TWI494685B - Photosensitive resin composition, antireflective film and antireflective hard coat film using the same - Google Patents

Description

Photosensitive resin composition, antireflection film using the same, and antireflection hard coat film

The present invention relates to a photosensitive resin composition, an antireflection film having a cured film thereof, and an antireflection hard coat film. More specifically, it is excellent in scratch resistance, abrasion resistance, stain resistance, and transparency, and is used in an antireflection film and an antireflection hard coat film at a low refractive index. A resin composition, an antireflection film having a cured film thereof, and an antireflection hard coat film.

At present, the plastics are widely used in various industries including the automotive industry, the home appliance industry, and the electrical and electronics industry. The reason why such a large amount of plastic is used is that it is excellent in workability and transparency, and is lightweight, inexpensive, and excellent in optical characteristics. However, plastic has the following disadvantages: it is softer than glass, and the surface is prone to damage. In order to improve these disadvantages, a means for applying a hard coat agent to the surface is generally employed. As the hard coat agent, a thermosetting type hard coat agent such as a polyfluorene-based paint, an acrylic paint, or a melamine paint is used. Among them, a polyoxymethylene-based hard coat agent is used in a large amount because of its high hardness and excellent quality. However, the polyoxygenated hard coat agent is not suitable for the hard coat layer provided on the continuously processed film because the hardening time is long and expensive.

In recent years, a photosensitive acrylic hard coat agent has been developed and used (see Patent Document 1). Since the photosensitive hard coat agent is immediately hardened by irradiation with an active energy ray such as ultraviolet rays to form a hard film, the processing speed is fast, and the hardness and scratch resistance are excellent, and the total cost becomes It is cheap, so it is now the mainstream in the field of hard coating. It is especially suitable for continuous processing of films such as polyester. As the film of plastic, there are polyester film, polyacrylate film, acrylic film, polycarbonate film, vinyl chloride film, triethylene cellulose film, polyether ruthenium film, cycloolefin polymer film, etc., polyester film The triethylene fluorene cellulose film is most widely used due to various excellent properties. Polyester film is widely used in glass anti-scatter film, or automotive light-shielding film, whiteboard surface film, system cabinet surface anti-fouling film, widely used in electronic materials for touch panels, CRT flat-panel TVs, plasma displays, etc. Sex film. The triacetonitrile cellulose film is used as a polarizing plate which is an essential material for a liquid crystal display. As described above, these are all coated with a hard coat agent so that the surface thereof is not damaged.

Further, in recent years, a display body such as a PDP (plasma display panel), an LCD (liquid crystal panel), or a CRT (Brown Tube) provided with a film coated with a hard coat agent has an unclear display image due to reflection. The eye is prone to fatigue, so it is necessary to perform a hard coat treatment with anti-reflection ability on the surface depending on the application. The method of preventing surface reflection is a method in which an inorganic filler or an organic filler is dispersed in a photosensitive resin composition for a hard coat layer, and a film is formed on the surface to prevent irregularities (AG: anti-glare treatment); Providing a layer having a plurality of layers having different refractive indices on a film, preventing reflection by light interference caused by a difference in refractive index (AR: anti-reflection treatment); or a method of AG/AR processing combining the above two methods ( Refer to Patent Document 2).

Here, the low-refractive-index layer used for the AR treatment is a thermosetting compound in which a decane compound is condensed by a sol-gel method (see Patent Document 3). However, there are problems in that the curing is time-consuming and the productivity is poor. Or the hard coat layer is cracked due to shrinkage by heating.

On the other hand, an active energy ray-curable resin using a (meth) acrylate having a fluorine atom (see Patent Document 4) has been developed, but there is a problem that the scratch resistance is insufficient or the chemical resistance is insufficient.

Based on the above-mentioned problems such as productivity or cracking due to heating, the industry has sought to use a low refractive index hard coat layer having an active energy ray-curable resin. However, the actual condition of the active energy ray-curable resin is that the scratch resistance is insufficient or the chemical resistance is insufficient.

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-48934

[Patent Document 2] Japanese Patent Laid-Open No. Hei 9-145903

[Patent Document 3] Japanese Patent No. 3776978

[Patent Document 4] Japanese Patent No. 3724144

An object of the present invention is to provide an easy-to-harden, high-hardness, scratch-resistant, abrasion-resistant, chemical-resistant, marker-scraping or fingerprint-scratching property such as stain resistance and transparency. A photosensitive resin composition of a low refractive index layer of a reflective film, an antireflection film using the same, and an antireflection hard coat film.

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found a photosensitive resin composition containing a specific compound to complete the present invention.

That is, the present invention relates to the following:

(1) A photosensitive resin composition comprising: a polyfunctional (meth) acrylate (A) having at least three (meth) acrylonitrile groups in a molecule, and an average particle diameter of from 1 to 200 nm; a colloidal cerium oxide (B) having a nanoporous structure, a polyoxy oxyalkylene (C) having a (meth) acrylonitrile group, and a photoradical polymerization initiator (D);

(2) The photosensitive resin composition according to the above (1), wherein the polyoxyalkylene (C) having a (meth)acryl fluorenyl group is a compound having 1 to 8 (meth)acryl fluorenyl groups in the molecule;

(3) The photosensitive resin composition according to (1) or (2) above, further comprising a diluent (E);

(4) An antireflection film which is disposed on a base film, and the hardened layer of the photosensitive resin composition according to any one of the above (1) to (3) is disposed as a low refractive index layer on the outermost layer;

(5) An antireflection hard coat film having a hard coat layer of a hard coat agent and a hardened layer of the photosensitive resin composition according to any one of the above (1) to (3). ;

(6) The antireflection hard coat film according to (5) above, wherein the hard coat agent contains a polyfunctional (meth) acrylate (A) having at least three (meth) acrylonitrile groups in the molecule, a photosensitive resin composition having a metal oxide (F) having an average particle diameter of 1 to 200 nm and a photoradical polymerization initiator (D);

(7) The antireflection hard coat film according to (6) above, wherein the metal oxide (F) having an average particle diameter of from 1 to 200 nm is doped with tin oxide of phosphorus.

According to the present invention, it is possible to provide a photosensitive resin composition which is easily hardened by an active energy ray and which has high hardness, scratch resistance, abrasion resistance, chemical resistance, transparency, mark wiping property or fingerprint It is excellent in stain resistance and the like, and can be used in the case of an antireflection film or an antireflection hard coat film to form a low refractive index layer having a low reflectance, and contains a specific compound.

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition of the present invention contains a polyfunctional (meth)acrylate (A) having at least three (meth)acrylonium groups in the molecule, and a nanoparticle having an average particle diameter of from 1 to 200 nm. A colloidal cerium oxide (B) having a porous structure, a polyoxy siloxane (C) having a (meth) acrylonitrile group, and a photoradical polymerization initiator (D).

As the polyfunctional (meth) acrylate (A) having at least three (meth) acrylonitrile groups in the molecule, it is preferably a polyfunctional group having 3 to 15 (meth) acryl fluorenyl groups in the molecule ( Examples of the methyl acrylate include polyfunctional urethane (meth) acrylates having a reaction of a polyfunctional (meth) acrylate compound having a hydroxyl group and a polyisocyanate compound, and trimethylolpropane. Tris(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) a polyester acrylate such as tetrakis (meth) acrylate, dipentaerythritol hexa (meth) acrylate or tripentaerythritol octa (meth) acrylate, or tris(propylene methoxyethyl) isocyanurate. Further, these may be used singly or in combination of two or more.

Examples of the polyfunctional (meth) acrylate compound having a hydroxyl group include pentaerythritol tri(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol. Pentaerythritols such as tris(meth)acrylate, dipentaerythritol di(meth)acrylate, methylol groups such as trimethylolpropane di(meth)acrylate, bisphenol A bis(meth)acrylate Epoxy (meth) acrylates such as esters. Among them, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are preferable. These polyfunctional (meth) acrylate compounds having a hydroxyl group may be used singly or in combination of two or more.

The polyisocyanate compound may, for example, be a polyisocyanate compound having a basic structure of a chain saturated hydrocarbon, a cyclic saturated hydrocarbon (alicyclic) or an aromatic hydrocarbon. Examples of such a polyisocyanate compound include 1,4-butane diisocyanate, 1,6-hexane diisocyanate, and 2,2,4-trimethyl-1 diisocyanate. , chain-saturated hydrocarbon polyisocyanate such as 6-hexane diester, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylene bis(4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenation Cyclic saturated hydrocarbon (alicyclic) polyisocyanate such as toluene diisocyanate or hydrogenated toluene diisocyanate, 2,4-toluene diisocyanate, 1,3-xylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl An aromatic polyisocyanate such as benzyl-4,4'-diphenyl diisocyanate, 6-isopropyl-1,3-benzene diisocyanate or 1,5-naphthalene diisocyanate. Preferable examples thereof include toluene diisocyanate, isophorone diisocyanate, and 1,6-hexane diisocyanate. These polyisocyanate compounds may be used singly or in combination of two or more.

The polyfunctional urethane (meth) acrylate compound can be obtained by reacting the above polyfunctional (meth) acrylate compound having a hydroxyl group with the above polyisocyanate compound. The isocyanate group equivalent of the polyisocyanate compound can be usually used in the range of 0.1 to 50 equivalents, preferably 0.1 to 10 equivalents, per equivalent of the hydroxyl group in the polyfunctional (meth) acrylate compound.

The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C.

The end point of the reaction was calculated by reacting the residual isocyanate with excess n-butylamine and back-counting the unreacted n-butylamine with 1 N hydrochloric acid to calculate the amount of residual isocyanate, and the polyisocyanate compound was 0.5% by weight. The following timing is set as the reaction end point.

In order to shorten the reaction time, a catalyst may also be added. As the catalyst, any of an alkaline catalyst or an acidic catalyst can be used. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine, and phosphines such as ammonia, tributylphosphine or triphenylphosphine. Further, examples of the acidic catalyst include metal alkoxides such as copper naphthenate, cobalt naphthenate, zinc naphthenate, aluminum tributoxide, trititanium tetrabutoxide, and zirconium tetrabutoxide, and aluminum chloride. Such as a Lewis acid, a tin compound such as 2-ethylhexyltin, octyltin trilaurate, dibutyltin dilaurate or octyltin diacetate. The amount of the catalyst added is usually 0.1% by weight or more and 1% by weight or less based on 100% by weight of the polyisocyanate.

Further, in the reaction, in order to prevent polymerization in the reaction, it is preferred to use a polymerization inhibitor (for example, p-methoxyphenol, hydroquinone, methyl hydroquinone, phenothiazine, etc.), the polymerization inhibitor The amount used is 0.01% by weight or more and 1% by weight or less, preferably 0.05% by weight or more and 0.5% by weight or less based on the reaction mixture.

In the photosensitive resin composition of the present invention, the content of the component (A) is usually from 5 to 90% by weight, preferably from 5 to 90% by weight, based on 100% by weight of the solid content of the photosensitive resin composition. 10 to 70% by weight. In the present invention, the solid component means all the remaining components of the composition excluding the diluent and the solvent in the case where the composition contains a diluent or a solvent.

The colloidal cerium oxide (B) having a nanoporous structure having an average particle diameter of 1 to 200 nm contained in the photosensitive resin composition of the present invention includes porous cerium oxide and hollow cerium oxide. In general, the refractive index n of the cerium oxide particles is about 1.45. On the other hand, the refractive index n of the porous cerium oxide and the hollow cerium oxide having air having a refractive index n=1 therein is 1.2 to 1.45. Thereby, a layer having a low refractive index can be preferably formed from the photosensitive resin composition of the present invention.

The colloidal cerium oxide (B) has a colloidal solution obtained by dispersing colloidal cerium oxide in a solvent, or a colloidal cerium oxide containing no fine powder of a dispersing solvent. Examples of the colloidal solution in which the colloidal cerium oxide is dispersed in a solvent include an ELCOM series manufactured by Catalyst Chemicals Co., Ltd., and a Thrulya series.

As a dispersion solvent of the colloidal solution in which the colloidal cerium oxide is dispersed in a solvent, for example, an alcohol such as water, methanol, ethanol, isopropanol or n-butanol, ethylene glycol, ethylene glycol monoethyl ether or propylene glycol can be used. Polyols such as monomethyl ether and propylene glycol monomethyl ether acetate and derivatives thereof, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and dimethyl acetamide, ethyl acetate And esters such as butyl acetate, non-polar solvents such as toluene and xylene, 2-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. (Meth) acrylates, or other general organic solvents. The amount of the dispersion solvent is usually from 100 to 900% by weight based on 100% by weight of the colloidal cerium oxide.

The average particle diameter in the present invention means the smallest particle diameter of the particles when the aggregation is destroyed, and can be measured by a BET method (specific surface area method), a dynamic light scattering method, an electron microscope observation or the like. As the colloidal cerium oxide (B), it is necessary to use an average particle diameter of 1 to 200 nm as measured by the above-mentioned methods, preferably an average particle diameter of 1 to 100 nm, more preferably an average. The particle size is 1~80 nm.

In the photosensitive resin composition of the present invention, when the solid content of the photosensitive resin composition is 100% by weight, the content of the component (B) is usually 5 to 90% by weight, preferably 10%. 80% by weight, more preferably 20 to 70% by weight.

Further, the surface of the colloidal cerium oxide may be surface-treated with a decane coupling agent or the like to improve the dispersibility.

The surface treatment method can be carried out by a known method, and there are a dry method and a wet method. The dry method is a method of treating a cerium oxide powder, and is a method of uniformly dispersing a stock solution or a solution of a decane coupling agent in a cerium oxide powder which is stirred at a high speed by a stirrer. The wet method is a method in which a decane coupling agent is added to a slurry obtained by dispersing cerium oxide in a solvent or the like and stirred. Any method can be used in the present invention. The amount (g) of the decane coupling agent is determined by the specific surface area (m ² /g) of the cerium oxide (g) × cerium oxide / the minimum coverage area (m ² /g) of the decane coupling agent. The amount below can be.

The polyoxyalkylene (C) having a (meth)acryl fluorenyl group contained in the photosensitive resin composition of the present invention may also be called polyoxy oxyacrylate, organically modified polyfluorene oxide, or organic modified polycondensation. Examples of the decane, the reaction-bonded organically modified polyoxy acrylate, and the like, for example, organic modification of one part of the linear dimethyl methoxy oxane by an alkyl group or a polyether group, etc. The (meth) acrylate group is imparted to the end of the plastid. By increasing the length of the main chain of the decane, it is possible to impart smoothness, mold release property, blocking resistance, fingerprint resistance, mark wiping property, fingerprint wiping property and the like to the surface. Moreover, by improving the organic reforming ratio, compatibility, recoatability (recoatability), and printability can be improved.

Preferably, a compound having a (meth) acrylonitrile group introduced into the end of the organic reforming unit is introduced, and a (meth) acrylonitrile group is introduced to make a polymerization reaction possible, thereby reducing the transfer property of the polyoxy siloxane to the interface. It is also possible to reduce the transfer to the back side of the film during the production and roll, and to improve the chemical resistance (alkaline solution, organic solvent, etc.).

Commercially available products can also be used as the polyoxyalkylene (C) having a (meth) acrylonitrile group, and examples thereof include BYK-UV3500 and BYK-UV3570 (all manufactured by BYK Chemie Co., Ltd.), and TEGO Rad 2100. , 2200N, 2250, 2500, 2600, 2700 (all manufactured by Degussa), X-22-2445, X-22-2455, X-22-2457, X-22-2458, X-22-2459, X- 22-1602, X-22-1603, X-22-1615, X-22-1616, X-22-1618, X-22-1619, X-22-2404, X-22-2474, X-22- 174DX, X-22-8201, X-22-2426, X-22-164A, X-22-164C (both manufactured by Shin-Etsu Chemical Co., Ltd.).

Further, the component (C) may be a fluorine atom.

The component (C) preferably has 1 to 8 (meth) acrylonitrile groups in the molecule, and the number of (meth) acrylonitrile groups is preferably 2 to 6.

In the photosensitive resin composition of the present invention, when the solid content of the photosensitive resin composition is 100% by weight, the content of the component (C) is usually 0.1 to 50% by weight, preferably 1 ~20% by weight.

Examples of the photoradical polymerization initiator (D) contained in the photosensitive resin composition of the present invention include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; Ketone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxy Acetophenones such as acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one; - anthracene such as ethyl hydrazine, 2-tert-butyl fluorene, 2-chloroindole, 2-pentyl hydrazine; 2,4-diethyl thia fluorenone, 2-isopropyl sulphide Thiolone such as ketone or 2-chlorothiazolone; ketals such as acetophenone dimethyl ketal and benzoin dimethyl ketal; benzophenone and 4-benzhydrazide Benzophenones such as benzyl-4'-methyldiphenyl sulfide and 4,4'-bis(methylamino)benzophenone; 2,4,6-trimethylbenzhydryldiphenyl Phosphine oxide such as phosphine oxide or bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide. Further, Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) and Irgacure 907 (2-methyl-1-[4-(methylthio)phenyl) manufactured by Ciba Specialty Chemicals Co., Ltd. can be easily purchased from the market. -2-(4-morpholinyl)propan-1-one), Lucirin TPO (2,4,6-trimethylbenzylidenediphenylphosphine oxide) manufactured by BASF Corporation, and the like. Further, these may be used singly or in combination of two or more.

In the photosensitive resin composition of the present invention, when the solid content of the photosensitive resin composition is 100% by weight, the content of the component (D) is usually 0.1 to 30% by weight, preferably 1 to 1%. 15% by weight.

Further, a sensitizer may be used in combination with the photosensitive resin composition of the present invention as needed. As the sensitizer which can be used, for example, ruthenium, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 2-ethyl-9 can be mentioned. , 10-dimethoxy hydrazine, 2-ethyl-9,10-diethoxy hydrazine, 2-ethyl-9,10-dipropoxy fluorene, 2-ethyl-9,10-di ( Methoxyethoxy) ruthenium, osmium, iridium, osmium, 4'-nitrobenzyl-9,10-dimethoxyindole-2-sulfonate, 4'-nitrobenzyl-9,10 -diethoxyanthracene-2-sulfonate, 4'-nitrobenzyl-9,10-dipropoxyfluorene-2-sulfonate, etc., in terms of solubility and phase with photosensitive resin composition In terms of solubility, it is particularly preferably 2-ethyl-9,10-bis(methoxyethoxy)anthracene.

When the sensitizer is used, the amount thereof is from 1 to 200% by weight, preferably from 5 to 150% by weight, based on 100% by weight of the photoradical polymerization initiator (D).

A diluent (E) can also be used in the photosensitive resin composition of the present invention. Examples of the diluent (E) include γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptanolactone, α-ethinyl-γ-butyrolactone, and s- a lactone such as caprolactone; dioxane, 1,2-dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, Ethylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether and other ethers; ethylene carbonate, propylene carbonate and other carbonates ; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone; phenols such as phenol, cresol, xylenol; ethyl acetate, butyl acetate, ethyl lactate, B Base cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, etc.; toluene, xylene, diethylbenzene Hydrocarbons such as cyclohexane; halogenated hydrocarbons such as trichloroethane, tetrachloroethane, and monochlorobenzene; petroleum solvents such as petroleum ether and petroleum spirit; 2,2,3,3-tetrafluorocarbon Fluorine alcohols such as propanol, perfluorobutyl methyl ether, all Butyl ether and the like hydrofluorocarbon ethers. These may be used singly or in combination of two or more.

In the photosensitive resin composition of the present invention, the content of the component (E) is from 0 to 99% by weight in the photosensitive resin composition of the invention.

Further, in the photosensitive resin composition of the present invention, a leveling agent, an ultraviolet absorber, a photostabilizer, an antifoaming agent, or the like may be added as needed, and the functionality for each purpose is imparted.

Examples of the leveling agent include a fluorine-based compound, a polyfluorene-based compound, and an acrylic compound; and examples of the ultraviolet absorber include a benzotriazole-based compound, a benzophenone-based compound, and a triazine-based compound. Examples of the photostabilizer include a hindered amine compound and a benzoate compound.

The photosensitive resin composition of the present invention can be obtained by mixing the above (A) component, (B) component, (C) component, (D) component, and optionally (E) component and other components in an arbitrary order.

The photosensitive resin composition of the present invention thus obtained is stable over time.

The antireflection film of the present invention can be obtained by providing a hardened layer of the above photosensitive resin composition on a base film (base film). The film thickness after drying on the substrate film is 0.05 to 0.5 μm, preferably 0.05 to 0.3 μm (preferably, the wavelength showing the minimum value of the reflectance is 500 to 700 nm, preferably 520 to 650 nm. In the method of setting the film thickness, the photosensitive resin composition of the present invention is applied, and after drying, the active energy ray is irradiated to form a cured film.

Further, a printed layer, a tackifying coating for improving adhesion, and a refractive index higher than the base film may be provided between the base film (base film) and the cured layer of the photosensitive resin composition of the present invention. A layer of a high refractive index layer (base film).

When the high refractive index layer is provided, the film thickness after drying is 0.05 to 5 μm, preferably 0.05 to 3 μm (preferably, the wavelength at which the maximum value is exhibited by the reflectance is 500 to 700 nm, preferably 520. The high refractive index coating agent is applied in such a manner that the film thickness is set to 650 nm, and after drying, the active energy ray is irradiated to form a hardened film.

The antireflection hard coat film of the present invention can be obtained by sequentially providing a hard coat layer and a photosensitive resin composition layer of the present invention on a base film (base film). First, a hard coat agent is applied to the base film so that the film thickness after drying is 1 to 30 μm, preferably 3 to 20 μm, and after drying, the active energy ray is irradiated to form a cured film. Then, the film thickness after drying is 0.05 to 0.5 μm, preferably 0.05 to 0.3 μm (preferably, the wavelength showing the minimum value of the reflectance becomes 500 to 700 nm, depending on the formed hard coat layer, The photosensitive resin composition of the present invention is applied to a film thickness of 520 to 650 nm, and is dried, and then irradiated with an active energy ray to form a cured film.

Further, a high refractive index layer having a refractive index higher than that of the hard coat layer may be provided between the hard coat layer and the hardened layer of the photosensitive resin composition of the present invention. In this case, the film thickness after drying is 0.05 to 5 μm, preferably 0.05 to 3 μm (preferably, the wavelength at which the reflectance shows the maximum value is 500 to 700 nm, preferably 520 to 650 nm). The film thickness is coated with a high refractive index coating agent, and after drying, the active energy ray is irradiated to form a hardened film.

Examples of the base film include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triethylcellulose, polyether oxime, and cycloolefin polymer. The film may also be a sheet having a certain thickness. The film to be used may also be a surface treated person such as a colored person or an easy-to-adhere layer.

As a coating method of the above-mentioned photosensitive resin composition, for example, bar coating, wire bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, reverse Micro gravure coating, die coating, vacuum die coating, dip coating, spin coating, and the like.

Examples of the active energy ray to be irradiated for curing include ultraviolet rays, electron beams, and the like. In the case of curing by ultraviolet light, an ultraviolet irradiation device having a xenon lamp, a high pressure mercury lamp, a metal halide lamp or the like is used as the light source, and the amount of light, the arrangement of the light source, and the like are adjusted as needed. In the case of using a high-pressure mercury lamp, it is preferable to use a lamp having an irradiation intensity of 80 to 240 W/cm and hardening at a conveying speed of 5 to 60 m/min.

Further, it is more preferable to perform hardening by irradiating an active energy ray in an environment substituted with an inert gas. The oxygen concentration is preferably 1% by volume or less, more preferably 0.5% by volume or less. As the inert gas, nitrogen gas is preferably used.

As the hard coat agent used for the first layer of the antireflection hard coat film of the present invention, a commercially available hard coat agent may be used as it is, or three or more (meth) acrylonitrile groups may be used as described above. A photosensitive resin composition of a polyfunctional (meth) acrylate (A) and a photoradical polymerization initiator (D), optionally a diluent (E) or other additives.

Further, for the purpose of increasing the refractive index of the hard coat layer or imparting antistatic properties to the hard coat layer, it is preferred to use a metal oxide (F) having an average particle diameter of 1 to 200 nm. Examples of the metal oxide (F) include metal oxides having an increased refractive index, such as titanium oxide, zirconium oxide, zinc oxide, tin oxide, iron oxide, indium tin oxide (ITO), antimony doped tin oxide (ATO), and the like. Zinc citrate, aluminum-doped zinc oxide, gallium-doped zinc oxide, tin-doped zinc citrate, phosphorus-doped tin oxide, etc.; among them, metal oxides which impart antistatic properties, namely tin oxide, indium tin oxide (ITO), Antimony-doped tin oxide (ATO), zinc antimonate, aluminum-doped zinc oxide, phosphorus-doped tin oxide, etc., in terms of price, stability, dispersibility, etc., especially for zinc phthalate, phosphorus-doped tin oxide; transparent From the viewpoint of sex, it is more preferable to dope with phosphorus tin oxide.

These may be obtained in the form of a fine powder or a dispersion dispersed in an organic solvent. ([0052] reciprocal L1)

Examples of the organic solvent which can be used in the dispersion liquid include alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether; methyl ethyl ketone; A ketone such as methyl isobutyl ketone or cyclohexanone; an ester such as ethyl acetate or butyl acetate; or a nonpolar solvent such as toluene or xylene. The amount of the organic solvent is usually 70 to 900% by weight based on 100% by weight of the metal oxide.

In addition, the average particle diameter refers to the minimum particle diameter of the particles when the aggregation is destroyed, and the average particle diameter of the metal oxide (F) can be measured by a BET method, a dynamic light scattering method, an electron microscope observation or the like.

In the case of the hard coat agent, when the solid content of the hard coat agent is 100% by weight, the content of the component (F) is usually 5 to 90% by weight, preferably 10 to 80% by weight.

Further, colloidal cerium oxide (G) having an average particle diameter of 1 nm or more and 200 nm or less can be added for the purpose of improving the hardness of the hard coat layer. The colloidal cerium oxide (G) having an average particle diameter of 1 nm or more and 200 nm or less can be used as a colloidal solution obtained by dispersing colloidal cerium oxide in a solvent or a colloidal solution of a micropowder containing no dispersing solvent. Yttrium oxide.

As the dispersion solvent of the colloidal cerium oxide (G), for example, alcohols such as water, methanol, ethanol, isopropanol, n-butanol, and diacetone alcohol, and polyhydric alcohols such as ethylene glycol and derivatives thereof can be used. Ketones such as ethyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate and n-butyl acetate; non-polar solvents such as toluene and xylene; and acrylates such as 2-hydroxyethyl acrylate. , dimethyl acetamide or other general organic solvents. The amount of the dispersion solvent is usually 100% by weight or more and 900% by weight or less based on 100% by weight of the colloidal cerium oxide.

These colloidal cerium oxide (G) can be produced by a known method, and a commercially available product can also be used. For example, an organic cerium oxide sol manufactured by Nissan Chemical Industries Co., Ltd.: MEK-ST or the like can be cited. It is necessary to use an average particle diameter of 1 nm or more and 200 nm or less, preferably 5 nm or more and 100 nm or less, and more preferably 10 nm or more and 50 nm or less. When the average particle diameter is 1 nm or more and 100 nm or less, transparency can be ensured, and when the average particle diameter is 1 nm or more and 50 nm or less, transparency and haze can be sufficiently obtained.

In addition, the average particle diameter refers to the minimum particle diameter of the particles when the aggregation is broken, and the average particle diameter of the colloidal cerium oxide (G) can be measured by a BET method, a dynamic light scattering method, an electron microscope observation or the like.

When the hard coating agent contains the component (G), when the solid content of the hard coat agent is 100% by weight, the content is usually 10 to 70% by weight, preferably 20 to 50% by weight. .

The component (A), the component (D), the component (E), the component (F), and the component (G) used in the hard coat agent may be blended and mixed in any order, and a leveling agent may be added as needed. Foaming agents, etc. or other additives.

A high refractive index coating is applied when a layer having a higher refractive index than a base layer (base film) and a layer of a high refractive index layer is provided between the base film (base film) and the hardened layer of the photosensitive resin composition of the present invention. a high refractive index coating agent when a layering agent and a hard coat layer on a base film are provided between a hardened layer of the photosensitive resin composition of the present invention and a high refractive index layer having a higher refractive index than a hard coat layer The component (A), the component (D), the component (E), the component (F), and other additives may be used in combination.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples. Further, in the examples, the parts represent % by weight unless otherwise specified.

Manufacturing example 1

a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Chemical Co., Ltd., KAYARAD DPHA) 37.5 parts, tetrahydrofurfuryl acrylate (manufactured by Osaka Organic Chemical Co., Ltd., Viscoat #150), 2.5 parts, 1.5 parts of Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.), 1 part of Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Celnax CX-Z603M-F2 (manufactured by Nissan Chemical Industries, Ltd., methanol-dispersed sol of zinc citrate, solid-formed into 60%, average particle size of 15~20 nm) 12.5 parts, methanol 8 parts, propylene glycol monomethyl ether 7.5 parts, diacetone alcohol 2.5 parts, methyl ethyl ketone 27 parts mixed, and the solid form is divided into 50% hard Coating agent.

The obtained hard coating agent was applied at a film thickness of about 5 μm on a triacetyl cellulose (TAC) film (manufactured by Konica Minolta Opto) having a thickness of 80 μm before the saponification treatment at 80 ° C. After drying, a high-pressure mercury lamp was used as an ultraviolet irradiation machine, and it was hardened under irradiation conditions of an irradiation intensity of 160 W/cm and a conveying speed of 5 m/min. The transmittance of the film after coating and hardening was 89%, the haze was 0.7%, the pencil hardness (load weight was 500 g) was 3H, and the adhesion of the cured film was also good.

Manufacturing Example 2

a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Chemical Co., Ltd., KAYARAD DPHA), 24 parts, tetrahydrofurfuryl acrylate (manufactured by Osaka Organic Chemical Co., Ltd., Viscoat #150), 1.8 parts of Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.), 1.2 parts of Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and Celnax CX-S505M (manufactured by Nissan Chemical Industries Co., Ltd., a methanol-dispersed sol of tin oxide, the solid content is 50%, 40 parts of an average particle diameter of 10 to 40 nm, 25 parts of 1-propanol, and 5 parts of diacetone alcohol were mixed, and a hard coating agent having a solid content of 50% was obtained.

The obtained hard coating agent was applied at a film thickness of about 5 μm on a triacetyl cellulose (TAC) film (manufactured by Konica Minolta Opto) having a thickness of 80 μm before the saponification treatment at 80 ° C. After drying, a high-pressure mercury lamp was used as an ultraviolet irradiation machine, and it was hardened under irradiation conditions of an irradiation intensity of 160 W/cm and a conveying speed of 5 m/min. The transmittance of the film after coating and hardening was 91%, the haze was 0.5%, the pencil hardness (load weight 500 g) was 3H, and the adhesion of the cured film was also good.

Example 1~2, Comparative Example 1~2

A photosensitive resin composition prepared by mixing the materials shown in Table 1 was prepared.

(Remarks)

DPHA: manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) ((A) component)

ELCOM: manufactured by Nippon Kasei Chemicals Co., Ltd., MIBK dispersion of nanoporous cerium oxide (solid formation is 20%, average particle size: 40~60 nm) ((B) component)

TEGO: manufactured by Degussa, TEGO Rad 2600 (acrylate functional group number: 6) ((C) composition)

X-22: manufactured by Shin-Etsu Chemical Co., Ltd., X-22-2445 (Acrylate functional group number: 2) ((C) component)

US270: Made in East Asia Synthetic (Shares), polyoxyalkylene graft polymer (solid formation is 30%) (for comparison with (C) ingredients)

ST103PA: manufactured by Dow Corning Toray, a polyoxyalkylene (for comparison with (C) ingredients)

Starting agent 1:1-hydroxycyclohexyl phenyl ketone ((D) component)

Starting agent 2: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one ((D) component)

MEK: methyl ethyl ketone ((E) component)

DAA: Diacetone alcohol ((E) component)

Example 3

The photosensitive resin composition of the present invention obtained in Example 1 was applied onto a TAC film having a hard coat layer obtained in Production Example 1, and dried at 80 ° C, and then a high pressure mercury lamp was used as an ultraviolet irradiation machine. The anti-reflection hard coat film was obtained by hardening under irradiation conditions of an irradiation intensity of 160 W/cm and a transport speed of 5 m/min. At this time, the film thickness was adjusted to about 0.1 μm so that the minimum value of the reflectance was in the wavelength region of 520 to 650 nm.

Example 4

The photosensitive resin composition of the present invention obtained in Example 1 was applied onto the TAC film having the hard coat layer obtained in Production Example 2, and dried at 80 ° C, and then a high pressure mercury lamp was used as the ultraviolet irradiation machine. The anti-reflection hard coat film was obtained by hardening under irradiation conditions of an irradiation intensity of 160 W/cm and a transport speed of 5 m/min. At this time, the film thickness was adjusted to about 0.1 μm so that the minimum value of the reflectance was in the wavelength region of 520 to 650 nm.

Example 5

The photosensitive resin composition of the present invention obtained in Example 1 was applied onto a TAC film having a hard coat layer obtained in Production Example 2, and dried at 80 ° C to have an oxygen concentration of 0.1% by volume. In a nitrogen atmosphere, a high-pressure mercury lamp was used as an ultraviolet irradiation machine, and it was hardened under irradiation conditions of an irradiation intensity of 160 W/cm and a conveying speed of 5 m/min to obtain an anti-reflection hard coat film. At this time, the film thickness was adjusted to about 0.1 μm so that the minimum value of the reflectance was in the wavelength region of 520 to 650 nm.

Example 6

The photosensitive resin composition of the present invention obtained in Example 2 was applied onto a TAC film having a hard coat layer obtained in Production Example 2, and dried at 80 ° C, and then a high pressure mercury lamp was used as an ultraviolet irradiation machine. The anti-reflection hard coat film was obtained by hardening under irradiation conditions of an irradiation intensity of 160 W/cm and a transport speed of 5 m/min. At this time, the film thickness was adjusted to about 0.1 μm so that the minimum value of the reflectance was in the wavelength region of 520 to 650 nm.

Comparative example 3

The photosensitive resin composition of the present invention obtained in Comparative Example 1 was applied onto a TAC film having a hard coat layer obtained in Production Example 2, and dried at 80 ° C, and then a high pressure mercury lamp was used as an ultraviolet irradiation machine. The anti-reflection hard coat film was obtained by hardening under irradiation conditions of an irradiation intensity of 160 W/cm and a transport speed of 5 m/min. At this time, the film thickness was adjusted to about 0.1 μm so that the minimum value of the reflectance was in the wavelength region of 520 to 650 nm.

Comparative example 4

The photosensitive resin composition of the present invention obtained in Comparative Example 2 was applied onto the TAC film having the hard coat layer obtained in Production Example 2, and dried at 80 ° C, and then a high pressure mercury lamp was used as the ultraviolet irradiation machine. The anti-reflection hard coat film was obtained by hardening under irradiation conditions of an irradiation intensity of 160 W/cm and a transport speed of 5 m/min. At this time, the film thickness was adjusted to about 0.1 μm so that the minimum value of the reflectance was in the wavelength region of 520 to 650 nm.

The following items were evaluated for the antireflection hard coat films obtained in Examples 3 to 6 and Comparative Examples 3 and 4, and the results are shown in Table 2.

(pencil hardness)

The pencil hardness of the coating film of the above composition was measured in accordance with JIS K 5600 using a pencil scratch tester. Specifically, the hardness of the pencil obtained as follows is obtained: on the film having the hardened film to be measured, the pencil is drawn at an angle of 45 degrees and a load of 500 g is applied from above to draw a scratch of about 5 mm, 5 There were more than 4 times in the second pencil hardness that did not result in scratches.

(scratch resistance)

A load of 500 g/cm ² was applied to the steel wool #0000, and the round trip was performed 10 times, and the condition of the flaw was visually determined.

Evaluation level 5: no scars

Level 4: 1 to 10 scars

Level 3: 10 to 30 scars

Level 2: Produces more than 30 scars

Level 1: Scratches on the entire surface, or spalling

(adhesiveness)

According to JIS K5600, six slits were cut out in the longitudinal direction and the transverse direction at intervals of 2 mm on the surface of the film having the hardened film, and 25 grids were produced. The adhesion is expressed as the number of meshes remaining without peeling off after peeling off the transparent tape on the surface.

(lowest reflectivity)

The measurement was carried out using UV-3150 manufactured by Shimadzu Corporation, an ultraviolet, visible, infrared spectrophotometer (share).

(Marker traces wiping)

The black/red color of the marker ink was used, and the text was written on the coated surface, and wiped with a Kimwipe (sweeping paper), and the wiping property was visually determined.

Evaluation A: Can be wiped off 10 times or more in the same part

B: It can be wiped 5~9 times in the same part.

C: It can be wiped off 1~4 times in the same part.

(total light transmittance)

The measurement was carried out using a TC-H3DPK manufactured by a haze meter Tokyo Electric Color Co., Ltd. (unit:%)

(haze)

The measurement was carried out using a haze meter TC-H3DPK manufactured by Tokyo Electrochrome Co., Ltd. (unit:%)

(surface resistivity)

The measurement was carried out using a HIRESTA IP manufactured by a Mitsubishi Chemical Corporation. (Unit: Ω / □)

(alkaline resistance)

A 1% and 3% aqueous NaOH solution was prepared. These droplets were applied to the surface of the coating film, and the surface state of the coating film after standing for 30 minutes was observed.

Evaluation A: No change

B: Discoloration occurs

C: film peeling

The above evaluation results are shown in Table 2.

It is clear from Table 2 that the antireflection hard coat films of Examples 3 to 6 showed good results in terms of pencil hardness, scratch resistance, adhesion, mark wiping resistance, and alkali resistance. In Comparative Example 3, the component (C) was changed to a graft polymer of polyoxyalkylene, and as a result, the scratch resistance was lowered, and the scratch resistance and alkali resistance of the mark were deteriorated. In Comparative Example 4, the component (C) was changed to a polyoxyalkylene group containing no acrylonitrile group, and as a result, the scratch resistance was lowered, and the transparency, the mark wiping property, and the alkali resistance were deteriorated.

[Industrial availability]

The cured film obtained from the photosensitive resin composition of the present invention is excellent in stain resistance such as hardness, scratch resistance, transparency, chemical resistance, and scratch resistance. Further, it is suitable to form an antireflection hard coat film having a low reflectance by being applied to a hard coat layer to be hardened. The antireflection hard coat film of the present invention is suitable for use in an antireflection film for a flat panel display called an LCD or a PDP, a plastic optical component, a touch panel, a mobile phone, a film liquid crystal element, and the like which require an antireflection function.

Claims (7)

A photosensitive resin composition comprising: a polyfunctional urethane (meth) acrylate selected from the group consisting of 3 to 15 (meth) acrylonitrile groups in a molecule, a polyester acrylate or Polyfunctional (meth) acrylate (A) of one or more compounds of tris(propylene methoxyethyl) isocyanurate, having a nanoporous structure having an average particle diameter of from 1 to 200 nm Colloidal cerium oxide (B) having a refractive index n = 1.2 to 1.45, polyoxy oxyalkylene (C) having a (meth) acrylonitrile group, and a photoradical polymerization initiator (D), content of component B It is 10 to 80% by weight of the resin composition, and does not contain a fluorine-containing polymer containing an ethylenic unsaturated group. The photosensitive resin composition of claim 1, wherein the polyoxyalkylene (C) having a (meth) acrylonitrile group has a compound having 1 to 8 (meth) acrylonitrile groups in the molecule. The photosensitive resin composition of claim 1 or 2, which further contains a diluent (E). An antireflection film which is disposed on a base film and which is disposed on the outermost layer of the photosensitive resin composition according to any one of claims 1 to 3 as a low refractive index layer. An anti-reflective hard coat film having a hard coat layer of a hard coat agent and a hardened layer of the photosensitive resin composition according to any one of claims 1 to 3, in this order. The antireflection hard coat film of claim 5, wherein the hard coat agent contains a polyfunctional (meth) acrylate (A) having at least three (meth) acrylonitrile groups in the molecule, and an average particle diameter of 1~200 nm metal oxide (F), and Photosensitive resin composition of photoradical polymerization initiator (D). The antireflection hard coat film of claim 6, wherein the metal oxide (F) having an average particle diameter of 1 to 200 nm is doped with tin oxide of phosphorus.