TW201940604A - Active energy ray-curable hard coating resin composition, cured film, laminate having excellent adhesion especially to a poorly-adhesive substrate such as an untreated cyclic olefin resin film, and is also capable of maintaining high hardness - Google Patents

Abstract

The problem to be solved by the present invention is to provide an active energy ray-curable hard coating resin composition which can obtain a cured film. The cured film has excellent adhesion especially to a poorly-adhesive substrate such as an untreated cyclic olefin resin film, and is also capable of maintaining high hardness. The solution of the present invention is an active energy ray-curable hard coating resin composition comprising a multifunctional (methyl) acrylate (A) and an alkyl diphenyl ketone (B).

Description

Active energy ray hardening resin composition for hard coating, hardened film, laminated body

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

The surfaces of plastic sheets and plastic films are relatively soft, easily damaged, and the hardness of pencils is low. Therefore, a hard coating is provided on the surface of these substrates to increase the surface hardness, thereby seeking to improve.

In applications such as flat panel displays and touch panels, although triethyl cellulose film (hereinafter also referred to as TAC) is the mainstream, in recent years, with the thinning of smartphones and tablet computers, the film has high moisture permeability. The properties are regarded as a problem, and instead, cyclic olefin resin films having excellent optical characteristics and low moisture permeability have attracted attention. However, compared with TAC, the adhesion of a cyclic olefin resin film to a hard-coat layer is inferior. Therefore, the resin composition for hard-coating is required to have an adhesion to a difficult-to-close substrate such as a cyclic olefin resin film. .

As a technique for improving the adhesion, for example, the present applicant has disclosed an active energy ray-curable composition containing a specific amount of a (meth) acrylfluorenyl group, a polypentaerythritol skeleton, and isocyanate. An oligomer of a cyanuric acid group and / or a biuret group (Patent Document 1). However, this technique has excellent adhesion to a substrate that is difficult to adhere to when pretreatment by corona or the like is performed. [Prior Art Literature] (Patent Literature)

Patent Document 1: Japanese Patent Application Laid-Open No. 2017-179368

[Problems to be Solved by the Invention] An object of the present invention is to provide an active energy ray-curable resin composition for hard coating, which can obtain a cured film which is particularly difficult for untreated cyclic olefin resin films and the like. The adhesive substrate has excellent adhesiveness and can maintain high hardness. [Technical means to solve the problem]

The present inventors made intensive research and found that an active energy ray-curable hard coating resin composition can solve the foregoing problem. The active energy ray-curable hard coating resin composition is doped with a polyfunctional (meth) acrylate Combined with a specific hardener, the present invention is completed. That is, this invention relates to the following active-energy-ray-curable hard-coat resin composition, hardened film, and laminated body.

An active energy ray-curable hard coating resin composition comprising a polyfunctional (meth) acrylate (A) and an alkyldiphenyl ketone (B).

2. The active energy ray-curable hard coating resin composition according to the above item 1, wherein the component (B) contains a material selected from the group consisting of 2-methyldiphenyl ketone, 3-methyldiphenyl ketone, and 4-formaldehyde. At least one of the group consisting of methyldiphenyl ketone, 2,4,6-trimethyldiphenyl ketone and 2,3,4-trimethyldiphenyl ketone.

3. The active energy ray-curable hard coating resin composition as described in the above item 1, wherein the content of the (B) component is 1 to 30 based on 100 parts by weight of the solid component. Parts by weight. 4. The active energy ray-curable hard coating resin composition according to the above item 2, wherein the content of the (B) component is 1 to 30 based on 100 parts by weight of the solid component. Parts by weight.

5. The active energy ray-curable hard coating resin composition according to any one of the preceding paragraphs 1 to 4, which does not contain a monofunctional (meth) acrylate (C).

6. A cured film, which is a cured film of the active energy ray-curable hard coating resin composition according to any one of the preceding paragraphs 1 to 5.

7. A laminated body having a cured film according to the above item 6 on at least one side of a substrate. [Effect of the invention]

The active energy ray-curable hard coating resin composition according to the present invention has the following characteristics: by using an alkyldiphenyl ketone, a strong cured film can be formed, and excellent adhesion to a substrate difficult to adhere to It also has excellent hardness.

The active energy ray-curable hard coating resin composition of the present invention includes a polyfunctional (meth) acrylate (A) (hereinafter referred to as (A) component) and an alkyldiphenyl ketone (B) (hereinafter (Referred to as (B) component).

The component (A) is not particularly limited as long as it has at least two (meth) acrylfluorenyl groups, and various known polyfunctional (meth) acrylates can be used. Examples include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9- Nonanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, cyclohexanediane methanol bis (methyl) Base) acrylate, tricyclodecane di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, bisphenol F ethylene oxide modified di (meth) acrylate And other bifunctional (meth) acrylates; trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, isocyanurate ethylene oxide modified tris (methyl) Trifunctional (meth) acrylates such as acrylate) acrylate, pentaerythritol tri (meth) acrylate; pentaerythritol tetraacrylate, dipentaerythritol tetra (meth) acrylate, di-trimethylolpropane tetra (methyl) ) 4-functional (meth) acrylates such as acrylates; dipentaerythritol penta (meth) acrylates, dipentaerythritol hexa (meth) acrylates, tripentaerythritol (meth) acrylates, etc. Or more (meth) acrylate. These polyfunctional (meth) acrylates may be used alone or in combination of two or more kinds. Among them, from the viewpoint of maintaining the high hardness of the cured film, it is preferable to include a trifunctional or higher (meth) acrylate (trifunctional (meth) acrylate, a tetrafunctional (meth) acrylate, or a 5-functional or higher). (Meth) acrylate), more preferably one selected from the group consisting of pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and tripentaerythritol acrylate. In addition, (meth) acrylfluorenyl means any of methacrylfluorenyl or acrylfluorenyl, and (meth) acrylate means any of methacrylate or acrylate By. The following (methyl) is also the same.

Examples of commercially available products include "Viscoat # 230", "Viscoat # 260", "Viscoat # 300", "Viscoat # 295", "Viscoat # 802" (the above are 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 "(the above are manufactured by Shin Nakamura Chemical Industry Co., Ltd.)," ARONIX M-305 "," ARONIX M-450 "," ARONIX "M-309", "ARONIX M-400", "ARONIX M-402" (the above are manufactured by Toa Synthesis Co., Ltd.), etc.

In addition, as the (A) component, for example, polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy poly (meth) acrylate, and the like can also be used. These polyfunctional (meth) acrylates may be used alone or in combination of two or more kinds. Further, it may be used in combination with the aforementioned bifunctional (meth) acrylate, trifunctional (meth) acrylate, tetrafunctional (meth) acrylate, and polyfunctional (meth) acrylate.

Examples of the polyurethane acrylate include an amine esterification reaction using various known polyols and polycyanates, and the obtained isocyanate-terminated prepolymer and a hydroxyl group-containing (meth) acrylate being amines. An esterification reaction to obtain an acrylate oligomer; or an amine esterification reaction of a polyhydric alcohol and a polycyanate to further cause the obtained hydroxyl-terminated prepolymer and an isocyanate-containing mono (methyl Acrylate) acrylate oligomer and the like obtained by the reaction.

The polyol is not particularly limited, and examples thereof include polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, and polyolefin polyol. These polyols may be used alone or in combination of two or more.

The polyether polyol is not particularly limited, and examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and ethylene oxide-propylene oxide copolymers. A polyalkylene oxide (alkylene oxide-other alkylene oxide) copolymer etc. are contained as a monomer component; These polyether polyols can be used individually or in combination of 2 or more types. Examples of commercially available products include ADEKA POLYETHER P-400, ADEKA POLYETHER G-400, ADEKA POLYETHER T-400, and ADEKA POLYETHER AM-302 (the above are manufactured by ADEKA Corporation).

The polyester polyol is not particularly limited, and examples thereof include a condensation polymer of a polyol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyol, a polycarboxylic acid, and a cyclic ester.者 的 反应 物 and so on.

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-pentane. Aliphatic diols such as glycols, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol; glycerol, trimethylolmethane, trimethylol Aliphatic triols such as ethane; cycloaliphatic diols such as 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol; bisphenol A, bisphenol Bisphenols such as F; sugar alcohols such as xylitol and sorbitol; these polyols may be used alone or in combination of two or more. The polycarboxylic acid is not particularly limited, and examples thereof include malonic acid, maleic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Aliphatic dicarboxylic acids; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; aromatics such as terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, etc. Dicarboxylic acids; aliphatic tricarboxylic acids such as propane-1,2,3-tricarboxylic acid; aromatic tricarboxylic acids such as trimellitic acid, trimesic acid, etc .; these polycarboxylic acids can be used alone or Two or more types can be combined. Further, the cyclic ester is not particularly limited, and examples thereof include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone. These cyclic esters may be used alone or as 2 or more combinations. Examples of commercially available polyester polyols include Kuraray Polyol P-510, Kuraray Polyol F-510 (the above is manufactured by Kuraray Co., Ltd.), PLACCEL 205 (made by Daicel Corporation), and the like.

The carbonate polyol is not particularly limited, and examples thereof include a reaction product of a polyol and phosgene, and a ring-opening polymer of a cyclic carbonate (such as alkylene carbonate). Examples of the polyol include the above-mentioned polyols. The alkylene carbonate is not particularly limited, and examples thereof include ethyl carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. These cyclic carbonates may be used alone or in combination. Combine 2 or more types. Examples of commercially available carbonate polyols include Kuraray Polyol C-590 (made by Kuraray Co., Ltd.) and the like.

The acrylic polyol is not particularly limited, and examples thereof include polymerizing an acrylic monomer having one or more hydroxyl groups in one molecule into a homopolymer or a copolymer, or copolymerizing these copolymers with other monomers. These acrylic polyols can be used alone or in combination of two or more. Examples of commercially available acrylic polyols include ARUFON UH-2041 (manufactured by Toa Synthesis Co., Ltd.) and the like.

The polyolefin polyol is not particularly limited, and examples thereof include polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene having two or more hydroxyl groups; these polyolefin polyols These polyolefin polyols can be used alone or in combination of two or more kinds. Examples of commercially available products include NISSO-PB GI-1000 (manufactured by Soda Co., Ltd.).

The polyisocyanate is not particularly limited, and examples thereof include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, diphenylmethane-4,4-diisocyanate, and 3 -Aromatic diisocyanates such as methyldiphenylmethane diisocyanate, naphthalene-1,5-diisocyanate; aliphatic diisocyanates such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc. Isocyanates; di-hexamers of these polyisocyanates, etc .; these polyisocyanates can be used alone or in combination of two or more kinds.

The mono (meth) acrylate containing a hydroxyl group is not particularly limited, and examples thereof include 1-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxy (meth) acrylate Propyl ester, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxycyclohexyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl (meth) acrylate Esters, 2- (hydroxymethyl) cyclohexylmethyl 2-hydroxypropionate, hydroxyphenyl (meth) acrylate, etc .; these mono (meth) acrylates containing hydroxyl groups can be used alone or in combination The above combination.

The isocyanate-containing (meth) acrylate is not particularly limited, and examples thereof include 2-isocyanatoethyl (meth) acrylate and 1,1- (bispropenyloxyethyl) isocyanate. ) Ethyl esters; these (meth) acrylates containing isocyanate groups can be used alone or in combination of two or more kinds.

The polyester (meth) acrylate is not particularly limited, and examples thereof include esterification of the aforementioned dicarboxylic acid (aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid) and a low-molecular-weight diol. (Meth) acrylic acid ester oligomer obtained by esterifying the obtained hydroxyl-terminated polyester with an unsaturated carboxylic acid, or by reacting the aforementioned dicarboxylic acid with a diol compound, The (meth) acrylate oligomer etc. obtained by performing the esterification reaction of the obtained carboxy-terminated polyester and the said hydroxyl-containing mono (meth) acrylate.

The unsaturated carboxylic acid is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid (anhydride), fumaric acid, and crotonic acid. These unsaturated carboxylic acids can be used alone. You can also combine 2 or more types.

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

The epoxy resin is not particularly limited, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, biphenol epoxy resin, phenol novolac epoxy resin, and cresol novolac epoxy resin. Epoxy resin, bisphenol A novolac epoxy resin, naphthalene diphenol epoxy resin, phenol dicyclopentadiene novolac epoxy resin, or hydrides of these epoxy resins; 3 ', 4'- Epoxy cyclohexanecarboxylic acid 3,4-epoxycyclohexyl methyl ester, 1,2-epoxy vinyl cyclohexene, bis (3,4-epoxycyclohexylmethyl) adipate, 1-epoxyethyl-3,4-epoxycyclohexane, 3,4-epoxycyclohexylmethanol, dicyclopentadiene diepoxide, 2,2-bis (hydroxymethyl)- Alicyclic epoxy resins such as 1,2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 1-butanol; these epoxy resins can be used alone or in combination Combine 2 or more types. Among the alicyclic epoxy resins, examples of the oligomeric alicyclic epoxy resin include epoxidized butane tetracarboxylic acid (3-cyclohexenylmethyl) ester modified ε -An epoxy resin or the like obtained by epoxidizing an alicyclic olefin, such as caprolactone (trade name "EPOLEAD GT401" manufactured by Daicel Corporation).

The physical properties of the component (A) are not particularly limited. From the viewpoint of maintaining high hardness of the cured film, for example, a weight average molecular weight (polystyrene conversion value measured by gel permeation chromatography) is preferred. ) Is about 150 to 100,000, and more preferably about 180 to 80,000.

The component (B) is a component which is used in order to exhibit excellent adhesion to a substrate that is difficult to be adhered, such as a cyclic olefin resin film. The component (B) is not particularly limited, and examples thereof include monoalkyldiphenylketones such as 2-methyldiphenylketone, 3-methyldiphenylketone, and 4-methyldiphenylketone. ; Trialkyldiphenyl ketones such as 2,4,6-trimethyldiphenyl ketone, 2,3,4-trimethyldiphenyl ketone and the like. These components can be used individually or in combination of 2 or more types. Among them, it is preferable to include a compound selected from the group consisting of 2-methyldiphenyl ketone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2,4,6-trimethyldiphenyl ketone, and 2 At least one of the group consisting of 3,4-trimethyldiphenyl ketone, and more preferably 4-methyldiphenyl ketone.

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

The active energy ray-curable hard coating resin composition 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-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethyl-1-one, and 1-cyclohexylbenzene Ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1 -Propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamine -1- (4-morpholinylphenyl) -1-butanone, bis (2,4,6-trimethylbenzyl) phenylphosphine oxide, 2,4,6-trimethylbenzene Formamidine diphenylphosphine oxide and the like. The content of the curing agent is not particularly limited, and it is usually less than 10 parts by weight, and preferably less than 5 parts by weight, based on 100 parts by weight of the component (A).

The active energy ray-curable hard coating resin composition of the present invention may further contain a monofunctional (meth) acrylate (C) (hereinafter referred to as (C) component), but from the viewpoint of maintaining high hardness of the cured film In other words, it is preferable that the component (C) is not contained. The component (C) 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, tertiary butyl (meth) acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate, n- (meth) acrylate Octyl ester, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, (formyl) N-undecyl acrylate, isoundecyl (meth) acrylate, n-dodecyl (meth) acrylate, isododecyl (meth) acrylate, n-lauryl (meth) acrylate , N-tetradecyl (meth) acrylate, iso-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate, n-octadecyl (meth) acrylate, (meth) acrylic acid Aliphatic mono (meth) acrylate such as 2-ethylhexyl ester; alicyclic (meth) acrylate such as cyclohexyl (meth) acrylate; aromatic mono such as phenyl (meth) acrylate (Meth) acrylate . These monofunctional (meth) acrylates can be used alone or in combination of two or more.

The active energy ray-curable hard coating resin composition of the present invention may further include 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; butyl acetate and propyl acetate Esters such as esters, ethyl acetate, propylene glycol monomethyl ether acetate; alcohols such as ethanol and 2-propanol; aliphatics such as n-hexane, cyclohexane, methylcyclohexane, and n-heptane Hydrocarbons; isopropyl ether, methyl cyperidine, ethyl cyperidine, 1,4-dioxane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetic acid Ethers such as esters and propylene glycol monomethyl ether acetate; chloroform, dimethylformamide and the like; these organic solvents may be used alone or in combination of two or more. The content of the organic solvent is not particularly limited, but is preferably adjusted so that the concentration of the solid content of the resin composition becomes 40 to 80% by weight.

The active energy ray-curable hard coating resin composition of the present invention may further include various known additives such as a surface modifier, a surfactant, a photosensitizer, a light stabilizer, an antioxidant, a leveling agent, a pigment, and an inorganic agent. Fillers, silane coupling agents, colloidal silica, defoamers, wetting agents, rust inhibitors, ultraviolet absorbers, antistatic agents, etc.

The active energy ray-curable hard coating resin composition of the present invention is obtained by mixing the component (A) and the component (B) with a solvent and an additive as necessary. The mixing means and mixing order are not particularly limited.

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

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

The laminated body of the present invention has the above-mentioned cured film on at least one side of the substrate, and the manufacturing method thereof is not particularly limited. For example, it can be obtained by coating the substrate with the active energy ray-curable hardener of the present invention. The resin composition is applied and irradiated with active energy rays.

The substrate is not particularly limited, and examples thereof include polyethylene terephthalate film (PET film), cyclic olefin resin film, polypropylene film, polybutene film, polybutadiene film, and polymethylmethacrylate. Vinylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionic polymer resin film, Ethylene / (meth) acrylic copolymer film, ethylene / (meth) acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. In addition, a crosslinked film or a laminated film of these substrates can be used. As these films, any of an untreated film, a film subjected to a light to heavy peeling treatment, and a film having an easily-adhesive layer can be used.

The coating method is not particularly limited, and examples thereof include a coater, a bar coater, a roll coater, a blade coater, and a gravure coater.

In the laminated body of the present invention, it is preferred that the substrate is coated with an active energy ray-curable hard coating resin composition on a substrate, and then pre-dried with a heat source to remove the organic solvent. The heat source is not particularly limited, and examples thereof include a circulating air dryer, an electric heating furnace, and a gas furnace. The drying conditions are not particularly limited. 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.

Then, the coating layer is hardened by irradiating active energy rays. The active energy ray is not particularly limited, and examples thereof include ultraviolet rays, visible light, electron rays, and free radiation. In the present invention, it is preferable to use ultraviolet rays from the viewpoint of the curability of the coating layer.

The ultraviolet light source is not particularly limited, and examples thereof include an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc lamp, a xenon lamp, and a metal halide lamp. The irradiation conditions differ depending on the light source used. Generally, the cumulative light amount is about 1 to 1000 mJ / cm ² and the irradiation intensity is about 1 to 1000 mW / cm ² .

The thickness of the obtained laminated body is not particularly limited, but is about 100 to 140 μm, and it is about 1 to 40 μm when only the cured film (hard coating resin layer) is used. [Example]

Hereinafter, the present invention will be described with examples, but the present invention is not limited to these examples. The parts and% in the examples and comparative examples are based on weight unless otherwise specified.

(Weight average molecular weight) The weight average molecular weight was measured by the gel permeation chromatography (GPC method) under the following conditions.・ Molecular weight measuring machine: Product name "HLC-8220GPC", manufactured by Tosoh Corporation. Coil: Product names "TSKgel G1000H" and "TSKgel G2000H", manufactured by Tosoh Corporation. Development solvent: Tetrahydrofuran. Flow rate: 0.35. mL / min ・ Concentration of sample: 0.5g / L ・ Standard substance: Polystyrene (1 standard polystyrene kit PStQuickA, B, C, manufactured by Tosoh Corporation)

<Manufacturing Example 1 (Polyurethane Acrylate Production)> 95 parts of Viscoat # 300 (pentaerythritol triacrylate and pentaerythritol tetraacrylate acrylic acid) was placed in a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube. After condensate), 5 parts of isophorone diisocyanate, 0.1 part of methoxyphenol, and 0.04 part of tin octoate as a catalyst, the temperature was raised to 80 ° C. and the temperature was maintained for 2 hours. After cooling, a polyurethane acrylate having a solid content of 100% and a weight average molecular weight of 900 was obtained.

<Manufacturing Example 2 (Production of epoxy polyacrylate)> A reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube was charged with 250 parts of glycidyl methacrylate and 1.3 parts of lauryl mercaptan. , 1000 parts of methyl isobutyl ketone and 7.5 parts of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN), it took about 1 hour to raise the temperature to 90 ° C under a nitrogen gas flow, and maintained the temperature 1 hour. Next, a dropping liquid funnel containing a mixture of 750 parts of glycidyl methacrylate (GMA), 3.7 parts of lauryl mercaptan, and 22.5 parts of AIBN was charged into the dropping funnel in advance under nitrogen gas flow for about 2 hours. Then, after maintaining the temperature at the same temperature for 3 hours, 10 parts of AIBN was further added, and the temperature was maintained for 1 hour. Then, the temperature was raised to 130 ° C, and the temperature was maintained for 2 hours. After cooling to 60 ° C, the nitrogen introduction tube was replaced with an air introduction tube, and 507 parts of acrylic acid (hereinafter referred to as AA), 2.3 parts of methoxyphenol and 6.0 parts of triphenylphosphine were mixed and mixed. In the case of air bubbles, the temperature was raised to 110 ° C. After maintaining the temperature at the same temperature for 8 hours, 1.6 parts of methoxyphenol was charged and cooled, and then methyl isobutyl ketone was added so that the concentration of the solid content became 60% to obtain a ring having a weight average molecular weight of 22,000. Oxypolyacrylate.

<Example 1> 100 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name "Viscoat # 300", manufactured by Osaka Organic Industry Co., Ltd.), 5 parts of 4-methyldiphenyl ketone, and 105 parts Toluene was used to obtain an active energy ray-curable hard coating resin composition having a solid content concentration of 50%.

<Examples 2 to 15 and Comparative Examples 1 to 2> The composition shown in Table 1 and toluene were blended to obtain an active energy ray-curable hard coating resin composition having a solid content concentration of 50%, respectively.

<Preparation of Laminate> Using a bar coater, the cyclic olefin resin film (untreated) having a thickness of 100 μm was coated with the active energy ray-curable hard coat of Example 1 so that the thickness of the coating layer was 10 μm. The resin composition was used and dried at 80 ° C for 1 minute. Then, the laminated body was obtained by hardening under a high-pressure mercury lamp (cumulative light amount: 1000 mJ / cm ² , irradiation intensity: 100 mW / cm ² ) (conveyance speed: 10 m / min) in the atmosphere. The active energy ray-curable hard coating resin compositions of Examples 2 to 15 and Comparative Examples 1 and 2 were also carried out in the same manner, and laminated bodies were obtained.

<Adhesiveness> The surface of each laminated body was scored at intervals of 1 mm until the score reached the substrate, and then a 100-square grid transparent tape peel test was performed to evaluate the initial adhesion. The results are shown in Table 1. The number of non-peeled squares (numerator) is expressed relative to 100 (denominator), and 100/100 indicates the best adhesion (the same applies hereinafter).

<Pencil hardness> It measured based on JIS K5600-5-4. B or more is made good.

[Table 1]

<(A) component> ・ A-1: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name "Viscoat # 300", manufactured by Osaka Organic Industry Co., Ltd.) ・ A-2: A-1 and production example Polyurethane acrylate mixture of 1 (A-1 / Production Example 1 = 50/50 (weight of solid content)) • A-3: A-1 and a mixture of epoxy polyacrylate of Production Example 2 (A- 1 / Production Example 2 = 50/50 (weight of solid content))-A-4: A-1, A mixture of polyurethane acrylate and 1,6-hexanediol diacrylate (HDDA) in Production Example 1 (A -1 / Production Example 1 / HDDA = 45/45/10 (weight of solid content))-A-5: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name "ARONIX M-400", East Asia (Synthetic Co., Ltd.) ・ A-6: Tripentaerythritol acrylate (trade name "Viscoat # 802", manufactured by Osaka Organic Industry Co., Ltd., also refer to the following chemical formula)

The "Viscoat # 802" (manufactured by Osaka Organic Industry Co., Ltd.) of A-6 is represented by the following chemical formula.

<(B) component> ・ 4-MBP: 4-methyldiphenyl ketone ・ 2-MBP: 2-methyldiphenyl ketone ・ TMBP: 2,3,4-trimethyldiphenyl ketone <Others Hardening agent ＞ ・ TPO: 2,4,6-trimethylbenzylphenylphenylphosphine oxide (trade name "Speedcure TPO", manufactured by Lambson Group Ltd.) ・ Irg184: 1-hydroxycyclohexylphenyl ketone (commercial product ("IRGACURE 184", manufactured by BASF Corporation, Japan)-Irg907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name " (IRGACURE 907 ", manufactured by BASF, Japan)

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Claims (7)

An active energy ray-curable hard coating resin composition includes a polyfunctional (meth) acrylate (A) and an alkyldiphenyl ketone (B). The active energy ray-curable hard coating resin composition according to claim 1, wherein the component (B) contains a material selected from the group consisting of 2-methyldiphenyl ketone, 3-methyldiphenyl ketone, and 4-methyl At least one of the group consisting of diphenyl ketone, 2,4,6-trimethyldiphenyl ketone and 2,3,4-trimethyldiphenyl ketone. The active-energy-ray-curable hard coating resin composition according to claim 1, wherein the content of the (B) component is 1 to 30% by weight based on 100 parts by weight of the solid component. Serving. The active energy ray-curable hard coating resin composition according to claim 2, wherein the content of the (B) component is 1 to 30% by weight relative to 100 parts by weight of the solid component. Serving. The active energy ray-curable hard coating resin composition according to any one of claims 1 to 4, which does not contain a monofunctional (meth) acrylate (C). The cured film which is a cured film of the active-energy-ray-curable hard-coat resin composition as described in any one of Claims 1-5. A laminated body having a cured film according to claim 6 on at least one side of a substrate.