KR20060126920A - Photosensitive resin composition and film having cured coat formed therefrom - Google Patents

Abstract

A photosensitive resin composition which cures with a radiation to give a film which is excellent in marring resistance and wearing resistance and has a low refractive index and which, when used as an antireflection film, has a low reflectance. The photosensitive resin composition is characterized by comprising (A) an epoxidized silicon compound obtained by condensing, in the presence of a basic catalyst, an epoxidized alkoxysilicon compound represented by the following general formula (1) ReSi(OR1)3 (1) (wherein Re represents a substituent having epoxy; and R1 represents C1- 4 alkyl) with itself or with a fluorinated alkoxysilicon compound represented by the following general formula (2) RfSi(OR 2)3 (2) (wherein Rf represents a substituent having 1 to 20 fluorine atoms; and R2 represents C1-4 alkyl) and (B) a cationic photopolymerization initiator and optionally containing (C) a fluorinated polymer, (D) colloidal silica having a primary-particle diameter of 1 to 200 nm, and (E) a polymer having a (poly)siloxane structure in a side chain.

Description

Photosensitive resin composition and film having cured coat formed therefrom

The present invention provides a photosensitive resin composition containing an epoxy group-containing silicon compound and its

It relates to a film having a cured coating. In detail, this invention is excellent in abrasion resistance, and when it is used with a low refractive index and an antireflection film, it is related with the photosensitive resin composition which has a low reflectance, and the film which has its cured film.

Currently, plastics are used in large quantities in various industries, including the automotive industry, the consumer electronics industry, and the electrical and electronics industry. The reason why plastics are used in large quantities in this way is because of their workability, transparency, light weight, low cost, and excellent optical characteristics. However, it has disadvantages, such as being softer than glass, and easy to damage a surface. In order to improve these defects, coating a hard coat agent on the surface is performed as a general means. As the hard coat agent, thermosetting hard coat agents such as silicone paints, acrylic paints, and melamine paints are used. Among these, silicone-based hard coat agents are particularly used because of their high hardness and excellent quality. However, hardening time is long, expensive, and it cannot be said that it is suitable as a hard coat layer arrange | positioned at the film processed continuously.

In recent years, the photosensitive acrylic hard coat agent was developed and used (refer Unexamined-Japanese-Patent No. 9-48934 and patent document 1). Since the photosensitive hard coat agent hardens | cures immediately by irradiating radiation, such as an ultraviolet-ray, and forms a hard film | membrane, since the processing speed is fast, it has the outstanding performance of hardness and abrasion resistance, and is cheap in terms of total cost, it is currently Has become the mainstream in the field of hard coat. In particular, it is suitable for continuous processing of films, such as polyester. Plastic films include polyester films, polyacrylate films, acrylic films, polycarbonate films, vinyl chloride films, trisacetylcellulose films, and polyether sulfone films, but polyester films are the most widely used because of their excellent properties. It is used. This polyester film is widely used as a functional film, such as an anti-scattering film of glass or a light shielding film of automobiles, a surface film for whiteboards, a system kitchen surface antifouling film, and electronic materials such as a touch panel, a liquid crystal display, and a CRT flat screen television. . All of these apply a hard coat to prevent damage to the surface thereof.

More recently, in display bodies such as CRTs and LCDs where a film coated with a hard coat agent is disposed, it is difficult to see the display screen due to reflection, and the eyes tend to be tired. A hard coat treatment is needed. As a method for preventing surface reflection, a method of coating a film obtained by dispersing an inorganic filler or an organic filler in a photosensitive resin on a film, and then indenting irregularities on the surface to prevent reflection (AG treatment), a high refractive index layer and a low refractive index layer on the film A multi-layer structure, a method of preventing reflection (AR processing), or an AG / AR processing method combining the above two methods in light of the use of interference of light due to a difference in refractive index. (See Japanese Patent Laid-Open No. 9-145903 and Patent Document 2.)

However, the low refractive index layer used for the AR treatment uses a thermosetting type such as condensing the silane compound by the sol-gel method (see Japanese Patent Application Laid-Open No. 10-000726, Patent Document 3), but hardening takes time. There is a problem that the productivity is poor or the hard coat layer shrinks due to heating and cracks are generated. On the other hand, radiation-curable resins using (meth) acrylates having a fluorine element have also been developed (see Japanese Patent Application Laid-Open No. 10-182745, Patent Document 4). However, scratch resistance is not sufficient or (meth) acrylate is sufficiently In order to harden | cure, it is necessary to harden | cure in vacuum or nitrogen atmosphere, and there also exists a problem that equipment also becomes expensive.

Due to problems such as productivity and cracking caused by heating, a low refractive index hard coat of a radiation curing type is required. In addition, the radiation-curable resin is not scratch-resistant enough, and it is a fact that it is necessary to add new equipment to developing lines, such as nitrogen substitution.

List of references:

Patent Document 1: Japanese Patent Application Laid-Open No. 9-48934

Patent Document 2: Japanese Patent Application Laid-Open No. 9-145903

Patent document 3: Unexamined-Japanese-Patent No. 10-000726

Patent Document 4: Japanese Patent Application Laid-Open No. 10-182745

Disclosure of the Invention

An object of the present invention is to provide a film having a photosensitive resin composition having a low reflectance when cured by radiation, excellent in scratch resistance, excellent in scratch resistance, and having a low reflectance when used as an antireflection film even without performing nitrogen substitution.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that the photosensitive resin composition which has a specific compound and a composition solved the said subject, and reached | attained this invention.

That is, the present invention relates to:

(1) Alkoxy silicon compounds having an epoxy group represented by the following general formula (1), or an alkoxy silicon compound having an epoxy group represented by the following general formula (1) and an alkoxysilicon compound having a fluorine atom represented by the following general formula (2) The photosensitive resin composition characterized by containing the epoxy group containing silicon compound (A) and the photocationic polymerization initiator (B) which can be obtained by condensing in presence of a basic catalyst,

R _e Si (OR ₁ ) ₃

In the food,

R _e represents a substituent having an epoxy group,

R ₁ is C ₁ To Represents an alkyl group of C ₄ .

R _f Si (OR ₂ ) ₃

In the food,

R _f represents a substituent having 1 to 20 fluorine atoms,

R ₂ is C ₁ To Represents an alkyl group of C ₄ .

(2) The compound of formula (1), wherein R _e is glycidoxy C ₁ To C ₄ C ₅ with alkyl or oxirane groups To C ₈ C ₁ substituted with a cycloalkyl group To C ₃ The photosensitive resin composition as described in said (1) which is an alkyl group,

(3) The compound of formula (1), wherein R _e is glycidoxy C ₁ To C ₄ C ₅ with an alkyl group and an oxirane group To C ₈ C ₁ substituted with a cycloalkyl group To C ₃ The photosensitive resin composition as described in said (1) using the compound which is an alkyl group,

(4) The photosensitive resin composition as described in any one of said (1)-(3) which further contains the high molecular compound (C) which has a fluorine atom,

(5) The photosensitive resin composition as described in any one of said (1)-(4) containing colloidal silica (D) whose primary particle diameter is 1-200 nanometers,

(6) The photosensitive resin composition as described in any one of said (1)-(5) containing the high molecular compound (E) which has a (poly) siloxane structure in a side chain,

(7) The polymer part (E) having a (poly) siloxane structure in the side chain is obtained by copolymerization of a polymerizable monomer with a modified silicone having a double bond at its end, and the stem part is an acrylic polymer, and the branch part is The photosensitive resin composition in any one of said (1)-(6) which is a comb graft polymer comprised from silicone,

(8) containing the diluent (F), The photosensitive resin composition in any one of said (1)-(7),

(9) Any of the above (1) to (8), wherein the ratio of the compound of formula (1) to the compound of formula (2) is 0.5 to 2 mol of compound of formula (2) relative to 1 mole of compound of formula (1) The photosensitive resin composition of one,

(10) An antifoamer (G) is contained, The photosensitive resin composition in any one of said (1)-(9) characterized by the above-mentioned.

(11) The photosensitive resin composition in any one of said (1)-(10) is apply | coated to a base material film in order, and apply | coated the high-refractive-index hard coat agent whose refractive index is 1.55 or more in order, and hardened | cured. Anti-reflective hard coat film applied and cured,

(12) The high refractive index hard coat agent is a photosensitive resin composition containing a polyfunctional (meth) acrylate (H), a metal oxide (I) having a primary particle size of 1 to 200 nanometers, and an optical radical polymerization initiator (J). The antireflective hard coat film as described in said (11) made into,

(13) The antireflection hard coat film according to the above (12), wherein the metal oxide (I) having a primary particle size of 1 to 200 nanometers is a conductive metal oxide (K).

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In the photosensitive resin composition of this invention, the alkoxy silicon compound which has the epoxy group represented by following General formula (1), or the alkoxy silicon compound which has the alkoxy group represented by said General formula (1), and the fluorine atom represented by following General formula (2) The alkoxy silicon compound which has is used.

R _e Si (OR ₁ ) ₃ (1)

In the formula, R _e represents a substituent having an epoxy group, and R ₁ is C ₁ To Represents an alkyl group of C ₄ .

R _f Si (OR ₂ ) ₃ (2)

In the formula, R _f represents a substituent having 1 to 20 fluorine atoms, and R ₂ represents C ₁ to Represents an alkyl group of C ₄ .

The R _e in the alkoxysilicon compound having an epoxy group represented by the general formula (1) used in the present invention is not particularly limited as long as it is a substituent having an epoxy group. For example, β- glycidoxy ethyl group and γ- glycidoxy propyl group. glycidoxy C ₁ to C ₄ , such as γ-glycidoxy butyl group Alkyl group, preferably glycidoxy C ₁ to C ₃ alkyl group, glycidyl group, β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) prowritten, β -(3,4-epoxycycloheptyl) ethyl group, β- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) butyl group, β- (3,4-epoxycyclo C ₅ having an oxirane group such as a hexyl) pentyl group C ₁ substituted with a cycloalkyl group from to C ₈ To C ₃ Alkyl group is mentioned.

Among them, β-glycidoxyethyl group, γ-glycidoxypropyl group, and β- (3,4-epoxycyclohexyl) ethyl group are preferable. As a preferable specific example of the compound which can be used as a compound of General formula (1) which has such a substituent R _e , (beta)-glycidoxy oxyethyl trimethoxysilane, (beta)-glycidoxy oxyethyl triethoxysilane, (gamma)-glycidoxy propyl Trimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. Can be mentioned.

In the general formula _(1), R 1 represents the group of C ₁ to C ₄ alkyl, is preferred as R ₁ in view of reaction conditions, is methyl, ethyl.

Moreover, as an alkoxy silicon compound which has a fluorine atom represented by the said General formula (2) used for this invention, substituent _Rf should just be a substituent which has 1-20 fluorine atoms. Specific examples thereof include trifluoropropyltrimethoxysilane, trifluoropropyltrimethoxysilane, nonafluorohexyltrimethoxysilane, nonafluorohexyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, hepta Decafluorodecyltriethoxysilane, 3-trimethoxysilylpropylpentadecafluorooctane, 3-triethoxysilylpropylpentadecaffluorooctate, 3-triethoxysilylpropylpentadecafluorooctyl Amide, 3-triethoxysilylpropyl pentadecafluorooctylamide, 2-trimethoxysilylethyl pentadeca fluorodecyl sulfide, 2-triethoxysilylethyl pentadecafluorodecyl sulfide, and the like. In view of compatibility with an alkoxysilicon compound which is readily available and easily has an epoxy group, trifluoropropyltrimethoxysilane is preferred.

In the formula (2), R ₂ is C ₁ Although an alkyl group of C to C ₄ is shown, methyl and ethyl are preferred as R ₂ in terms of reaction conditions.

The compound represented by the formula (2) can be obtained on the market. As a commercial item

Examples include KBM-7103 and KBM-7803 (manufactured by Shin-Etsu Chemical Co., Ltd.).

In the condensation reaction to obtain a silicon compound (A) having an epoxy group used in the present invention, alkoxysilicon compounds having an epoxy group of formula (1) or alkoxysilicon compounds of formula (1) and a fluorine atom of formula (2) The alkoxysilicon compound can be obtained by (co) condensing in the presence of a basic catalyst. As for the (co) condensation ratio of the compound of General formula (1) and the compound of General formula (2), 0.5-2 mol of the compound of General formula (2) is preferable with respect to 1 mol of the compound of General formula (1) from a hardening point or a refractive index. Moreover, in order to promote (co) condensation, water can be added as needed. The addition amount of water is 0.05-1.5 mol normally, Preferably it is 0.07-1.2 mol with respect to 1 mol of alkoxy groups of the whole reaction mixture.

The catalyst used in the condensation reaction is not particularly limited as long as it is basic, but inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, ammonia and triethylamine Organic bases such as diethylenetriamine, n-butylamine, dimethylaminoethanol and tetramethylammonium hydroxide can be used. Among them, inorganic bases or ammonia are preferable, in view of easy catalyst removal from the product. As addition amount of a catalyst, it is 5 * 10 <^{-4> -7.5} to 7.5weight% normally with respect to the sum total of the alkoxy silicon compound (formula (1)) which has an epoxy group, and the alkoxy silicon compound (formula (2)) which has a fluorine atom, Preferably it is 1x. 10 ^-3 to 5% by weight.

The condensation reaction can be carried out in a solvent or a solvent. The solvent in the case of using the solvent is not particularly limited as long as it is a solvent in which the alkoxysilicon compound having an epoxy group and the alkoxysilicon compound having a fluorine atom are dissolved. Examples of such a solvent include aprotic polar solvents such as dimethylformamide, dimethylacetoamide, tetrahydrofuran, methyl ethyl ethyl ketone and methyl isobutyl ketone, and aromatic hydrocarbons such as toluene and xylene, and the like. Preferably, they are methyl ethyl ketone and methyl isobutyl ketone.

In the photosensitive resin composition of this invention, a photocationic polymerization initiator (B) is used. The photocationic polymerization initiator (B) is a catalyst which accelerate | stimulates a cationic polymerization reaction under light irradiation, and cationic polymerization, such as Lewis acid, by irradiating an ultraviolet-ray etc. It may be used to produce a catalyst. For example, a diazonium salt, a sulfonium salt, an iodonium salt, etc. are mentioned. Specifically, benzenediazonium hexafluoro antimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate, triphenylsulfonium hexafluoroan monate, triphenylsulfonium hexafluorophosphate, Triphenylsulfonium hexafluoroborate, 4,4'-bis [bis (2-hydroxyethoxyphenyl) sulfonio] phenylsulphibisbis hexafluorophosphate, diphenyliodium hexafluoroantimonate, Diphenyl iodonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, etc. are mentioned, Preferably it is iodonium salts. These can be used individually or in mixture of 2 or more types.

These photo cationic polymerization initiators (B) can be easily obtained from a market. Commercially available products of the photo cationic polymerization initiator (B) include, for example, UVI-6990 (trade name; manufactured by Union Carbide), Adeka Off Toma SP-150, Adeka Off Toma SP-170 (trade name; all manufactured by Asahi Denkasha), CIT-1370 , CIT-1682, CIP-1866S, CIP-2048S, CIP-2064S (trade name; all manufactured by Nihon Sodatsusha), 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-1-03, TPS-105, MDS-103, MDS-105, DTS-102, DTS-103 (Brand name; all are manufactured by Midori Kagakusha), etc. are mentioned.

As for the usage-amount of a photocationic polymerization initiator (B), when the solid content in the photosensitive resin composition is 100 weight part, 0.5-20 weight part is preferable, Especially preferably, it is 1-15 weight part.

In the photosensitive resin composition of this invention, a sensitizer can also be used together as needed. The sensitizer which can be used is what promotes photocationic polymerization. Specifically, anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxy anthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10 Diethoxyanthracene, 2-ethyl-9,10-dipropoxycanthracene, 2-ethyl-9,10-di (methoxyethoxy) anthracene, fluorene, pyrene, stilbene, 4'-nitrobenzyl-9.10 Dimethoxyanthracene-2-sulfonate, 4'-nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, 4'-nitrobenzyl-9,10-dipropoxycanthracene-2-sulfonate, and the like. Although it is mentioned, 2-ethyl-9,10- di (methoxyethoxy) anthracene is especially preferable at the point of compatibility with solubility and the photosensitive resin composition. The usage-amount in the case of using these sensitizers is 1-200 weight part with respect to 100 weight part of photocationic polymerization initiators (B), Preferably it is 5-150 weight part.

The high molecular compound (C) which has a fluorine atom is used for the photosensitive resin composition of this invention. As the high molecular compound (C) having a fluorine atom, a high molecular compound having various fluorine atoms can be used, but for example, polytetrafluoroethylene, polyvinylidene fluoride, trifluoroethyl (meth) acrylate, tetrafluoropropyl ( Meta) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexa Decafluorononyl (meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, hexafluoropropyl (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- Trifluoromethyl1H, 1H, 2H, 3H, 3H-octafluoroheptyl (meth) acrylate, 2-hydroxy-8- Compounds having fluorine atoms and ethylenically unsaturated groups, such as lifluoromethyl-1H, 1H, 2H, 3H, 3H-dodecafluorononyl (meth) acrylate, alone or two or more, or fluorine atoms and ethylenic compounds The polymer etc. which superposed | polymerized the compound which has an unsaturated group, and the compound which has an ethylenically unsaturated group which does not contain a fluorine atom are mentioned.

In the photosensitive resin composition of the present invention, colloidal silica (D) having a primary particle size of 1 to 200 nanometers is used. As colloidal silica (D) which can be used, the colloidal solution which disperse | distributed colloidal silica in the solvent, or the fine powder colloidal silica which does not contain a dispersion solvent are mentioned, for example.

As a dispersion solvent of the colloidal solution which disperse | distributed colloidal silica to the solvent, For example, alcohol, such as water, methanol, ethanol, isopropanol, n-butanol, ethylene glycol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Polyhydric alcohols such as ether acetate and derivatives thereof, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, amides such as dimethylacetoamide, esters such as ethyl acetate and n-butyl acetate, toluene, (Meth) acrylates, such as nonpolar solvents, such as xylene, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, and other general organic Solvents can be used. The amount of the dispersion solvent is usually 100 to 900 parts by weight based on 100 parts by weight of colloidal silica.

Such colloidal silica can be produced by a known method and commercially available. It is necessary to use the particle size whose primary particle size is 1-200 nanometers, Preferably the primary particle size is 5-100 nanometers, More preferably, the primary particle size is 10-80 nanometers. In addition, it is preferable to use colloidal silica having a pH of 2 to 6 in the present invention.

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

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

The treatment method can be treated by a known method. Specifically, there are a dry method and a wet method, and the dry method is a method of treating with silica powder, which is a method of uniformly dispersing a stock solution or a solution of an alkoxysilicon compound in a silica powder that is rapidly stirred by a stirrer. In addition, the wet method is a method of treating by adding and stirring an alkoxysilicon compound to a slurry obtained by dispersing silica in a solvent or the like. In the present invention, any method may be used. The throughput may be equal to or less than the amount obtained from the throughput (g) = silica weight (g) x specific surface area (m ² / g) of silica / minimum covering area (m ² / g) of the alkoxysilicon compound.

In the photosensitive resin composition of this invention, the high molecular compound (E) which has a (poly) siloxane structure in a side chain is used.

This compound (E) is a comb graft polymer obtained by copolymerization of a modified silicone having a terminal double bond with a polymerizable monomer, wherein the stem portion is an acrylic polymer and the branch portion is composed of silicone. The said (E) component can be manufactured according to the method of Unexamined-Japanese-Patent No. 7-81113, for example. The ratio of silicone in (E) component is 10-50 weight part with respect to 100 weight part of (E) component, Preferably it is 20-40 weight part, More preferably, it is 20-30 weight part. Regarding the molecular weight, only 5 to 10 are preferable.

As a commercial item of the high molecular compound (E) which has a (poly) siloxane structure in a side chain, Cymac US-270, US-350, US-352, US-380 (all are manufactured by Toagosei) etc. are mentioned, for example.

A diluent (F) can be used for the photosensitive resin composition of this invention. As a diluent (F) which can be used, For example, (gamma) -butyrolactone, (gamma) -valerolactone, (gamma) -caprolactone, (gamma) -heptalactone, (alpha) -acetyl- (gamma) -butyrolactone, (epsilon) -caprolactone, etc. Lactones; 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, tri Ethers such as ethylene glycol diethyl ether, tetraethylene glycol dimethyl ether and tetraethylene glycol diethyl ether; 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 xyleneol; Esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; Hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane; Organic solvents, such as petroleum solvents, such as petroleum ether and petroleum naphtha, such as halogenated hydrocarbons, such as trichloroethane, tetrachloroethane, and monochlorobenzene, are mentioned. These can be used individually or in mixture of 2 or more types.

Antifoamer (G) can be used in the photosensitive resin composition of this invention. In particular, when a fluorine-based material is used, problems of foaming tend to occur, and the improvement by addition of the antifoaming agent (G) is very useful at the time of coating. Examples of the antifoaming agent (G) include a silicone antifoaming agent, a fluorine antifoaming agent, a breakable polymer, a high boiling point solvent, and the like, and specifically, BYK-060N, BYK-066N (manufactured by Vikchemy Co., Ltd.), AF- 600, AF-630 (made by Shin-Etsu Kagaku Kogyo Co., Ltd.), etc. are preferable.

You may use these individually or in mixture of 2 or more types.

Moreover, it is also possible to add a leveling agent, an ultraviolet absorber, a light stabilizer, etc. to the photosensitive resin composition of this invention as needed, and to give a target functionality respectively. Examples of the leveling agent include fluorine compounds, benzophenone compounds, triazone compounds, and sterically hindered amine compounds and benzoate compounds.

The photosensitive resin composition of this invention is the said (A) component and (B) component, and if needed, (C) component, (D) component, and (E) component or if necessary (F) component, (G) component, and It can obtain by mixing other components in arbitrary order. Moreover, the usage-amount is conventionally 0.5-50 weight% of (A) component, 0.05-50 weight% of (B) component, 0-30 weight% of (C) component, 0-39.5 weight% of (D) component, (E) component 0-15 weight%, (G) component 0-5 weight%, About (F) component 0-99.45 weight% in a photosensitive resin composition, Furthermore, 50-98 weight% is preferable.

The photosensitive resin composition of this invention obtained in this way is stable even if time passes.

The antireflective hard coat film of this invention can be obtained by arrange | positioning each layer in order of a hard coat layer, a high refractive index hard coat layer, and the said photosensitive resin composition layer on a base film (base film). First, a hard coat agent is applied on a base film so that a dry thick film thickness may be 1-30 micrometers, Preferably it is 3-20 micrometers, and a dry post radiation is irradiated to form a cured film. After that, a high refractive index hard coat agent having a refractive index of 1.55 or more on the formed hard coat layer is set to have a film thickness of 0.05 to 5 탆, preferably 0.05 to 3 탆 (wavelength representing a maximum reflectance of 500 to 700 nm). It is preferable to make it), and after drying, a radiation film is irradiated to form a cured film. Furthermore, after drying the photosensitive resin composition of this invention on the high refractive index hard-coat layer, the film thickness is 0.05-0.5 micrometer, Preferably it is 0.05-0.3 micrometer (The wavelength which shows the minimum value of a reflectance is 500-700 nm, Preferably it is 520- It is preferred to set the film thickness to 650 nm), and to obtain a cured film by irradiating radiation after drying.

As a base film, polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, trisacetyl cellulose, polyether sulfone, a cycloolefin type polymer etc. are mentioned, for example. The film may be on a somewhat thick sheet. The film to be used may be a surface treatment such as a pattern or a layer for bonding, or a 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, microgravure coating, die coater coating, dip coating, spin coat coating and the like.

As radiation to irradiate for hardening, an ultraviolet-ray, an electron beam, etc. are mentioned, for example. When hardening by ultraviolet-ray, the ultraviolet irradiation apparatus which has a xenon lamp, a high pressure mercury lamp, a metal halide lamp, etc. is used, and light quantity, arrangement | positioning of a light source, etc. are adjusted as needed. When using a high pressure mercury lamp, it is preferable to cure at a conveyance speed of 5 to 60 m / min for a lamp 1 lamp having an energy of 80 to 120 W / cm ² .

As a hard coat agent used for 1 layer of the anti-reflective hard coat film of this invention,

A commercially available hard coat agent may be used as it is, or a polyfunctional (meth) acrylate (H), a radical photopolymerization initiator (J), and a diluent (F) may be used in combination. As a specific example of polyfunctional (meth) acrylate (H), for example, (epsilon) -caprolactone of polyethyleneglycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and neopentyl glycol hydroxypivalate Di (meth) acrylate of an adduct (for example, Nippon Kayaku Co., Ltd. make, KAYARAD HX-220, HX-620, etc.), di (meth) acrylate of the EO adduct of bisphenol A, trimethylol propane tri (meth) acryl Latex, trimethylolpropane polyethoxytri (meth) acrylate, pentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri Pentaerythritol octa (meth) acrylate, polyglycidyl compound (bisphenol A type epoxy resin, phenol novolak type epoxy resin, trisphenol methane type epoxy resin, polyethyl Ethylene glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, etc.) and epoxy (meth) acrylate (pentaerythritol) tri (meth) acrylic, which is a reaction product of (meth) acrylic acid Latex, dipentaerythritol penta (meth) acrylate, tripentaerythritol penta (meth) acrylate, and the polyisocyanate compound (trilenediisocyanate, isophorone diisocyanate, xylene diisocyanate, hexamethylene Polyfunctional urethane (meth) acrylate which is a reactant of diisocyanate etc.) is mentioned. You may use these individually or in mixture of 2 or more types. Preferred are trifunctional or higher (meth) acrylates.

As an optical radical polymerization initiator (J), For example, benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,11-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclo Acetophenones such as hexylphenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one; Anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; Thioxanthones, such as 2, 4- diethyl thioxanthone, 2-isopropyl thioxanthone, and 2-chloro thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide and 4,4'-bismethylaminobenzophenone; Phosphine oxides such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

These may be used alone or as a mixture of two or more thereof, and further include tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, and N, N-dimethylaminobenzoic acid isoamyl ester. It can be used in combination with polymerization promoters, such as a benzoic acid derivative.

As the diluent (F) used in the hard coat agent, the diluent (F) may be used.

(H) component, (J) component, and (F) component used for the said hard coat agent can be mix | blended and mixed in arbitrary order, A leveling agent, an antifoamer, etc. can be added as needed. The use ratio of each component is 80-99.5 weight% of (H) component, 0.5-20 weight% of (J) component, and (F) component is 0-90 weight% in a hard coat composition, Preferably it is 20-80 weight %to be.

Although the high refractive index hard coat agent used for the two layers of the antireflective hard coat film of this invention should just be refractive index 1.55 or more, Preferably it is a polyfunctional (meth) acrylate (H) and a primary particle diameter is 1-200 nanometers. The photosensitive resin composition obtainable from a metal oxide (I), a radical photopolymerization initiator (J), and a diluent (F) as needed is preferable.

The compound described above can be used for a polyfunctional (meth) acrylate (H), a radical photopolymerization initiator (J), and a diluent (F).

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

As an organic solvent used for a dispersion liquid, For example, alcohols, such as methanol, ethanol, isopropanol, n-butanol, polyhydric alcohols, such as ethylene glycol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and methyl ethyl Ketones such as ketone, methyl isopropyl ketone, 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 based on 100 parts by weight of the metal oxide.

In addition, the conductive metal oxide (K) can be used as the metal oxide (I) for imparting antistatic performance to the antireflective hard coat film of the present invention. Examples of the conductive metal oxide (K) include tin oxide, indium tin oxide (ITO), antimony dope tin oxide (ATO), zinc antimonate, aluminum dope zinc oxide, and the like. Zinc antimonate is preferable from price, stability, dispersibility, etc.

(H) component, (I) component and (J) component used for a high refractive index hard coat agent, and (F) component can be mix | blended in arbitrary order as needed, and a leveling agent, an antifoamer, etc. can be mixed as needed. Can be added. The use ratio of each component is 19.5-79.5 weight% of (H) component, 20-80 weight% of (I) component, and 0.5-20 weight% of (J) component in a high refractive index hard-coat composition, ( F) The component is 0 to 99% by weight, preferably 50 to 98% by weight.

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by these Examples. In addition, unless otherwise specified in an Example, a part means a weight part. Each physical property value in an Example was measured with the following method.

(1) Epoxy equivalent: It measures by the method according to JISK-7236.

(2) Refractive index: measured at 25 ° C with Abbe refractometer

Synthesis Example 1

(Synthesis of epoxy group-containing silicon compound)

47.2 parts of (gamma)-glycidoxy propyl trimethoxysilane, 43.6 parts of trifluoropropyl trimethoxysilane, and 90.8 parts of methyl isobutyl ketones were charged to the reaction container, and it heated up at 80 degreeC. After heating up, 21.6 parts of 0.1 weight% aqueous potassium hydroxide aqueous solution was dripped continuously over 30 minutes. After completion of the dropwise addition, the reaction was carried out at 80 ° C for 5 hours while removing the generated methanol. After completion of the reaction, water washing was repeated until the washing liquid became neutral. Subsequently, 65 parts of epoxy group containing silicon compounds (A-1) were obtained by removing a solvent under reduced pressure. The epoxy equivalent of the obtained compound was 319 g / eq and the refractive index 1.433. In addition, gelation was not observed even after 1 month at room temperature.

Synthesis Example 2

(Synthesis of epoxy group-containing silicon compound)

47.2 parts of γ- glycidoxy propyl trimethoxysilane, 113.7 parts of 1H, 1H, 2H, 2H-heptadecafluorodecyltrimethoxysilane, and 160.9 parts of methyl isobutyl ketone were charged to a reaction vessel, and the temperature was raised to 80 ° C. did. After heating up, 21.6 parts of 0.1 weight% potassium hydroxide aqueous solution was dripped continuously over 30 minutes. After completion of the dropwise addition, the reaction was carried out at 80 ° C. for 5 hours while removing the generated methanol. After the reaction was completed, water washing was repeated until the washing liquid became neutral. Subsequently, 109 parts of epoxy group containing silicon compounds (A-2) of this invention were obtained by removing a solvent under reduced pressure. The epoxy equivalent of the obtained compound was 679 g / eq and the refractive index 1.392. Also, no gelation was observed even after one month at room temperature.

Synthesis Example 3

(Synthesis of epoxy group-containing silicon compound)

 94.4 parts of gamma- glycidoxy propyl trimethoxysilane and 94.4 parts of methyl isobutyl ketones were charged to the reaction container, and it heated up at 80 degreeC. After heating up, 21.6 parts of 0.1 weight% aqueous potassium hydroxide aqueous solution was dripped continuously over 30 minutes. After completion of the dropwise addition, the reaction was carried out at 80 ° C for 5 hours while removing the generated methanol. After the completion of the reaction, water washing was repeated until the washing liquid became neutral. Subsequently, 67 parts of epoxy group containing silicon compounds (A-3) were obtained by removing a solvent under reduced pressure. The epoxy equivalent of the obtained compound was 166g / eq. Gelation was not observed even after 1 month at room temperature.

Preparation Example 1

42 parts of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA), 5 parts 1,6-hexanediol diacrylate (manufactured by Kayaku Satomer Co., Ltd., KS-HDDA) 3 parts of cure 184 (made by Ciba Specialty Chemicals), 25 parts of methyl ethyl ketone, and 25 parts of methyl isobutyl ketone were mixed and dissolved.

The obtained hard coat agent was apply | coated so that a film thickness might be set to about 5 micrometers on a PET film (Toyo Hoseki Co., Ltd. make, A-4300, film thickness of 188 micrometers) with a microgravure coater, and it dried at 80 degreeC, and was an ultraviolet irradiation machine Cured by

Preparation Example 2

Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA), 1.2 parts, Irugacure 184 (Shiba Specialty Chemicals) 0.15 parts, Irgacure 907 (Shiba Specialty Chemicals) 0.15 parts, Cernax CX-Z600M-3F2 (manufactured by Nissan Chemical Industries, Ltd., manufactured by Nishisan Kagyo Kogyo Co., Ltd., methanol dispersion sol of zinc antimonate, solid content 60%), 7.5 parts, methanol 31 parts, propylene glycol monomethyl ether 60 parts, solid 6 A high refractive index hard coat agent of% was obtained.

Subsequently, the high refractive index hard coat obtained on the PET film in which the hard coat layer obtained in the manufacture example 1 was formed was apply | coated with a microgravure coater, and it dried at 80 degreeC, and hardened | cured by the ultraviolet irradiator. At this time, the film thickness was adjusted so that the maximum value of reflectance might be 500-700 nm.

Examples 1 to 8 and Comparative Example 1

The photosensitive resin composition which mix | blended the material shown in Table 1 was apply | coated with the microgravure coater on the PET film formed to the high refractive index hard-coat layer obtained by the manufacture example 2, and after drying at 80 degreeC, it hardened | cured by an ultraviolet irradiator and hardened antireflection A coat film was obtained. At this time, the film thickness was adjusted so that the minimum value of reflectance might become 520-650 nm. In Table 1, a unit represents "part".

(week)

KD200: Guantou Denka Kogyo Co., Ltd., Fluoropolymer (solid content 29.3%)

NK-4: Guantou Denka Kogyo Co., Ltd., Fluoropolymer (42% of solids)

NK-8: Guantou Denka Kogyo Co., Ltd., Fluoro-based polymer (solid content 30%)

BYK-060N: Big Chemie, Antifoam (Solid 3%)

MEK-ST: Nissan Kagaku Kogyo Co., Ltd. make, organic silica sol MEK-ST (solid content 30%)

US-270: Toa Kosei Co., Ltd., high molecular compound having a (poly) siloxane structure in the side chain (solid content 30%)

DPHA: Nippon Kayaku Co., Ltd., KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and pentaacrylate, crosslinking agent)

UVI-6990: Union Carbide, triphenylsulfonium fluoro phosphate

Irg.184: Shiga Specialty Chemicals, Irgacure 184 (1-hydroxycyclohexyl phenylketone)

PI2074: Rhodia Japan Co., Ltd. make, photo cationic polymerization initiator

BBI-102: Midori Chemical Co., Ltd. make, photo cationic polymerization initiator

MFS-10P: manufactured by Nissan Chemical Industries, Ltd., Magnesium Fluoride Sol (10% solids)

MEK: methyl ethyl ketone

Test Example 1

The following items were evaluated about the antireflective hard coat film obtained in Examples 1-4 and the comparative example 1, and the result is shown in Table 2.

(Pencil hardness)

The pencil hardness of the coating film of the said composition was measured using the pencil scraping tester according to JISK5400. Specifically, a pencil was placed on a polyester film having a cured film to be measured at a 45 degree angle, subjected to a load of 1 kg, scraped about 5 mm, and the degree of damage was confirmed. Five measurements were taken.

Rating 5/5: 5 out of 5 total

0/5: Damage in 5 out of 5

(Scratch resistance test)

A load of 200 g / cm ² was put on the steel wool # 0000 to reciprocate 20 times, and the damage situation was determined on the neck side.

Rating A: No Damage

B: Some damage

C: No damage up to 10 round trips

D: Some damage in 10 round trips

E: 10 round trips cause significant damage

(Adhesiveness)

At intervals of 1 mm on the surface of the film with a cured film measured according to JIS K 5400

Make 100 check marks by putting 11 cuts across. The cellophane tape was adhered to the surface and then peeled off at once to show the number of masses remaining without peeling.

(reflectivity)

It measured by the thin film measuring apparatus F20 manufactured by Pilmetrics. In order to prevent reflection from the back surface of a film, black magic was apply | coated to the opposite surface of an application surface, and the black vinyl tape was adhere | attached.

The evaluation results are shown in Table 2.

 The antireflective hard coat films of Examples 1 to 4 exhibited excellent effects in all of the pencil hardness, scratch resistance, adhesiveness, and minimum reflectance, but the antireflective hard coat film of Comparative Example 1 had a pencil hardness, scratch resistance, and minimum reflectance. Not good.

Test Example 2

About the antireflection hard coat film obtained in Examples 5-8 and Comparative Example 1, the following item was evaluated and the result was shown in Table 3.

(Pencil hardness)

The pencil hardness of the coating film of the said composition was measured using the pencil scraping tester according to JISK5400. Specifically, on a polyester film having a cured film to be measured, a pencil was scratched by about 5 mm with a load of 1 kg at a 45 degree angle from the top, and the hardness of the pencil was not more than 4 times out of 5 times.

(Scratch resistance test)

A load of 200 g / cm ² was applied on the steel wool # 0000 to reciprocate 10 times, and the damage situation was determined on the neck side.

Rating A: No Damage

B: Some damage

C: Damage to the whole

(Wear resistance)

The gauze was commercially rubbed with gauze and peeling with the lower layer was observed from the neck side.

Evaluation A: No Change

B: no damage but no color change

C: peeling occurrence

(Vesicular)

5 g of the liquid adjusted to the solid content of 10% is prepared, placed in a 10 cc transparent glass bottle, and the lid is securely closed and shaken vigorously for 10 seconds. It is left to stand and the state after 30 minutes is observed.

Rating A: No Bubble

B: Only large bubbles, almost none

C: Foam remains overall

(Adhesiveness)

At intervals of 1 mm on the surface of the film with a cured film measured according to JIS K 5400

Make 100 check marks by putting 11 cuts across. The cellophane tape was adhered to the surface and then peeled off at once to show the number of masses remaining without peeling.

(reflectivity)

It measured by the spectrophotometer UV-3150 by Shimadzu Corporation. In order to prevent reflection from the back surface of a film, black magic was apply | coated to the opposite surface of an application surface, and the black vinyl tape was adhere | attached.

The evaluation results are shown in Table 3.

The antireflective hard coat film of Examples 5 to 7 exhibited excellent effects in all of pencil hardness, scratch resistance, abrasion resistance, antifoaming property, adhesiveness, and minimum reflectance. Abrasion resistance, adhesion, and minimum reflectance all showed excellent effects. However, the hard coat film of Comparative Example 1 did not have good pencil hardness, scratch resistance, and minimum reflectance.

A novel silicon compound having an epoxy group and a fluorine atom and a photocationic polymerization initiator are essential components, and a polymer compound having a fluorine atom, colloidal silica, and a polymer compound having a (poly) siloxane bond in the side chain, as necessary. The cured film obtained by the photosensitive resin composition of this invention is excellent in abrasion resistance, abrasion resistance, antifoaming property, adhesiveness, and is suitable for manufacturing an antireflection film with low reflectance by apply | coating and hardening | curing on a high refractive index layer. Such a film of the present invention is particularly suitable for fields requiring antireflection functions such as plastic optical components, touch panels, flat panel displays, film liquid crystal elements, and the like.

Claims (13)

The alkoxy silicon compound which has the epoxy group represented by following General formula (1), or the alkoxy silicon compound which has an epoxy group represented by following General formula (1), and the alkoxy silicon compound which has a fluorine atom represented by following General formula (2) is basic A photosensitive resin composition comprising an epoxy group-containing silicon compound (A) and a photocationic polymerization initiator (B) obtained by condensation in the presence of a catalyst: R _e Si (OR ₁ ) ₃ (1) In the food, R _e represents a substituent having an epoxy group, R ₁ is C ₁ To Represents an alkyl group of C ₄ . R _f Si (OR ₂ ) ₃ (2) In the food, R _f represents a substituent having 1 to 20 fluorine atoms, R ₂ is C ₁ To Represents an alkyl group of C ₄ . The compound of formula (1) according to claim 1, wherein R _e is glycidoxy C ₁ To C ₄ C ₅ with alkyl or oxirane groups To C ₈ C ₁ substituted with a cycloalkyl group To C ₃ Photosensitive resin composition which is an alkyl group. The compound of formula (1) according to claim 1, wherein R _e is glycidoxy C ₁ To C ₅ alkyl group and C ₅ with oxirane groups To C ₈ C ₁ substituted with a cycloalkyl group To C ₃ The photosensitive resin composition characterized by using a compound which is an alkyl group. The photosensitive resin composition of any one of Claims 1-3 which further contains the high molecular compound (C) which has a fluorine atom. The photosensitive resin composition according to any one of claims 1 to 4, which contains colloidal silica (D) having a primary particle diameter of 1 to 200 nanometers. The photosensitive resin composition of any one of Claims 1-5 containing the high molecular compound (E) which has a (poly) siloxane structure in a side chain. The polymer compound (E) according to any one of claims 1 to 6, wherein the polymer compound (E) having a (poly) siloxane structure in the side chain can be obtained by copolymerization of a polymerizable monomer with a modified silicone having a double bond at its terminal. The photosensitive resin composition whose stem part is an acryl-type polymer and whose branch part is a comb graft polymer comprised from silicone. The photosensitive resin composition of any one of Claims 1-7 containing a diluent (F). The compound of formula (2) according to any one of claims 1 to 8, wherein the ratio of the compound of formula (1) to the compound of formula (2) is 0.5 to 2 relative to 1 mole of compound of formula (1). Molar photosensitive resin composition. The photosensitive resin composition of any one of Claims 1-9 containing an antifoamer (G).  The hard coat agent and the high refractive index hard coat agent whose refractive index are 1.55 or more are apply | coated in order on a base film, and the photosensitive resin composition of any one of Claims 1-10 is apply | coated and hardened on the hard coat layer which hardened | cured. Anti-reflective hard coat film. 12. The photosensitive resin composition according to claim 11, wherein the high refractive index hard coat agent contains a polyfunctional (meth) acrylate (H), a metal oxide (I) having a primary particle diameter of 1 to 200 nanometers, and an optical radical polymerization initiator (J). It is an anti-reflective hard coat film characterized by the above-mentioned. The antireflection hard coat film according to claim 12, wherein the metal oxide (I) having a primary particle size of 1 to 200 nanometers is a conductive metal oxide (K).