KR20190111809A - Active energy ray curable resin composition for hard coat, cured film, laminate - Google Patents

Abstract

The present invention relates to a resin composition for active energy ray-curable hard coat, which specially has excellent adhesive force with respect to hard-bonding base materials, such as an untreated cyclic olefin resin film or the like and creates a cured film in which high hardness is also maintained. The resin composition for active energy ray-curable hard coat comprises polyfunctional (meth)acrylate (A) and alkyl benzophenone (B).

Description

Resin composition, cured film, laminated body for active energy ray hardening type hard coat {ACTIVE ENERGY RAY CURABLE RESIN COMPOSITION FOR HARD COAT, CURED FILM, LAMINATE}

The present invention relates to a resin composition for an active energy ray-curable hard coat, a cured film, and a laminate.

Since the surface of a plastic sheet or a plastic film is relatively flexible, it is easy to be damaged, and pencil hardness is low, the improvement by making a hard-coat layer on the surface of such a base material and improving surface hardness is being tried.

In addition, triacetyl cellulose film (hereinafter also referred to as TAC) is the mainstream for flat panel displays and touch panels. However, with the recent thinning of smartphones and tablets, high moisture permeability of the film is problematic. Attention has been paid to cyclic olefin resin films having excellent optical properties and low moisture permeability. However, cyclic olefin resin film is inferior in adhesiveness with a hard coat layer etc. compared with TAC, and adhesiveness with respect to hard-adhesive base materials, such as cyclic olefin resin film, is calculated | required by the resin composition for hard coats.

As a technique of improving adhesiveness, for example, the present applicant has an active energy ray-curable type containing a specific amount of an oligomer having a (meth) acryloyl group, a polypentaerythritol skeleton, and an isocyanurate group and / or a biuret group. The composition is disclosed (patent document 1). However, in this technique, when the pre-treatment by corona etc. was performed with respect to a highly adhesive base material, it had the outstanding adhesive force.

Published Unexamined 2017-179368

This invention is providing the resin composition for active energy ray hardening-type hard coats which especially gives the cured film which has the outstanding adhesive force to hard-adhesive base materials, such as an untreated cyclic olefin resin film, and also maintains high hardness.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the resin composition for active energy ray hardening-type hard coats which mix | blended the specific hardening | curing agent with polyfunctional (meth) acrylate solved the said subject, and came to complete this invention. That is, this invention relates to the following resin compositions for active energy ray hardening-type hard coats, cured films, and laminated bodies.

1. Resin composition for active energy ray hardening-type hard-coat containing polyfunctional (meth) acrylate (A) and alkyl benzophenone (B).

2. Component (B) is selected from the group consisting of 2-methyl benzophenone, 3-methyl benzophenone, 4-methyl benzophenone, 2,4,6-trimethyl benzophenone and 2,3,4-trimethyl benzophenone The resin composition for active energy ray hardening type hard coats of said 1 containing at least 1 sort (s) used.

3. The resin composition for active energy ray-curable hard coat according to the above 1, wherein the content of the component (B) is 1 to 30 parts by weight based on 100 parts by weight of the solid content weight (A) component.

4. The resin composition for active energy ray-curable hard coat according to the above 2, wherein the content of the component (B) is 1 to 30 parts by weight based on 100 parts by weight of the solid content weight (A) component.

5. Resin composition for active energy ray hardening-type hard coats in any one of said 1-4 which does not contain monofunctional (meth) acrylate (C).

6. The cured film of the resin composition for active energy ray hardening type hard coats of any one of said 1-4.

7. The laminated body which has the cured film of said 6 on at least one surface of a base material.

According to the resin composition for active energy ray hardening type hard coat of this invention, a strong cured film is formed by using alkyl benzophenone, it has the outstanding adhesive force with respect to a hard-contacting base material, and has the outstanding characteristic also in hardness.

The resin composition for active energy ray hardening type hard coat of this invention is called polyfunctional (meth) acrylate (A) (henceforth (A) component), and alkyl benzophenone (B) (henceforth (B) component). ).

The component (A) is not particularly limited as long as it has at least two (meth) acryloyl groups, and various known ones can be used. For example, 1, 4- butanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acryl Latex, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, tricyclodecane di (meth) acrylate Bifunctional (meth) acrylates such as bisphenol A ethylene oxide modified di (meth) acrylate and bisphenol F ethylene oxide modified di (meth) acrylate; Trifunctional (meth) such as trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate ) Acrylate; Tetrafunctional (meth) acrylates such as pentaerythritol tetra acrylate, dipentaerythritol tetra (meth) acrylate, and trimethylol propane tetra (meth) acrylate; (Meth) acrylate of 5 or more functional groups, such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tripentaerythritol (meth) acrylate, etc. are mentioned. These may be individual or may combine 2 or more types. Especially, from the point which maintains the high hardness of a cured film, what contains trifunctional or more (meth) acrylate (trifunctional (meth) acrylate, tetrafunctional (meth) acrylate, and (meth) acrylate) of 5 or more functionalities Preferably, it comprises one selected from the group consisting of pentaerythritol triacrylate, pentaerythritol tetra acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and tripentaerythritol acrylate It is more preferable. In addition, a (meth) acryloyl group means either methacryloyl group or acryloyl group, and a (meth) acrylate means one of methacrylate or acrylate. The following (meta) is also the same.

In addition, as a commercial item, "BISCOOT # 230", "BISCOOT # 260", "BISCOOT # 300", "BISCOOT # 295", "BISCOOT # 802" (above, Osaka organic chemical industry company make) ), `` NK ester A-HD-N '', NK ester HD-N, NK ester A-NOD-N, NK ester NOD-N, NK ester A-TMM-3, NK Ester A-TMM-3L "," NK ester A-TMMT "," NK ester A-9550 "(above, Shin-Nakamura Chemical Industry Co., Ltd. product)," Aronix M-305 "," Aronix M-450 And "Aronix M-309", "Aronix M-400", "Aronix M-402" (above, manufactured by Toagosei Co., Ltd.), and the like.

Furthermore, as (A) component, polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy poly (meth) acrylate, etc. can be used other than this, for example. These may be individual or may combine 2 or more types. Moreover, you may use together with said bifunctional (meth) acrylate, trifunctional (meth) acrylate, tetrafunctional (meth) acrylate, and (meth) acrylate of 5 or more functionalities.

As a polyurethane acrylate, the acrylate oligomer obtained by carrying out a urethanation reaction of a hydroxyl group containing (meth) acrylate with the isocyanate group terminal prepolymer obtained by urethanating various well-known polyol and polyisocyanate, and a polyol, The acrylate oligomer etc. which are obtained by making an isocyanate group containing mono (meth) acrylate react with the hydroxyl group terminal prepolymer obtained by carrying out a urethanation reaction of polyisocyanate are mentioned.

The polyol is not particularly limited, and examples thereof include polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, polyolefin polyols, and the like. These may be individual or may combine 2 or more types.

The polyether polyol is not particularly limited and, for example, various alkylenes as monomer components such as ethylene oxide-propylene oxide copolymer, in addition to polyalkylene glycols such as polyethylene glycol, polypropylene glycol, poly tetramethylene glycol, and the like. And copolymers containing an oxide (alkylene oxide-other alkylene oxide), and these may be used alone or in combination of two or more thereof. Adeka polyether P-400, adeka polyether G-400, adeka polyether T-400, adeka polyether AM-302 (above, Adeka Corporation) etc. are mentioned as a commercial item.

It does not specifically limit as polyester polyol, For example, Condensation polymer of a polyol and polycarboxylic acid; Ring-opening polymers of cyclic esters (lactones); And trivalent reactants of polyols, polycarboxylic acids and cyclic esters.

The polyol is not particularly limited, and for example, diethylene glycol, propylene glycol, 1,3-propane diol, 1,4-butane diol, 2-methyl-1,3-propane diol, 1,5-pentane diol Aliphatic diols such as neopentyl glycol, 1,6-hexane diol, 1,9-nonane diol, and 1,10-decane diol; Aliphatic triols such as glycerin, trimethylol propane and trimethylol ethane; Alicyclic diols such as 1,2-cyclohexane diol, 1,4-cyclohexane diol, and 1,4-cyclohexane dimethanol; Bisphenols such as bisphenol A and bisphenol F; Sugar alcohols, such as xylitol and sorbitol, etc. are mentioned, These may combine 2 or more types independently. Moreover, it does not specifically limit as polycarboxylic acid, For example, Aliphatic dicarboxylic acid, such as malonic acid, a maleic acid, succinic acid, adipic acid, a sublinic acid, azeline acid, sebacic acid, a dodecane diacid; Alicyclic dicarboxylic acids such as 1,4-cyclohexane dicarboxylic acid; Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid and 2,6-naphthalene dicarboxylic acid; Aliphatic tricarboxylic acids such as propane-1,2,3-tricarboxylic acid; And aromatic tricarboxylic acids such as trimellitic acid and trimesic acid. These may be used alone or in combination of two or more thereof. Moreover, it does not specifically limit as cyclic ester, For example, propio lactone, (beta) -methyl- (delta) -valerolactone, (epsilon) -caprolactone, etc. are mentioned, These may be individual or may combine 2 or more types. . As a commercial item of a polyester polyol, Kuraray polyol P-510, Kuraray polyol F-510 (above, Kuraray Co., Ltd.), Fraxel 205 (made by Daicel Co., Ltd.), etc. are mentioned.

The polycarbonate polyol is not particularly limited, and examples thereof include reactants of polyols with phosgene; The ring-opening polymer of cyclic carbonate (alkylene carbonate etc.) etc. are mentioned. Examples of the polyols include the above. It does not specifically limit as alkylene carbonate, For example, ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, etc. are mentioned, These may be individual or may combine 2 or more types. As a commercial item of a polycarbonate polyol, Kuraray polyol C-590 (made by Kuraray) etc. is mentioned.

The acryl polyol is not particularly limited, and examples thereof include those obtained by copolymerizing an acrylic monomer having at least one hydroxyl group in one molecule with a homopolymer or a copolymer or copolymerizing another monomer with the copolymer. You may combine 2 or more types of figures. As a commercial item of an acryl polyol, ARUFON UH-2041 (made by Toagosei Co., Ltd.) etc. are mentioned.

The polyolefin polyol is not particularly limited, and examples thereof include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, such chlorinated compounds, and these alone or in combination of two or more thereof. Also good. As a commercial item, NISSO-PB GI-1000 (made by Nippon Soda Co., Ltd.) etc. is mentioned.

It does not specifically limit as polyisocyanate, It is 2, 4- tolylene diisocyanate, 2, 6- tolylene diisocyanate, 1, 3- xylene diisocyanate, diphenylmethane -4, 4- diisocyanate, 3-methyldi Aromatic diisocyanates such as phenylmethane diisocyanate and 1,5-naphthalene diisocyanate; Aliphatic diisocyanates such as dicyclo hexylmethane diisocyanate, isophorone diisocyanate and hexa methylene diisocyanate; These dimers etc. are mentioned, These may be individual or may combine 2 or more types.

It does not specifically limit as hydroxyl-containing mono (meth) acrylate, 1-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate 4-hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, 4- (hydroxymethyl) cyclohexyl methyl (meth) acrylate, 2-hydroxy propionic acid 4 -(Hydroxymethyl) cyclohexyl methyl, hydroxyphenyl (meth) acrylate, etc. are mentioned, These may be individual or may combine 2 or more types.

The isocyanate group-containing (meth) acrylate is not particularly limited, and 2-isocyanatoethyl (meth) acrylate, 1,1- (bisacryloyl oxymethyl) ethyl isocyanate and the like can be given, and these are single Also as a combination of two or more.

It does not specifically limit as polyester (meth) acrylate, The hydroxyl group obtained by esterifying with said dicarboxylic acid (aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid) and low molecular diol. The hydroxyl group-containing mono (meth) acryl is further added to the (meth) acrylate oligomer obtained by esterifying the unsaturated carboxylic acid to the terminal polyester and the carboxylic group terminal polyester obtained by reacting the dicarboxylic acid and the diol compound. (Meth) acrylate oligomer etc. which are obtained by esterifying a rate are mentioned.

The unsaturated carboxylic acid is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, fumaric acid, and crotonic acid, and these may be used alone or in combination of two or more thereof. good.

As an epoxy poly (meth) acrylate, the acrylate oligomer obtained by addition-reacting the said carboxyl group containing mono (meth) acrylate with the epoxy resin which has at least two epoxy groups in one molecule is mentioned, for example.

It does not specifically limit as an epoxy resin, For example, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, a bisphenol A novolak-type Epoxy resins, naphthalene diol type epoxy resins, phenol dicyclo pentadiene novolac type epoxy resins or their hydrides; 3,4-epoxycyclohexyl methyl-3 ', 4'-epoxycyclohexane carboxylate, 1,2-epoxyvinylcyclohexene, bis (3,4-epoxycyclohexylmethyl) adipate, 1-epoxyethyl- 1,2-epoxy-4- (2 of 3,4-epoxycyclohexane, 3,4-epoxycyclohexyl methanol, dicyclo pentadiene diepoxide, 2,2-bis (hydroxymethyl) -1-butanol Alicyclic epoxy resins, such as an oxiranyl) cyclohexane addition product, etc. are mentioned, These may combine 2 or more types. In addition, as an oligomer type thing in alicyclic epoxy resin, Epoxidized butane tetracarboxylic-acid tetrakis- (3-cyclohexenylmethyl) modified (epsilon) -caprolactone (for example, brand name "Eporide GT401) And epoxy resins obtained by epoxidizing alicyclic olefins such as Daicel Co., Ltd.).

Although it does not specifically limit as a physical property of (A) component, For example, the weight average molecular weight (polystyrene conversion value by gel permeation chromatography) is preferable about 150-100,000 from the point which maintains the high hardness of a cured film, More preferably about 180 to 80,000.

(B) component is a component used in order to exhibit the outstanding adhesive force also to hard-adhesive base materials, such as a cyclic olefin resin film. It does not specifically limit as (B) component, For example, Monoalkyl benzophenone, such as 2-methyl benzophenone, 3-methyl benzophenone, 4-methyl benzophenone; And trialkyl benzophenones such as 2,4,6-trimethyl benzophenone and 2,3,4-trimethyl benzophenone. These may be individual or may combine 2 or more types. In particular, it includes at least one selected from the group consisting of 2-methyl benzophenone, 3-methyl benzophenone, 4-methyl benzophenone, 2,4,6-trimethyl benzophenone and 2,3,4-trimethyl benzophenone. It is preferable to, and 4-methyl benzophenone is more preferable.

Although content of (B) component is not specifically limited, About 1-30 weight part is preferable with respect to 100 weight part of solid content weight (A) component from the point which maintains the high hardness of a cured film, About 1-5 weight part More preferred.

The resin composition for active energy ray-curable hard coats of the present invention may further contain other curing agents (hereinafter, referred to as "other curing agents") other than the component (B). It does not specifically limit as another hardening | curing agent, For example, 1-hydroxy cyclohexyl phenyl ketone, 2, 2- dimethoxy- 1, 2- diphenyl ethan-1-one, 1-cyclohexyl phenyl ketone, 2- Hydroxy-2-methyl-1-phenyl propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl amino-1- (4-morpholino phenyl) -1-butanone, Bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, and the like. Moreover, it is not specifically limited also in the content, Generally it is 10 weight part or less with respect to 100 weight part of (A) component, Preferably it is less than 5 weight part.

Although the resin composition for active energy ray hardening-type hard coats of this invention may contain monofunctional (meth) acrylate (C) (henceforth (C) component), it contains from the point which maintains the high hardness of a cured film. It is desirable not to. It does not specifically limit as (C) component, For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl ( Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, iso Octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-undecyl (meth) acrylate , Isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, isododecyl (meth) acrylate n-lauryl (meth) acrylate, n-myristyl (meth) acrylate, isomiri Steel (meth) acrylate, n-cetyl (meth) acrylate, n-stearyl (meth Aliphatic mono (meth) acrylates such as) acrylate and 2-ethylhexyl (meth) acrylate; Alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate; Aromatic mono (meth) acrylates, such as phenyl (meth) acrylate, etc. are mentioned. These may be individual or may combine 2 or more types.

The resin composition for active energy ray-curable hard coats of the present invention may further contain an organic solvent. It does not specifically limit as an organic solvent, For example, Ketones, such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; Aromatic hydrocarbons such as toluene and benzene; Esters such as butyl acetate, propyl acetate, ethyl acetate, propylene glycol mono methyl ether acetate; Alcohols such as ethanol and 2-propanol; aliphatic hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, and n-heptane; Ethers such as isopropyl ether, methyl cellosolve, ethyl cellosolve, 1,4-dioxane, didiglyme, propylene glycol mono methyl ether, ethylene glycol mono ethyl ether acetate, propylene glycol mono methyl ether acetate; Chloroform, dimethylformamide and the like, and these may be used alone or in combination of two or more thereof. Although the content of the organic solvent is not specifically limited, It is preferable to adjust so that it may become 40 to 80 weight% at solid content concentration of a resin composition.

The resin composition for active energy ray-curable hard coats of the present invention further contains surface conditioners, surfactants, photosensitizers, light stabilizers, antioxidants, leveling agents, pigments, inorganic fillers, silane coupling agents, colloidal silica, antifoaming agents, and wetting agents. Various known additives, such as a rust inhibitor, a ultraviolet absorber, and an antistatic agent, can be included.

The resin composition for active energy ray hardening-type hard coats of this invention can be obtained by mixing (A) component, (B) component, a solvent, and an additive as needed. The mixing means and the mixing order are not particularly limited.

The cured film of this invention hardens the resin composition for active energy ray hardening-type hard coats of this invention.

It does not specifically limit as thickness of the cured film of this invention, Generally, it is about 1-40 micrometers, Preferably it is about 3-20 micrometers.

The laminated body of this invention has the said cured film in at least one surface of a base material, The method is not specifically limited, For example, apply the active energy ray hardening-type hard coat resin composition of this invention to a base material, and to make active energy It is obtained by irradiating a line.

It does not specifically limit as a base material, For example, a polyethylene terephthalate film (PET film), a cyclic olefin resin film, a polypropylene film, a polybutyene film, a polybutadiene film, a polymethyl pentene film, a polyvinyl chloride film, chloride Vinyl copolymer film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene (meth) acrylic acid copolymer film, ethylene (meth) acrylic acid ester copolymer film , Polystyrene film, polycarbonate film, polyimide film, fluororesin film and the like. Moreover, you may use these crosslinked films or laminated | multilayer film. These films may use either untreated, light to medium peeling treatments, or those having an adhesive layer.

Moreover, it does not specifically limit as a coating method, For example, an applicator, a bar coater, a roll coater, a knife coater, a gravure coater etc. are mentioned.

It is preferable that the laminated body of this invention removes an organic solvent by previously drying with a preliminary heat source after coating the resin composition for active energy ray hardening-type hard-coats to a base material. It does not specifically limit as a heat source, A pure air dryer, an electric oven, a gas oven, etc. are mentioned. It does not specifically limit as dry conditions, Generally, temperature is about 40-150 degreeC, Preferably it is about 50-120 degreeC, Time is about 15 second-about 5 minutes, Preferably it is about 30 second-about 3 minutes.

Next, an active energy ray is irradiated to harden a coating layer. It does not specifically limit as an active energy ray, For example, an ultraviolet-ray, a visible ray, an electron beam, an ionizing radiation etc. are mentioned. In this invention, it is preferable to use an ultraviolet-ray from the sclerosis | hardenability of a coating layer.

Although it does not specifically limit as a light source of an ultraviolet-ray, For example, an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon lamp, a metal halide lamp, etc. are mentioned. Moreover, as irradiation conditions, although it changes with the light source to be used, generally, the accumulated light amount is about 1-1000 mJ / cm <^2> , and irradiation intensity is about 1-1000 mW / cm <^2> .

It does not specifically limit as thickness of the obtained laminated body, It is about 1-40 micrometers only about 100-140 micrometers and a cured film (hard coat resin layer).

EXAMPLE

Hereinafter, the present invention will be described through Examples, but the present invention is not limited thereto. In addition, parts and% in the examples and the comparative examples are based on weight unless otherwise specified.

(Weight average molecular weight)

According to gel permeation chromatography (GPC method), the weight average molecular weight was measured under the following conditions.

Molecular weight measuring instrument (product name "HLC-8220GPC", product of Toso Corporation)

Column (product name "TSKgel G1000H", "TSKgel G2000PH" Toso Corporation make)

Developing Solvent: Tetrahydrofuran

Flow rate: 0.35 mL / min

Sample concentration: 0.5 g / L

Standard material: polystyrene (standard polystyrene kit, PStQuickA, B, C, manufactured by Tosoh Corporation)

Preparation Example 1 (Preparation of Polyurethane Acrylate)

95 parts of biscoat # 300 (pentaerythritol triacrylate and pentaerythritol tetraacrylate acrylic acid condensate) and 5 parts isophorone diisocyanate in a reaction vessel equipped with a stirring device, a cooling tube, a dropping rod and a nitrogen introduction tube And 0.1 part of metoquinone and 0.04 part of tin octylic acid as a catalyst, and the temperature was raised to 80 ° C. for 2 hours. It cooled and obtained the polyurethane acrylate of 100% of solid content concentration, and the weight average molecular weight 900.

Preparation Example 2 (Preparation of Epoxy Polyacrylate)

In a reaction vessel equipped with a stirring device, a cooling tube, a dropping rod and a nitrogen introduction tube, 250 parts of glycidyl methacrylate, 1.3 parts of lauryl mercaptan, 1000 parts of methyl isobutyl ketone and 2,2'-azobis iso After adding 7.5 parts of butylonitrile (henceforth AIBN), it heated up until it became 90 degreeC over about 1 hour under nitrogen stream, and warmed for 1 hour. Next, the mixed liquid consisting of 750 parts of GMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN was previously added to a dropping rod, added dropwise into the system over about 2 hours under a stream of nitrogen, and further kept warm at the same temperature for 3 hours. 10 parts was added and it warmed for 1 hour. Then, the temperature was raised to 130 ° C. and kept warm for 2 hours. After cooling to 60 ° C., the nitrogen inlet tube was replaced with an air inlet tube, 507 parts of acrylic acid (hereinafter referred to as AA), 2.3 parts of metoquinone and 6.0 parts of triphenyl phosphine were added and mixed, followed by 110 ° C. under air bubbling. It heated up to. After keeping at the same temperature for 8 hours, 1.6 parts of metoquinone was added, cooled, and methyl isobutyl ketone was added so as to have a solid content of 60% to obtain an epoxy polyacrylate having a weight average molecular weight of 22,000.

Example 1

Solid content concentration by mixing 100 parts of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name "Biscote # 300" manufactured by Osaka Organic Industry Co., Ltd.), 5 parts of 4-methylbenzophenone and 105 parts of toluene 50% of the active energy ray-curable hard coat resin composition was obtained.

Examples 2-15, Comparative Examples 1-2

The composition and toluene shown in Table 1 were mix | blended, and the resin composition for active energy ray hardening-type hard coats of 50% of solid content concentration was obtained, respectively.

<Production of Laminate>

The resin composition for active energy ray hardening type hard coat of Example 1 was coated by the bar coater so that the thickness of a coating layer might be 10 micrometers, and it dried at 80 degreeC for 1 minute in 100 micrometers cyclic olefin resin film (untreated). Next, in the air, it was passed under a high pressure mercury lamp (accumulated light amount: 100 mJ / cm ² , irradiation intensity: 100 mW / cm ² ) (conveying speed 10 m / min), and cured to obtain a laminate. It carried out by the same method also in the resin composition for active energy ray hardening-type hard coats of Examples 2-15 and Comparative Examples 1 and 2, and obtained the laminated body, respectively.

<Adhesiveness>

The sheath leading to a base material at 1 mm space | interval was put into the surface of each laminated body, the 100-cell board cellophane tape peeling test was done, and initial stage adhesiveness was evaluated. Table 1 shows the results. With respect to 100 cells (denominator), 100/100 represented by the number (molecules) of the cells which did not peel off indicates the best adhesion (hereinafter, the same).

<Pencil hardness>

It measured according to JIS K5600-5-4. B or more was made favorable.

(A) Component (Ｂ) Ingredients Other curing agents Laminate Kinds Parts by weight Kinds Parts by weight Kinds Parts by weight Adhesiveness Hardness Example 1 A-1 100 4-MXP 5 － 100/100 Ｂ Example 2 A-1 100 4-MXP 30 － 100/100 Ｂ Example 3 A-1 100 4-MXP 20 － 100/100 Ｂ Example 4 A-1 100 4-MXP 10 － 100/100 Ｂ Example 5 A-1 100 4-MXP One － 100/100 Ｂ Example 6 A-2 100 4-MXP 5 － 100/100 Ｂ Example 7 A-3 100 4-MXP 5 － 100/100 Ｂ Example 8 A-4 100 4-MXP 5 － 100/100 Ｂ Example 9 A-5 100 4-MXP 5 － 100/100 HH Example 10 A-6 100 4-MXP 5 － 100/100 F Example 11 A-1 100 2-MXP 5 － 100/100 Ｂ Example 12 A-1 100 ＴＭＢＰ 5 － 100/100 Ｂ Example 13 A-1 100 4-MXP 5 ＴＰＯ 3 100/100 H Example 14 A-1 100 4-MXP 5 イ ｒｇ184 3 100/100 F Example 15 A-1 100 4-MXP 5 イ ｒｇ907 3 100/100 HH Comparative Example 1 A-1 100 － ＴＰＯ 5 0/100 F Comparative Example 2 A-1 100 － イ ｒｇ184 5 0/100 F

<(A) component>

A-1: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name "BISCOTT # 300" manufactured by Osaka Organic Industry Co., Ltd.)

A-2: mixture of A-1 and polyurethane acrylate of Preparation Example 1 (A-1 / Preparation Example 1 = 50/50 (solid weight))

A-3: A mixture of A-1 and epoxy polyacrylate of Preparation Example 2 (A-1 / Preparation Example 2 = 50/50 (solid weight))

A-4: A-1, mixture of polyurethane acrylate of Preparation Example 1 and 1,6-hexanediol diacrylate (HDDA) (A-1 / Preparation Example 1 / HDDA = 45/45/10 (solid content) weight))

A-5: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexa acrylate (trade name "Aronix M-400" manufactured by Toagosei Co., Ltd.)

A-6: tripentaerythritol acrylate (trade name "Biscote # 802" manufactured by Osaka Organic Chemical Industry Co., Ltd., see following formula)

In addition, "biscoat # 802" (Osaka Organic Chemical Industry Co., Ltd.) of A-6 is represented by the following chemical formula.

[Formula 1]

<(B) component>

4-MBP: 4-methyl benzophenone

2-MBP: 2-methyl benzophenone

TMBP: 2,3,4-trimethyl benzophenone

<Other curing agents>

TPO: 2,4,6-trimethylbenzoyl diphenylphosphine oxide (trade name "Speedcure TPO" manufactured by Lambson Group Ltd.)

Irg184: 1-hydroxy cyclohexyl phenyl ketone (trade name "Irugakyua 184" made by BASF Japan Co., Ltd.)

Irg907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name "Irugakyua 907" made by BASF Japan Co., Ltd.)

Claims (7)

Resin composition for active energy ray hardening-type hard-coat containing polyfunctional (meth) acrylate (A) and alkyl benzophenone (B).
The method of claim 1,
The component (B) is at least selected from the group consisting of 2-methyl benzophenone, 3-methyl benzophenone, 4-methyl benzophenone, 2,4,6-trimethyl benzophenone and 2,3,4-trimethyl benzophenone The resin composition for active energy ray hardening type hard coat containing 1 type.
The method of claim 1,
The resin composition for active energy ray-curable hard coats, wherein the content of the component (B) is 1 to 30 parts by weight based on 100 parts by weight of the solid content weight (A) component.
The method of claim 2,
The resin composition for active energy ray-curable hard coats, wherein the content of the component (B) is 1 to 30 parts by weight based on 100 parts by weight of the solid content weight (A) component.
The method according to any one of claims 1 to 4,
The resin composition for active energy ray hardening-type hard coats which does not contain a monofunctional (meth) acrylate (C).
The cured film of the resin composition for active energy ray hardening type hard coats of any one of Claims 1-4.
The laminated body which has the cured film of Claim 6 on at least one surface of a base material.