, JP 2001-181617, JP 2002-181816, JP 2002-181617, JP 2002-056776. It is possible to apply the contents described in each publication. Moreover, it is preferable to use together with the content of each gazette of Unexamined-Japanese-Patent No. 2001-148291, Unexamined-Japanese-Patent No. 2001-221916, and Unexamined-Japanese-Patent No. 2001-231443.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

<Hard coat film>
[Preparation of coating solution for each layer]
[Preparation of coating solution for hard coat layer]
Each component shown in Table 6 below was put into a mixing tank, stirred, and then filtered through a polypropylene filter having a pore size of 30 μm to prepare hard coat layer coating solutions HCL-1 to HCL-11.

Each of the above components is as follows.
“DPHA”: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, refractive index 1.52, manufactured by Nippon Kayaku Co., Ltd.
“Irgacure 127”: photopolymerization initiator, “MX-150” manufactured by Ciba Specialty Chemicals Co., Ltd .: polymethyl methacrylate fine particles, average particle size 2.0 μm, manufactured by Soken Chemical Co., Ltd.
“MX-300”: polymethyl methacrylate fine particles, average particle size 5.0 μm, manufactured by Soken Chemical Co., Ltd.
“MX-1200”: polymethyl methacrylate fine particles, average particle size 10.0 μm, manufactured by Soken Chemical Co., Ltd.
“MX-1500”: polymethyl methacrylate fine particles, average particle size 15 μm, manufactured by Soken Chemical Co., Ltd.
“MX-2000”: polymethyl methacrylate fine particles, average particle size 20 μm, manufactured by Soken Chemical Co., Ltd.
“SSX106TN”: polymethyl methacrylate fine particles, average particle size 6.0 μm, manufactured by Sekisui Plastics Co., Ltd.
“SSX108HLE”: polymethyl methacrylate fine particles, average particle size 8.0 μm, manufactured by Sekisui Plastics Co., Ltd.

[Preparation of coating solution for low refractive index layer]
(Preparation of sol solution a)
In a reactor equipped with a stirrer and a reflux condenser, 120 parts by mass of methyl ethyl ketone, 100 parts by mass of acryloxypropyltrimethoxysilane “KBM-5103” (manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts by mass of diisopropoxyaluminum ethyl acetoacetate After adding a part and mixing, 30 mass parts of ion-exchange water was added, and it was made to react at 60 degreeC for 4 hours, Then, it cooled to room temperature and obtained the sol liquid a. The mass average molecular weight was 1800, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100% by mass. From the gas chromatography analysis, the raw material acryloxypropyltrimethoxysilane did not remain at all.

{Preparation of hollow silica fine particle dispersion (A-1)}
Hollow silica fine particle sol (particle size of about 40 to 50 nm, shell thickness of 6 to 8 nm, refractive index of 1.31, solid content concentration of 20% by mass, main solvent isopropyl alcohol, according to Preparation Example 4 of JP 2002-79616 A 500 parts by mass, 30 parts by mass of acryloyloxypropyltrimethoxysilane “KBM-5103” {manufactured by Shin-Etsu Chemical Co., Ltd.}, and diisopropoxyaluminum ethyl acetoacetate “Kelope EP-12” “{Hope Pharmaceutical Co., Ltd.} 1.5 parts by mass was added and mixed, and then 9 parts by mass of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature, 1.8 parts of acetylacetone was added, and the hollow silica dispersion liquid (A-1) was obtained. The resulting hollow silica dispersion had a solid content concentration of 18% by mass and a refractive index after solvent drying of 1.31.

{Preparation of coating solution for low refractive index layer (LL-1)}
44.0 parts by mass of a fluorine-containing copolymer (P-3) (weight average molecular weight of about 50000) described in JP-A-2004-45462, dipentaerythritol pentaacrylate and dipentaerythritol with respect to 100 parts by mass of methyl ethyl ketone Hexaacrylate mixture “DPHA” {manufactured by Nippon Kayaku Co., Ltd.} 6.0 parts by mass, terminal methacrylate group-containing silicone “RMS-033” (manufactured by Gelest) 3.0 parts by mass, “Irgacure 907” {Ciba 3.0 parts by mass of Specialty Chemicals Co., Ltd.} was added and dissolved. Thereafter, 195 parts by mass of the hollow silica fine particle dispersion (A-1) (39.0 parts by mass as the solid content of silica + surface treatment agent) and 17.2 parts by mass of the sol liquid a (5.0 parts by mass as the solid part) were added. Added. The coating liquid for low refractive index layer (LL-1) was prepared by diluting with cyclohexane and methyl ethyl ketone so that the solid content concentration of the entire coating liquid was 6% by mass and the ratio of cyclohexane and methyl ethyl ketone was 10:90.

[Production of hard coat film]
[Coating of hard coat layer]
Using a slot die coater described in FIG. 1 of Japanese Patent Application Laid-Open No. 2003-211052, the 80 μm-thick triacetyl cellulose film “TAC-TD80U” (manufactured by FUJIFILM Corporation) is unwound in a roll form. The hard coat layer coating liquids (HCL-1) to (HCL-11) were applied so as to have the average film thickness shown in Table 1 above, dried at 30 ° C. for 15 seconds and 90 ° C. for 20 seconds, and then further nitrogen. A hard coat film (HC-1) in which a coating layer was cured by irradiating an ultraviolet ray with an irradiation amount of 130 mJ / cm ² using a 160 W / cm “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.} under a purge. ) To (HC-17) were prepared and wound up.

[Coating of low refractive index layer]
For the sample (HC-7), the coating solution for low refractive index layer (LL-1) was further applied on the hard coat layer using the slot die coater described in FIG. 1 of JP-A No. 2003-211052. Then, wet coating was applied so that the dry film thickness of the low refractive index layer was 90 nm, drying at 60 ° C. for 50 seconds, and further by nitrogen purge, an “air-cooled metal halide lamp” of 240 W / cm in an atmosphere with an oxygen concentration of 100 ppm {Igraphics Co., Ltd.} was used to irradiate ultraviolet rays with an irradiation amount of 400 mJ / cm ² , a low refractive index layer was formed and wound to prepare a hard coat film (HC-7).

[Evaluation of hard coat film]
[Strain degree of surface roughness (Rsk)]
The average interval (Sm) and 10-point average roughness (Rz) of the surface roughness irregularities were measured using a stylus type surface roughness meter “Surfcoder SE3500” {manufactured by Kosaka Laboratory Ltd.}. [Hardcoat layer] was set according to the table described above, and a value derived from the surface roughness meter was adopted.

[Average particle size]
Using an optical microscope, the produced hard coat film is photographed at 200 × magnification. 100 photographed particles were randomly selected, and an average value of 100 particle diameters was defined as an average particle diameter.

[Average film thickness]
Using an electron microscope “S-3400N” {manufactured by Hitachi High-Technologies Corporation}, a cross section of the produced hard coat film is photographed at a magnification of 5000 times. Ten points of the thickness of the hard coat layer are measured at random to derive an average value. This operation was performed for three fields of view, and the average value was defined as the average film thickness.

[Blocking resistance]
After the produced hard coat film was cut into A4 plates, the hard coat treated surface and the untreated surface (TAC surface) were brought into contact with each other and sandwiched between two glass plates. In this state, the film was left for 1 month while applying a pressure of 30 g / cm ² and then peeled off, and the occurrence of blocking was evaluated according to the following criteria.
○: No peeling noise and adhesion trace Δ: Peeling noise is generated but no adhesion trace remains on the hard coat film surface ×: Adhesion trace remains on the hard coat film surface

[Pencil hardness]
The pencil hardness of the prepared hard coat film was evaluated by a pencil hardness test according to JIS-K5400: 1990. Those having a pencil hardness of 3H or more were evaluated as ◯, those having 2H as Δ, those having H or less as ×, and those having Δ or higher as a pass.

[curl]
The curl of the prepared hard coat film was measured by the stencil method for curl measurement of Method A in “Measuring Method of Curling of Photographic Film” of JIS-K7619-1988.
The measurement conditions are 25 ° C., relative humidity 60%, humidity control time 10 hours, and when the value when curl is expressed by the following equation is minus 15 or less and plus 15 or more, ×, minus 15 to minus 10, When the value was plus 10 to plus 15, it was judged as Δ, and when it was minus 10 to plus 10, it was judged as ○. A triangle or higher was accepted. 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 represents a radius of curvature (m).)

  The layer constitution of the obtained hard coat film and the measured properties are shown in the following table.

<Polarizing plate>
[Preparation of polarizing plate]
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. Each of the hard coat films (HC1) to (HC-13) is saponified and attached to one side of the polarizing film using a polyvinyl alcohol adhesive so that the cellulose triacetate side of each hard coat film is the polarizing film side. I attached. Further, a commercially available cellulose triacetate film “Fujitac TD80UF” (manufactured by Fuji Film Co., Ltd.) was attached to the side of the polarizing film opposite to the side on which the hard coat film was applied using a polyvinyl alcohol adhesive. In this way, polarizing plates (HKH-01) to (HKH-13) with a hard coat film were produced.

[Evaluation of polarizing plate]
32-inch full high-definition LCD TV “LC-32GS10” {Sharp Co., Ltd., pixel size: 370 μm} viewing side polarizing plate is peeled off, and polarizing plates (HKH-01) to (HKH-13) are hard-coated instead. The film was pasted on the viewing side through an adhesive so that the film would be the outermost surface.

[White brown feeling]
Remove the polarizing plate on the viewing side of the 32-inch full high-definition LCD TV “LC-32GS10” {manufactured by Sharp Corporation}, and replace the polarizing plates (HKH-01) to (HKH-13) with the hard coat film as the outermost surface. It stuck on the visual recognition side through the adhesive so that it might become. In general, the panel was driven with a black display in a general home environment (about 200 Lx) using a TV, and the white-brown feeling was visually confirmed. The criteria for visual inspection were as follows: ◯ when the degree of black was good, △ when the degree of black was good, x when white browning occurred, and △ or more as acceptable.

[Statue of bokeh]
When characters were displayed on the liquid crystal TV with the polarizing plates (HKH-01) to (HKH-13) pasted, it was judged that the character blur was not observed ○, and the character blur observed was ×. . The following table shows the layer constitution of the obtained polarizing plate and the measured properties.

  As is clear from the above table, the hard coat film of the present invention is excellent in antiblocking effect, pencil hardness and curl, and the image display device provided with the hard coat film has no image blur and high quality. It turns out that it becomes an image display apparatus.

  Further, as is apparent from the above table, it can be seen that when Rz and Sm are in the following regions, both blocking resistance and image blur are particularly well-balanced. This is because when Rz and Sm are in the following regions, the particle spacing (Sm) is short when the height (Rz) of the convex portion is small, and the particle spacing (Sm) when the height (Rz) of the convex portion is large. ) Is widened, it is expected to be the most suitable region for preventing blocking while keeping the surface clear.

0.12 mm <Sm <0.8 mm
0.1 μm <Rz <1.0 μm
Rz (μm)> 1.32 × Sm (mm) −0.2
Rz (μm) <1.32 × Sm (mm) +0.1

  Further, it can be seen that when a low refractive index layer is provided on the hard coat film, the white-brown color of the screen is suppressed, and an image display device with higher quality can be obtained.

It is a schematic diagram of the hard coat film of the present invention in an embodiment having the hard coat layer of the present invention and a low refractive index layer.

Explanation of symbols

1 Support 2 Antiglare Layer 3 Low Refractive Index Layer

Claims (6)

  A hard coat film having at least one hard coat layer containing a binder and fine particles on a transparent support, wherein the average film thickness of the hard coat layer is smaller than the average particle size of the fine particles, and the average particle size of the fine particles is 3 μm or more and 15 μm or less, the average film thickness of the hard coat layer is 0.01 to 3.0 μm smaller than the average particle diameter of the fine particles, and the fine particles are 0.0001 to the total solid content forming the hard coat layer. Hard coat film containing 0.01% by mass. The hard coat film according to claim 1, wherein the number of particles per 1 mm ^{2 of the} hard coat layer is in the range of 0.1 or more and 20 or less.   The hard coat film according to claim 1 or 2, wherein an average interval (Sm) of irregularities on the surface of the hard coat layer is 0.12 mm <Sm <0.8 mm.   The hard coat film according to claim 1, wherein the 10-point average roughness (Rz) of the hard coat layer surface is 0.1 μm <Rz <1.0 μm.   The polarizing plate which has a polarizing film and a protective film on both sides of this polarizing film, Comprising: Any one of this protective film is a hard coat film of any one of Claims 1-4.   The image display apparatus which has the hard coat film of any one of Claims 1-4, or the polarizing plate of Claim 5.

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