JP2023034659A - Active energy ray-curable composition, cured product and film - Google Patents

Abstract

To provide an active energy ray-curable composition which can achieve both excellent adhesion to a base material and hard coat property without requiring pretreatment such as primer treatment and corona treatment by being applied onto a surface of the base material such as a COP film and cured, and provide a cured product of the same and a film using the same.SOLUTION: There are provided an active energy ray-curable composition which contains polyfunctional group (meth)acrylate (A), (meth)acrylate (B) having a hydrogen-donating functional group, and a hydrogen-drawing type photoinitiator (C); a cured product of the active energy ray-curable composition; and a film having a cured coated film of the active energy ray-curable composition on at least one surface of a cyclic olefin resin base material or an olefin resin film base material.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an active energy ray-curable composition, a cured product thereof, and a film using the composition.

Cyclic olefin resin (COP) films are excellent in high transparency, low birefringence, low hygroscopicity, low moisture permeability, etc., and are widely used in applications such as optical members, medical care, packaging films, automobiles, and semiconductors. . In particular, for optical applications, the use of COP films as a substitute for conventionally used plastic films such as polyethylene terephthalate (PET) and triacetylcellulose (TAC) is being studied as displays such as televisions become larger. .

On the other hand, since COP films have insufficient surface hardness, they may be scratched during processing or use. A protective layer such as a hard coat layer made of a coating film may be provided.
However, since the main structure of the COP film is an alicyclic structure, the polarity of the film surface is low, the wettability of the surface is poor, and it is difficult to be eroded by solvents. Therefore, when an active energy ray-curable composition for forming a hard coat layer is applied to a COP film, the coating material is difficult to spread and there is a problem that the adhesion between the COP surface and the hard coat layer is low. rice field.

As a method for improving the adhesion between the COP film and the hard coat layer, a method of making the surface of the COP film hydrophilic by pretreatment such as primer treatment or corona treatment has been proposed (for example, Patent Document 1 reference.). Although this method can improve the adhesion between the COP film surface and the hard coat layer, it increases the number of steps due to the coating and drying of the primer layer, resulting in problems such as a decrease in yield, an increase in cost, and the occurrence of environmental impact. Therefore, there is a demand for a coating material that adheres to the COP film without pretreatment.

In order to solve the above-described problems, the invention described in Patent Document 2 provides a benzophenone-based initiator and/or a thioxanthone-based initiator and silica fine particles as an active energy ray-curable composition for forming a hard coat layer. It is proposed to obtain a hard coat layer excellent in scratch resistance and substrate adhesion without pretreatment by using urethane (meth)acrylate.

JP 2004-284158 A JP 2018-203887 A

The problem to be solved by the present invention is that by coating and curing the surface of a substrate such as a COP film, excellent adhesion to the substrate can be achieved without the need for pretreatment such as primer treatment or corona treatment. An object of the present invention is to provide an active energy ray-curable composition having both good properties and hard coat properties, a cured product thereof, and a film using the same.

As a result of extensive research to solve the above problems, the present inventors have found that pretreatment such as primer treatment and corona treatment can be achieved by using a hydrogen abstraction type photoinitiator and a resin having a hydrogen-donating functional group in combination. is omitted and silica fine particles are not used.

That is, the present invention relates to the following inventions.
(1) a polyfunctional (meth)acrylate (A), a (meth)acrylate having a hydrogen-donating functional group (B), a hydrogen-abstracting photoinitiator (C), and an organic solvent (D); and the (meth)acrylate (A) and the (meth)acrylate (B) are different compounds.
(2) The (meth)acrylate (A) is selected from the group consisting of dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate and pentaerythritol tri(meth)acrylate. The active energy ray-curable composition of (1), which is at least one selected acrylate.
(3) The (meth)acrylate (B) is a (meth)acrylate having at least one or more of a (poly)alkylene oxide structure, an amine skeleton, and a thiol skeleton (1) or (2) ) active energy ray-curable composition.
(4) The active energy ray-curable composition according to any one of claims 1 to 3, wherein the (meth)acrylate (B) is a (meth)acrylate containing three or more acryloyl groups in the molecule.
(5) The active energy ray-curable composition according to any one of (1) to (4), wherein the hydrogen abstraction type photoinitiator (C) is any one of a benzophenone-based, thioxanthone-based, and xanthone-based photoinitiator. .
(6) The amount of the hydrogen abstraction type photoinitiator (C) is in the range of 2 to 6 parts by mass with respect to the total 100 parts by mass of the solid components contained in the composition (1) to (5) ) active energy ray-curable composition.
(7) When the total of the (meth)acrylate (A) and the (meth)acrylate (B) is 100 parts by mass, the amount of the (meth)acrylate (B) added is 10 to 30 parts by mass. The active energy ray-curable composition according to any one of (1) to (6).
(8) The active energy ray curability according to any one of (1) to (7), wherein the (meth)acrylate (B) is contained in an amount of 4.5 to 15 parts by mass when the total composition is 100 parts by mass. Composition.
(9) The active energy ray-curable composition according to any one of (1) to (8), wherein the organic solvent (D) contains at least one or both of a ketone solvent and an ester solvent.
(10) A cured product of the active energy ray-curable composition according to any one of (1) to (9).
(11) A cyclic olefin resin film substrate, or a film having a cured coating film of the active energy ray-curable composition of any one of (1) to (9) on at least one surface of the olefin resin film substrate.

The active energy ray-curable composition of the present invention can be applied to the surface of a substrate such as a COP film and then cured, so that the substrate can be cured without pretreatment such as primer treatment or corona treatment. It is possible to form a hard coat layer having excellent adhesion to.
Moreover, since the cured product and cured coating film of the active energy ray-curable composition of the present invention have high hardness and excellent scratch resistance, they can be used in a wide range of applications.

The active energy ray-curable composition of the present invention (hereinafter sometimes simply referred to as "composition") comprises a polyfunctional (meth)acrylate (A) and a (meth)acrylate having a hydrogen-donating functional group. (B), a hydrogen abstraction type photoinitiator (C), and an organic solvent (D). In the present invention, "(meth)acrylate" refers to one or both of acrylate and methacrylate, and "(meth)acryloyl group" refers to one or both of acryloyl group and methacryloyl group.

[Polyfunctional (meth)acrylate (A)]
Polyfunctional (meth)acrylate (A) (hereinafter sometimes referred to as "(A) component") is a compound having two or more (meth)acryloyl groups in one molecule and does not correspond to the (B) component described later. It is.
Examples of the polyfunctional (meth)acrylate (A) include 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, (meth)acrylates, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, di(meth)acrylates of dihydric alcohols such as tricyclodecane dimethanol di(meth)acrylate; di(meth)acrylates of tris(2-hydroxyethyl)isocyanurate, 2 moles of ethylene oxide per 1 mole of bisphenol A or Diol di(meth)acrylate obtained by addition of propylene oxide, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, tris(2-(meth) acryloyloxyethyl)isocyanurate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipenta Polyfunctional (meth)acrylates such as erythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, and polypentaerythritol poly(meth)acrylate , and urethane (meth)acrylates.

The component (A) may be used singly or in combination of two or more.
Among them, as the component (A), a high degree of cross-linking is obtained after curing, and the hardness and scratch resistance of the cured product and cured film are further improved. Tetraacrylate is more preferred.

[(Meth)acrylate (B) having a hydrogen-donating functional group]
(Meth)acrylate (B) having a hydrogen-donating functional group (hereinafter sometimes referred to as "(B) component") is a compound having at least a hydrogen-donating group and a (meth)acryloyl group.
A hydrogen-donating group in the present invention refers to a functional group in which an alkyl group is covalently bonded to a highly electronegative atom such as oxygen, nitrogen, or sulfur. Specific examples include an alkylene oxide structure and an amine skeleton such as a thiol group.
(Meth)acrylates (B) include, for example, (poly)ethylene glycol dipentaerythritol hexa(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)ethylene glycol (meth)acrylate, (poly) Propylene glycol dipentaerythritol (meth)hexaacrylate, (poly)propylene glycol di(meth)acrylate, (poly)propylene glycol (meth)acrylate, ethoxylated dipentaerythritol poly(meth)acrylate, neopentyl glycol 4 per mol Alkylene oxide structures such as di(meth)acrylates of diols obtained by adding ethylene oxide or propylene oxide in a molar amount or more, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, etc. acrylate having an amine skeleton; acrylate having an amine skeleton such as amine-modified polyether tetraacrylate; acrylate having a thiol group such as ethanedithiol-modified poly(meth)acrylate.
In the present invention, "(poly)ethylene glycol" refers to one or both of polyethylene glycol and ethylene glycol, and "(poly)propylene glycol" refers to one or both of polypropylene glycol and propylene glycol.

The hydrogen-donating group of the component (B) is preferably an ethoxy group or a propoxy group, more preferably an ethoxy group, from the viewpoint of high adhesion between the cured coating film obtained by curing the composition of the present invention and the substrate.
In addition, the component (B) preferably has three or more (meth)acryloyl groups in one molecule in order to improve the scratch resistance of the cured product obtained by curing the composition of the present invention and the cured coating film. .

The component (B) may be used singly or in combination of two or more.
As will be described later, the chemical bonding of the component (B) to the substrate enhances the adhesion between the cured coating film of the present invention and the substrate. That is, the amount of component (B) may be an amount that allows chemical bonding with the base material, and the compound having a polymerizable group in the composition (component (A) + component (B)) accounts for the majority. Since it is not necessary, the cost can be reduced accordingly. Specifically, the amount of component (B) is preferably 1 to 80 parts by mass, more preferably 5 to 50 parts by mass, and 10 parts by mass with respect to 100 parts by mass of components (A) and (B). ~30 parts by weight is particularly preferred. Furthermore, the amount of component (B) to be blended is preferably 1 to 19 parts by mass, more preferably 4.5 to 15 parts by mass, when the total amount of the composition of the present invention is 100 parts by mass.

[Hydrogen abstraction type photoinitiator (C)]
The hydrogen-abstracting photoinitiator (C) (hereinafter sometimes referred to as "component (C)") is contained to chemically bond the component (B) and the substrate. Furthermore, it is also contained in the composition of the present invention in order to initiate the polymerization reaction of components (A) and (B).
The hydrogen-abstraction type photoinitiator here changes the state in the order of a singlet excited state and a triplet excited state by irradiation with an active energy ray, and causes hydrogen abstraction from another compound in the same system to generate radical species. A compound that can be generated, for example a ketone compound.
In the present invention, the component (C) is excited by the irradiation of the active energy ray, causing hydrogen abstraction from the component (B), thereby generating a radical species derived from the component (C) and a radical derived from the component (B). Each species arises. Radical species derived from the component (B) are covalently bonded to the component (B) and the substrate by abstracting hydrogen from the cycloolefin skeleton or the like contained in the substrate. As a result, it can be considered that the adhesiveness between the cured coating film obtained by curing the composition of the present invention and the substrate is enhanced.

Hydrogen abstraction photoinitiators (C) include, for example, benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide. , acrylated benzophenone, 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone benzophenone-based compounds such as; 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and other thioxanthone-based compounds; xanthone, 2-isopropylxanthone, 2,4-dimethylxanthone , 2,4-diethylxanthone and 2,4-dichloroxanthone; and polymers having a benzophenone skeleton such as polybutylene glycol bis(4-benzoylphenoxy)acetate.

Component (C) may be used alone or in combination of two or more.
Among them, as the component (C), a benzophenone-based compound is preferable because the adhesiveness of the cured product is further improved.
Furthermore, when the amount of component (C) in the composition of the present invention is large, when the composition of the present invention is applied to a substrate and then irradiated with an active energy ray, the active energy ray is absorbed on the surface of the composition. increase in the amount of As a result, the active energy ray may not reach the interface between the composition and the substrate, and the adhesion between the cured coating film and the substrate may decrease.
Therefore, the amount of component (C) to be blended is preferably 0.1 to 10 parts by mass, particularly preferably 2 to 6 parts by mass, based on 100 parts by mass of the total solids in the composition.

[Organic solvent (D)]
The organic solvent is useful for appropriately adjusting the solution viscosity of the composition of the present invention, and facilitates the adjustment of the film thickness, particularly for thin film coating. Examples of organic solvents that can be used here include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and t-butanol; esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate. ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and glycol ethers such as propylene glycol monomethyl ether. These solvents can be used singly or in combination of two or more.
The active energy ray-curable composition of the present invention can be formed into a cured coating film by applying an active energy ray-curable composition onto a substrate, volatilizing the solvent, and then irradiating with an active energy ray. In addition, if a large amount of solvent with high hydrogen-donating ability such as alcohol or ether remains without completely volatilizing, hydrogen abstraction from component (B) may not proceed sufficiently, and adhesion of the cured coating film to the substrate may be poor. There is
On the other hand, even when only an alcohol-based solvent or an ether-based solvent is used, high substrate adhesion can be obtained if the solvent can be sufficiently volatilized. In addition, it is particularly preferable to use a solvent containing at least one solvent having no hydrogen-donating group, such as a ketone solvent or an ester solvent.

In the active energy ray-curable composition of the present invention, other components other than the above components (A) to (D) may include a photosensitizer, a polymerization inhibitor, and an antifoaming agent, depending on the application and required properties. , surface modifiers such as leveling agents, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, UV absorbers, antioxidants, organic pigments, inorganic pigments, pigment dispersants, silica beads, organic beads, etc. Additives: Inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia and antimony pentoxide can be blended. These other formulations can be used alone or in combination of two or more.

The composition of the present invention may be used as a cured coating film by applying an active energy ray after coating at least one surface of a substrate such as a film, or by irradiating an active energy ray without using a substrate. It may be used as a cured product.

As the material of the substrate for obtaining the cured coating film, highly transparent resins are preferable, and examples thereof include cyclic olefin copolymers; Polyolefin resins such as polymethylpentene-1; cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate, etc. Cellulose resins; Acrylic resins such as polymethyl methacrylate; Vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl acetate copolymer; Polystyrene; polyether ether ketone; polyimide-based resins such as polyimide and polyetherimide; be done. Furthermore, two or more types of base materials made of these resins may be bonded together to be used.

ADVANTAGE OF THE INVENTION The active-energy-ray-curable composition of this invention has favorable adhesiveness with respect to the cyclic olefin resin (COP) which was considered difficult to improve the substrate adhesiveness of a hard-coat layer conventionally. Specifically, the (C) component in the excited state of the composition of the present invention abstracts hydrogen from the (B) component to generate radicals derived from the (B) component. Radicals derived from component (B) are bonded while abstracting hydrogen from the cycloolefin site of the COP base material, and then crosslinked by copolymerization of component (A) and component (B) or polymerization of components (A) with each other. , contributes to the improvement of adhesion to the COP substrate.
Therefore, the composition of the present invention can be suitably used as a cured coating film using COP as a base material.

The substrate for obtaining the cured coating film may be in the form of a film or a sheet, and its thickness is preferably in the range of 1 to 500 μm. When a film-like base film is used, its thickness is preferably in the range of 20 to 200 μm, more preferably in the range of 30 to 150 μm, even more preferably in the range of 40 to 130 μm. By setting the thickness of the film substrate within this range, curling can be easily suppressed even when a hard coat layer is provided on one side of the film using the active energy ray-curable composition of the present invention.

A COP film substrate is obtained by forming a COP on a film. Commercially available COPs include, for example, “ZEONOR (registered trademark)” and “ZEONEX (registered trademark)” manufactured by Zeon Corporation; “ARTON (registered trademark)” manufactured by JSR Corporation; "TOPAS (registered trademark)" manufactured by Mitsui Chemicals, Inc.; "APEL (registered trademark)" manufactured by Mitsui Chemicals, Inc.;
The composition of the present invention provides good adhesion to the COP film even when the COP film substrate is not pretreated. However, for the purpose of further improving the adhesion, the surface of the COP film is subjected to roughening treatment such as sandblasting, solvent treatment, electrical treatment (corona discharge treatment, atmospheric pressure plasma treatment), chromic acid treatment, and flame treatment. treatment, hot air treatment, ozone/ultraviolet/electron beam irradiation treatment, oxidation treatment, and the like.

Examples of methods for applying the active energy ray-curable composition of the present invention to the film substrate include die coating, micro gravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, and dip coating. , spinner coating, brush coating, solid coating by silk screen, wire bar coating, flow coating, and the like.

As described above, the active energy rays for curing the active energy ray-curable composition of the present invention include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Here, when ultraviolet rays are used as active energy rays, devices for irradiating the ultraviolet rays include, for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, electrodeless lamps (fusion lamps), chemical lamps, Black light lamps, mercury-xenon lamps, short arc lamps, helium-cadmium lasers, argon lasers, sunlight, LED lamps and the like.

When forming a cured coating film of the active energy ray-curable composition of the present invention on the film substrate, the thickness of the cured coating film is such that the cured coating film has sufficient hardness and the coating film is cured. Since curling of the film due to shrinkage can be suppressed, the range is preferably 1 to 30 μm, more preferably 2 to 15 μm, and even more preferably 3 to 10 μm.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples.

(Example 1)
Pentaerythritol tetraacrylate (PETTA) 70 parts by mass, benzophenone (hereinafter abbreviated as "initiator 1") 4 parts by mass, hydrogen donating acrylate ("A-DPH-6E" manufactured by Shin-Nakamura Chemical Co., Ltd.; hereinafter, abbreviated as “B-1”.) 30 parts by mass, 52 parts by mass of propylene glycol monomethyl ether (PGME), and 52 parts by mass of methyl ethyl ketone (MEK) are uniformly mixed to form an active energy ray-curable composition (1). It was adjusted.

(Examples 2 to 15, Comparative Examples 1 to 5)
Active energy ray-curable compositions (2) to (15) and (R1) to (R5) were obtained in the same manner as in Example 1, except that the compositions were changed to those shown in Tables 1 to 3.

[Preparation of sample for evaluation]
The active energy ray-curable composition of each example was applied to a 100 μm thick COP film (“ZEONOR (registered trademark) film ZF-16” manufactured by Nippon Zeon Co., Ltd.) with a bar coater, and the solvent was applied under constant temperature conditions. After drying for a certain period of time under a nitrogen atmosphere, it is irradiated with an irradiation light amount of 3 kJ/m ² using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., high-pressure mercury lamp) to form a cured coating film with a thickness of 4 μm. A COP film was obtained. The following evaluation was not performed in Comparative Examples 1 and 2 because the coating film was not cured when the active energy ray-curable compositions (R1) and (R2) were used.

[Adhesion evaluation]
The surface of the cured coating film of the COP film of each example was cut vertically and horizontally at intervals of 1 mm to form 100 squares. Next, a cellophane tape (“Cellotape (registered trademark) CT-18” manufactured by Nichiban Co., Ltd.) was adhered to the surface, and then peeled off at once, which was repeated twice. The initial adhesion was evaluated according to the following criteria from the ratio of the remaining area without peeling. A grade of B or higher was determined to be acceptable.
A: The remaining area ratio is 100%.
B: The remaining area ratio is 95% or more and less than 100%.
C: The remaining area ratio is 10% or more and less than 95%.
D: The residual area ratio is less than 10%.

[Hardness evaluation]
The surface of the cured coating film of the COP film of each example was measured for pencil hardness under a load of 750 g according to JIS K5600-5-4 (1999). Each hardness was measured 5 times, and the surface hardness of the laminated film was defined as the hardness at which 4 or more measurements did not cause damage.
The hardness of the pencil is 2H, H, F, HB, and B in descending order of hardness.

[Scratch resistance evaluation]
The surface of the cured coating film of the COP film of each example was tested using a crockmeter type friction tester (circular friction element with a diameter of 1.0 cm, steel wool #0000, load of 500 g, 10 reciprocations), and cured after the test. The coating film surface was visually observed, and the scratch resistance was evaluated according to the following criteria. An evaluation of 4 or more was judged to be acceptable.
5: No damage.
4: 5 or less shallow scratches.
3: There are 5 or less scratches.
2: There are many scratches.
1: There are many remarkably deep scratches.

The abbreviations shown in Tables 1-3 refer to the following compounds.
"PETTA": pentaerythritol tetraacrylate "DPHA": dipentaerythryl hexaacrylate "UA1": aliphatic urethane acrylate ("Miramer (registered trademark) MU9500" manufactured by MIWON)
"UA2": Aliphatic urethane acrylate ("Miramer PU610" manufactured by MIWON)
"B-1": Polyethylene glycol dipentaerythritol hexaacrylate ("NK Ester A-DPH-6E" manufactured by Shin-Nakamura Chemical Co., Ltd.)
"B-2": Polypropylene glycol dipentaerythritol hexaacrylate ("NK Ester A-DPH-6P" manufactured by Shin-Nakamura Chemical Co., Ltd.)
"B-3": Polyethylene glycol #400 diacrylate ("A-400" manufactured by Shin-Nakamura Chemical Co., Ltd.)
"B-4": Tripropylene glycol diacrylate ("NK Ester APG-200" manufactured by Shin-Nakamura Chemical Co., Ltd.)
"B-5": 2-(2-ethoxyethoxy) ethyl acrylate ("Miramer (registered trademark) M-170" manufactured by MIWON)
"B-6": amine-modified polyether acrylate ("EBECRYL (registered trademark) 80" manufactured by Daicel Ornex)
"Initiator 1": benzophenone "Initiator 2": 2,4-diethylthioxanthone ("Omnirad DETX" manufactured by IGM)
"Initiator 3": polybutylene glycol bis(4-benzoylphenoxy) acetate ("Omnipol BP" manufactured by IGM)
"Initiator 4": 1-benzoylcyclohexanol ("Runtecure 1104" manufactured by IGM)
"PGME": propylene glycol monomethyl ether "MEK": methyl ethyl ketone "MIBK": methyl isobutyl ketone "EtAc": ethyl acetate "IPA": isopropanol

It was confirmed that the cured coating film of the active energy ray-curable composition of the present invention has excellent adhesion to the COP film and is excellent in hardness and scratch resistance.
On the other hand, Comparative Examples 1 and 2 using compositions containing only the (A) component as the resin without containing the (B) component were not cured and could not be evaluated. It was confirmed that Comparative Examples 3 and 4, which did not contain the component (B) and used the component (A) containing urethane acrylate as the resin, were inferior in adhesion to the substrate. It was also confirmed that Comparative Example 5, in which 1-benzoylcyclohexanol, which is an intramolecularly cleavable photoinitiator, was used as the component (C) was similarly inferior in adhesion to the substrate.

Claims (11)

Containing a polyfunctional (meth)acrylate (A), a (meth)acrylate having a hydrogen-donating functional group (B), a hydrogen-abstracting photoinitiator (C), and an organic solvent (D) ,
An active energy ray-curable composition, wherein the (meth)acrylate (A) and the (meth)acrylate (B) are different compounds. The (meth)acrylate (A) is at least selected from the group consisting of dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate and pentaerythritol tri(meth)acrylate. 2. The active energy ray-curable composition according to claim 1, which is one type of acrylate. 3. The active energy ray-curable composition according to claim 1, wherein the (meth)acrylate (B) is a (meth)acrylate having at least one or more of an alkylene oxide structure, an amine skeleton, and a thiol skeleton. thing. The active energy ray-curable composition according to any one of claims 1 to 3, wherein the (meth)acrylate (B) is a (meth)acrylate containing three or more acryloyl groups in the molecule. The active energy ray-curable composition according to any one of claims 1 to 4, wherein the hydrogen abstraction type photoinitiator (C) is any one of a benzophenone-based, thioxanthone-based, and xanthone-based photoinitiator. 6. The amount of the hydrogen abstraction type photoinitiator (C) is in the range of 2 to 6 parts by mass with respect to the total 100 parts by mass of the solid components contained in the composition. The active energy ray-curable composition as described. When the total of the (meth)acrylate (A) and the (meth)acrylate (B) is 100 parts by mass, the amount of the (meth)acrylate (B) added is 10 to 30 parts by mass. 7. The active energy ray-curable composition according to any one of 6. The active energy ray-curable composition according to any one of Claims 1 to 7, wherein the (meth)acrylate (B) is contained in an amount of 4.5 to 15 parts by mass when the entire composition is 100 parts by mass. The active energy ray-curable composition according to any one of claims 1 to 8, wherein the organic solvent (D) contains at least one or both of a ketone solvent and an ester solvent. A cured product of the active energy ray-curable composition according to any one of claims 1 to 9. A film having a cured coating film of the active energy ray-curable composition according to any one of claims 1 to 9 on at least one surface of a cyclic olefin resin film substrate or an olefin resin film substrate.