JP2003080644A - Film having hard coat layer, method for producing the same, and product to which film having hard coat layer is applied - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a slipping agent by effectively bleeding out a slip agent blended in an ionizing radiation-curable resin composition to form a hard coat layer onto the surface of a coating film. It is an object of the present invention to eliminate the point that it was difficult to achieve both the improvement of the degree of crosslinking of the coating film. SOLUTION: The composition is constituted by using a side chain-modified or one-terminal-modified non-reactive modified silicone, and a polyfunctional monomer or / and a polyfunctional oligomer each having two or more functional groups. The coating is coated with an oxygen-impermeable material and irradiated with ionizing radiation, and the oxygen-impermeable material is peeled off and cured by irradiating with ionizing radiation from the peeled side. Could be solved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a hard coat layer having improved physical and chemical properties such as hardness of scratch resistance and stain resistance of the surface of various plastic films. The present invention relates to a film, a method for producing the film, and a display device-related product to which the film having a hard coat layer is applied.

[0002]

2. Description of the Related Art Films having improved physical and chemical properties such as scratch resistance and stain resistance, and stain resistance on the surface of various plastic films are improved in surface hardness by coating. Therefore, the term “film having a hard coat layer” or the term “film” may be simply used to refer to the term “hard coat”. When producing such a "film having a hard coat layer", a coating film is formed using a thermosetting resin or an ionizing radiation curable resin, and in the former case, the coating film is heated, In some cases, the coating film is irradiated with ionizing radiation to crosslink the film, thereby imparting necessary properties. Recently, from the viewpoint of processing speed during manufacturing, the latter method, which uses an ionizing radiation-curable resin, is often used for irradiation with ionizing radiation.

By the way, in order to improve the scratch resistance of the surface, it is effective to add a slip agent for imparting slipperiness to the surface in addition to increasing the degree of crosslinking, and the ionizing radiation curability is improved. By applying a mixture of a resin composition with a slip agent and curing by irradiating with ionizing radiation from the applied surface, the outermost surface of the applied layer is in contact with air, so the solvent volatilizes. Along with the curing of the ionizing radiation-curable resin composition and the sliding agent, the sliding agent bleeds out on the surface of the coated layer to provide the sliding property. However, in the above method, although slipperiness is imparted, since oxygen in the air inhibits the curing of the ionizing radiation curable resin composition, the crosslinking tends to be insufficient, and both the degree of crosslinking and the slipperiness are obtained. I can't be satisfied. Further, in order to impart an antiglare property to the hard coat layer, when an inorganic or organic filler is blended,
The surface tends to have a patchy distribution of these fillers.

Therefore, in the case of imparting antiglare property,
Using a concavo-convex roll having the required concavo-convex shape, a layer of an ionizing radiation-curable resin composition is provided on the surface of the concavo-convex roll, covered with a transparent plastic film, and irradiated with ionizing radiation from the transparent plastic film side to crosslink By the method, it was found that anti-glare properties can be imparted to the cured product layer without adding a filler. Upon irradiation, since the layer of the ionizing radiation curable resin composition is covered with a transparent plastic film,
Bleed-out of the slip agent is less likely to occur, and it is difficult to provide slipperiness.

[0005]

DISCLOSURE OF THE INVENTION In the present invention, the slipperiness, which has hitherto been difficult, is effectively bleeded out to the surface of the coating film by effectively bleeding out the slippery agent blended in the ionizing radiation curable resin composition. It is an object to satisfy both of the provision and the improvement of the degree of crosslinking of the coating film by irradiation with ionizing radiation at the same time.

[0006]

In the present invention, a side chain-modified or one-terminal-modified non-reactive modified silicone is used in an ionizing radiation-curable resin composition for constituting a coating film provided on a transparent substrate film. It has been possible to solve the problem by blending the above and using a polyfunctional monomer or / and a polyfunctional oligomer each having a functionality of two or more as the ionizing radiation curable compound. Further, after or simultaneously with the formation of the coating film on the transparent substrate film, after coating the coating film with an oxygen impermeable material, it is irradiated with ionizing radiation from the transparent substrate film side for curing. After that, the oxygen impermeable material and the cured product layer are peeled off, and the cured product layer is irradiated again with ionizing radiation from the side opposite to the transparent base material film side in random order, so that slipperiness is improved. It was possible to realize both the impartation of the resin and the improvement of the degree of crosslinking.

A first aspect of the present invention is a polyfunctional monomer or bifunctional polyfunctional monomer in which a side chain-modified or one-end-modified non-reactive modified silicone is blended on a transparent substrate film as a slip agent, or And a hard coat layer comprising a layer of a cured product of an ionizing radiation curable resin composition composed of a polyfunctional oligomer is laminated, on the side opposite to the transparent substrate film side of the hard coat layer, The present invention relates to a film having a hard coat layer, which has a sliding layer containing a large amount of a sliding agent.
A second invention is the first invention, wherein the non-reactive modified silicone has a molecular weight of 3,000 to 25,000,
In addition, the present invention relates to a film having a hard coat layer, which has a Si content of 20 to 45% on a mass basis. A third invention relates to the film having a hard coat layer according to the first or second invention, wherein the non-reactive modified silicone is a polyether modified silicone. A fourth invention is composed of a polyfunctional monomer or / and a polyfunctional oligomer each of which is bifunctional or more, in which a side chain-modified or one-end-modified non-reactive modified silicone is blended on a transparent substrate film. The ionizing radiation curable resin composition is applied to form an ionizing radiation curable layer, and after or simultaneously with the formation, the ionizing radiation curable layer is coated with an oxygen impermeable material, and after coating, it is transparent. By curing the ionizing radiation-curable layer by irradiating it with ionizing radiation from the side of the substrate film, a layer of a cured product of the ionizing radiation-curable resin composition is generated, and thereafter, with the oxygen-impermeable material. Peeling between the layer of the cured product and irradiating the layer of the cured product with ionizing radiation from the side opposite to the transparent substrate film side. A process for producing a film having a coating layer. A fifth invention is the hard coat according to the fourth invention, wherein the non-reactive modified silicone has a molecular weight of 3,000 to 25,000 and a Si content of 20 to 45% on a mass basis. The present invention relates to a method for producing a film having a layer. A sixth invention relates to the method for producing a film having a hard coat layer according to the fourth or fifth invention, wherein the non-reactive modified silicone is a polyether modified silicone. In a seventh aspect of the invention, a substrate having an electrode layer and a sheet on the observation side are laminated with a minute gap therebetween by the electrode layers of each facing each other and a spacer interposed therebetween, and The present invention relates to a product to which a film having a hard coat layer is applied, wherein the film having the hard coat layer according to any one of claims 1 to 3 is applied to a sheet side to form a touch panel. An eighth invention relates to a product to which a film having a hard coat layer is applied, wherein the film having the hard coat layer of any one of the first to third inventions is applied to the observation side of the display device. It is a thing. In a ninth aspect based on the eighth aspect, the display device is a liquid crystal display, and a polarizing plate formed by laminating protective layers on both sides of a polarizer is laminated on a surface of the liquid crystal display, and the polarizing plate is formed. As a protective layer on the side opposite to the liquid crystal display side, a film having a hard coat layer is laminated such that the transparent substrate film is on the liquid crystal display side. It relates to a product to which a film is applied.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The film having a hard coat layer of the present invention is basically a transparent base material film on which a hard coat layer is laminated. It has a sliding layer on the side not facing the transparent substrate film side). A primer layer may be provided between the transparent substrate film and the hard coat layer for the purpose of improving the adhesive strength between the two, and a treatment for improving the adhesiveness may be performed. The surface of the hard coat layer may have irregularities (or fine irregularities) for various purposes.

As the transparent substrate film, those having transparency and smoothness in a visual sense and free of foreign matter are preferable, and those having mechanical strength for processing and use. preferable. Further, when the heat is transmitted to the display such as when it is attached to the front surface of a display device (display), it is preferable that it has heat resistance.

Generally, preferred transparent substrate films are cellulose resin systems such as cellulose diacetate, cellulose triacetate or cellulose acetate butyrate, polyethylene terephthalate (PE).
T) and the like polyester, polyamide, polyimide, norbornene, polyether sulfone (PES), polysulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polymethyl methacrylate, polycarbonate, polyurethane, etc. It is a film of a thermoplastic resin.

As the transparent substrate film, a polyester resin film which is often used as a substrate for photographic films, and cellulose triacetate (which is also often used for photographic films because it has high transparency and no optical anisotropy). = Triacetyl cellulose, or TAC) film is usually particularly preferred. The thickness is preferably about 8 to 1000 μm, but in the case of a plate-shaped material, this range may be exceeded.

Although these thermoplastic resin films are flexible and easy to use, there is no need to bend them even during handling, and when a rigid and hard film is desired, the resin plate described above is used. Alternatively, a plate-shaped material such as a glass plate can also be used.

When an ultraviolet ray curable resin composition is used as the ionizing radiation curable resin composition for forming the hard coat layer, the transparent substrate film contains an ultraviolet ray absorbent for the purpose of preventing deterioration by ultraviolet rays. It is possible to use either those kneaded and made to be UV-absorbing or those not. However, when using a transparent substrate film kneaded with an ultraviolet absorber, when irradiated with ultraviolet rays from the transparent substrate film side, based on the characteristics of the kneaded ultraviolet absorber, it absorbs ultraviolet rays in a specific wavelength range. The transmission of ultraviolet rays in the wavelength range may be suppressed. Therefore, when the transparent substrate film is made to be UV-absorbing, the hard coat layer contains UV light containing a photopolymerization initiator capable of initiating polymerization in a wavelength range other than the wavelength range absorbed by the transparent base film. It is preferably formed using a curable resin composition. When the electron beam curable resin composition is used as the ionizing radiation curable resin composition, the above-mentioned restrictions are not imposed.

In order to improve the adhesiveness with the layer formed on the transparent substrate film, in addition to various treatments which are usually performed, that is, physical treatments such as corona discharge treatment and oxidation treatment. As described above, a coating called a anchor agent or a primer agent may be applied in advance to form the primer layer.

The hard coat layer is formed so that the outermost surface of the film having the hard coat layer of the present invention is not scratched.
In addition to improving scratch resistance, it is intended to improve various physical and chemical properties.

The scratches are firstly due to the difference in hardness from the substance causing the scratches, and in some cases, it may be composed of a composition containing a thermoplastic resin as a resin component. In general, it is more preferable that the composition containing a thermosetting resin as a resin component is cured, and a composition containing a polyurethane resin or the like as a resin component is used because it has flexibility. It is also possible to configure.

When it is desired to further improve the scratch resistance, the hard coat layer may be composed of a cured product obtained by crosslinking and curing an ionizing radiation-curable resin composition such as an acrylate system by irradiation with ionizing radiation. preferable. The hardness of the hard coat layer is preferably "H" or more in a pencil hardness test according to JIS K5400.

As the ionizing radiation curable resin composition, it is preferable to use a mixture of a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule.

Examples of prepolymers and oligomers in the ionizing radiation-curable resin composition include unsaturated polyesters such as condensation products of unsaturated dicarboxylic acids and polyhydric alcohols, polyester methacrylates, polyether methacrylates, polyol methacrylates, melamines. Methacrylates such as methacrylate, polyester acrylate,
Epoxy acrylates, urethane acrylates, polyether acrylates, polyol acrylates, acrylates such as melamine acrylate, and cationic polymerization type epoxy compounds are mentioned, and in the sense of improving the curing degree, 2
It is preferably polyfunctional or higher functional, and one type or two or more types can be used.

Examples of the monomer in the ionizing radiation curable resin composition include ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate and triethylene glycol diacrylate. Compounds, polyfunctional compounds such as dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, and / or polythiol compounds having two or more thiol groups in the molecule, for example trimethylolpropane tri Bifunctional or higher polyfunctional compounds such as thioglycolate, trimethylolpropane trithiopropylate, and pentaerythritol tetrathioglycolate are mentioned. It can be used alone or in combination.

When flexibility is required when the ionizing radiation curable resin composition is applied and cured, it is preferable to reduce the amount of the monomer or use an acrylate monomer having a small number of functional groups. When abrasion resistance, heat resistance, and solvent resistance when an ionizing radiation curable resin composition is applied and cured are required, use an acrylate monomer having three or more functional groups, such as ionizing radiation. It is possible to design a curable resin composition. Examples of those having 2 functional groups include ethylene glycol diacrylate and 1,6-hexanediol diacrylate. 3 functional groups
Examples of the above include trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

In order to adjust the physical properties such as flexibility and surface hardness when the ionizing radiation curable resin composition is applied and cured, a resin that is not cured by irradiation with ionizing radiation is added to the ionizing radiation curable resin composition. It can also be added. The following are specific examples of the resin. It is a thermoplastic resin such as polyurethane resin, cellulose resin, polyvinyl butyral resin, polyester resin, acrylic resin, polyvinyl chloride resin, or polyvinyl acetate. Above all, the addition of polyurethane resin, cellulose resin, polyvinyl butyral resin and the like is preferable from the viewpoint of improving flexibility.

When the ionizing radiation curable resin composition is an ultraviolet curable resin composition, a photopolymerization initiator or a photopolymerization accelerator is added. As the photopolymerization initiator, generally, in the case of a resin system having a radically polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether and the like are used alone or in combination. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metacelone compound, a benzoin sulfonic acid ester or the like is used alone or as a mixture as a photopolymerization initiator. .

The content of the photopolymerization initiator is 0.1 to 10 parts by mass with respect to 100 parts by mass of the ultraviolet curable composition.
Depending on the thickness of the hard coat layer, if blended too much,
The adhesion between the transparent substrate film and the hard coat layer may be reduced. It is also possible to further improve the adhesion between the transparent substrate film and the hard coat layer by blending the photopolymerization initiator in the primer layer.

When the transparent substrate film is UV-absorbing, it is preferable to use a photopolymerization initiator that can react in the wavelength range of 340 nm or more, preferably 350 nm to 450 nm. This lower limit value takes into consideration the absorption by the ultraviolet absorber which is likely to be contained in the transparent substrate film, and when a photopolymerization initiator capable of reacting at less than 340 nm is used, the reaction does not sufficiently occur. On the other hand, if the amount exceeds the upper limit, the hard coat layer may be colored because it has visible absorption to human eyes.

For example, 2,4,6- (trimethylbenzoyl) -diphenylphosphine oxide (manufactured by BASF Corporation, trade name; available as Lucillin-TPO) has a wavelength around 375 nm (350 nm to 350 nm).
(400 nm) is a photopolymerization initiator capable of initiating photopolymerization using ultraviolet rays, and is particularly preferable, and the compounding ratio described above, particularly 2 to 6 parts by weight, may be used relative to 100 parts by weight of the ultraviolet curable composition. preferable. In addition, screw (2,4,6-
(Trimethylbenzoyl) -diphenylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.,
(Trade name; available as Irgacure 819) also shows almost the same performance as the above 2,4,6- (trimethylbenzoyl) -diphenylphosphine oxide,
The reactivity is high even in the wavelength range of 0 nm to 450 nm, and unless the blending ratio is reduced, the hard coat layer 4 looks colored, and therefore, with respect to 100 parts by mass of the ultraviolet curable resin composition,
It is preferable to use the compounding ratio described above, particularly 0.1 to 5 parts by mass. Furthermore, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name; available as Irgacure 907) is a TAC film. Although it is not very effective when using as a base material,
Since it has high reactivity over a wide wavelength range, it is effective when a PET film or the like is used as a base material, and the above compounding ratio, particularly 1 to 6 with respect to 100 parts by mass of the ultraviolet curable resin composition. It is preferable to use parts by mass. Similarly,
2-Benzyl-2-dimethylamino-1- (morpholinophenyl) -butanone-1 (Ciba Specialty.
Chemicals Co., Ltd., trade name; available as Irgacure 369) has high reactivity in an even wider wavelength range, and is therefore 2-methyl-1 [4- (methylthio) phenyl].
The internal hardenability is superior to the case of using 2-morpholinopropan-1-one, and a good hard coat layer can be obtained even when the coating film thickness is large. In addition, a photopolymerization initiator that initiates photopolymerization in another wavelength range may be added and used in combination with the above particularly preferable photopolymerization initiator within a range that does not inhibit the photopolymerization initiation function. This is because the combined use brings about advantages such as an increase in curing speed.

The following organic reactive silicon compounds may be used in combination with the ionizing radiation curable composition. For example, the first is represented by the general formula R _m Si (OR ′) _n
And R'represents an alkyl group having 1 to 10 carbon atoms, and the subscript m of R and the subscript n of R'are each an integer satisfying the relationship of m + n = 4, Two
Is a silane coupling agent, 3 of the organic reactive silicon compound is an ionizing radiation curable silicon compound, and there are other compounds.

The compounds represented by the general formula R _m Si (OR ') _n , which is one of the organic reactive silicon compounds, are specifically tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra- n-propoxysilane, tetra-n-butoxysilane, tetra-s
ec-butoxysilane, tetra-tert-butoxysilane, tetrapentaethoxysilane, tetrapenta-i
so-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-te
rt-Butoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyl Examples thereof include diethoxysilane and hexyltrimethoxysilane.

Specific examples of the silane coupling agent for the organic reactive silicon compound 2 include γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ- (2-
Aminoethyl) aminopropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropylmethoxysilane, N
-Β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, aminosilane, methylmethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane , Γ-chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, methyltrichlorosilane, dimethyldichlorosilane and the like.

As the ionizing radiation-curable silicon compound 3 of the organosilicon compound which can be used in combination with the ionizing radiation-curable composition, specifically, a plurality of functional groups which react and crosslink upon irradiation with ionizing radiation, for example, polymerization. Examples of the organic silicon compound having a molecular weight of 5,000 or less having a polymerizable double bond group, and more specifically, a vinyl silane functionalized at one end thereof,
Examples thereof include vinyl functional polysilane at both ends, vinyl functional polysiloxane at both ends, vinyl functional polysiloxane at both ends, vinyl functional polysilane obtained by reacting these compounds, vinyl functional polysiloxane, and the like.

More specifically, the compounds are as follows.

[0032]

[Chemical 1]

Other organosilicon compounds that can be used in combination with the ionizing radiation-curable composition include (meth) acryl compounds such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropylmethyldimethoxysilane. Roxysilane compounds and the like can be mentioned.

In order to improve the scratch resistance of the hard coat layer, it is preferable to form a slipping layer containing a slipping agent on top of the hard coat layer in addition to improving the degree of curing. The sliding layer does not change the hardness of the hard coat layer, but the frictional force between the hard coat layer and the material that comes into contact with the hard coat is reduced, so that the abrasion resistance is apparently improved.

As the slip agent for forming the slip layer,
It is preferable to use a non-reactive modified silicone, such as polyether modified, methylstyryl modified, alkyl modified, higher fatty acid ester modified, hydrophilic special modified, higher alkoxy modified, higher fatty acid-containing, or fluorine modified. Of these, if necessary, two or more kinds may be used in combination. Here, the non-reactive modified silicone is preferred because it has no or substantially no reaction with the ionizing radiation-curable resin in the ionizing radiation-curable resin composition constituting the hard coat layer. It is considered that the compound does not bond with the ionizing radiation curable resin at the time of curing and does not hinder the bleed-out. On the other hand, the reactive modified silicone has a poor effect of improving the slipperiness even when added. It is considered that this is because bleed-out is suppressed by the reaction with the ionizing radiation-curable resin composition for forming the hard coat layer.

The non-reactive modified silicone has a molecular weight of 30.
It is preferably from 0 to 25,000 and the Si content is from 20% to 40% on a mass basis. When the molecular weight of the non-reactive modified silicone is less than 3,000, bleeding out easily occurs in the hard coat layer, but slipperiness is not sufficiently obtained, and as a result, the effect of improving scratch resistance is poor. In addition, when the molecular weight of the non-reactive modified silicone exceeds 25,000, the movement in the hard coat layer is hindered, so that slipperiness is not sufficiently obtained, and as a result, the effect of improving scratch resistance is not obtained. poor. The Si content in the non-reactive modified silicone is 2 on a mass basis.
It is preferably 0 to 45%. When the Si content in the non-reactive modified silicone is less than 20% or the Si content exceeds 45%, the effect of imparting slipperiness is poor and sufficient scratch resistance of the hard coat layer cannot be obtained. .

Among the non-reactive modified silicones,
The functional group introduced by modification is C ₂H_FourO (Ethylene
Kide) and C₃H₆O (propylene oxide,
When descending, combine the former with EO and the latter with PO
Therefore, it may be expressed as EO / PO. ) Is
However, the combined effect is particularly high. EO is crystalline at room temperature
And has good affinity with organic binders,
Has the effect of retaining the responsive modified silicone in the coating film,
O has the same effect as EO, but is more fluid than EO
Rather high flowability to non-reactive modified silicone
Is given. Therefore, the proportion of EO is better than that of PO.
It is preferable that the ratio is equal to or higher than the total ratio.

As the slip agent in the present invention, it is preferable to use a non-reactive modified silicone in which the position of the functional group introduced by the modification is a side chain or one end.

The above-mentioned non-reactive modified silicone is 0.3% in 100 parts by weight of the ionizing radiation-curable resin in the ionizing radiation-curable resin composition for forming the hard coat layer.
It is preferable to blend 2 to 2 parts by mass, and if the blending amount of the slipping agent is less than the lower limit, the effect of improving the scratch resistance due to the blending becomes poor, and if it exceeds the upper limit, curing occurs during formation of the hard coat layer. Not done enough.

The hard coat layer is coated on the transparent substrate film by a known coating method using the above composition, and after the coating, ionizing radiation is selectively irradiated.
Crosslink and cure the coating. It should be noted that, if necessary, after the hard coat layer is made into a product, an ultraviolet absorber may be blended for the purpose of preventing deterioration due to ionizing radiation, as long as it does not hinder the initiation of photopolymerization.

The thickness of the hard coat layer is preferably 0.
It is 5 to 30 μm, more preferably 2 to 15 μm. Even in the case of a film having a hard coat layer, and also when the film having a hard coat layer is further processed into an antireflection film, if the thickness of the hard coat layer is too thin, the resulting surface hardness and If the durability such as stain resistance is insufficient, and if it is too thick, the flexibility of the whole is reduced, and it takes a long time to cure, leading to a reduction in production efficiency.

By forming irregularities or fine irregularities on the surface of the hard coat layer, the surface texture or antiglare property can be imparted. In the case of an antiglare film having antiglare properties, when applied to a display, it is possible to diffuse incident light on the display surface and prevent reflection of a fluorescent lamp or the like. Further, by designing the unevenness to be minute, it is possible to mitigate the phenomenon that the brightness of a specific portion on the film becomes high and glare, which occurs between the light emitted from the inside of the display and the unevenness. Further, by further laminating an antireflection film on the surface of the hard coat layer on which fine irregularities are formed, the contrast of the image on the display is improved and the visibility of characters can be improved.

The formation of irregularities or fine irregularities can be achieved by solidifying the coating film with a patterning film having irregularities when the hard coat layer is coated and formed on the transparent substrate film, or by forming the formed coating film. Or by pressing with a molding means such as a molding roll while heating if necessary,
Alternatively, a hard coat layer may be applied and formed on a releasable base material having irregularities on the release surface to form a transfer sheet, and transfer may be performed using the transfer sheet. However, it is preferably made of metal or the like. An embossing plate or an embossing roll made of an oxygen impermeable material having a property that the ionizing radiation curable resin composition does not adhere to the hard coat layer when it is formed is used.

By the way, in general use,
It is not necessary to form the hard coat layer surface in an uneven shape,
The degree of unevenness is various, and if you want to obtain a surface with different gloss,
Even flat ones are called flat embossing. Therefore, in this specification, the unevenness is
Flatness is also included, and accordingly, the unevenness of the embossing plate and the embossing by the embossing plate also correspond to such a broadly-defined "unevenness". In the present invention,
Whether to give unevenness in a narrow sense or to form a flat or mirror surface in an extreme case, a transparent substrate while covering the coating film with an embossing plate or an embossing roll made of an oxygen impermeable material. It is preferable to irradiate ionizing radiation from the film side.

As the oxygen-impermeable material, a plate-like material having metal, plastic or the like as a surface material and appropriately lined or a roll-like material having an inner side reinforced can be used, and preferably made of a material other than a thin plastic film. To be done. The degree of unevenness when imparting unevenness to the coating film is such that the difference in height of the unevenness is preferably 0.2 to 10 μm, more preferably 3 μm.
m or less, and the pitch is preferably about 20 to 200 μm,
Ra is 0.10 to 0.40 μm and Rz is 1.10 to 6.
00 μm and Sm are preferably 10 to 70 μm, and more preferably 20 to 50 μm. All of them relate to the surface roughness defined by JIS, Ra is the arithmetic average roughness, Rz is the 10-point average roughness, and Sm is the average interval.

In the present invention, even if the transparent substrate film contains an ultraviolet absorber, as a photopolymerization initiator to be blended in the ultraviolet curable resin composition, it is preferably 340 nm or more, as described above. Is 350 nm to 450 n
By using a material capable of reacting in the wavelength range of m, it is possible to irradiate ultraviolet rays from the transparent substrate film side.
It can be adhered to an oxygen impermeable material such as a metal embossing plate or a metal embossing roll, that is, it can be irradiated with ultraviolet rays while oxygen is blocked, and the curing of the coating film can be advanced to a high degree. In addition, when a metal embossing plate or metal embossing roll is used, adhesion of the coating film does not occur, so the plastic film is not consumed as it is when irradiated with ultraviolet light after covering with a plastic film. There is an advantage that no waste of goods occurs. When the electron beam curable resin composition and the electron beam are used, since the electron beam has high permeability, the electron beam is irradiated from the transparent base material film side containing the ultraviolet absorber to cure the electron beam. The resin composition can be cured.

By the way, when the hard coat layer is cured by irradiation with ionizing radiation from the transparent substrate film side, even if the problem of the ionizing radiation absorber contained in the transparent substrate film is aside, from the transparent substrate film side. The incident ionizing radiation, when transmitted through the transparent substrate film and the coating film of the ionizing radiation-curable resin composition, gradually decreases in intensity according to the distance through which the ionizing radiation penetrates. Therefore, when the hard coat layer is viewed microscopically, curing progresses toward the transparent base film side of the hard coat layer, while the side opposite to the side of the hard coat layer on which the transparent base film is laminated. Then, the degree of curing becomes low. Such a difference in the degree of curing depends on the amount of the compounded amount when the photopolymerization initiator is used,
It is also affected by the amount of UV absorber added to increase the light stability of the product.

Therefore, primarily, irradiation with ionizing radiation is performed from the transparent substrate film side, and thereafter, irradiation with ionizing radiation is also performed from the hard coat layer side to enhance the degree of curing. . When performing irradiation from the latter hard coat layer side, it is preferable that the hard coat layer is coated with an oxygen impermeable material, but curing has already progressed by irradiation with ionizing radiation from the transparent substrate film side. Therefore, even if the coating with the oxygen impermeable material is omitted, there is practically no problem. Of course, if the irradiation from the hard coat layer side is performed in an N ₂ gas atmosphere, oxygen inhibition is eliminated and the degree of curing can be further enhanced.
Note that irradiation of ionizing radiation from both sides can be performed at the same time if it is only for increasing the degree of curing of the hard coat layer and irradiation of ionizing radiation from the hard coat layer side is possible.

When the hard coat layer is formed using the ionizing radiation-curable resin composition containing the above-mentioned slipping agent, it is first irradiated with ionizing radiation from the transparent substrate film side. By polymerizing the ionizing radiation-curable resin in the ionizing radiation-curable resin composition, the non-reactive modified silicone in the composition is gradually extruded from the portion where polymerization has occurred, and as a result, the transparent group of the hard coat layer. Bleed out to the side opposite the side with the material film.

As this kind of non-reactive modified silicone, it is usual to select one which also has an affinity in the ionizing radiation-curable resin composition. Therefore, even if the above bleed-out occurs, ionizing radiation is generated. The curable resin or its cured product and the non-reactive modified silicone do not separate with a clear boundary, and actually, the upper surface of the hard coat layer (the side laminated with the transparent substrate film) (Side opposite to)
In addition, the sliding layer containing a large amount of the non-reactive modified silicone in the cured product of the ionizing radiation curable resin is formed. In this sliding layer, the content of the non-reactive modified silicone increases as it approaches the side opposite to the side where the transparent substrate film is present, that is, a concentration gradient of the non-reactive modified silicone occurs. There is.

In the sliding layer, the content ratio of the ionizing radiation-curable resin decreases toward the upper surface side, so that the ionizing radiation from only the transparent substrate film side is difficult to completely cure. Therefore, ionizing radiation is further irradiated from the upper surface side of the hard coat layer to cure the sliding layer and, if necessary, the upper surface side of the hard coat layer. When cured from the upper surface side of the hard coat layer in this way, since a slight amount of the cured product of the ionizing radiation curable resin is present on the upper surface of the sliding layer and near the upper surface, the non-reactive modified silicone is fixed in the sliding layer. And is well retained on the hard coat layer.
Therefore, for example, when applied to the surface of a touch panel, the rate at which the non-reactive modified silicone decreases due to friction during use can be reduced. When this second irradiation of ionizing radiation is carried out, since the non-reactive silicone is present at a high concentration on the side of irradiation, that is, on the upper surface side of the hard coat layer, curing by irradiation will result in unreacted ionization. Since there is a large amount of radiation curable resin, which proceeds from the inside, bleeding out of the silicones to the surface occurs further. Therefore, by performing the second irradiation of ionizing radiation, the slipperiness of the surface is further improved.

Therefore, bleed-out of silicones,
Further, for the purpose of curing the sliding layer, two irradiations of ionizing radiation are carried out: irradiation of the ionizing radiation from the transparent substrate film side and irradiation of the ionizing radiation from the upper surface side of the hard coat layer.
These two irradiations of ionizing radiation may be performed simultaneously as described above, but more preferably, they may be sequentially performed in the order described.

The film having the hard coat layer of the present invention can be used by laminating it on various objects, and in particular, it is applied to the surface of various display devices (displays) for the purpose of preventing reflection and scratches. The effect can be exerted when applied to a touch panel which is often attached or touched by people in particular.

Examples of the display device include a CRT, a liquid crystal display, a plasma display, an eclectroluminescence display, and the like, and a film having a hard coat layer and a hard coat layer on the observation side of the hard coat layer through an adhesive. A film having a hard coat layer, for example, by laminating toward the observation side, or by utilizing what is already attached to those observation sides as a transparent substrate film and laminating a hard coat layer on the observation side. Can be applied.

When the display device is a liquid crystal display,
A polarizing plate is attached to the surface with an adhesive or the like for application. Generally, a polarizing plate is one in which a TAC film or the like is laminated as a protective layer on both sides of a polarizer made of PVA doped with iodine and stretched. The film having the hard coat layer of the present invention is a TAC film. Etc. as a base, with the hard coat layer on the outside as one protective layer of the polarizing plate, so to speak, a polarizing plate with a hard coat layer has been manufactured. When applied to a liquid crystal display so as to be on the outer side, a liquid crystal display having improved physical and chemical properties such as hardness of surface scratch resistance and stain resistance can be obtained.

The touch panel has a sheet having an electrode layer on a substrate (or a sheet) having an electrode layer on the observing side of the display device as described above, so that the respective electrode layers face each other, and They are stacked with a minute gap through a spacer. By touching (pushing), both electrode layers become conductive, so that it is possible to select and input the point indicated by the screen of the display device. Although it is possible, in this case, a film having a hard coat layer, such as via an adhesive, is laminated in front of the sheet on the most observing side, with the hard coat layer facing the observing side, or the film on the touch panel is the most A film having a hard coat layer can be applied by using the observation side sheet as a transparent substrate film and laminating a hard coat layer on the observation side. That.

[0057]

Example (Example 1) As a transparent substrate, a thickness of 100 μm
The thing which laminated | stacked the primer layer on the PET film of m was prepared. As a composition for forming a hard coat layer, DPH
A (dipentaerythritol hexaacrylate) / P
ETA (pentaerythritol triacrylate) = 3
/ 7 (mass ratio, hereinafter ratios and parts are based on mass.)
EO / PO modified dimethyl siloxane (side chain modified, Si content; 34%,
Molecular weight; 17,000) as 1 part by mass, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name; using Irgacure 184) as a photopolymerization initiator, 2 parts by mass, and 2
-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name; using Irgacure 907), 2 parts by mass, respectively The solvent was prepared.

The composition for forming a hard coat layer described above was laminated on the primer layer of the PET film described above.
By the reverse roll coating method, the applied amount is 5g /
It was applied so as to be m ² . After coating, an embossed plate having a fine uneven surface on the coated surface is overlapped so that the fine uneven surface side is in contact, and in the stacked state, 300 mJ of ultraviolet rays are irradiated from the PET film side to cure the coating film. Let
Then, the embossing plate was peeled and removed, and after the removal, ultraviolet rays of 300 mJ were irradiated from the coated surface side to obtain a film having a hard coat layer having fine scratches and high scratch resistance. The surface of the hard coat layer of the obtained product was loaded with # 0000 steel wool under a load of 2K.
It was reciprocated by applying a load of g / cm ² , but it was not scratched even after rubbing 100 times, and the scratch resistance was good.

Example 2 A PET film as a base material was applied to a TAC film having a thickness of 80 μm, EO / PO-modified dimethylsiloxane was added, and the same parts by weight of EO-modified dimethylsiloxane (one-end modified, Si content: 45%, Molecular weight: 170
00), among the photopolymerization initiators, 2-methyl-1 [4-
(Methylthio) phenyl] -2-morpholinopropan-1-one in the same mass part by weight of 2,4,6- (trimethylbenzoyl) -diphenylphosphine oxide (manufactured by BASF Corporation, trade name; Lucillin-TPO)
use. ), Except that each was changed, and the same results were obtained as in Example 1.

COMPARATIVE EXAMPLE 1 Example 1 was repeated except that the EO / PO-modified dimethyl siloxane was changed to the same parts by weight of EO-modified dimethyl siloxane (side chain modification, Si content: 54%, molecular weight: 46000). A film having a hard coat layer was obtained in the same manner. To this one, # 0000
When the steel wool was used to reciprocate under a load of ² kg / cm ² , it was scratched at the time of rubbing 50 reciprocations.

(Comparative Example 2) EO / PO-modified dimethylsiloxane was mixed with the same parts by weight of EO-modified dimethylsiloxane (modified at both ends, Si content: 36%, molecular weight: 16000).
A film having a hard coat layer was obtained in the same manner as in Example 2 except that the above was changed to. To this one, # 000
When steel wool of 0 was used and a load of 2 kg / cm ² was applied for reciprocation, scratches were formed at the time of rubbing 30 reciprocations.

[0062]

According to the first aspect of the present invention, the hard coat layer and the sliding layer are ionizing radiation-curable resin compositions composed of a polyfunctional component having two or more functional groups, and a side chain or one end modified non-reactive. It is formed from a cured product containing modified silicone, and since the sliding layer is formed as a portion with a high content of a sliding agent, it is a hard coat with excellent scratch resistance that satisfies both the degree of crosslinking and the sliding property. A film having layers can be provided. According to the invention of claim 2, in addition to the effect of the invention of claim 1, the molecular weight of the non-reactive modified silicone,
Since the content of Si and the content of Si are regulated, the slipping agent is likely to bleed out, and moreover, the slipping property is easily exhibited, so that it is possible to provide a film having a hard coat layer with further excellent scratch resistance. According to the invention of claim 3, in addition to the effect of the invention of claim 1 or 2, since the non-reactive modified silicone is limited to the polyether modified silicone, a hard coat layer having further excellent scratch resistance can be obtained. A film having the same can be provided. Claim 4
According to the invention, a transparent substrate film is prepared by using a composition in which an ionizing radiation curable resin composition comprising a polyfunctional component having two or more functional groups and a side chain or one end modified non-reactive modified silicone are blended. Composition, oxygen-impermeable material is irradiated with ionizing radiation from the transparent substrate film side in a laminated state, after that, the oxygen-impermeable material is peeled off, from the peeled side, ionizing radiation is again irradiated. As compared with the case of irradiating with ionizing radiation from only one side, the bleed-out of the non-reactive modified silicone progresses, so that the slipperiness is further exerted, and the side of the hard coat layer opposite to the transparent substrate film side. It is possible to provide a method for producing a film having a hard coat layer capable of sufficiently crosslinking the ionizing radiation-curable resin composition in the vicinity of noodles. According to the invention of claim 5, in addition to the effect of the invention of claim 4, since the molecular weight of the non-reactive modified silicone to be used and the Si content are specified, the slip agent that exhibits a high slip property is bleed out. As a result, it is possible to provide a method for producing a film having a hard coat layer that can reliably proceed. According to the invention of claim 6, in addition to the effect of the invention of claim 4 or 5, since the non-reactive modified silicone used is limited to the polyether modified silicone, the slipperiness exhibited is higher and the abrasion resistance is higher. It is possible to provide a method for producing a film having a hard coat layer capable of further improving the properties. According to the invention of claim 7, since the film having the hard coat layer having the effect of any one of claims 1 to 3 is applied to the observation side, even when repeatedly touched during use, Since the surface has excellent scratch resistance, it is possible to provide a product to which a film having a hard coat layer is applied, which can be used as a touch panel that is not easily scratched. According to the invention of claim 8, since the film having the hard coat layer having the effect of any one of claims 1 to 3 is applied to the viewing side of the display device, it is repeatedly touched during use. However, since the surface has excellent scratch resistance, it is possible to provide a product to which a film having a hard coat layer is applied, which can be used as a touch panel that is not easily scratched. According to the invention of claim 9, in addition to the effect of the invention of claim 8, the polarizing plate applied to the liquid crystal display and the film having the hard coat layer can also serve as the polarizing plate. It is possible to provide a product to which a film having a hard coat layer is applied, which does not require application of another film having a hard coat layer.

Front page continuation (51) Int.Cl. ⁷ Identification symbol FI theme code (reference) C08F 290/00 C08F 290/00 4J026 G02B 1/10 G02F 1/1335 510 4J027 1/11 G09F 9/00 302 5G435 G02F 1 / 1335 510 313 G09F 9/00 302 G02B 1/10 Z 313 A F term (reference) 2H091 FA08X FA08Z FA37X FA50X FB02 FB06 FC25 GA16 LA02 2K009 AA12 AA15 BB28 CC12 CC42 CC47 DD02 DD05 CA34 DB02 CA34 DB02 DB38 DB40 DB43 DB48 DB50 DB53 DC24 EA07 EA10 EA21 EB22 EB35 EB37 EB38 EB46 EB52 EB56 EC07 EC54 4F100 AK01A AK42 AK52B AK52C BA03 BA07 BA10B BA10C BA27 CA19B CA19C CC00B CC00C EJ53B EJ53C EJ91B JA07B JB14B JB14C JK12 JL06 JN01A YY00B 4J011 PA99 PB15 PB18 PB19 PB33 PB40 PC02 PC08 4J026 AB44 BA28 BA29 BA30 BA50 BB03 BB08 CA01 DB06 DB26 DB36 FA05 GA08 4J027 AB02 AB03 AC06 AE01 AG01 BA19 BA20 BA21 BA24 BA25 BA26 BA27 BA28 CA10 CB10 CC05 CD00 5G435 AA08 AA17 BB12 FF05 HH02 KK07

Claims (9)

[Claims] 1. A slip agent on a transparent substrate film,
A cured product of an ionizing radiation curable resin composition containing a polyfunctional monomer or / and a polyfunctional oligomer, each of which is bifunctional or more, and which is blended with a side chain-modified or one-end-modified non-reactive modified silicone. A hard coat layer consisting of layers is laminated, and a hard coat layer characterized by having a sliding layer having a large content of the sliding agent on the side opposite to the transparent substrate film side of the hard coat layer. Film with. 2. The non-reactive modified silicone has a molecular weight of 3,000 to 25,000 and a Si content of 20 to 45% on a mass basis.
A film having the described hard coat layer. 3. The non-reactive modified silicone is a polyether modified silicone.
Alternatively, a film having the hard coat layer according to 2. 4. A transparent substrate film on which side chain-modified or one-end-modified non-reactive modified silicone is blended.
An ionizing radiation curable layer is formed by applying an ionizing radiation curable resin composition composed of a polyfunctional monomer or / and a polyfunctional oligomer each of which is bifunctional or more,
After or simultaneously with formation, by coating the ionizing radiation-curable layer with an oxygen-impermeable material, after coating, by irradiating ionizing radiation from the transparent substrate film side to cure the ionizing radiation-curable layer. , Generating a layer of a cured product of the ionizing radiation curable resin composition, and then peeling between the oxygen impermeable material and the layer of the cured product,
And a method for producing a film having a hard coat layer, which comprises irradiating the layer of the cured product with ionizing radiation from the side opposite to the side of the transparent substrate film. 5. The non-reactive modified silicone has a molecular weight of 3,000 to 25,000 and a Si content of 20 to 45% on a mass basis.
A method for producing a film having a hard coat layer as described above. 6. The non-reactive modified silicone is a polyether modified silicone.
Or a method for producing a film having a hard coat layer according to item 5. 7. A substrate having an electrode layer and a sheet on the observation side are laminated in such a manner that the electrode layers of each face each other, and a minute gap is formed by interposing a spacer, and Claims 1 to 3 on the side
A product to which a film having a hard coat layer is applied, wherein the film having a hard coat layer according to any one of the above is applied to form a touch panel. 8. A product to which a film having a hard coat layer is applied, wherein the film having the hard coat layer according to any one of claims 1 to 3 is applied to an observation side of a display device. 9. The display device is a liquid crystal display, and a polarizing plate comprising a protective layer laminated on both surfaces of a polarizer is laminated on the surface of the liquid crystal display, and the polarizing plate is on the liquid crystal display side. As a protective layer on the other side,
The product to which the film having a hard coat layer is applied, wherein the film having a hard coat layer is laminated so that the transparent substrate film is on the liquid crystal display side.