JP2006169328A - Photosensitive resin composition and film having its cured coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is cured by radiation, is excellent in scratch resistance and wear resistance, shows a low refractive index and shows a low reflectance when used to produce an antireflective film, and a film having its cured coating. <P>SOLUTION: The photocurable resin composition contains a fluorine atom-containing silicon compound (A), a cationic photopolymerization initiator (B), a comb polymer (C) whose backbone is composed of a fluoropolymer and side chains are composed of silicones and a polymer compound (D) having a fluorine atom. The fluorine atom-containing silicon compound (A) is obtained by fusing alkoxy-silicon compounds of formula (1): R<SB>f</SB>Si(OR<SB>1</SB>)<SB>3</SB>, each having a fluorine atom or by fusing the alkoxy-silicon compound of formula (1) having a fluorine atom and an alkoxy-silicon compound of formula (2): R<SB>e</SB>Si(OR<SB>2</SB>)<SB>3</SB>having an epoxy group in the presence of a basic catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive resin composition containing a fluorine atom-containing silicon compound and a film having a cured film thereof. More specifically, the present invention relates to a photosensitive resin composition excellent in scratch resistance, abrasion resistance and stain resistance, having a low refractive index and a low reflectance, 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, silicon hard coating 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 the case of display bodies such as CRTs and LCDs provided with a film coated with a hard coating agent in recent years, there is a problem that the screen of the display body becomes difficult to see due to reflection, and the eyes are likely to get tired. A functional hard coat treatment 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.)

  However, a thermosetting type (see Patent Document 3) that condenses a silane compound by a sol-gel method is used for the low refractive index layer used in the AR treatment. There is a problem that 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. In addition, the radiation curable resin is not sufficient in scratch resistance, and the fact is that it cannot be carried out unless new equipment is added to the current line 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 having a specific compound and composition can solve the above problems, and have reached the present invention.

That is, the present invention
(1) The following general formula (1)
R _f Si (OR ₁ ) ₃ (1)
(Wherein R _f represents a substituent having 1 to 20 fluorine atoms, R ₁ represents a C _{1 to} C ₄ alkyl group) or between alkoxysilicon compounds having a fluorine atom, or An alkoxysilicon compound having a fluorine atom represented by the general formula (1) and the following general formula (2)
R _e Si (OR ₂ ) ₃ (2)
(Wherein R _e represents a substituent having an epoxy group; R ₂ represents a C _{1 to} C ₄ alkyl group) and an alkoxysilicon compound having an epoxy group represented by the presence of a basic catalyst Below, a fluorine atom-containing silicon compound (A) obtained by condensation, a photocationic polymerization initiator (B), a comb polymer (C) in which the trunk portion is made of a fluorine-based polymer and the branch portion is made of silicone, and fluorine A photosensitive resin composition comprising a polymer compound (D) having an atom;
(2) In the compound of the general formula (2), R _e is a C ₁ -C ₃ alkyl group substituted with a glycidoxy C ₁ -C ₄ alkyl group or a C ₅ -C ₈ cycloalkyl group having an oxirane group. The photosensitive resin composition according to (1),
(3) The fluorine atom-containing silicon compound (A) is obtained by condensing an alkoxysilicon compound having a fluorine atom represented by the formula (1) and an alkoxysilicon compound having an epoxy group represented by the formula (2). The photosensitive resin composition according to item (1) or (2), which is a fluorine atom-containing silicon compound obtained,
(4) The photosensitive resin composition according to any one of (1) to (3) above, which contains colloidal silica (E) having a primary particle size of 1 to 200 nanometers,
(5) The photosensitive resin composition according to any one of (1) to (4) above, which contains a monomer (F) having a fluorine atom,
(6) The photosensitive resin composition as described in (5) above, wherein the terminal of the monomer (F) having a fluorine atom has an epoxy group or a (meth) acrylate group,
(7) The photosensitive resin composition according to the above item (5) or (6), wherein the number of fluorine atoms in one molecule of the monomer (F) having a fluorine atom is 3 to 20,
(8) The photosensitive resin composition according to any one of (1) to (7) above, which contains a photoradical polymerization initiator (G),
(9) The photosensitive resin composition according to any one of (1) to (8) above, which contains a diluent (H),
(10) A hard coating agent and a high refractive index hard coating agent having a refractive index of 1.55 or more are applied in this order on the base film, and then cured on the hard coating layer (1) to (9) ) An anti-reflective hard coat film coated and cured with the photosensitive resin composition according to any one of
(11) Photosensitivity in which the high refractive index hard coat agent contains a polyfunctional (meth) acrylate (I), a metal oxide (J) having a primary particle size of 1 to 200 nanometers, and a radical photopolymerization initiator (G). An antireflective hard coat film as described in (10) above, which is an adhesive resin composition,
(12) The antireflection hard coat film according to (11), wherein the metal oxide (J) having a primary particle size of 1 to 200 nanometers is a conductive metal oxide (K),
About.

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

  Hereinafter, the present invention will be described in detail.

The photosensitive resin composition of the present invention has the following general formula (1)
R _f Si (OR ₁ ) ₃ (1)
(Wherein R _f represents a substituent having 1 to 20 fluorine atoms, R ₁ represents a C _{1 to} C ₄ alkyl group) or between alkoxysilicon compounds having a fluorine atom, or An alkoxysilicon compound having a fluorine atom represented by the general formula (1) and the following general formula (2)
R _e Si (OR ₂ ) ₃ (2)
(Wherein R _e represents a substituent having an epoxy group; R ₂ represents a C _{1 to} C ₄ alkyl group) and an alkoxysilicon compound having an epoxy group represented by the presence of a basic catalyst The fluorine atom-containing silicon compound (A) obtained by condensation is used below.

As the alkoxysilicon compound having a fluorine atom represented by the general formula (1) used in the present invention, the substituent _Rf may be any substituent having 1 to 20 fluorine atoms. Specific examples include triethoxyfluorosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, pentafluorophenyltriethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 3-heptafluoroiso Propoxypropyltrimethoxysilane, (tridecafluoro-1,1,2,2, -tetrahydrooctyl) triethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, (heptadecafluoro-1,1 , 2,2-tetrahydrodecyl) triethoxysilane, nonafluorohexyltrimethoxysilane, nonafluorohexyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecylto Ethoxysilane, 3-trimethoxysilylpropyl pentadecafluorooctate, 3-triethoxysilylpropylpentadecafluorooctate, 3-trimethoxysilylpropylpentadecafluorooctylamide, 3-triethoxysilylpropylpentadecafluorooctylamide , 2-trimethoxysilylethyl pentadecafluoropropyl sulfide, 2-triethoxysilylethyl pentadecafluorodecanyl sulfide, and the like, which are easily available, and are trifluoro from the compatibility with alkoxy silicon compounds having an epoxy group. Propyltrimethoxysilane is preferred. These may be used alone or in combination of two or more.

In the general formula (1), R ₁ represents a C _{1 to} C ₄ alkyl group, and examples thereof include methyl, ethyl, propyl, and the like. In the present invention, methyl and ethyl are preferable as R ₁ in terms of reaction conditions.

  The compound represented by the general formula (1) can be obtained from the market. Examples of commercially available products include KBM-7103, KBM-7803 (manufactured by Shin-Etsu Chemical Co., Ltd.), T1770 (manufactured by Tokyo Chemical Industry Co., Ltd.), TSL8257, and TSL8233 (manufactured by GE Toshiba Silicone Co., Ltd.). .

As the R _e of the alkoxy silicon compound having an epoxy group represented by the formula used in the present invention (2) is not particularly limited as long as it is a substituent having an epoxy group, for example, β- glycidol Kishiechiru group, .gamma.-glycidoxypropyl group, .gamma. glycidoxy such as glycidoxy butyl group C ₁ -C _4, preferably glycidoxy C ₁ -C ₃ alkyl group, a glycidyl group, beta-(3,4-epoxy (Cyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- (3,4-epoxycyclohexyl) propyl group, β- (3, C substituted with a C ₅ -C ₈ cycloalkyl group having an oxirane group such as 4-epoxycyclohexyl) butyl group and β- (3,4-epoxycyclohexyl) pentyl group It includes ₁ -C ₃ alkyl group.

Among these, β-glycidoxyethyl group, γ-glycidoxypropyl group, and β- (3,4-epoxycyclohexyl) ethyl group are preferable. Specific preferred examples of compounds which can be used as the compound of the general formula (1) having these substituents R _e, beta-glycidoxyethyl trimethoxysilane, beta-glycidoxyethyl triethoxysilane, .gamma. Examples include glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like. It is done. These may be used alone or in combination of two or more.

In the general formula (2), R ₂ represents a C _{1 to} C ₄ alkyl group, and examples thereof include methyl, ethyl, propyl, and the like. In the present invention, methyl and ethyl are preferable as R ₂ in terms of reaction conditions.

  The fluorine atom-containing silicon compound (A) used in the present invention can be produced, for example, by the method described in JP-A-10-324749, JP-A-6-32903, and JP-A-6-298940. In the present invention, in the presence of a basic catalyst, alkoxysilicon compounds having a fluorine atom of general formula (1), or an alkoxysilicon compound having a fluorine atom of general formula (1) and an epoxy group of general formula (2) are included. It can be obtained by (co) condensation with an alkoxysilicon compound. The (co) condensation ratio of the compound of the general formula (1) and the compound of the general formula (2) is that of the general formula (2) with respect to 1 mol of the compound of the general formula (1) from the viewpoint of curability and refractive index. 0.5-2 mol of a compound is preferable. Moreover, in order to accelerate | stimulate (co) condensation, water can be added as needed. The amount of water added is usually 0.05 to 1.5 mol, preferably 0.07 to 1.2 mol, relative to 1 mol of alkoxy groups in the entire reaction mixture.

The catalyst used in the above condensation reaction is not particularly limited as long as it is basic, but inorganic such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. Organic bases such as base, ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, tetramethylammonium hydroxide can be used. Among these, an inorganic base or ammonia is preferable because the catalyst can be easily removed from the product. The addition amount of the catalyst is usually 5 × 10 ^{−4 to} 7 with respect to the total amount of the alkoxysilicon compound having a fluorine atom (general formula (1)) and the alkoxysilicon compound having an epoxy group (general formula (2)). 0.5% by weight, preferably 1 × 10 ^{−3 to} 5% by weight.

  The condensation reaction can be carried out without a solvent or in a solvent. The solvent in the case of using a solvent is not particularly limited as long as it is a solvent that dissolves an alkoxy silicon compound having an epoxy group and an alkoxy silicon compound having a fluorine atom. Examples of such solvents include aprotic polar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, and methyl isobutyl ketone, and aromatic hydrocarbons such as toluene and xylene, preferably methyl ethyl ketone and methyl isobutyl ketone. It is.

  In the resin composition of the present invention, the amount of the component (A) used is preferably 0.1 to 50% by weight with respect to the solid content of the resin composition of the present invention.

  In the photosensitive resin composition of this invention, a photocationic polymerization initiator (B) is used. The cationic photopolymerization initiator (B) is a catalyst that accelerates the cationic polymerization reaction under light irradiation, and can be used to generate a cationic polymerization catalyst such as Lewis acid by irradiating ultraviolet rays or the like. 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, di Eniru -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 (B) can be easily obtained from the market.
Commercially available products of the photocationic polymerization initiator (B) include, for example, UVI-6990, UVI-6922 (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 resin composition of the present invention, the amount of the component (B) used is preferably 0.1 to 20% by weight with respect to the solid content of the resin composition of the present invention.

  A sensitizer can be used in combination with the photosensitive resin composition of the present invention as required. As the sensitizer that can be used, one that promotes photocationic polymerization is used. Specifically, anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-di Ethoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 2-ethyl-9,10-di (methoxyethoxy) anthracene, fluorene, pyrene, stilbene, 4′-nitrobenzyl-9,10-dimethoxyanthracene-2 -Sulfonates, 4'-nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, 4'-nitrobenzyl-9,10-dipropoxyanthracene-2-sulfonate, etc., but soluble and photosensitive resins Especially in terms of compatibility with the composition, 2-ethyl-9,10-di Methoxyethoxy) anthracene are preferable. When these sensitizers are used, the amount used is 1 to 200 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of the cationic photopolymerization initiator (B).

  In the photosensitive resin composition of the present invention, a comb polymer (C) having a trunk portion made of a fluorine-based polymer and a branch portion made of silicone is used.

  This compound (C) can be obtained by polymerizing a hydrocarbon monomer, fluoroethylene, methacrylate-modified silicone or the like. 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, Kanto Denka Kogyo Co., Ltd. super antifouling silicone-containing fluororesin F Clear KD270 can be mentioned.

  In the resin composition of the present invention, the amount of the component (C) used is preferably 0.1 to 30% by weight with respect to the solid content of the resin composition of the present invention.

  In the photosensitive resin composition of the present invention, a polymer compound (D) having a fluorine atom is used. As the polymer compound (D) having a fluorine atom, various polymer compounds having a fluorine atom can be used. For example, polytetrafluoroethylene, polyvinylidene fluoride, trifluoroethyl (meth) acrylate, tetra Fluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meta ) Acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, 2-hydroxy-1H, 1H, 2H, 3H, 3H-nonafluoroheptyl ( (Meth) acrylate 2-hydroxy-1H, 1H, 2H, 3H, 3H-tridecafluorononyl (meth) acrylate, 2-hydroxy-6-trifluoromethyl-1H, 1H, 2H, 3H, 3H-octafluoroheptyl (meth) A single or two or more compounds having a fluorine atom and an ethylenically unsaturated group, such as acrylate, 2-hydroxy-8-trifluoromethyl-1H, 1H, 2H, 3H, 3H-dodecafluorononyl (meth) acrylate, or Examples thereof include a polymer obtained by polymerizing a compound having a fluorine atom and an ethylenically unsaturated group and a compound having an ethylenically unsaturated group not containing a fluorine atom.

  In the resin composition of the present invention, the amount of the component (D) used is preferably 0.1 to 30% by weight with respect to the solid content of the resin composition of the present invention.

  In the photosensitive resin composition of the present invention, colloidal silica (E) having a primary particle size of 1 to 200 nanometers can be used. Examples of the colloidal silica (E) that can be used include a colloidal solution in which colloidal silica is dispersed in a solvent, or fine powdered colloidal silica containing no dispersion solvent.

  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.

  These colloidal silicas can be manufactured and marketed by a known method. It is necessary to use a particle size having a primary particle size of 1 to 200 nanometers, preferably a primary particle size of 5 to 100 nanometers, more preferably a primary particle size of 10 to 80 nanometers. is there. In the present invention, colloidal silica having a pH of 2 to 6 is preferably used.

  In the resin composition of the present invention, the amount of the component (E) used is preferably 0 to 30% by weight with respect to the solid content of the resin composition of the present invention.

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

  Moreover, the surface of colloidal silica can be surface-treated with an alkoxysilicon compound having a fluorine atom represented by the formula (1) or an alkoxysilicon compound having an epoxy group represented by the formula (2).

The processing method can be performed by a known method. Specifically, there are a dry method and a wet method, and the dry method is a method of treating silica powder, in which a stock solution or a solution of an alkoxysilicon compound is uniformly dispersed in a silica powder that is rapidly stirred by a stirrer. Is the method. In addition, the wet method is a method in which an alkoxysilicon compound is added to and stirred in a slurry obtained by dispersing silica in a solvent or the like. 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) × the specific surface area of silica (m ² / g) / the minimum covering area (m ² / g) of the alkoxysilicon compound.

  In the photosensitive resin composition of the present invention, a monomer (F) having a fluorine atom can be used. Examples of the monomer (F) having a fluorine atom include trifluoroethyl acrylate (refractive index 1.348), trifluoroethyl methacrylate, tetrafluoropropyl acrylate (refractive index 1.363), and octafluoropentyl acrylate (refractive index). 1.347), (meth) acrylate compounds such as octafluoropentyl methacrylate, and perfluoroalkylene oxides such as perfluorobutyl propylene oxide, perfluorohexyl propylene oxide, and perfluorooctyl propylene oxide.

  The monomer (F) having a fluorine atom preferably has a refractive index of 1.38 or less, and the terminal preferably has a photopolymerizable (meth) acrylate group and / or an epoxy group. Moreover, it is preferable that the number of fluorines in one molecule of the monomer (F) having a fluorine atom is 3 to 20. You may use these individually or in mixture of 2 or more types.

  In the resin composition of the present invention, the amount of the component (F) used is preferably 0 to 60% by weight with respect to the solid content of the resin composition of the present invention.

  In the resin composition of the present invention, when a compound having a (meth) acrylate group is used for the monomer (F) having a fluorine atom, it is preferable to add a radical photopolymerization initiator (G).

  Examples of the photo radical polymerization initiator (G) 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-morpholinopropane Acetophenones such as -1-one; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; 2,4-diethylthioxan , Thioxanthones such as 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, and the like.

These can be used singly or as a mixture of two or more, and further, tertiary amines such as triethanolamine and methyldiethanolamine, secondary amines such as diethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N -It can be used in combination with a polymerization accelerator such as a benzoic acid derivative such as dimethylaminobenzoic acid isoamyl ester.

  In the resin composition of the present invention, the amount of the component (G) used is preferably 0 to 10% by weight with respect to the solid content of the resin composition of the present invention.

  A diluent (H) can be used in the photosensitive resin composition of the present invention. Diluents (H) that can be used include, for example, lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, and ε-caprolactone; , 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. Ethers of ethylene; carbonates such as ethylene carbonate and propylene carbonate; methyl ethyl Ketones such as ketone, methyl isobutyl ketone, cyclohexanone, acetophenone; phenols such as phenol, cresol, xylenol; ethyl acetate, butyl acetate, ethyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene Esters such as glycol monomethyl ether acetate; Hydrocarbons such as toluene, xylene, diethylbenzene, cyclohexane; Halogenated hydrocarbons such as trichloroethane, tetrachloroethane, and monochlorobenzene, and petroleum solvents such as petroleum ether and petroleum naphtha Organic solvents, fluorine alcohols such as 2H, 3H-tetrafluoropropanol, perfluorobutyl methyl ether, perfluorobutyl Like hydrofluoroethers such as Chirueteru like. You may use these individually or in mixture of 2 or more types.

  In the resin composition of the present invention, the amount of the component (H) used is preferably 0 to 99% by weight in the resin composition 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 (C), component (D) and optionally component (E), component (F), component (G), (H) It can obtain by mixing a component and another component in arbitrary orders.

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

  The antireflection hard coat film of the present invention is obtained by providing each layer in the order of a hard coat layer, a high refractive index hard coat layer and the photosensitive resin composition layer on a base film (base film). First, a hard coat agent is applied onto a 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. Then, after drying a high refractive index hard coat agent having a refractive index of 1.55 or more on the formed hard coat layer, 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 It can be obtained by coating so that the film thickness is 500 to 700 nm, preferably 520 to 650 nm, and irradiating with radiation after drying to form a cured film. .

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 include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, die coater coating, and dip 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 the light source, and the amount of light, 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 conveying speed of 5 to 60 m / min for one lamp having an energy of 80 to 120 W / cm ² .

  As the 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 polyfunctional (meth) acrylate (I) and radical photopolymerization start. You may mix | blend and use an agent (G) and a diluent (H). Specific examples of the polyfunctional (meth) acrylate (I) include, for example, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and di (meth) of ε-caprolactone adduct of hydroxypivalate neopentyl glycol. Acrylate (for example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.), di (meth) acrylate of bisphenol A EO adduct, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy Tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) Acrylate, polyglycidyl compound (bisphenol A type epoxy resin, phenol novolac type epoxy resin, trisphenolmethane type epoxy resin, polyethylene glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, etc.) and (meth) acrylic acid Epoxy (meth) acrylate, polyfunctional (meth) acrylate having a hydroxyl group (pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, etc.) and poly Isocyanate compounds (tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate Like polyfunctional urethane (meth) acrylate which is a reaction product of such). You may use these individually or in mixture of 2 or more types. Preference is given to trifunctional or higher functional (meth) acrylates.

As the radical photopolymerization initiator (G), the compounds described above can be used.
Moreover, it can be used in combination with the said polymerization accelerator etc.

As the diluent (H) used in the hard coat agent, the diluent (H) can be used.

  The (I) component, (G) component, and (H) component used in the hard coat agent can be blended and mixed in any order, and a leveling agent, an antifoaming agent, etc. can be added as necessary. it can. The use ratio of each component is (I) component 30 to 99.5 wt%, (G) component 0.5 to 20 wt%, and (H) component is 0 to 90 wt% in the hard coat agent composition, preferably 20 to 80% by weight.

The high refractive index 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, polyfunctional (meth) acrylate (I), A photosensitive resin composition obtained from a metal oxide (J) having a primary particle size of 1 to 200 nanometers, a radical photopolymerization initiator (G), and a diluent (H) is preferable.
As the polyfunctional (meth) acrylate (I), the radical photopolymerization initiator (G), and the diluent (H), the above-described compounds can be used.

  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 that can be 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. Examples thereof include ketones such as isobutyl 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.

  Moreover, in order to provide 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). 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 (I) component, (J) component, (G) component, and (H) component used in the high refractive index hard coat agent can be blended and mixed in an arbitrary order. A foaming agent etc. can be added. The ratio of each component used is usually 19.5 to 79.5% by weight of component (I), 20 to 80% by weight of component (J), and 0.5 to 20 of component (G) in the high refractive index hard coat agent composition. The component (H) is 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. In addition, each physical property value in an Example was measured with the following method.
(1) Epoxy equivalent: measured by a method according to JIS K-7236.
(2) Refractive index: Measured with an Abbe refractometer at 25 ° C

Synthesis example (Synthesis of fluorine atom-containing silicon compound)
In a reaction vessel, 47.2 parts of γ-glycidoxypropyltrimethoxysilane, 43.6 parts of trifluoropropyltrimethoxysilane, 181.8 parts of methyl isobutyl ketone, and 10.8 parts of 0.1 wt% potassium hydroxide aqueous solution were used. The mixture was charged, heated to 80 ° C., and reacted for 5 hours. After completion of the reaction, washing with water was repeated using a 0.5 wt% aqueous acetic acid solution until the washing solution became neutral. Subsequently, 65 parts of fluorine atom containing silicon compounds (A-1) were obtained by removing a solvent under pressure reduction. The obtained compound had an epoxy equivalent of 317 g / eq and a refractive index of 1.435. In addition, gelation was not observed even at room temperature for 1 month.

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) (Made by Chemicals) 3 parts, 25 parts of methyl ethyl ketone and 25 parts of methyl isobutyl ketone were mixed and dissolved.
The obtained 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, dried at 80 ° C., and then irradiated with ultraviolet light. Cured with an irradiator. 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, Celnax CX-Z600M-3F2 (manufactured by Nissan Chemical Industries, Ltd., methanol dispersion sol of zinc antimonate, solid content 60%, primary particle size 15-20 nm) 7.5 parts, methanol 31 parts, propylene 60 parts of glycol monomethyl ether was mixed to obtain a high refractive index hard coat agent having a solid content of 6%.

  Next, the high refractive index hard coat agent obtained on the PET film on which the hard coat layer obtained in Production Example 1 was formed was applied with a micro gravure coater, dried at 80 ° C., and then cured with an ultraviolet irradiator. 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 to 5 and Comparative Example 1
The photosensitive resin composition containing the materials shown in Table 1 was applied on the PET film formed up to the high refractive index hard coat layer obtained in Production Example 2, dried at 80 ° C., and then cured by an ultraviolet irradiator. An antireflection hard coat film was obtained. 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
A-1 1.35 1.02 0.96 0.48 1.35
NK-8 1.75 1.70 2.40 1.60 1.75
NK-13 1.50 1.00 1.50 1.50
KD270 1.50
DPHA 0.85
Initiator 1 0.15 0.15 0.15 0.15 0.15
Initiator 2 0.02 0.04 0.15
MEK-ST 1.75 1.75
H010 1.02
V-3F 1.40
V-8F 0.70
MFS-10P 20.00
MEK 93.50 95.11 94.27 94.83 93.50 79.00

(note)
NK-8: Fluoropolymer (solid content 30%), manufactured by Kanto Denka Kogyo Co., Ltd.
NK-13: manufactured by Kanto Denka Kogyo Co., Ltd., polysiloxane graft polymer (comb polymer in which the trunk portion is composed of a fluorine-based polymer and the branch portion is composed of silicone) (solid content 30%)
KD270: manufactured by Kanto Denka Kogyo Co., Ltd., polysiloxane graft polymer (comb polymer in which the trunk portion is composed of a fluorine-based polymer and the branch portion is composed of silicone) (solid content 30%)
DPHA: manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and pentaacrylate, cross-linking agent)
Initiator 1: Bis (4-t-butylphenyl) iodonium hexafluorophosphate initiator 2: 1-hydroxycyclohexyl phenyl ketone MEK-ST: manufactured by Nissan Chemical Industries, Ltd., organosilica sol (solid content 30%, primary particle size 10-15nm)
H010: manufactured by Tosoh F-Tech Co., Ltd., perfluorooctylpropylene oxide (refractive index: 1.318)
V-8F: manufactured by Osaka Organic Industry Co., Ltd., octafluoropentyl acrylate (refractive index: 1.347)
V-3F: manufactured by Osaka Organic Industry Co., Ltd., trifluoroethyl acrylate (refractive index: 1.348)
MFS-10P: manufactured by Nissan Chemical Industries, Ltd., magnesium fluoride sol (solid content 10%)
MEK: Methyl ethyl ketone

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

(Pencil hardness)
According to JIS K 5400, the pencil hardness of the coated film having the above composition was measured using a pencil scratch tester. Specifically, on a polyester film having a cured film to be measured, a pencil is applied at a 45 degree angle, a load of 1 kg is applied from the top, and it is scratched about 5 mm. expressed.

(Abrasion resistance)
The steel wool # 0000 was subjected to a load of 500 g / cm ² for 10 reciprocations, and the condition of the scratch was judged visually.
Evaluation A: 0 to 5 no scratch B: 6 to 9 scratches generated C: 10 or more scratches generated

(Abrasion resistance)
A load of 1 kg / cm ² was applied to a commercially available cloth and reciprocated 200 times, and the state of scratches and peeling were visually observed.
Evaluation A: No change B: Scratched but no change in color C: Peeling occurred

(Adhesion)
In accordance with JIS D 0202, 100 grids are made by making 11 vertical and horizontal cuts at 1 mm intervals on the surface of the film having the cured 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 was measured for each material, and the refractive index at a solid content of 100% was calculated.
The evaluation results are shown in Table 2.

Table 2
Pencil hardness Abrasion resistance Abrasion resistance Adhesiveness Liquid refractive index Example 1 3H A A 100/100 1.43
Example 2 3H A A 100/100 1.39
Example 3 3H B A 100/100 1.41
Example 4 3H A A 100/100 1.39
Example 5 3H B A 100/100 1.43
Comparative Example 1 2H C B 100/100 1.43

  The antireflection hard coat films of Examples 1 to 5 showed good results with respect to pencil hardness, scratch resistance, abrasion resistance, and adhesion. Comparative Example 1 was inferior in pencil hardness, scratch resistance, and wear resistance.

  A novel silicon compound having a fluorine atom, a photocationic polymerization initiator, a polymer compound having a (poly) siloxane bond in the side chain, a polymer compound having a fluorine atom, colloidal silica, and a monomer having a fluorine atom. The cured film obtained with the photosensitive resin composition is excellent in scratch resistance, abrasion resistance, stain resistance and adhesion, and has low reflectivity by being coated on a high refractive index layer and cured. Suitable for producing antireflection film. 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 (12)

The following general formula (1)
R _f Si (OR ₁ ) ₃ (1)
(Wherein R _f represents a substituent having 1 to 20 fluorine atoms, R ₁ represents a C _{1 to} C ₄ alkyl group) or between alkoxysilicon compounds having a fluorine atom, or An alkoxysilicon compound having a fluorine atom represented by the general formula (1) and the following general formula (2)
R _e Si (OR ₂ ) ₃ (2)
(Wherein R _e represents a substituent having an epoxy group; R ₂ represents a C _{1 to} C ₄ alkyl group) and an alkoxysilicon compound having an epoxy group represented by the presence of a basic catalyst Below, a fluorine atom-containing silicon compound (A) obtained by condensation, a photocationic polymerization initiator (B), a comb polymer (C) in which the trunk portion is made of a fluorine-based polymer and the branch portion is made of silicone, and fluorine A photosensitive resin composition comprising a polymer compound (D) having an atom. In the compound of the general formula (2), R _e is a C ₁ -C ₃ alkyl group substituted by a glycidoxy C ₁ -C ₄ alkyl group or a C ₅ -C ₈ cycloalkyl group having an oxirane group. The photosensitive resin composition as described in 2. Fluorine obtained by condensing a fluorine atom-containing silicon compound (A) with an alkoxysilicon compound having a fluorine atom represented by the formula (1) and an alkoxysilicon compound having an epoxy group represented by the formula (2) The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is an atom-containing silicon compound. The photosensitive resin composition according to any one of claims 1 to 3, comprising colloidal silica (E) having a primary particle size of 1 to 200 nanometers. The photosensitive resin composition according to any one of claims 1 to 4, which contains a monomer (F) having a fluorine atom. The photosensitive resin composition according to claim 5, wherein the terminal of the monomer (F) having a fluorine atom has an epoxy group or a (meth) acrylate group. The photosensitive resin composition according to claim 5 or 6, wherein the number of fluorine atoms in one molecule of the monomer (F) having a fluorine atom is 3 to 20. The photosensitive resin composition as described in any one of Claims 1 thru | or 7 containing radical photopolymerization initiator (G). The photosensitive resin composition as described in any one of Claims 1 thru | or 8 containing a diluent (H). The hard coat agent and a high refractive index hard coat agent having a refractive index of 1.55 or more are applied in this order on the base film, and then cured on the hard coat layer. An antireflective hard coat film obtained by coating and curing the photosensitive resin composition described in 1. A photosensitive resin composition in which the high refractive index hard coat agent contains a polyfunctional (meth) acrylate (I), a metal oxide (J) having a primary particle size of 1 to 200 nanometers, and a radical photopolymerization initiator (G). The antireflection hard coat film according to claim 10, which is a product. The antireflection hard coat film according to claim 11, wherein the metal oxide (J) having a primary particle size of 1 to 200 nanometers is a conductive metal oxide (K).