JP2002235018A - Photosensitive resin composition for hard coat agent, and film having its cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin composition capable of being cured by radioactive rays, having good adhesion to a plastic, usable for a thick film coating because of little curling properties, hardly causing crack and suitable for hard coat, and further to prepare a film having the cured film thereof. SOLUTION: The photosensitive resin composition for a hard coat agent is characterized in that the composition contains (A) a (meth)acrylic ester mixture of a reaction product of (meth)acrylic acid with (I) a mixture of (a) dipentaerythritol, (b) tripentaerythritol, (c) tetrapentaerythritol and a pentaerythritol as an optional component, and (B) a photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition for a hard coat agent and a film having a cured film thereof. More specifically, the present invention relates to a photosensitive resin composition for a hard coat agent which improves the scratch resistance and pencil hardness of plastics such as polyester, acrylic, polycarbonate and polyether sulfone, and a film having a cured film thereof.

[0002]

2. Description of the Related Art At present, plastics are widely used in various industries including the automobile industry, the home appliance industry, and the electric and electronic industry. The reason why plastics are used in large quantities is because of their workability, transparency, light weight, low cost, and optical characteristics. However, it has drawbacks such as being softer than glass and the like, and being easily scratched on the surface. In order to improve these drawbacks, coating a surface with a hard coat agent has been generally performed. As the hard coat agent, a thermosetting hard coat agent such as a silicone paint, an acrylic paint, or a melamine paint is used. Among them, silicon-based hard coat agents have been frequently used because of their high hardness and excellent quality. Most high-value-added products such as glasses and lenses use this type of coating agent. However, since the curing time is long and the curing is performed, it cannot be said that it is suitable for a hard coat of a film to be processed continuously.

[0003] In recent years, photosensitive acrylic hard coat agents have been developed and used. The photosensitive hard coating agent cures quickly and forms a hard film by irradiating radiation such as ultraviolet rays, so it has a high processing speed, and has excellent performance such as hardness and scratch resistance. Because it becomes cheap in terms of cost,
It is now the mainstream in the hard court field. In particular, it is suitable for continuous processing of films such as polyester. Plastic films include polyester film, polyacrylate film, acrylic film, polycarbonate film, vinyl chloride film, triacetyl cellulose film, polyethersulfone film, etc., and polyester film is most widely used due to its various excellent features. Is a kind of film. This polyester film can be used as a glass shatterproof film, a car light-shielding film, a whiteboard surface film, a system kitchen surface antifouling film, or a functional film for electronic materials such as touch panels, liquid crystal displays, and CRT flat TVs. Widely used. These are all coated with a hard coat so that their surfaces are not damaged.

Further, in recent years, in a display such as a CRT or an LCD provided with a film coated with a hard coat agent, the display screen becomes difficult to see due to reflection, and a problem that eyes are easily tired occurs. Hard coat treatment with surface antireflection ability is required. As a method of preventing surface reflection, a method in which an inorganic filler or an organic fine particle filler is dispersed in a photosensitive resin is coated on a film, and the surface is made uneven to prevent reflection (AG treatment); A method of providing a multilayer structure on a high-refractive-index layer and a low-refractive-index layer in that order, and reflecting the difference in refractive index to prevent reflection (AR processing), or an AG / AR processing method combining the above two methods and so on.

[0005]

While a hard coat having a functional property is required, many studies have been conducted to further improve the hardness, which is the original purpose of the hard coat. However, while the thickness of the base film is limited, various studies have been made in order to develop a harder hard coating agent. This is the actual situation. The present invention improves the above disadvantages,
An object of the present invention is to provide a hard coat agent of a photosensitive resin composition having a pencil hardness of more than 4H on PET and a film having a cured film thereof, which is capable of forming a thick film with low curl, does not generate cracks, and has a cured film. .

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a photosensitive resin composition having a novel acrylate monomer can solve the above-mentioned problems, and have made the present invention. Completed.

That is, the present invention relates to (1) a mixture of dipentaerythritol (a), tripentaerythritol (b), tetrapentaerythritol (c) and optionally pentaerythritol (d) as a mixture (I) and (meth) A photosensitive resin composition for a hard coat agent containing a (meth) acrylate mixture (A) which is a reactant of acrylic acid and a photopolymerization initiator (B); (2) at least two or more ethylene atoms in a molecule (1) characterized by containing an ethylenically unsaturated group-containing urethane oligomer (C) obtained by reacting a compound (a) containing an ethylenically unsaturated group and active hydrogen with a polyisocyanate compound (b). The photosensitive resin composition for a hard coat agent as described in (3), wherein the primary particle size is 1 to 2
(1) The photosensitive resin composition for a hard coat agent according to (1) or (2), which further comprises (D) a diluent (E). The photosensitive resin composition for a hard coat agent according to (1) to (3), and the photosensitive resin composition for a hard coat agent according to (5) (1) to (4) are coated and cured on a film. Hard coated film.

[0008]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, a (meth) acrylate mixture (A) is used. The (meth) acrylic acid ester mixture (A) used is a mixture (I) of dipentaerythritol (a), tripentaerythritol (b) and tetrapentaerythritol (c) and optionally pentaerythritol (d) and ( It can be obtained by reacting (meth) acrylic acid. Mixture (I) is readily available from the market. For example, Tri-PE (produced by Koei Chemical Industry Co., Ltd., as a result of component analysis by gas chromatography, dipentaerythritol 5.39%, tripetaerythritol 67.26)
%, Tetrapentaerythritol 17.6%, pentaerythritol 1.12%). The smaller the amount of pentaerythritol in the mixture (I) used in the present invention, the more preferable it is.

(Meth) acrylic ester mixture (I)
The carboxylic acid of (meth) acrylic acid is reacted in an amount of 0.9 to 5.0 moles, more preferably 1 to 1.5 moles, per 1 equivalent of the hydroxyl group. The reaction temperature is 80-180 ° C, and furthermore, 9
0 ° C to 150 ° C is preferred. The reaction time is terminated by the amount of water generated by the dehydration reaction between the (meth) acrylate mixture (I) and (meth) acrylic acid,
5 to 8 hours are preferred. The amount of generated water can be easily calculated from the charged amounts of the (meth) acrylate mixture (I) and (meth) acrylic acid. After completion of the reaction, excess (meth) acrylic acid may be neutralized and washed using an aqueous alkali solution. The concentration of the alkaline aqueous solution used is 5 to 40%
Furthermore, 10 to 30% is preferable.

In the above reaction, a dehydration catalyst may be used to accelerate the reaction. Examples of the dehydration catalyst include acidic compounds such as sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and phosphoric acid. The amount used is
It is preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, based on (meth) acrylic acid.

During the reaction, a polymerization inhibitor is preferably used in order to prevent polymerization of the (meth) acryloyl group. Examples of the polymerization inhibitor include methoquinone, hydroquinone, methylhydroquinone, phenothiazine and the like. The amount used is preferably from 0.01 to 3% by weight, more preferably from 0.05 to 3% by weight, based on (meth) acrylic acid.
1.5% by weight is preferred.

In the above reaction, a diluting solvent may be used. As the diluting solvent, for example, benzene, toluene, xylene, ethylbenzene, diethylbenzene,
Organic solvents such as cyclohexane are exemplified. The diluting solvents may be used alone or in combination of two or more. The amount used is preferably 0 to 80% by weight, more preferably 5 to 50% by weight, based on the reaction raw material mixture.

In the present invention, a photopolymerization initiator (B) is used. Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2. -Phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-
Acetophenones such as hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone And anthraquinones such as 2-amylanthraquinone; 2,4-diethylthioxanthone, 2-isopropylthioxanthone,
Thioxanthones such as chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-
Benzophenones such as 4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone;
Examples thereof include phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

These can be used alone or as a mixture of two or more. Further, tertiary amines such as triethanolamine and methyldiethanolamine, ethyl N, N-dimethylaminobenzoate, N, N-dimethylaminobenzoate It can be used in combination with an accelerator such as a benzoic acid derivative such as acid isoamyl ester.

In the present invention, an ethylenically unsaturated group-containing compound obtained by reacting a compound (a) containing at least two or more ethylenically unsaturated groups and active hydrogen in a molecule with a polyisocyanate compound (b) is used. Urethane oligomers (C) can be used.

The compound (a) containing at least two ethylenically unsaturated groups and active hydrogen in the molecule includes:
For example, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di ( (Meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol tetra (meth) acrylate,
Tripentaerythritol tri (meth) acrylate,
Tripentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, epoxy obtained by reacting an epoxy resin having two or more epoxy groups in one molecule with an ethylenically unsaturated group-containing monocarboxylic acid (Meth) acrylate and the like can be mentioned.

Examples of the epoxy resin having two or more epoxy groups in one molecule used for the epoxy (meth) acrylate include bisphenol type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, and cresol novolak. Glycidyl ethers such as epoxy resin of epoxy type, trisphenol methane type epoxy resin, brominated epoxy resin, biquinolol type epoxy resin and biphenol type epoxy resin; 3,
4-epoxy-6-methylcyclohexylmethyl-3,
4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4
Alicyclic epoxy resins such as epoxycyclohexanecarboxylate and 1-epoxyethyl-3,4-epoxycyclohexane; glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate and glycidyl dimer; tetraglycidyl Glycidylamines such as diaminophenylmethane; heterocyclic epoxy resins such as triglycidyl isocyanurate; Epicoat series (Epicoat 100
9, 1031: Yuka Shell Epoxy Co., Ltd.).

Examples of the ethylenically unsaturated group-containing monocarboxylic acid include acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction of a saturated or unsaturated dibasic acid with an unsaturated group-containing monoglycidyl compound. Things. As acrylic acids, for example, a dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, a saturated or unsaturated dibasic anhydride and one hydroxyl group in one molecule Half esters which are an equimolar reaction product with a (meth) acrylate derivative, and half esters which are an equimolar reaction product of a saturated or unsaturated dibasic acid and a monoglycidyl (meth) acrylate derivative are exemplified.

The reaction between the epoxy resin and the ethylenically unsaturated group-containing monocarboxylic acid compound is carried out in such a manner that the carboxyl group of the total amount of the ethylenically unsaturated group-containing monocarboxylic acid is added to one equivalent of the epoxy group of the epoxy resin. 0.3 ~
It is preferable to react 1.2 equivalents.
1.05 equivalents are preferred. One or more diluents (E) described below can be used during or after the reaction.

Furthermore, a catalyst can be used to promote the reaction. Examples of the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, triphenylstilbin, triphenylphosphine and the like. The amount used is preferably 0.1 to 10% by weight, more preferably 0.3 to 5% by weight, based on the reaction raw material mixture.

During the reaction, a polymerization inhibitor is preferably used to prevent polymerization of the ethylenically unsaturated group. Examples of the polymerization inhibitor include methoquinone, hydroquinone, methylhydroquinone, phenothiazine and the like. The amount used is preferably from 0.01 to 1% by weight, more preferably from 0.05 to 0.5% by weight, based on the reaction raw material mixture. The reaction temperature is 60-150 ° C, and furthermore, 8
0-120 ° C is preferred. The reaction time is preferably 5 to 60 hours.

Among the above compounds (a) having two or more ethylenically unsaturated groups and active hydrogen in the molecule, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferred. It is. These compounds (a) may be used alone or in combination of two or more.

Examples of the polyisocyanate compound (b) include chain saturated hydrocarbon isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and methylene bis (4 −
Cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclic saturated hydrocarbon isocyanate such as hydrogenated tolylene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3 , 3'-Dimethyl-4,4 '
And aromatic isocyanates such as -diisocyanate, 6-isopropyl-1,3-phenyldiisocyanate and 1,5-naphthalenediisocyanate. These polyisocyanate compounds may be used alone or in combination of two or more.

The urethane oligomer having an ethylenically unsaturated group (C) comprises a compound (a) containing at least two ethylenically unsaturated groups and active hydrogen in the above-mentioned molecule and a polyisocyanate compound (b) Is reacted. The polyisocyanate compound (b) is usually used in an amount of 0.1 to 50 as an isocyanate group equivalent per 1 equivalent of an active hydrogen group of the compound (a) containing at least two or more ethylenically unsaturated groups and active hydrogen in the molecule. And preferably in the range of 0.1 to 10. The reaction temperature is usually from room temperature to 150 ° C, preferably 5 ° C.
It is in the range of 0-100 ° C. The reaction is confirmed by a decrease in the amount of isocyanate.

A catalyst may be added for the purpose of shortening the reaction time. As the catalyst, either a basic catalyst or an acidic catalyst is used. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine, and ammonia, and phosphines such as tributylphosphine and triphenylphosphine. As the acidic catalyst,
For example, metal alkoxides such as copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, trititanium tetrabutoxide, zirconium tetrabutoxide, Lewis acids such as aluminum chloride, 2-ethylhexanetin, octyltin trilaurate And tin compounds such as dibutyltin dilaurate and octyltin diacetate. Of these, acidic catalysts are preferred, and tin compounds are more preferred. The addition amount is 0.1 to 1 part by weight based on 100 parts by weight of the polyisocyanate compound.

In the present invention, colloidal silica (D) having a primary particle size of 1 to 200 nanometers can be used. Examples of the colloidal silica (D) include a colloidal solution in which colloidal silica is dispersed in a solvent, and fine powdered colloidal silica containing no dispersion solvent. Examples of a dispersion medium of a colloidal solution in which colloidal silica is dispersed in a solvent include water, alcohols such as methanol, ethanol, isopropanol, and n-butanol, ethylene glycol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and 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, and 4-hydroxybutyl (meth) acrylate; Other general organic solvents, can be used for. The amount of the dispersion medium is usually 100 colloidal silica.
It is 100 to 900 parts by weight based on parts by weight.

As these colloidal silicas, commercially available ones manufactured by a known method can be used. The particle size is
It is necessary to use one having a diameter of 1 to 200 nm, preferably 5 to 100 nm, more preferably 10 to 80 nm. In the present invention, it is preferable to use colloidal silica having a pH of 2 to 6.

In the present invention, a diluent (E) can be used. Examples of the diluent (E) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, carbitol (meth) acrylate, acryloylmorpholine, Acid anhydrides of hydroxyl group-containing (meth) acrylates (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc.) and polycarboxylic acid compounds ( For example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) half ester, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, Trimethi Dipropanetri (meth) acrylate, trimethylolpropanepolyethoxytri (meth) acrylate, glycenepolypropoxytri (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of hydroxypivalate neopenglycol (for example, Japan KAY manufactured by Kayaku Co., Ltd.
ARAD HX-220, HX-620, etc.), pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of a reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, mono or polyglycidyl Compounds (for example, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
Epoxy which is a reaction product of (meth) acrylic acid with hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether, etc. (Meth) acrylate, a reactive diluent (E-1), γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α
Lactones such as -acetyl-γ-butyrolactone and ε-caprolactone; 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 Ethers such as triethylene 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; phenol, cresol; Xylenol, etc. Phenols; esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate; hydrocarbons such as toluene, xylene, diethylbenzene, cyclohexane; trichloroethane; Organic solvents such as petroleum solvents such as petroleum ethers, petroleum naphtha, etc. (E-
2) and the like. The diluents may be used alone or as a mixture of two or more.

In the present invention, if necessary, a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, various inorganic and organic fillers, a polymer and the like may be added to impart functionality.

The photosensitive resin composition for a hard coat agent used in the present invention may contain any of the above components (A), (B), (C), (D), (E) and other components. By mixing in the following order. The amount of the component (A) is usually 30 to 9 in terms of solid content.
9% by weight, 1 to 10% by weight of component (B), 0 to component (C)
60% by weight, 0 to 60% by weight of the component (D), and 0 to 20% by weight of the component (E-1). Regarding the component (E-2),
(A) + (B) + (C) + (D) + (E-1) = 100
0 to 300 parts by weight based on parts by weight is preferred. The photosensitive resin composition used in the present invention is stable over time.

The film of the present invention comprises the above photosensitive resin composition on a film base (base film) having a weight after drying of the photosensitive resin composition of ² to 50 g / m ² , preferably 5 to 30 g. / M ² ( ^{2 to} 50 μm, preferably 5 to 30 μm in thickness), dried and then irradiated with radiation to form a cured film. , Polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetylcellulose, polyethersulfone, and the like. The film may be on a sheet.

Examples of the method of applying the photosensitive resin composition include bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating,
Examples include offset printing, flexographic printing, and screen printing. In this case, the film to be used may be provided with a pattern or an easy-adhesion layer.

As the radiation to be irradiated, for example, ultraviolet rays,
Electron beam and the like. When curing with ultraviolet light, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, etc. is used as a light source,
The amount of light, the arrangement of the light source, and the like are adjusted as needed. When a high-pressure mercury lamp is used, it is preferable to cure at a transport speed of 5 to 60 m / min for one lamp having a light amount of 80 to 120 W / cm. On the other hand, when curing with an electron beam, it is preferable to use an electron beam accelerator having an energy of 100 to 500 eV.

[0034]

Next, examples of embodiments of the present invention will be described below.
In the following description, “parts” indicates “parts by weight”. Synthesis Example 1 (Synthesis of (meth) acrylic acid ester mixture (A)) In a round bottom flask equipped with a stirrer, a cooling tube, a thermometer, and a glass tube for removing generated water, dipentaerythritol 5.
A mixture of 39%, 67.26% of tripentaerythritol, 17.60% of tetrapentaerythritol and 1.12% of pentaerythritol (Koei Chemical Industry Co., Ltd.)
300 g, acrylic acid 477 g, sulfuric acid 25 g, hydroquinone 25
g and 300 g of toluene, and heated and refluxed at 120 ° C. for 7 hours to cause a reaction. 108 g of product water was obtained. Then, the mixture was cooled and 1500 g of toluene was added.
It was neutralized and washed with an OH aqueous solution. After liquid separation, the aqueous layer was removed, and further washed three times with 300 ml of a 15% aqueous NaCl solution. Then, 0.25 g of p-methoxyphenol was charged into the toluene layer, and toluene was distilled off under reduced pressure to obtain an acrylic ester mixture ( A) 532 g were obtained. The obtained product had a viscosity of 18000 mPa · s (25 ° C.) and a specific gravity of 1.2.
00 (25 ° C.).

Synthesis Example 2 (Synthesis of urethane oligomer (C) containing an ethylenically unsaturated group) A round bottom flask equipped with a stirrer and a condenser was charged with pentaerythritol triacrylate (KAYARAD PE
T-30; Nippon Kayaku Co., Ltd.) 1020 parts, dibutyltin dilaurate 0.6 parts, methoquinone 0.6 parts,
The mixture was heated and stirred at 80 ° C. Thereafter, 177.8 parts of isophorone diisocyanate (IPDI) was added dropwise over 1 hour, and the mixture was further stirred for 2 hours to obtain a urethane oligomer (C). The isocyanate value was 0.3 or less.

EXAMPLES AND COMPARATIVE EXAMPLES A photosensitive resin composition for a hard coat agent containing the materials shown in Table 1 was applied to a polyester film (manufactured by Toyobo: A-4300, film) using a bar coater (No. 20). 188 μm), left in a drying oven at 80 ° C. for 1 minute, and then placed under a high-pressure mercury lamp of 120 W / cm 10 in an air atmosphere.
Ultraviolet rays were irradiated at a conveyor speed of 5 m / min from a distance of 5 cm to obtain a film having a cured film (10 to 15 μm).

Table 1 Compounding amount (parts by weight) Example Comparative Example 1 2 3 4 1 2 Synthesis Example 1 43 21.5 25.7 12.9 Synthesis Example 2 21.5 12.8 DPHA * 1 50 28.6 HDDA * 2 7 7 2.9 2.9 MEK-ST * 3 71.4 71.4 71.4 Irg. 184 * 4 2.3 2.3 1.3 1.3 2.3 1.3 Luciline TPO * 5 0.3 0.3 0.2 0.2 0.3 0.2 MEK 50 50 50

Note) * 1: DPHA; KAYARAD, manufactured by Nippon Kayaku Co., Ltd.
DPHA (dipentaerythritol hexaacrylate) * 2: HDDA; KS-HD, manufactured by Kayaku Sartomer Co., Ltd.
DA (hexanediol diacrylate) * 3: MEK-ST; manufactured by Nissan Chemical Industries, Ltd., organosilica sol MEK-ST (solid content 30%) * 4: Irg. 184; Ciba Specialty Chemicals (1-hydroxy-cyclohexyl-phenyl-ketone) * 5: Lucylin TPO; BASF Japan Ltd. (2,4,6-trimethylbenzoyldiphenylphosphine oxide)

(Pencil Hardness) According to JIS K 5400, the pencil hardness of the coating film having the above composition was measured using a pencil scratch tester. Specifically, a pencil is placed on a PET film having a cured film (15 μm) to be measured.
At an angle of 5 degrees, a load of 1 kg was applied from above to scratch about 5 mm, and the degree of scratching was confirmed. Five measurements were made.

(Scratch resistance test) Steel wool # 000
0, apply a load of 200 g / cm ² and reciprocate 10 times,
The condition of the scratch was visually determined.

(Adhesion) According to JIS K 5400,
The film surface is cut into 11 vertical and horizontal lines at 1 mm intervals to make 100 grids. After the cellophane tape was brought into close contact with the surface, the number of squares remaining without being peeled off at a stretch was indicated.

(Measurement of Curl by Curing Shrinkage) A PET film having a cured film (10 to 15 μm) to be measured
It was cut into a cm × 5 cm, left in a drying oven at 80 ° C. for 1 hour, and then returned to room temperature. The height of each of the four raised sides was measured on a horizontal table, and the average value was taken as a measured value (unit: mm). At this time, the curl of the substrate itself is 0 mm
Met.

(Appearance) Surface cracks, whitening, cloudiness and the like were visually determined.

Table 2 shows the evaluation results. Table 2 Evaluation Results Pencil Hardness 4H Scratches Adhesion Curl Appearance Example 1 5/5 100 7 ○ Example 2 5/5 100 6 ○ Example 3 5/5 100 6 ○ Example 4 5/5 ○ 100 5 ○ Comparative Example 1 5/5 ○ 100 10 × Comparative Example 2 5/5 ○ 100 8 △

[0045]

The photosensitive resin composition for a hard coat agent of the present invention and a film having a cured film thereof have a pencil hardness,
It has good curl and adhesion to a substrate, and is particularly suitable for fields requiring high hardness, such as plastic optical components, touch panels, flat displays, and film liquid crystal elements.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F100 AA20B AK01A AK25A AK25B AK25J AK41A AK45A AK51B AK51J AL01B AL05B BA02 CA30B DE01B EJ54 GB33 GB41 JB14 JK12B JK14 JL04 JL11 JM01B JN17 FAB 314

Claims (5)

[Claims] 1. Dipentaerythritol (a), tripentaerythritol (b), tetrapentaerythritol (c) and optionally pentaerythritol (d)
A photosensitive resin composition for a hard coat agent, comprising a (meth) acrylic ester mixture (A), which is a reaction product of the mixture (I) with (meth) acrylic acid, and a photopolymerization initiator (B). 2. An ethylenically unsaturated group-containing urethane oligomer obtained by reacting a compound (a) containing at least two or more ethylenically unsaturated groups and active hydrogen in a molecule with a polyisocyanate compound (b). The photosensitive resin composition for a hard coat agent according to claim 1, comprising (C). 3. The photosensitive resin composition for a hard coat agent according to claim 1, further comprising a colloidal silica sol (D) having a primary particle size of 1 to 200 nanometers. 4. The photosensitive resin composition for a hard coat agent according to claim 1, further comprising a diluent (E). 5. A hard coat film obtained by coating and curing the photosensitive resin composition for a hard coat agent according to claim 1 on a film.