KR102535069B1 - Active energy ray curable resin composition for hard coat, cured film, laminate - Google Patents

Abstract

[Problem] It is to provide a resin composition for an active energy ray-curable hard coat that provides a cured film having excellent adhesive strength to a difficult-to-adhesive substrate such as an untreated cyclic olefin resin film in particular and maintaining high hardness.
[Solution] A resin composition for an active energy ray-curable hard coat comprising a polyfunctional (meth)acrylate (A) and an alkyl benzophenone (B).

Description

Resin composition for active energy ray curable 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 plastic film is relatively soft and easily scratched and has low pencil hardness, efforts have been made to improve the surface hardness by forming a hard coat layer on the surface of such a substrate.

In addition, for applications such as flat panel displays and touch panels, triacetyl cellulose films (hereinafter also referred to as TAC) are mainstream, but with the recent thinning of smartphones and tablets, the high moisture permeability of the film is a problem, and as an alternative A cyclic olefin resin film having excellent optical properties and low moisture permeability has attracted attention. However, cyclic olefin resin films are inferior in adhesion to hard coat layers and the like compared to TAC, and adhesion to difficult-to-adhesive substrates such as cyclic olefin resin films is required for resin compositions for hard coats.

As a technique for improving adhesion, the present applicant, for example, uses an active energy ray curing type containing a specific amount of an oligomer having a (meth)acryloyl group, a polypentaerythritol backbone, and an isocyanurate group and/or a non-uret group. A composition is disclosed (Patent Document 1). However, in the present technology, excellent adhesive strength was obtained when a pretreatment by corona or the like was performed on a difficult-to-adhesive substrate.

Special Publication No. 2017 - No. 179368

The present invention is to provide a resin composition for an active energy ray-curable hard coat that provides a cured film that has excellent adhesive strength to a difficult-to-adhesive substrate such as an untreated cyclic olefin resin film in particular and maintains high hardness.

As a result of intensive studies, the inventors of the present invention have found that a resin composition for an active energy ray-curable hard coat in which a specific curing agent is blended with a polyfunctional (meth)acrylate solves the above problems, and has completed the present invention. That is, this invention relates to the following resin compositions for active energy ray-curable hard coats, cured films, and laminates.

1. A resin composition for an active energy ray-curable hard coat containing polyfunctional (meth)acrylate (A) and alkyl benzophenone (B).

2. The 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-curable hard coats of the said item 1 containing at least 1 sort(s) which becomes.

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

4. The active energy ray-curable hard coat resin composition 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 component (A).

5. The resin composition for an active energy ray-curable hard coat according to any one of the above items 1 to 4, which does not contain a monofunctional (meth)acrylate (C).

6. The cured film of the resin composition for active energy ray-curable hard coats in any one of said 1st item|item to 4th item|item.

7. A laminate having the cured film of item 6 above on at least one surface of a base material.

According to the active energy ray-curable hard coat resin composition of the present invention, a strong cured film is formed by using alkyl benzophenone, has excellent adhesive strength to a difficult-to-adhesive substrate, and has excellent hardness.

The resin composition for an active energy ray-curable hard coat of the present invention is a polyfunctional (meth)acrylate (A) (hereinafter referred to as component (A)) and an alkyl benzophenone (B) (hereinafter referred to as component (B)) ).

The component (A) is not particularly limited as long as it has at least two or more (meth)acryloyl groups, and various known ones can be used. For example, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate Late, 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)acrylates such as trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate ) acrylate; tetrafunctional (meth)acrylates such as pentaerythritol tetraacrylate, dipentaerythritol tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate; Dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol (meth)acrylate, and the like. These may be independent or may combine 2 or more types. Among them, from the viewpoint of maintaining high hardness of the cured film, it is preferable to include trifunctional or higher functional (meth)acrylates (trifunctional (meth)acrylate, tetrafunctional (meth)acrylate, or pentafunctional or higher functional (meth)acrylate). Preferably, containing one selected from the group consisting of pentaerythritol triacrylate, pentaerythritol tetra acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and tripentaerythritol acrylate it is more preferable Further, the (meth)acryloyl group means either a methacryloyl group or an acryloyl group, and (meth)acrylate means either methacrylate or acrylate. The following (meta) is also the same.

In addition, as commercially available products, "Biscott # 230", "Viscoat # 260", "Viscoat # 300", "Viscoat # 295", "Viscoat # 802" (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.) ), "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, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), "Aronix M-305", "Aronix M-450 ”, “Aronix M-309”, “Aronix M-400”, “Aronix M-402” (above, manufactured by Toagosei Co., Ltd.), and the like.

Further, as the component (A), for example, polyurethane (meth)acrylate, polyester (meth)acrylate, epoxy poly (meth)acrylate and the like can be used. These may be independent or may combine 2 or more types. Moreover, you may use together with said bifunctional (meth)acrylate, trifunctional (meth)acrylate, tetrafunctional (meth)acrylate, and pentafunctional (meth)acrylate.

As the polyurethane acrylate, an acrylate oligomer obtained by urethane-forming an isocyanate group terminal prepolymer obtained by urethane-forming various known polyols and polyisocyanates, and further hydroxyl-containing (meth)acrylates, and polyols An acrylate oligomer obtained by reacting an isocyanate group-containing mono(meth)acrylate with a hydroxyl terminal prepolymer obtained by urethanizing polyisocyanate, and the like are exemplified.

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

The polyether polyol is not particularly limited, and examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, as well as various alkylenes as monomer components such as ethylene oxide-propylene oxide copolymers. oxide-containing (alkylene oxide - other alkylene oxide) copolymers; and the like, which may be used singly or in combination of two or more. Examples of commercially available products include Adeka Polyether P-400, Adeka Polyether G-400, Adeka Polyether T-400, and Adeka Polyether AM-302 (above, manufactured by Adeka Co., Ltd.).

It does not specifically limit as a polyester polyol, For example, the condensation polymer of a polyol and polycarboxylic acid; ring-opening polymers of cyclic esters (lactones); polyols, polycarboxylic acids, and ternary reactants of cyclic esters; and the like.

The polyol is not particularly limited, and examples thereof include diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, and 1,5-pentanediol. 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 be independent and may combine 2 or more types. Further, the polycarboxylic acid is not particularly limited, and examples thereof include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, adipic acid, sberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; 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; Aromatic tricarboxylic acids, such as trimellitic acid and trimesic acid, etc. are mentioned, These may be independent or may combine 2 or more types. Further, the cyclic ester is not particularly limited, and examples thereof include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone, and these may be used alone or in combination of two or more. . Examples of commercially available polyester polyols include Kuraray Polyol P-510, Kuraray Polyol F-510 (above, manufactured by Kuraray Co., Ltd.), and Fraxel 205 (manufactured by Daicel Co., Ltd.).

The polycarbonate polyol is not particularly limited, and examples thereof include a reaction product of a polyol and phosgene; ring-opening polymers of cyclic carbonic acid esters (such as alkylene carbonate); and the like. Examples of the polyol include those described above. The alkylene carbonate is not particularly limited, and examples thereof include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like, and these may be used alone or in combination of two or more. Commercially available polycarbonate polyols include Kuraray Polyol C-590 (manufactured by Kuraray Co., Ltd.).

The acrylic polyol is not particularly limited, and examples thereof include homopolymers or copolymers of acrylic monomers having at least one hydroxyl group in one molecule, or copolymers of these copolymers with other monomers. You may combine 2 or more types of FIG. Examples of commercially available acrylic polyols include ARUFON UH-2041 (manufactured by Toagosei Co., Ltd.).

Examples of the polyolefin polyol include, but are not particularly limited to, polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and chlorinated compounds of these, either alone or in combination of two or more. also good As a commercial item, NISSO-PB GI-1000 (Nippon Soda Co., Ltd. product) etc. are mentioned.

The polyisocyanate is not particularly limited, and 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, diphenylmethane-4,4-diisocyanate, and 3-methyldi aromatic diisocyanates such as phenylmethane diisocyanate and 1,5-naphthalene diisocyanate; aliphatic diisocyanates such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate; These 2-hexamers etc. are mentioned, These may be independent or may combine 2 or more types.

The hydroxyl group-containing mono(meth)acrylate is not particularly limited, and 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 examples thereof include 2-isocyanatoethyl (meth)acrylate, 1,1-(bisacryloyloxymethyl) ethyl isocyanate, and the like. It is also good to combine two or more species.

The polyester (meth)acrylate is not particularly limited, and a hydroxyl group obtained by esterification with the above dicarboxylic acids (aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids) and low-molecular-weight diols. A (meth)acrylate oligomer obtained by esterifying an unsaturated carboxylic acid with a terminal polyester and a carboxyl group terminal polyester obtained by reacting the dicarboxylic acid and diol compound with the above-mentioned hydroxyl group-containing mono(meth)acryl and (meth)acrylate oligomers obtained by subjecting a rate to an esterification reaction.

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

Examples of the epoxy poly(meth)acrylate include acrylate oligomers obtained by subjecting the carboxyl group-containing mono(meth)acrylate to an addition reaction to an epoxy resin having at least two epoxy groups in one molecule.

The epoxy resin is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, and bisphenol A type novolak type. epoxy resins, naphthalene diol type epoxy resins, phenol dicyclopentadiene novolak type epoxy resins or hydrides thereof; 3,4-epoxycyclohexyl methyl-3',4'-epoxycyclohexane carboxylate, 1,2-epoxyvinylcyclohexene, bis(3,4-epoxycyclohexylmethyl) adipate, 1-epoxyethyl- 3,4-epoxycyclohexane, 3,4-epoxycyclohexyl methanol, dicyclopentadiene diepoxide, 1,2-epoxy-4-(2 of 2,2-bis(hydroxymethyl)-1-butanol - Alicyclic epoxy resins, such as an oxiranyl) cyclohexane adduct, etc. are mentioned, These may combine 2 or more types. In addition, among the alicyclic epoxy resins, oligomer-type ones include, for example, epoxidized butane tetracarboxylic acid tetrakis-(3-cyclohexenylmethyl)-modified ε-caprolactone (for example, trade name “Eporide GT401 ", an epoxy resin obtained by epoxidizing an alicyclic olefin, such as Daicel Co., Ltd.), etc. are mentioned.

The physical properties of the component (A) are not particularly limited, but from the viewpoint of maintaining high hardness of the cured film, for example, the weight average molecular weight (value in terms of polystyrene by gel permeation chromatography) is preferably about 150 to 100,000, , more preferably about 180 to 80,000.

Component (B) is a component used in order to exhibit excellent adhesive strength also to difficult-to-adhesive substrates such as cyclic olefin resin films. The component (B) is not particularly limited, and examples thereof include monoalkyl benzophenones such as 2-methyl benzophenone, 3-methyl benzophenone, and 4-methyl benzophenone; trialkyl benzophenones such as 2,4,6-trimethyl benzophenone and 2,3,4-trimethyl benzophenone; and the like. These may be independent or may combine 2 or more types. In particular, 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, and 4-methyl benzophenone is more preferable.

The content of the component (B) is not particularly limited, but is preferably about 1 to 30 parts by weight, about 1 to 5 parts by weight, based on 100 parts by weight of the solid content (A) component, from the viewpoint of maintaining high hardness of the cured film. more preferable

The resin composition for an active energy ray-curable hard coat of the present invention may further contain other curing agents (hereinafter referred to as "other curing agents") other than the component (B). The other curing agent is not particularly limited, and examples thereof include 1-hydroxycyclohexyl 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-dimethylamino-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. Also, the content thereof is not particularly limited, and is generally 10 parts by weight or less, preferably less than 5 parts by weight, based on 100 parts by weight of component (A).

The resin composition for an active energy ray-curable hard coat of the present invention may further contain a monofunctional (meth)acrylate (C) (hereinafter referred to as component (C)), but it is included from the viewpoint of maintaining high hardness of the cured film. It is preferable not to do so. (C) The component is not particularly limited, and examples thereof include 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 , isoundecyl (meth)acrylate, n-dodecyl (meth)acrylate, isododecyl (meth)acrylate, n-lauryl (meth)acrylate, n-myristyl (meth)acrylate, isomiristyl aliphatic mono(meth)acrylates such as steel (meth)acrylate, n-cetyl (meth)acrylate, n-stearyl (meth)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 independent or may combine 2 or more types.

The resin composition for an active energy ray-curable hard coat of the present invention may further contain an organic solvent. The organic solvent is not particularly limited, and examples thereof include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene and benzene; esters such as butyl acetate, propyl acetate, ethyl acetate, and propylene glycol monomethyl 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, diglyme, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate; Chloroform, dimethylformamide, etc. are mentioned, These may be used individually or in combination of 2 or more types. The content of the organic solvent is not particularly limited, but is preferably adjusted to be 40 to 80% by weight in terms of the solid content of the resin composition.

The active energy ray curable hard coat resin composition of the present invention further contains a surface conditioner, a surfactant, a photosensitizer, a light stabilizer, an antioxidant, a leveling agent, a pigment, an inorganic filler, a silane coupling agent, colloidal silica, an antifoaming agent, and a wetting agent. , rust inhibitors, ultraviolet absorbers, and various known additives such as antistatic agents may be included.

The resin composition for an active energy ray-curable hard coat of the present invention can be obtained by mixing component (A) and component (B), and, if necessary, a solvent and an additive. The mixing means and order of mixing are not particularly limited.

The cured film of the present invention is obtained by curing the active energy ray-curable hard coat resin composition of the present invention.

The thickness of the cured film of the present invention is not particularly limited, and is generally about 1 to 40 μm, preferably about 3 to 20 μm.

The laminate of the present invention has the cured film on at least one surface of a substrate, and the method is not particularly limited. For example, the active energy ray-curable hard coat resin composition of the present invention is coated on the substrate to activate It is obtained by irradiating the 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 polybutien film, a polybutadiene film, a polymethylpentene 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 films, polycarbonate films, polyimide films, fluororesin films, and the like. Also, these crosslinked films or laminated films may be used. For these films, either an untreated film, a film subjected to light to medium peeling treatment, or a film having an adhesive layer may be used.

In addition, 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.

In the laminate of the present invention, after coating the resin composition for an active energy ray-curable hard coat on a substrate, it is preferable to dry in advance with a preliminary heat source to remove the organic solvent. It does not specifically limit as a heat source, A forward air dryer, an electric oven, a gas oven, etc. are mentioned. The drying conditions are not particularly limited, and generally the temperature is about 40 to 150°C, preferably about 50 to 120°C, and the time is about 15 seconds to 5 minutes, preferably about 30 seconds to 3 minutes.

Next, the coating layer is cured by irradiation with active energy rays. The active energy ray is not particularly limited, and examples thereof include ultraviolet rays, visible rays, electron beams, and ionizing radiation. In this invention, it is preferable to use an ultraviolet-ray from the point of curability of a coating layer.

The light source of the ultraviolet rays is not particularly limited, but examples thereof include ultra-high pressure mercury lamps, high-pressure mercury-vapor lamps, low-pressure mercury lamps, carbon arcs, xenon lamps, metal halide lamps, and the like. In addition, although it changes with the light source used as irradiation conditions, generally, the integrated light amount is about 1-1000 mJ/cm ^<2> , and the irradiation intensity is about 1-1000 mW/cm ^<2> .

The thickness of the obtained layered product is not particularly limited, and is about 100 to 140 μm, and about 1 to 40 μm only with the cured film (hard coat resin layer).

[Example]

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

(weight average molecular weight)

The weight average molecular weight was measured by gel permeation chromatography (GPC method) under the following conditions.

Molecular weight analyzer (product name "HLC-8220GPC", manufactured by Tosoh Co., Ltd.)

Column (product name "TSKgel G1000H", "TSKgel G2000PH" manufactured by Tosoh Co., Ltd.)

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 Co., Ltd.)

Preparation Example 1 (Preparation of Polyurethane Acrylate)

Into a reaction vessel equipped with a stirrer, cooling pipe, dropping rod and nitrogen inlet pipe, 95 parts of Viscott #300 (pentaerythritol triacrylate and pentaerythritol tetraacrylate acrylic acid condensate), 5 parts of isophorone diisocyanate Then, 0.1 part of methoquinone and 0.04 part of tin octylate as a catalyst were immersed in the mixture, and the temperature was raised to 80° C. and kept warm for 2 hours. After cooling, polyurethane acrylate having a solid content concentration of 100% and a weight average molecular weight of 900 was obtained.

Preparation Example 2 (Preparation of Epoxy Polyacrylate)

In a reaction vessel equipped with a stirring device, a cooling pipe, a dropping rod and a nitrogen inlet pipe, 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 butyronitrile (hereinafter referred to as AIBN), the temperature was raised until the temperature reached 90°C over about 1 hour under a nitrogen stream, and kept warm for 1 hour. Next, a mixture of 750 parts of GMA, 3.7 parts of lauryl mercaptan, and 22.5 parts of AIBN was previously put into a dropping rod, dropped into the system over about 2 hours under a nitrogen stream, kept warm at the same temperature for 3 hours, and then AIBN 10 parts were added and kept warm for 1 hour. Thereafter, 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, and 507 parts of acrylic acid (hereinafter referred to as AA), 2.3 parts of methoquinone, and 6.0 parts of triphenylphosphine were added, mixed, and then heated to 110°C under air bubbling. was heated up to After keeping it warm at the same temperature for 8 hours, 1.6 parts of methoquinone was added, cooled, and methyl isobutyl ketone was added so that the solid content concentration was 60%, thereby obtaining epoxy polyacrylate having a weight average molecular weight of 22,000.

Example 1

100 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name "Biscott # 300" manufactured by Osaka Organic Industry Co., Ltd.), 5 parts of 4-methyl benzophenone, and 105 parts of toluene were mixed, solid content concentration A 50% active energy ray-curable hard coat resin composition was obtained.

Examples 2 to 15, Comparative Examples 1 to 2

The compositions shown in Table 1 and toluene were blended to obtain active energy ray-curable hard coat resin compositions having a solid content concentration of 50%, respectively.

<Manufacture of laminated body>

The active energy ray curable hard coat resin composition of Example 1 was applied to a 100 μm thick cyclic olefin resin film (untreated) with a bar coater to a thickness of 10 μm, and dried at 80° C. for 1 minute. 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 ) (conveyance speed: 10 m/min), and cured to obtain a laminate. Examples 2 to 15 and the resin compositions for active energy ray curable hard coats of Comparative Examples 1 and 2 were also carried out in the same manner to obtain laminated bodies, respectively.

<Adhesion>

The surface of each laminate was cut at 1 mm intervals extending to the base material, and a 100 cellophane checkered cellophane tape peel test was conducted to evaluate initial adhesion. Table 1 shows the results. For 100 squares (denominator), 100/100 expressed as the number of non-peeled squares (numerator) indicates the best adhesion (the same below).

<Pencil Hardness>

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

(A) Ingredients (B) component other hardener laminate type parts by weight type parts by weight type parts by weight adhesion Hardness Example 1 A-1 100 4-MBP 5 - 100/100 B Example 2 A-1 100 4-MBP 30 - 100/100 B Example 3 A-1 100 4-MBP 20 - 100/100 B Example 4 A-1 100 4-MBP 10 - 100/100 B Example 5 A-1 100 4-MBP One - 100/100 B Example 6 A-2 100 4-MBP 5 - 100/100 B Example 7 A-3 100 4-MBP 5 - 100/100 B Example 8 A-4 100 4-MBP 5 - 100/100 B Example 9 A-5 100 4-MBP 5 - 100/100 HB Example 10 A-6 100 4-MBP 5 - 100/100 F Example 11 A-1 100 2-MBP 5 - 100/100 B Example 12 A-1 100 TMBP 5 - 100/100 B Example 13 A-1 100 4-MBP 5 TPO 3 100/100 H Example 14 A-1 100 4-MBP 5 Irg184 3 100/100 F Example 15 A-1 100 4-MBP 5 Irg907 3 100/100 HB Comparative Example 1 A-1 100 - TPO 5 0/100 F Comparative Example 2 A-1 100 - Irg184 5 0/100 F

<Component (A)>

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

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

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

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

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

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

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

[Formula 1]

<Component (B)>

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-hydroxycyclohexyl phenyl ketone (trade name "Irgacure 184" manufactured by BASF Japan Co., Ltd.)

・Irg907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (trade name “Irugacua 907” manufactured by BASF Japan Co., Ltd.)

Claims (7)

containing polyfunctional (meth)acrylates (A) and alkyl benzophenones (B);
(A) a mixture of pentaerythritol tri (meth) acrylate and pentaerythritol tetra acrylate, a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and tri A resin composition for an active energy ray-curable hard coat comprising 45 parts by weight or more of at least one selected from the group consisting of pentaerythritol (meth)acrylate.
According to claim 1,
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 A resin composition for an active energy ray-curable hard coat containing one kind.
According to claim 1,
The content of the component (B) is 1 to 30 parts by weight in terms of solid weight, based on 100 parts by weight of the component (A), active energy ray-curable hard coat resin composition.
According to claim 2,
The content of the component (B) is 1 to 30 parts by weight in terms of solid weight, based on 100 parts by weight of the component (A), active energy ray-curable hard coat resin composition.
According to any one of claims 1 to 4,
A resin composition for an active energy ray-curable hard coat that does not contain a monofunctional (meth)acrylate (C).
A cured film of the resin composition for an active energy ray-curable hard coat according to any one of claims 1 to 4.
A laminate having the cured film of claim 6 on at least one surface of a substrate.