JP2006306950A - Photosensitive resin composition and film having cured coating thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which is cured by radiation, has excellent scratch resistance, abrasion resistance, solvent resistance and stain resistance, and has a low refractive index, so that it provides a curing coating having a low refractive index when it is used for an antireflection film, and to provide a film having cured coating thereof. <P>SOLUTION: The photosensitive resin composition comprises a polymer compound (A) composed of a hydrocarbon polymer backbone and a silicone branch, a compound (B) having a (meth)acryloyl group, a colloidal silica (C) having a nanoporous structure with a primary particle size of 1-200 nanometer, and a photoradical polymerization initiator (D). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition utilizing a polymerization function of a photocuring system and a film having a cured film thereof.

  At present, plastics are used in large quantities in various industries including the automobile industry, the home appliance industry, and the electrical and electronic industry. The reason why such a large amount of plastic is used is that, in addition to its processability and transparency, it is lightweight, inexpensive and has excellent optical properties. However, it has disadvantages such as being softer than glass and being easily scratched on the surface. In order to improve these drawbacks, it is a common means to coat the surface with a hard coating agent. As the hard coat agent, thermosetting hard coat agents such as silicone paints, acrylic paints, and melamine paints are used. Of these, silicone hard coat agents are particularly frequently used because of their high hardness and excellent quality. However, it has a long curing time, is expensive, and cannot be said to be suitable for a hard coat layer provided on a continuously processed film.

  In recent years, photosensitive acrylic hard coating agents have been developed and used (see Patent Document 1). The photosensitive hard coat agent is cured immediately upon irradiation with radiation such as ultraviolet rays to form a hard film, so the processing speed is fast, and it has excellent performance in terms of hardness and scratch resistance. Now it has become the mainstream in the hard coat field because it is cheaper. It is particularly suitable for continuous processing of films such as polyester. Examples of plastic films include polyester films, polyacrylate films, acrylic films, polycarbonate films, vinyl chloride films, triacetyl cellulose films, and polyethersulfone films. Polyester films are the most widely used because of their excellent properties. ing. This polyester film is a glass anti-scattering film, or a car light-shielding film, a whiteboard surface film, a system kitchen surface antifouling film, and functional films such as touch panels, liquid crystal displays, and CRT flat TVs in terms of electronic materials. Is widely used. All of these are coated with a hard coat so as not to scratch the surface.

  Furthermore, in display bodies such as CRTs, LCDs, and PDPs provided with a film coated with a hard coating agent in recent years, the problem is that the screen of the display body is difficult to see due to reflection or the eyes are easily tired. A hard coat treatment having an anti-surface ability is required. As a method for preventing surface reflection, a film in which inorganic filler or organic filler is dispersed in a photosensitive resin is coated on the film, and the surface is made uneven to prevent reflection (AG treatment). High refraction on the film A method of preventing reflection by providing a multilayer structure in the order of a refractive index layer and a low refractive index layer and using light interference due to a difference in refractive index (AR processing), or AG / AR processing combining the above two methods There are methods. (See Patent Document 2.)

  A thermosetting type (see Patent Document 3) that condenses a silane compound by a sol-gel method is used for the uppermost low-refractive index layer used in the AR treatment. And the hard coat layer shrinks by heating and cracks occur. On the other hand, a radiation curable resin using a (meth) acrylate having a fluorine atom has also been developed (see Patent Document 4), but the scratch resistance is not sufficient or the (meth) acrylate is sufficiently cured. There is a problem that it is necessary to cure in a vacuum or in a nitrogen atmosphere, and the equipment becomes expensive.

  A radiation-curing type low refractive index hard coat is demanded from the problems of productivity and generation of cracks due to heating. However, the reality is that radiation curable resins do not have sufficient scratch resistance or can only be equipped with new equipment such as nitrogen substitution.

Japanese Patent Laid-Open No. 9-48934 JP-A-9-145903 JP-A-10-000726 Japanese Patent Laid-Open No. 10-182745

  The present invention is a photosensitive resin composition that is easily cured by radiation without nitrogen substitution or the like, has excellent scratch resistance, abrasion resistance, and contamination resistance, and has a low reflectance when used in an antireflection film. And providing a film having the cured film.

  As a result of intensive studies to solve the above problems, the present inventors have found that a photosensitive resin composition containing a specific compound can solve the above problems, and have reached the present invention.

That is, the present invention
(1) High molecular compound (A) in which the trunk portion is made of a hydrocarbon-based polymer and the branch portion is made of silicone, the compound (B) having a (meth) acryloyl group, and having a primary particle size of 1 to 200 nanometers A photosensitive resin composition comprising colloidal silica (C) having a nanoporous structure and a radical photopolymerization initiator (D);
(2) The photosensitive resin composition according to (1), wherein the polymer compound (A) has a hydroxyl group,
(3) The photosensitive resin composition according to (1), wherein the polymer compound (A) is a copolymer of a compound having a fluorine atom and an ethylenically unsaturated group, a hydrocarbon monomer having a hydroxyl group, and a reactive silicone. ,
(4) The photosensitive resin composition according to any one of (1) to (3), wherein the compound (B) having a (meth) acryloyl group is a polyfunctional (meth) acrylate (E),
(5) The compound (B) having a (meth) acryloyl group is a mixture of a polyfunctional (meth) acrylate (E) and a (meth) acrylate compound (F) having 1 to 20 fluorine atoms (1) to (4) The photosensitive resin composition as described in any one of
(6) The photosensitive resin composition according to any one of (1) to (5), which contains a diluent (G),
(7) The photosensitive resin composition according to any one of (1) to (6), comprising a silane coupling agent (H) and a photocationic initiator (I),
(8) The hardened layer of the first hard coat agent on the base film, the hardened layer of the second hard coat agent having a refractive index of 1.55 or more, and any one of (1) to (7) An antireflection hard coat film having a cured layer of the photosensitive resin composition in this order,
(9) The second hard coat agent contains a polyfunctional (meth) acrylate (E), a metal oxide (J) having a primary particle size of 1 to 200 nanometers, and a radical photopolymerization initiator (D). The antireflection hard coat film according to (8), which is a photosensitive resin composition,
(10) The antireflection hard coat film according to (9), wherein the metal oxide (J) having a primary particle size of 1 to 200 nanometers is a conductive metal oxide (K),
About.

  A film obtained by curing the photosensitive resin composition of the present invention is tough and excellent in scratch resistance, abrasion resistance, and stain resistance.

  Hereinafter, the present invention will be described in detail.

  In the photosensitive resin composition of the present invention, the polymer compound (A) in which the trunk portion is made of a hydrocarbon polymer and the branch portion is made of silicone is used. Examples of the compound (A) include a comb-type graft polymer in which a trunk portion is an acrylic polymer and a branch portion is made of silicone, and this compound has a (poly) siloxane structure in a side chain (branch portion). It can be obtained by copolymerization of a modified silicone having a terminal double bond and a polymerizable monomer. Examples of commercially available products include Cymac US-350, 352, 380 (all manufactured by Toagosei Co., Ltd.).

Moreover, when it has a hydroxyl group, what has a hydroxyl group in any of a trunk part and a branch part can be used. Examples of commercially available products include Cymac US-270 and Reseda GS-1015 (both manufactured by Toagosei Co., Ltd.).

  Furthermore, the polymer compound (A) in which the trunk portion is made of a hydrocarbon polymer and the branch portion is made of silicone may be a material containing a fluorine atom. The polymer compound (A) containing a fluorine atom can be obtained, for example, by copolymerizing a compound having a fluorine atom and an ethylenically unsaturated group, a hydrocarbon monomer having a hydroxyl group, and a reactive silicone. Examples of the compound having a fluorine atom and an ethylenically unsaturated group include polytetrafluoroethylene, polyvinylidene fluoride, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadeca Fluorodecyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 2,2,3,4,4,4-hexa Fluorobutyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, 2-hydroxy-1H, 1H, 2H, 3H, 3H-nonafluoroheptyl (meth) acrylate, 2-hydroxy-1H, 1H, 2H, 3H, 3H -Tridekafu Orononyl (meth) acrylate, 2-hydroxy-6-trifluoromethyl-1H, 1H, 2H, 3H, 3H-octafluoroheptyl (meth) acrylate, 2-hydroxy-8-trifluoromethyl-1H, 1H, 2H , 3H, 3H-dodecafluorononyl (meth) acrylate, etc., and as the hydrocarbon monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) ) Hydroxyalkyl (meth) acrylates such as acrylate, hydroxyalkyl vinyl ether, and the like, and reactive silicones include (meth) acryl-modified polysiloxane. A polymer compound obtained by copolymerizing a compound having a fluorine atom and an ethylenically unsaturated group, a hydrocarbon monomer having a hydroxyl group and a reactive silicone has a fluorine atom and a hydroxyl group in the trunk portion, and the branch portion is silicone. Is a comb-shaped graft polymer. By grafting silicone onto the polymer, bleeding out of silicone from the surface of the coating film can be suppressed, and water repellency and oil resistance and antifouling properties can be imparted by the main chain fluororesin. Also, it is soluble in common solvents due to the hydrocarbon polymer. Specifically, super-fouling-proof silicone-containing fluororesin F Clear KD270 (OH value: 115 mgKOH / g, fluorine content: 40 wt%) manufactured by Kanto Denka Kogyo Co., Ltd., antifouling paint Ftone AT manufactured by Daikin Industries, Ltd. -100 etc. are mentioned.

  In the photosensitive resin composition of the present invention, the content of the component (A) is usually 1 to 30% by weight, preferably 5 to 20 when the solid content of the resin composition of the present invention is 100% by weight. % By weight.

  In the photosensitive resin composition of this invention, the compound (B) which has a (meth) acryloyl group is used. The compound (B) having a (meth) acryloyl group is not particularly limited as long as it is a compound having a (meth) acryloyl group, but a polyfunctional (meth) acrylate (E) or (E) and a fluorine atom of 1 to A mixture of 20 (meth) acrylates (F) is preferred.

  In the photosensitive resin composition of the present invention, the content of the component (B) is usually 45 to 85% by weight, preferably 50 to 75 when the solid content of the resin composition of the present invention is 100% by weight. % By weight.

  Examples of the polyfunctional (meth) acrylate (E) include polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and di (meth) acrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate (for example, KAYARAD HX-220, HX-620, etc. manufactured by Nippon Kayaku Co., Ltd.), di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meta) ) Acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate And polyglycidyl compounds (bisphenol A type epoxy resin, phenol novolac type epoxy resin, trisphenol methane type epoxy resin, polyethylene glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, etc.) and (meth) acrylic Epoxy (meth) acrylate which is a reaction product of acid, polyfunctional (meth) acrylate having hydroxyl group (pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, etc.) and Polyisocyanate compounds (tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, etc.) Such polyfunctional urethane (meth) acrylates which are reaction products thereof. You may use these individually or in mixture of 2 or more types. Preference is given to trifunctional or higher functional (meth) acrylates.

  In the photosensitive resin composition of the present invention, the content of the component (E) is usually 10 to 60% by weight, preferably 15 to 35% by weight when the component (B) of the present invention is 100% by weight. It is.

  Examples of the (meth) acrylate (F) having 1 to 20 fluorine atoms include trifluoroethyl acrylate (refractive index 1.348), trifluoroethyl methacrylate, tetrafluoropropyl acrylate (refractive index 1.363), Examples include octafluoropentyl acrylate (refractive index 1.347), octafluoropentyl methacrylate, and heptadecafluorodecyl acrylate (refractive index 1.334).

  The (meth) acrylate (F) having 1 to 20 fluorine atoms preferably has a refractive index of 1.38 or less. These are preferably used by mixing with the polyfunctional (meth) acrylate (E), and the component (F) may be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, the content of the component (F) is usually 40 to 90% by weight, preferably 50 to 80% by weight when the component (B) of the present invention is 100% by weight. It is.

  In the photosensitive resin composition of the present invention, colloidal silica (C) having a nanoporous structure with a primary particle size of 1 to 200 nanometers is used. Examples of colloidal silica having a nanoporous structure include porous silica and hollow silica. While ordinary silica particles have a refractive index n = 1.46, the refractive index of silica having air with a refractive index n = 1 therein is n = 1.2-1.45.

  The colloidal silica (C) includes colloidal solution in which colloidal silica is dispersed in a solvent, or fine powdered colloidal silica containing no dispersion solvent. Specific examples of the colloidal solution in which colloidal silica is dispersed in a solvent include ELCOM series manufactured by Catalyst Chemical Industry Co., Ltd.

  Examples of the dispersion solvent for colloidal solution in which colloidal silica is dispersed in a solvent include water, methanol, ethanol, isopropanol, n-butanol and other alcohols, ethylene glycol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol Polyhydric alcohols such as monomethyl ether acetate and derivatives thereof, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and dimethylacetamide, esters such as ethyl acetate and butyl acetate, nonpolar solvents such as toluene and xylene, 2-hydroxy (Meth) acrylates such as butyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like Other general organic solvents, can be used. The amount of the dispersion solvent is usually 100 to 900 parts by weight with respect to 100 parts by weight of colloidal silica.

  The particle size of these colloidal silicas (C) must be those having a primary particle size of 1 to 200 nanometers, preferably a primary particle size of 5 to 100 nanometers, more preferably primary particles. The diameter is 10 to 80 nanometers.

  In the photosensitive resin composition of the present invention, the content of the component (C) is usually 10 to 50% by weight, preferably 15 to 40% when the solid content of the resin composition of the present invention is 100% by weight. % By weight.

  Further, the surface of the colloidal silica may be surface treated with a silane coupling agent or the like.

The processing method can be performed by a known method. Specifically, there are a dry method and a wet method. The dry method is a method of treating silica powder, and the stock solution or solution of the silane coupling agent is uniformly dispersed in the silica powder that is rapidly stirred by a stirrer. Is the way to do. The wet method is a method in which silica is dispersed in a solvent or the like to form a slurry and a silane coupling agent is added and stirred. In the present invention, either method may be used. The treatment amount may be equal to or less than the treatment amount (g) = silica weight (g) × specific surface area of silica (m ² / g) / minimum coating area of silane coupling agent (m ² / g). .

  In the photosensitive resin composition of the present invention, a photo radical initiator (D) is used. Examples of the photo radical polymerization initiator (D) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1, 1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4 Acetophenones such as -morpholinyl) -1-propanone; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethyl Thioxanthones such as oxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone Benzophenones such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc., preferably 1-hydroxycyclohexylphenyl Ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl) -1-propanone, 2,4,6-trimethylbenzoyldipheni Phosphine oxide, and the like. Specifically, Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) and Irgacure 907 (2-methyl-1- (4- (methylthio) phenyl) -2- (4-) manufactured by Ciba Specialty Chemicals are available from the market. Morpholinyl) -1-propanone), BASF's Lucillin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) and the like can be easily obtained.

  You may use these (D) components individually or in mixture of 2 or more types.

  In the photosensitive resin composition of the present invention, the content of the component (D) is usually 0.1 to 5% by weight, preferably 1 when the solid content of the resin composition of the present invention is 100% by weight. ~ 3 wt%.

  In the photosensitive resin composition of the present invention, a diluent (G) can be used. Examples of the diluent (G) include lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, and ε-caprolactone; methanol, ethanol, butanol, Alcohols such as isopropanol and diacetone alcohol; dioxane, 1,2-dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl Ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, etc. Tells; carbonates such as ethylene carbonate and propylene carbonate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone; phenols such as phenol, cresol and xylenol; ethyl acetate, butyl acetate, ethyl lactate, ethyl cellosolve acetate, Esters such as butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; Hydrocarbons such as toluene, xylene, diethylbenzene, and cyclohexane; Halogenated hydrocarbons such as trichloroethane, tetrachloroethane, and monochlorobenzene Organic solvents such as petroleum solvents such as petroleum ether and petroleum naphtha, 2H, 3H-tetrafluoroprop Fluorine-based alcohols such Lumpur, perfluorobutyl methyl ether, hydrofluoroethers such as perfluorobutyl ethyl ether. You may use these individually or in mixture of 2 or more types.

  In the photosensitive resin composition of the present invention, the amount of component (G) used is usually 0 to 98% by weight in the resin composition of the present invention.

  In the photosensitive resin composition of the present invention, a silane coupling agent (H) can be used. Examples of the silane coupling agent (H) include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxy. Alkoxy silicon compounds substituted with epoxy groups such as silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, triethoxyfluorosilane, trifluoro Propyltrimethoxysilane, trifluoropropyltriethoxysilane, pentafluorophenyltriethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 3-heptafluoroisopropoxypropyltrimethoxysilane, (trideca (Luoro 1,1,2,2, -tetrahydrooctyl) triethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxy Silane, nonafluorohexyltrimethoxysilane, nonafluorohexyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, 3-trimethoxysilylpropyl pentadecafluorooctate, 3-triethoxysilylpropyl Pentadecafluorooctate, 3-trimethoxysilylpropylpentadecafluorooctylamide, 3-triethoxysilylpropylpentadecafluorooctylamide, 2-trimethoxysilylethylpentadecaful Examples thereof include alkoxysilicon compounds substituted with groups having 1 to 20 fluorine atoms such as olopropyl sulfide, 2-triethoxysilylethyl pentadecafluorodecanyl sulfide, etc., and these may be used alone or in combination of two or more. May be used.

  In the photosensitive resin composition of the present invention, the amount of component (H) used is 0 to 50% by weight, preferably 0 to 30% by weight, based on the polymer compound (A) used in the present invention. It is.

  When using a silane coupling agent (H), a photocationic initiator (I) is used in combination. In this case, the acid generated from the photocation initiator serves as a catalyst for the dehydration reaction of the silane coupling agent. When the polymer compound (A) used at this time has a hydroxyl group, the crosslinking reaction is further promoted and a tough film is obtained.

  The photocationic initiator (I) is a catalyst that promotes a cationic polymerization reaction under light irradiation, and a photocationic initiator (I) that generates a cationic polymerization catalyst such as Lewis acid by irradiation with ultraviolet rays or the like can be used. For example, a diazonium salt, a sulfonium salt, an iodonium salt, etc. are mentioned. Specifically, benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroborate, 4,4 ′ -Bis [bis (2-hydroxyethoxyphenyl) sulfonio] phenyl sulfide bishexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, bis (4 -T-butylphenyl) iodonium hexafluoroantimonate, Phenyl-4-thio-phenoxyphenyl hexafluorophosphate and the like, preferably, iodonium salts. You may use these individually or in mixture of 2 or more types.

These photocationic polymerization initiators (I) can be easily obtained from the market.
Commercially available products of the photocationic polymerization initiator (I) include, for example, UVI-6990, UVI-6992 (trade names: all manufactured by Dow Chemical Co.), Adekaoptomer SP-150, Adekaoptomer SP-170 (Products) Name: Asahi Denka Co., Ltd.), CIT-1370, CIT-1682, CIP-1866S, CIP-2048S, CIP-2064S (Brand names: all manufactured by Nippon Soda Co., Ltd.), IBPF, IBCF, TS-01, TS -02 (trade names: all manufactured by Sanwa Chemical Co., Ltd.), DPI-101, DPI-102, DPI-103, DPI-105, MPI-103, MPI-105, BBI-101, BBI-102, BBI-103 , BBI-105, TPS-101, TPS-102, TPS-103, TPS-105, MDS-103, MD -105, DTS-102, DTS-103 (trade names, all, Midori Kagaku Co., Ltd.), and the like.

  In the photosensitive resin composition of the present invention, the amount of component (I) used is 10 to 30% by weight with respect to the silane coupling agent (H) of the present invention.

  Furthermore, a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, and the like are added to the photosensitive resin composition of the present invention as necessary, to the photosensitive resin composition of the present invention. Functionality can also be imparted. Fluorine compounds, silicone compounds, acrylic compounds, etc. as leveling agents, benzotriazole compounds, benzophenone compounds, triazine compounds, etc. as UV absorbers, hindered amine compounds, benzoate compounds as light stabilizers Compounds and the like.

  The photosensitive resin composition of the present invention comprises the above component (A), component (B) (component (E), component (E) and component (F)), component (C), component (D) and as necessary. (G) component, (H) component, (I) component and other components can be obtained by mixing in any order.

  The photosensitive resin composition of the present invention has a liquid refractive index of 1.45 at 25 ° C. with respect to the components excluding the diluent (G) (when the nonvolatile component in the photosensitive resin composition is 100%). Or less, more preferably 1.42 or less, and still more preferably 1.40 or less. In addition, the liquid refractive index can be calculated by measuring the liquid refractive index of each component at 25 ° C. and by ratio with the content of each component.

  By reducing the refractive index of the photosensitive resin composition of the present invention, the refractive index of the obtained film is also lowered, and as a result, the antireflection function is improved.

  The antireflection hard coat film of the present invention is obtained by providing each layer in the order of the first hard coat layer, the second hard coat layer and the photosensitive resin composition layer of the present invention on a base film (base film). It is done. First, the first hard coat agent is applied onto the base film so that the film thickness after drying is 1 to 30 μm, preferably 3 to 20 μm, and after drying, radiation is irradiated to form a cured film. Thereafter, a second hard coat agent having a refractive index of 1.55 or more is dried on the formed hard coat layer, and the film thickness is 0.05 to 5 μm, preferably 0.05 to 3 μm (maximum reflectance). The film thickness is preferably set so that the wavelength indicating the value is 500 to 700 nm), and after drying, radiation is irradiated to form a cured film. Further, after drying the photosensitive resin composition of the present invention on the high refractive index hard coat layer, the film thickness is 0.05 to 0.5 μm, preferably 0.05 to 0.3 μm (the minimum value of reflectance is The film is coated so that the wavelength is 500 to 700 nm, preferably 520 to 650 nm, and is dried, irradiated with radiation, and then subjected to heat treatment or aging treatment to obtain a cured film. Can be obtained.

Examples of the base film include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetyl cellulose, polyether sulfone, and cycloolefin polymer. The film may be a thick sheet. The film to be used may be one provided with a handle or an easy-adhesion layer, or one subjected to surface treatment such as corona treatment.

  Examples of the method for applying the photosensitive resin composition of the present invention include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, die coater coating, and dip coating. Examples thereof include coating and spin coating.

Examples of radiation irradiated for curing include ultraviolet rays and electron beams. In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp or the like is used as a light source, and the light amount, the arrangement of the light source, etc. are adjusted as necessary. When using a high-pressure mercury lamp, it is preferable to cure at a conveyance speed of 5 to 60 m / min for one lamp having an energy of 80 to 120 W / cm ² .

  As the first hard coat agent used in 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 a polyfunctional (meth) acrylate (E) and light. You may mix | blend and use a radical polymerization initiator (D) and a diluent (G). About polyfunctional (meth) acrylate (E), radical photopolymerization initiator (D), and diluent (G), what was shown above can be used.

  The (E) component, (D) component, and (G) component used in the first hard coat agent can be blended and mixed in any order, and leveling agents, antifoaming agents, etc. are added as necessary. can do. When the solid content of the first hard coat agent is 100% by weight, each component is usually (E) component 80 to 99.5% by weight, (D) component 0.5 to 20% by weight, (G) The component is contained in the hard coat agent composition in an amount of 0 to 99% by weight, preferably 50 to 98% by weight.

  The second hard coat agent used in the second layer of the antireflection hard coat film of the present invention may be one having a refractive index of 1.55 or more, preferably, a polyfunctional (meth) acrylate (E), A photosensitive resin composition obtained from a metal oxide (J) having a primary particle size of 1 to 200 nanometers, a radical photopolymerization initiator (D), and a diluent (G) is preferable.

  The compound of the said description can be used for a polyfunctional (meth) acrylate (E), radical photopolymerization initiator (D), and a diluent (G).

  Examples of the metal oxide (J) having a primary particle size of 1 to 200 nanometers include titanium oxide, zirconium oxide, zinc oxide, tin oxide, iron oxide, indium tin oxide (ITO), antimony-doped tin oxide (ATO), Examples thereof include zinc antimonate, aluminum-doped zinc oxide, gallium-doped zinc oxide, and tin-doped zinc antimonate. These can be obtained as a fine powder or a dispersion liquid dispersed in an organic solvent.

  Examples of the organic solvent used in the dispersion include alcohols such as methanol, ethanol, isopropanol, and n-butanol, polyhydric alcohols such as ethylene glycol, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether, methyl ethyl ketone, and methyl isobutyl. Examples include ketones such as ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, and nonpolar solvents such as toluene and xylene. The amount of the organic solvent is usually 70 to 900 parts by weight with respect to 100 parts by weight of the metal oxide.

  In order to impart antistatic performance to the antireflection hard coat film of the present invention, a conductive metal oxide (K) can be used as the metal oxide (J) having a primary particle size of 1 to 200 nm. Examples of the conductive metal oxide (K) include tin oxide, indium tin oxide (ITO), antimony-doped tin oxide (ATO), zinc antimonate, and aluminum-doped zinc oxide. Zinc antimonate is preferred because of its price, stability and dispersibility.

  The (E) component, (J) component, (D) component, and (G) component used in the second hard coat agent can be blended and mixed in an arbitrary order. A foaming agent etc. can be added. When the solid content of the second hard coat agent is 100% by weight, each component is usually (E) component 19.5 to 79.5% by weight, (J) component 20 to 80% by weight, (D) component The component (G) is contained in the hard coating agent composition in an amount of 0.5 to 20% by weight, 0 to 99% by weight, preferably 50 to 98% by weight.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by these Examples. Moreover, unless otherwise indicated in an Example, a part shows a weight part.

Production Example 1
42 parts dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA), 5 parts 1,6-hexanediol diacrylate (manufactured by Kayaku Sartomer Co., Ltd., KS-HDDA), Irgacure 184 (Ciba Specialty) (Chemicals Co., Ltd.) 3 parts, 25 parts of methyl ethyl ketone and 25 parts of methyl isobutyl ketone were mixed and dissolved to obtain a first hard coat agent.
The obtained first hard coat agent was applied on a PET film (A-4300, manufactured by Toyobo Co., Ltd., film thickness: 188 μm) with a micro gravure coater so that the film thickness was about 5 μm, and dried at 80 ° C. Thereafter, it was cured by an ultraviolet irradiator to obtain a PET film provided with a hard coat layer. The pencil hardness of the cured film was 3H.

Production Example 2
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 1.2 parts, Irgacure 184 (Ciba Specialty Chemicals) 0.15 part, Irgacure 907 (Ciba Specialty Chemicals) 0 .15 parts, 7.5 parts of Celnax CX-Z600M-3F2 (manufactured by Nissan Chemical Industries, Ltd., zinc antimonate methanol dispersion sol, solid content 60%, primary particle size 10-20 nm), 31 parts of methanol, propylene 60 parts of glycol monomethyl ether was mixed to obtain a second hard coat agent having a solid content of 6%.
Next, this high refractive index hard coat agent was applied to the PET film on which the hard coat layer obtained in Production Example 1 was formed with a micro gravure coater, dried at 80 ° C., and then cured with an ultraviolet irradiator. A PET film provided with a second hard coat layer was obtained. At this time, the film thickness was adjusted so that the maximum reflectance was 500 to 700 nm. The adhesion of the cured film was good.

Examples 1-5 and Comparative Examples 1-2
A photosensitive resin composition containing the materials shown in Table 1 was applied on the second hard coat layer of the PET film provided with the first hard coat layer and the second hard coat layer obtained in Production Example 2. After drying at 80 ° C., it was cured with an ultraviolet irradiator to obtain an antireflection hard coat film. At this time, the film thickness was adjusted so that the minimum reflectance was 520 to 650 nm. In Table 1, the unit represents “part”.

Table 1
Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2
US-350 1.00 1.00 1.00 1.00 1.00
KD270 0.083
DPHA 1.30 0.81 0.398 0.53 0.81 1.60 1.30
V-17F 1.08 1.458 1.59 1.08
ELCOM 6.75 4.05 3.98 2.65 4.05 6.75
MEK-ST 4.50
Irg.184 0.05 0.05 0.05 0.05 0.04 0.05 0.05
KBM-7103 0.052
Initiator 0.01
MEK 70.90 73.01 53.114 54.18 73.875 71.60 73.15
Cyclohexanone 20.00 20.00 20.00 20.00
DAA 40.00 40.00 20.00
Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00

(note)
US-350: manufactured by Toagosei Co., Ltd., silicone graft acrylic polymer (component (A))
KD270: manufactured by Kanto Denka Kogyo Co., Ltd., hydroxyl group-containing silicone graft fluoropolymer (solid content 30%) (component (A))
DPHA: manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate / pentaacrylate (component (E))
V-17F: Heptadecafluorodecyl acrylate (component (F)), manufactured by Osaka Organic Industry Co., Ltd.
ELCOM: MIBK dispersion of nanoporous silica manufactured by Catalyst Kasei Kogyo Co., Ltd. (solid content 20%, primary particle size 40-60 nm) (component (C))
MEK-ST: manufactured by Nissan Chemical Industries, Ltd., silica sol MEK dispersion (solid content 30%, primary particle size 10-15 nm)
Irg. 184: 1-hydroxycyclohexyl phenyl ketone (component (D))
KBM7103: Shin-Etsu Chemical Co., Ltd., trifluoropropyltrimethoxysilane (component (H))
Initiator: bis (4-t-butylphenyl) iodonium hexafluorophosphate (component (I))
MEK: Methyl ethyl ketone (component (G))
DAA: diacetone alcohol (component (G))

  The following items were evaluated for the present invention and comparative antireflection hard coat films obtained in Examples 1 to 5 and Comparative Examples 1 and 2, and the results are shown in Table 2.

(Pencil hardness)
In accordance with JIS K 5600-5-4, the pencil hardness of each film was measured using a pencil scratch tester. Specifically, on each film to be measured, the pencil was scratched at an angle of 45 degrees, applied with a load of 1 kg from above, and scratched for about 5 mm, and expressed as the hardness of the pencil that was not scratched.

(Abrasion resistance)
Using a Gakushin rub resistance tester (RT-200, manufactured by Daiei Kagaku Kogyo Co., Ltd.), a load of 500 g / cm ² was applied to steel wool # 0000, and 10 reciprocations were performed. .
Evaluation A: 0 to 5 no scratch B: 6 to 9 scratches generated C: 10 or more scratches generated

(Abrasion resistance)
Using a Gakushin rub resistance tester (RT-200, manufactured by Daiei Kagaku Kogyo Co., Ltd.), apply a load of 1 kg / cm ² on a commercially available cloth (glasses wipe) and reciprocate 200 times to determine the state of scratches and peeling. Was visually observed.
Evaluation A: No change B: Scratched but no change in color C: Peeling occurred, color change

(Adhesion)
In accordance with JIS K 5600-5-6, 100 grids are made by making 11 vertical and horizontal cuts at 1 mm intervals on the surface of each film to be measured. After the cellophane tape was brought into close contact with the surface, the number of cells remaining without peeling was shown.

(Liquid refractive index)
Measured with an Abbe refractometer. The liquid refractive index at 25 ° C. was measured for each component, and the refractive index when the nonvolatile content was 100% by weight was calculated. (The refractive index is calculated from the ratio of the content of each component.)

(MEK rubbing resistance)
Each film was impregnated with methyl ethyl ketone and measured 10 times with Kimwipe (manufactured by Crecia Co., Ltd.) by hand, and the resulting surface was observed.
Evaluation A: No change B: No scratches or peeling C: Peeling

(Magic contamination)
On the cured film to be measured, a line was drawn with magic ink very thick black (oiliness, writing line width 18 mm), and wiping with Kimwipe was confirmed.
Evaluation Wiping A: Wipe completely within 5 times
B: Can be wiped off 6 times or more
C: Can not be wiped off

Table 2
Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2
Pencil hardness 2H 2H 2H 2H 2H 2H 2H
Scratch resistance A A A A A C A
Abrasion resistance A A A A A B A
Adhesion 100/100 100/100 100/100 100/100 100/100 100/100 100/100
Liquid refractive index 1.39 1.38 1.36 1.37 1.38 1.39 1.48
MEK rubbing A A A A A A A
Magic Wipe A A A A A C A

  The photosensitive resin compositions of Examples 1 to 5 each have a liquid refractive index of 1.4 or less and the obtained antireflection hard coat film has pencil hardness, scratch resistance, abrasion resistance, adhesion, Good results were also shown for stain resistance. In Examples 3 and 4, the use of DAA made the coated surface very uniform and good. About the comparative example 1 which did not use a high molecular compound (A), it became a result inferior in abrasion resistance, abrasion resistance, and magic wiping property. Comparative Example 2 has a high refractive index and is not suitable as a low refractive index material.

  A polymer compound (A) having a trunk portion made of a hydrocarbon-based polymer and a branch portion being made of silicone, a compound (B) having a (meth) acryloyl group, and a nanoporous structure having a primary particle size of 1 to 200 nanometers The cured film obtained by curing the photosensitive resin composition of the present invention containing the colloidal silica (C) and the radical photopolymerization initiator (D) has scratch resistance, abrasion resistance, adhesion, and solvent resistance. It is suitable for producing an antireflection film having a low reflectivity by being coated and cured on a high refractive index layer. Such a film of the present invention is particularly suitable for fields requiring an antireflection function, such as plastic optical components, touch panels, flat panel displays, mobile phones, and film liquid crystal elements.

Claims (10)

A polymer compound (A) having a trunk portion made of a hydrocarbon polymer and a branch portion made of silicone, a compound (B) having a (meth) acryloyl group, and a nanoporous structure having a primary particle size of 1 to 200 nanometers A photosensitive resin composition comprising colloidal silica (C) and a radical photopolymerization initiator (D). The photosensitive resin composition according to claim 1, wherein the polymer compound (A) has a hydroxyl group. The photosensitive resin composition according to claim 1, wherein the polymer compound (A) is a copolymer of a compound having a fluorine atom and an ethylenically unsaturated group, a hydrocarbon monomer having a hydroxyl group, and a reactive silicone. The photosensitive resin composition according to any one of claims 1 to 3, wherein the compound (B) having a (meth) acryloyl group is a polyfunctional (meth) acrylate (E). The compound (B) having a (meth) acryloyl group is a mixture of a polyfunctional (meth) acrylate (E) and a (meth) acrylate compound (F) having 1 to 20 fluorine atoms. A photosensitive resin composition according to claim 1. The photosensitive resin composition according to any one of claims 1 to 5, further comprising a diluent (G). The photosensitive resin composition according to claim 1, comprising a silane coupling agent (H) and a photocationic initiator (I). A cured layer of a first hard coat agent on a substrate film, a cured layer of a second hard coat agent having a refractive index of 1.55 or more, and the photosensitive resin composition according to any one of claims 1 to 7. An antireflection hard coat film having a cured layer of the product in this order. Photosensitive resin in which the second hard coat agent contains a polyfunctional (meth) acrylate (E), a metal oxide (J) having a primary particle size of 1 to 200 nanometers, and a radical photopolymerization initiator (D) The antireflection hard coat film according to claim 8, which is a composition. The antireflection hard coat film according to claim 9, wherein the metal oxide (J) having a primary particle size of 1 to 200 nanometers is a conductive metal oxide (K).