JP6895917B2 - Active energy ray-curable composition - Google Patents

Description

The present invention relates to an active energy ray-curable composition. More specifically, the present invention relates to a photocurable composition that provides a cured product having high scratch resistance and excellent adhesion to a base material and a metal.

Conventionally, the active energy ray-curable resin composition is widely used as a coating agent for plastics and the like (see, for example, Patent Documents 1 and 2). In recent years, display devices such as liquid crystal displays (LCDs) and touch panel displays provided with a plastic film having an active energy ray-curable resin composition as a protective layer on the surface have become widespread, and the coating film can prevent scratches on the surface. It is used for the purpose of surface protection such as prevention of dust adhesion.

In recent years, electronic devices such as smartphones and tablet terminals equipped with a touch panel that can be operated by directly touching the screen with a finger or a pen have become widespread, and such devices are required to further improve the hardness of the touch panel surface.

Further, in general, when the composition is coated, an organic solvent is often contained in order to ensure the coatability, but a device for volatilizing the solvent and a process such as heating are indispensable. On the other hand, it is environmentally and economically preferable to omit these devices and processes, and in order to achieve this, a solvent-free active energy ray-curable composition has been studied.
However, the coating process that does not use an organic solvent has a problem that the adhesion to a polycarbonate base material is significantly lowered, and there is a stricter requirement for the adhesion.

Furthermore, when the coating layer is used for mobile terminals, display devices such as notebook PCs and LCD TVs, it must have decorative properties such as metal vapor deposition and metal ink (metal powder-containing ink) coating properties. Is preferable.

As a method for imparting decorative properties such as metal vapor deposition and metal ink coating properties, a method of introducing a functional group such as a hydroxyl group or a carboxyl group into an active energy ray-curable hard coat composition has been proposed. However (see, for example, Patent Documents 3 to 5), the effect is not sufficient.

Japanese Unexamined Patent Publication No. 2010-248505 Japanese Unexamined Patent Publication No. 2003-0269225 Japanese Unexamined Patent Publication No. 2006-316249 Japanese Unexamined Patent Publication No. 2014-162864 Japanese Unexamined Patent Publication No. 2014-131782

An object of the present invention is to provide an active energy ray-curable composition which has high scratch resistance and gives a cured product having excellent adhesion to a polycarbonate base material and adhesion to a metal ink.

The present inventors have arrived at the present invention as a result of studies for achieving the above object.
That is, the present invention relates to a 2-3 functional (meth) acrylate (A) having an isocyanul skeleton, a polyfunctional (meth) acrylate (B) having no isocyanul skeleton, and a monofunctional (meth) acrylate having an aromatic ring. An active energy ray-curable composition containing C), a hindered amine light stabilizer (D) having a (meth) acrylic group, and a photopolymerization initiator (E); the active energy ray-curable composition is cured. It is a cured product.

The active energy ray-curable composition of the present invention has the effect of providing a cured product having high scratch resistance. Further, since the cured product has very excellent adhesion to the polycarbonate base material, the adhesion does not decrease even after, for example, hot water immersion treatment. In addition, it has excellent adhesion to decorative materials such as metal ink.

The active energy ray-curable composition of the present invention has a 2-3 functional (meth) acrylate (A) having an isocyanul skeleton, a polyfunctional (meth) acrylate (B) having no isocyanul skeleton, and a simple aromatic ring. It contains a functional (meth) acrylate (C), a hindered ami light stabilizer (D) having a (meth) acrylic group, and a photopolymerization initiator (E) as essential components.

In the present specification, "(meth) acrylate" means "acrylate or methacrylate", and "(meth) acryloyl group" means "acryloyl group or methacryloyl group".
Further, monofunctional means that the number of (meth) acryloyl groups is one, and bifunctional or higher means that the number of (meth) acryloyl groups is two or more. Is used.

Below, 2-3 functional (meth) acrylates (A) with an isocyanul skeleton, polyfunctional (meth) acrylates (B) without an isocyanul skeleton, monofunctional (meth) acrylates (C) with an aromatic ring, (meth). ) A hindered amine light stabilizer (D) having an acrylic group and a photopolymerization initiator (E) will be described in order.

The (meth) acrylate (A) having an isocyanul skeleton in the present invention needs to have an isocyanul skeleton and the number of (meth) acryloyl groups must be 2 to 3 from the viewpoint of hardness and adhesion to a metal ink. is there. In (A), one type may be used alone or two or more types may be used in combination.

Specific examples of the 2-3 functional (meth) acrylate (A) having an isocyanuric skeleton include isocyanuric acid alkylene oxide-modified di (meth) acrylate, isocyanuric acid alkylene oxide-modified tri (meth) acrylate, and tris [2- (meth). Examples thereof include acryloyloxyethyl] isocyanurate and ε-caprolactone-modified tris [2- (meth) acryloyloxyethyl] isocyanurate.
As the alkylene oxide in the case of alkylene oxide modification, ethylene oxide is preferable, and the degree of polymerization of the alkylene oxide used is preferably 1 to 10.

The polyfunctional (meth) acrylate (B) having no isocyanul skeleton in the present invention needs to have at least two (meth) acryloyl groups from the viewpoint of hardness, but has three to six (meth) acryloyl groups. Polyfunctional (meth) acrylate having is preferable.

Specific examples of the polyfunctional (meth) acrylate (B) having no isocyanul skeleton include di (meth) acrylate (B1), trifunctional or higher (meth) acrylate (B2), polyester (meth) acrylate (B3), and the like. Examples thereof include urethane (meth) acrylate (B4), epoxy (meth) acrylate (B5), (meth) acryloyl group-modified butadiene polymer (B6), and (meth) acryloyl group-modified dimethylpolysiloxane polymer (B7).

Examples of the di (meth) acrylate (B1) include di (meth) acrylate of polyoxyalkylene glycol, di (meth) acrylate of a linear or branched aliphatic dihydric alcohol having 2 to 30 carbon atoms, and 6 to 30 carbon atoms. Di (meth) acrylate of the alicyclic dihydric alcohol of the above can be mentioned.

As the di (meth) acrylate of polyoxyalkylene glycol, polyoxyalkylene glycol (alkylene has 2 to 4 carbon atoms) [chemical formula amount of 106 or more and number average molecular weight {number average by gel permeation chromatography (GPC) method). Molecular weight: Hereinafter abbreviated as Mn. } 3,000 or less] di (meth) acrylates [polyethylene glycol (Mn400), polypropylene glycol (Mn200), polytetramethylene glycol (Mn650) di (meth) acrylates, etc.] and the like can be mentioned.

Examples of the di (meth) acrylate of the linear or branched aliphatic dihydric alcohol having 2 to 30 carbon atoms include neopentyl glycol and each di (meth) acrylate of 1,6-hexanediol.

Examples of the di (meth) acrylate of the alicyclic dihydric alcohol having 6 to 30 carbon atoms include di (meth) acrylate of dimethyloltricyclodecane, di (meth) acrylate of cyclohexanedimethanol, and di (meth) acrylate of hydrogenated bisphenol A. Meta) acrylate and the like can be mentioned.

Examples of the trivalent or higher (meth) acrylate (B2) include poly (meth) acrylates of polyhydric alcohols having 3 to 40 carbon atoms and their AO adducts [trimethylol propantri (meth) acrylate, tri (meth) of glycerin. Acrylate, each tri (meth) acrylate of EO3 mol or PO3 mol adduct of trimethylolpropane, each tri (meth) acrylate of EO3 mol or PO3 mol adduct of glycerin, tri (meth) acrylate of pentaerythritol, pentaerythritol Tetra (meth) acrylate, tetra (meth) acrylate of EO4 molar adduct of pentaerythritol, penta (meth) acrylate of dipentaerythritol, hexa (meth) acrylate of dipentaerythritol, etc.] and the like can be mentioned.

The polyester (meth) acrylate (B3) has a plurality of ester bonds obtained by esterification of a polyvalent carboxylic acid, a polyhydric alcohol, and an ester-forming acryloyl group-containing compound, and two or more (meth) acryloyl groups. Examples thereof include polyester acrylates having a chemical formula amount of 150 or more and Mn 4,000 or less.

Examples of the above-mentioned polyvalent carboxylic acid include aliphatic polyvalent carboxylic acids [for example, reactions of malonic acid, maleic acid (anhydride), adipic acid, sebacic acid, succinic acid and acid anhydride (dipentaerythritol and maleic anhydride). Acid reactants, etc.)] and alicyclic polyvalent carboxylic acids [eg, cyclohexanedicarboxylic acid, tetrahydro (maleic) phthalic acid and methyltetrahydro (maleic anhydride) phthalic acid].

The urethane (meth) acrylate (B4) has a chemical formula of 400 or more and Mn 5,000 having a plurality of urethane bonds and two or more acryloyl groups obtained by the urethanization reaction of polyisocyanate, polyol and hydroxyl group-containing (meth) acrylate. The following urethane (meth) acrylates can be mentioned.

Examples of the polyisocyanate used in (B4) include aliphatic polyisocyanates [hexamethylene diisocyanate and the like] and alicyclic polyisocyanates [isophorone diisocyanate and 4,4'-methylenebis (cyclohexyl isocyanate) and the like].
Examples of the polyol used in (B4) include ethylene glycol, 1,4-butanediol, neopentyl glycol, polyether polyol, polycaprolactone polyol, polyester polyol, polycarbonate polyol, and polytetramethylene glycol.
Examples of the hydroxyl group-containing (meth) acrylate used in (B4) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

Examples of the epoxy (meth) acrylate (B5) include epoxy (meth) acrylates having a chemical formula of more than the chemical formula obtained by the reaction of a multivalent (2 to 4 valent) epoxide and (meth) acrylic acid and Mn of 5,000 or less.

Examples of the (meth) acryloyl group-modified butadiene polymer (B6) include polybutadiene poly (meth) acrylate (Mn 500 to 500,000) having a (meth) acryloyl group in the main chain and / or side chain.

Examples of the (meth) acryloyl group-modified dimethylpolysiloxane polymer (B7) include Mn300 to 20,000 dimethylpolysiloxane poly (meth) acrylates having a (meth) acryloyl group in the main chain and / or side chains.

Of these (B1) to (B7), (B2) to (B5) are preferable from the viewpoint of hardness of the cured product, and (B2) is more preferable. In (B), one type may be used alone or two or more types may be used in combination.

The monofunctional (meth) acrylate (C) having an aromatic ring in the present invention has an aromatic ring skeleton such as a phenyl group and a substituted phenyl group, and is particularly long as it is a compound having only one (meth) acryloyl group. Not limited to the compound (C1) represented by the following general formula (1), the compound (C2) represented by the general formula (2), and a monofunctional (meth) having an aromatic ring other than (C1) and (C2). ) Acrylate (C3) and the like can be mentioned.

^{R 1} in the general formula (1) represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of curability.
m represents the number of moles of ethylene oxide added and is an integer of 1 to 5.

^{R 2} in the general formula (2) represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of curability. R ³ represents a hydrogen atom, a phenyl group, a phenoxy group, a methyl group or a hydroxyl group. n is 1 or 2.

Specific examples of the compound (C1) represented by the general formula (1) include phenoxyethyl (meth) acrylate and phenoxypolyethylene glycol (meth) acrylate.

Specific examples of the compound (C2) represented by the general formula (2) include benzyl (meth) acrylate, o-, m- or p-phenylbenzyl (meth) acrylate, o-, m- or p-phenoxy. Benzyl (meth) acrylate, o-, m- or p-methylbenzyl (meth) acrylate and o-, m- or p-hydroxybenzyl (meth) acrylate and the like can be mentioned.

Examples of the monofunctional (meth) acrylate (C3) having an aromatic ring other than (C1) and (C2) include o-, m- or p-phenylphenoxyethyl (meth) acrylate and nonylphenoxypolyethylene glycol (meth) acrylate. Can be mentioned.
In (C), one type may be used alone or two or more types may be used in combination.

The hindered amine light stabilizer (D) having a (meth) acrylic group in the present invention is a so-called hindered amine light stabilizer having a (meth) acrylic group in the molecule. For example, a light stabilizer having a piperidine ring in which a plurality of sterically hindering substituents are bonded to two adjacent carbon atoms of a nitrogen atom, and a compound having a (meth) acrylic group in the molecule can be mentioned. .. Examples of the substituent exhibiting such a steric hindrance action include a methyl group and the like.

Aside from the presence or absence of a (meth) acrylic group, a so-called hindered amine light stabilizer is a compound having a photostability effect / action, and specific examples are described in, for example, Japanese Patent No. 5283485.
The (D) that can be used in the present invention has at least one (meth) acrylic group in the molecule, and is, for example, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate [ADEKA]. ADEKA STAB LA-87], 2,2,6,6-tetramethyl-4-piperidinyl methacrylate [ADEKA Corporation, ADEKA STAB LA-82], bis (1,2,2,6) , 6-Pentamethyl-4-piperidinyl) p-methoxybenzylidene malonate [Hostavin PR-31, manufactured by Clariant Chemical Co., Ltd.] and other hindered amine light stabilizers.
In (D), one type may be used alone or two or more types may be used in combination.

The photopolymerization initiator (E) in the present invention includes a phosphine oxide compound (E1), a benzoylformate compound (E2), a thioxanthone compound (E3), an oxime ester compound (E4), a hydroxybenzoyl compound (E5), and a benzophenone. Examples thereof include compound (E6), ketal compound (E7), α-aminoalkylphenone compound (E8) and the like.

Examples of the phosphine oxide compound (E1) include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Examples of the benzoyl format compound (E2) include methyl benzoyl format.
Examples of the thioxanthone compound (E3) include isopropyl thioxanthone and the like.
Examples of the oxime ester compound (E4) include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and etanone, 1- [9-ethyl-6- (2-). Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) and the like can be mentioned.

Examples of the hydroxybenzoyl compound (E5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, benzoin alkyl ether and the like.
Examples of the benzophenone compound (E6) include benzophenone and the like.
Examples of the ketal compound (E7) include benzyldimethyl ketal and the like.
Examples of the α-aminoalkylphenone compound (E8) include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopro-butanone-1 and 2- (dimethylamino) -2-[(4-methylphenyl). Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like can be mentioned.

Of these, phosphine oxide compound (E1), hydroxybenzoyl compound (E5), and α-aminoalkylphenone compound (E8) are preferable from the viewpoint of curability and coloring of the cured product.
In (E), one type may be used alone or two or more types may be used in combination.

The content of (A) in the active energy ray-curable resin composition is preferably 1 to 50% by weight based on the total weight of (A) to (E) from the viewpoint of hardness and adhesion to metal ink. , More preferably 10 to 50% by weight.

The content of (B) in the active energy ray-curable resin composition is preferably 1 to 50% by weight, more preferably 10 to 50%, based on the total weight of (A) to (E) from the viewpoint of hardness. By weight%.

The content of (C) in the active energy ray-curable resin composition is preferably 1 to 30% by weight, more preferably 1 to 30% by weight, based on the total weight of (A) to (E) from the viewpoint of adhesion to the substrate. It is preferably 10 to 30% by weight.

The content of (D) in the active energy ray-curable resin composition is preferably 1 to 20% by weight, more preferably 1 to 20% by weight, based on the total weight of (A) to (E) from the viewpoint of adhesion to the metal ink. It is preferably 10 to 20% by weight.

The content of the photopolymerization initiator (E) in the active energy ray-curable resin composition is preferably 0.1 to 0 based on the total weight of (A) to (E) from the viewpoint of curability and transparency. It is 10% by weight, more preferably 0.2 to 7% by weight, and particularly preferably 0.5 to 5% by weight.

The composition of the present invention can be diluted with a solvent, if necessary, in order to adjust the viscosity to be suitable for coating and to improve the adhesion to the substrate.
The amount of the solvent used is preferably 2,000% by weight or less, more preferably 10 to 500% by weight, based on the weight of the active energy ray-curable resin composition. The viscosity of the coating material is the temperature at the time of use (preferably 5 to 60 ° C.) from the viewpoint of coatability, preferably 5 to 5,000 mPa · s, and more preferably 50 to 1,000 mPa · s.

The solvent is not particularly limited as long as it dissolves the resin component in the composition of the present invention. Specifically, aromatic hydrocarbons (eg toluene, xylene and ethylbenzene), esters or ether esters (eg ethyl acetate, butyl acetate and methoxybutyl acetate), ethers (eg diethyl ether, tetrahydrofuran, ethylene glycol monoethyl ether, ethylene). Glycol monobutyl ether, propylene glycol monomethyl ether and diethylene glycol monoethyl ether), ketones (eg acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone), alcohols (eg methanol, ethanol, n- or i-propanol) , N-, i-, sec- or t-butanol, 2-ethylhexyl alcohol and benzyl alcohol), amides (eg dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), sulfoxides (eg dimethylsulfoxide), water and these. Two or more mixed solvents can be mentioned.

Among these solvents, esters, ketones and alcohols having a boiling point of 70 to 100 ° C. are preferable from the viewpoint of smoothness of the coating film and efficiency of solvent removal, and ethyl acetate, methyl ethyl ketone, i-propanol and these are more preferable. It is a mixture.
One type of solvent may be used alone, or two or more types may be used in combination.

The active energy ray-curable resin composition of the present invention is diluted with a solvent, if necessary, applied to at least a part of at least one side of the substrate, dried if necessary, and then irradiated with light to be cured. A resin coating having a cured film can be obtained.
For coating, for example, a coating machine [bar coater, gravure coater, roll coater (size press roll coater, gate roll coater, etc.), air knife coater, spin coater, blade coater, etc.] can be used.
The coating film thickness is preferably 0.5 to 300 μm as the film thickness after curing and drying. A more preferable upper limit is 250 μm from the viewpoint of drying property and curability, and a further preferable lower limit is 1 μm from the viewpoint of abrasion resistance, solvent resistance and stain resistance.

Examples of the base material include those made of resins such as polycarbonate, methyl methacrylate (co) polymer, polyethylene terephthalate, popolitriacetyl cellulose and polycycloolefin.

When the active energy ray-curable resin composition of the present invention is diluted with a solvent and used, it is preferable to dry it after coating. Examples of the drying method include hot air drying (dryer, etc.).
The drying temperature is preferably 10 to 200 ° C., a more preferable upper limit is 150 ° C. from the viewpoint of smoothness and appearance of the coating film, and a further preferable lower limit is 30 ° C. from the viewpoint of drying speed.

The active energy ray-curable resin composition of the present invention may contain various additives (F), if necessary, as long as the effects of the present invention are not impaired.
Additives (F) include plasticizers, organic solvents, dispersants, defoamers, thixotropy-imparting agents (thickeners), slip agents, leveling agents, antioxidants, and hindered amines that do not have (meth) acrylic groups. Examples include light stabilizers and ultraviolet absorbers. For example, a polyether-modified polysiloxane or a polyether-modified fluorine compound is useful because it has both a slip agent and a leveling agent.
As the additive, one type may be used alone or two or more types may be used in combination.

When the active energy ray-curable resin composition of the present invention is cured by ultraviolet rays, various ultraviolet irradiation devices [for example, an ultraviolet irradiation device [model number "VPS / I600", manufactured by Fusion UV Systems Co., Ltd.] can be used.
Examples of the lamp used include a high-pressure mercury lamp and a metal halide lamp. The dose of ultraviolet rays is preferably a flexible viewpoint of curability and cured product of a composition 10~10,000mJ / cm ^2, more preferably from 100~5,000mJ / cm ^2.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, parts indicate parts by weight.

Example 1
In a reaction vessel equipped with a stirrer and a thermometer, 10.0 parts of isocyanuric acid EO-modified diacrylate (A-1) [trade name: Aronix M-215, manufactured by Toa Synthetic Co., Ltd.], dipentaerythritol hexaacrylate ( B-1) [Product name: Light acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.] 40.0 parts, Bisphenol fluorene EO 2 mol additive Diacrylate (B-3) [Product name: Ogsol EA-0200, Osaka Gas Chemical Co., Ltd.] 10.0 parts, benzyl acrylate (C-1) [Product name: Viscort # 160, manufactured by Osaka Organic Chemical Industry Co., Ltd.] 30.0 parts, 2,2,6,6-tetramethyl -4-piperidyl Methacrylate (D-1) [Product Name: Adecaster LA-87, manufactured by ADEKA Co., Ltd.] 10.0 parts and 2-Methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropane -1-On (E-1) [trade name: Irgacure 907, manufactured by BASF] was added in an amount of 5.0 parts, and the mixture was mixed and stirred at 70 ° C. until uniform to obtain an active energy ray-curable composition.

Examples 2-11 and Comparative Examples 1-7
In the same manner as in Example 1, the raw materials and the number of copies shown in Table 1 were uniformly mixed to obtain active energy ray-curable compositions of Examples 2 to 11 and Comparative Examples 1 to 7.

The raw materials used in Table 1 are as follows.
(A-1): Isocyanuric acid EO-modified diacrylate [Product name: Aronix M-215, manufactured by Toagosei Co., Ltd.]
(A-2): Isocyanuric acid EO-modified triacrylate [Product name: Aronix M-315, manufactured by Toagosei Co., Ltd.]
(A-3): ε-caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate [trade name: A9300-1CL, manufactured by Shin-Nakamura Kogyo Co., Ltd.]
(B-1): Dipentaerythritol hexaacrylate [Product name: Light acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.]
(B-2): Pentaerythritol tetraacrylate [Product name: Neomer EA-300, manufactured by Sanyo Chemical Industries, Ltd.]
(B-3): Diacrylate of 2 mol adduct of bisphenol fluorene ethylene oxide (EO) [Product name: Ogsol EA-0200, manufactured by Osaka Gas Chemical Co., Ltd.]
(C-1): Benzyl acrylate [Product name: Viscote # 160, manufactured by Osaka Organic Chemical Industry Co., Ltd.]
(C-2): Phenoxyethyl acrylate [Product name: Light acrylate PO-A, manufactured by Kyoeisha Chemical Co., Ltd.]
(C-3): m-phenoxybenzyl acrylate [Product name: Light acrylate POB-A, manufactured by Kyoeisha Chemical Co., Ltd.]
(C'-1): Isobornyl acrylate [Product name: IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.]
(D-1): 2,2,6,6-tetramethyl-4-piperidyl methacrylate [trade name: ADEKA STAB LA-87, manufactured by ADEKA Corporation, 1 methacrylic group]
(D-2): 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate [trade name: ADEKA STAB LA-82, manufactured by ADEKA Corporation, 1 methacrylic group]
(D'-1): Triethylamine [manufactured by Tokyo Kasei Co., Ltd.]
(D'-2): Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate [Product name: ADEKA STAB LA-77Y, manufactured by ADEKA Corporation]
(E-1): 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one [Product name: Irgacure 907, manufactured by BASF Limited]
(E-2): 1-Hydroxycyclohexylphenyl ketone [trade name: Irgacure 184, manufactured by BASF Ltd.]
(F-1): alkylene oxide-modified polydimethylsiloxane [trade name: BYK-333, manufactured by Big Chemie Japan Co., Ltd.]
(F-2): Fluorine atom-containing nonionic surfactant having a (meth) acrylic group [Product name: Megafuck RS-90, manufactured by DIC Corporation]

The films obtained by curing the active energy ray-curable compositions of Examples 1 to 11 and Comparative Examples 1 to 7 under the following conditions were subjected to the initial and hot water treatment polycarbonate substrates by the following methods. The performance of adhesion, scratch resistance, and adhesion to metal ink was evaluated. The results are shown in Table 1.

[Evaluation of adhesion]
<Curing film manufacturing method>
The active energy ray-curable composition was applied to one side of a 0.8 mm-thick polycarbonate resin base material using a bar coater so that the cured film thickness was 5 μm, and the temperature was adjusted at 60 ° C. for 90 seconds. , Ultraviolet irradiation device [model number "VPS / I600", manufactured by Fusion UV Systems Co., Ltd.] ^{irradiated 400 mJ / cm 2} of ultraviolet rays in a nitrogen atmosphere to prepare a cured film.

<Evaluation of initial adhesion>
This was done in accordance with JIS K5600-5-6. That is, after allowing the cured film to stand for 24 hours in an environment of 23 ° C. and a relative humidity of 50%, a grid (10 × 10 pieces) was prepared by making a cut in a width of 1 mm with a cutter knife.
A cellophane adhesive tape was attached on the grid, peeled at 90 degrees, and the peeled state of the cured product from the polycarbonate resin base material was visually observed. The number of squares in 100 squares that were in close contact with each other without peeling was counted and evaluated.
The initial adhesion of the cured product of the active energy ray-curable composition of the present invention to the substrate is preferably that there is no peeling from the substrate.

<Evaluation of adhesion after hot water immersion treatment>
In order to confirm the adhesion under more severe conditions, the adhesion after immersion in hot water was also evaluated.
After immersing the cured film in hot water at 90 ° C. for 10 minutes and pulling it up, the moisture on the surface was wiped off, and the film was allowed to stand for 24 hours in an environment of 23 ° C. and 50% relative humidity. In accordance with JIS K5600-5-6, the number of squares that were in close contact with each other without peeling was counted and evaluated in the same manner as in the above evaluation of initial adhesion. In terms of adhesion after immersion in hot water, it is preferable that the number of squares that are in close contact with each other without peeling is 90 or more.

[Evaluation of scratch resistance]
The resin surface of the cured film was rubbed 10 times back and forth with a load of ^{500 g / cm 2} using steel wool of # 0000 (fiber center diameter of about 0.012 mm).
The haze values (%) before and after scraping are measured in accordance with JIS-K7105 using a total light transmittance measuring device [trade name "haze-gard dual" manufactured by BYK gardener Co., Ltd.] and scraped. The difference between the haze value (%) after and the haze value (%) before scraping was calculated.
Under these evaluation conditions, the difference in haze values is generally preferably 1% or less.

[Evaluation of adhesion with metal ink]
Using a 300 mesh screen printing machine, a metal ink (mirror surface ink 700CX silver manufactured by Seiko Advance Co., Ltd.) is applied to the resin surface of the cured film so that the thickness after drying is 5 μm, and the temperature is 25 ° C. It was dried at 80 ° C. for 5 hours for 1 hour. The cured film was allowed to stand for 24 hours in an environment of 23 ° C. and a relative humidity of 50%, and then cuts were made in a width of 1 mm with a cutter knife to prepare a grid (10 × 10 pieces). A cellophane adhesive tape was attached on the grid, peeled at 90 degrees, and the peeling state of the mirror ink from the cured film surface was visually observed. The number of squares in 100 squares that were in close contact with each other without peeling was counted and evaluated.
The adhesion of the metal ink to the active energy ray-curable composition of the present invention is preferably that there is no peeling from the substrate.

From the results in Table 1, the cured film obtained by curing the active energy ray-curable composition of Examples 1 to 11 of the present invention has initial adhesion to a polycarbonate resin base material, adhesion after hot water immersion treatment, and resistance. It can be seen that it has excellent scratch resistance and excellent adhesion to metal ink.
On the other hand, the composition of Comparative Example 1 containing a 2-3 functional polyfunctional (meth) acrylate (A) having an isocyanul skeleton has insufficient scratch resistance of the cured product and insufficient adhesion to the metal. Is. Further, the composition of Comparative Example 2 which does not contain the polyfunctional (meth) acrylate (B) having no isocyanul skeleton has insufficient scratch resistance of the cured product.
Further, a composition of Comparative Example 3 using a monofunctional (meth) acrylate (C'-1) having no aromatic ring skeleton and a comparative example not using a monofunctional (meth) acrylate (C) having an aromatic ring skeleton. The composition of No. 4 has poor initial adhesion and adhesion after hot water immersion treatment.
The composition of Comparative Example 5 using an amine compound (D'-1) having a non-hindered amine skeleton and the composition of Comparative Example 7 using a hindered amine light stabilizer (D) having a (meth) acrylic group were composed of a metal ink. The composition of Comparative Example 6 using a hindered amine light stabilizer (D'-2) having poor adhesion to metal ink and having no (meth) acrylic group has poor scratch resistance in addition to adhesion to metal ink. It becomes.

The cured product obtained by curing the active energy ray-curable composition of the present invention has excellent initial adhesion to a polycarbonate resin base material, adhesion after hot water immersion treatment, and scratch resistance, and adheres to a metal ink. It also has excellent properties, such as plastic lenses (prism lenses, lenticular lenses, microlenses, frennel lenses, viewing angle improving lenses, etc.), optical compensation films, retardation films and other optical components, electrical and electronic components, and decorative films. It is also useful as.

Claims (5)

A 2-3 functional (meth) acrylate (A) having an isocyanul skeleton, a polyfunctional (meth) acrylate (B) not having an isocyanul skeleton, a monofunctional (meth) acrylate (C) having an aromatic ring, and (meth). ) An active energy ray-curable composition containing a hindered amine light stabilizer (D) having an acrylic group and a photopolymerization initiator (E). The active energy ray-curable composition according to claim 1, wherein the content of (A) is 1 to 50% by weight based on the total weight of (A) to (E). The active energy ray-curable composition according to claim 1 or 2, wherein the content of (C) is 1 to 30% by weight based on the total weight of (A) to (E). The active energy ray-curable composition according to any one of claims 1 to 3, wherein the content of (D) is 1 to 20% by weight based on the total weight of (A) to (E). A cured product obtained by curing the active energy ray-curable composition according to any one of claims 1 to 4.