JP2018165358A - Active energy ray-curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: 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. SOLUTION: 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 (C) having an aromatic ring. An active energy ray-curable composition containing a hindered amine light stabilizer (D) having a (meth) acrylic group and a photopolymerization initiator (E). [Selection diagram] None

Description

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

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

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

In general, when a composition is applied, an organic solvent is often contained in order to ensure applicability. However, an apparatus for volatilizing the solvent and a process such as heating are essential. On the other hand, omitting these apparatuses and processes is environmentally and economically preferable. In order to achieve this, a solventless active energy ray-curable composition has been studied.
However, in a coating process that does not use an organic solvent, for example, there is a problem that adhesion to a polycarbonate base material is significantly lowered, and there is a stricter requirement for adhesion.

  In addition, when the coating layer is used in display devices such as mobile terminals, notebook PCs, and liquid crystal televisions, it must have decorative properties such as metal deposition and metal ink (metal powder-containing ink) paintability. Is preferred.

  As a method for imparting decorative properties such as metal vapor deposition and metal ink paintability, 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, the effect is not sufficient.

JP 2010-248505 A Japanese Patent Laid-Open No. 2003-026925 JP 2006-316249 A JP 2014-162864 A JP 2014-131882 A

  An object of the present invention is to provide an active energy ray-curable composition that provides a cured product having high scratch resistance and excellent adhesion to a polycarbonate substrate and adhesion to a metal ink.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention relates to a bifunctional to trifunctional (meth) acrylate (A) having an isocyanuric skeleton, a polyfunctional (meth) acrylate (B) not having an isocyanuric skeleton, and a monofunctional (meth) acrylate having an aromatic ring ( C), an active energy ray-curable composition containing a hindered amine light stabilizer (D) having a (meth) acrylic group and a photopolymerization initiator (E); curing the active energy ray-curable composition; It is a cured product.

  The active energy ray-curable composition of the present invention has an effect of giving a cured product having high scratch resistance. Furthermore, since the cured product is very excellent in adhesion to the polycarbonate substrate, the adhesion does not decrease even after, for example, hot water immersion treatment. Moreover, the adhesiveness with respect to decorating materials, such as metal ink, is also excellent.

  The active energy ray-curable composition of the present invention includes a bifunctional to trifunctional (meth) acrylate (A) having an isocyanuric skeleton, a polyfunctional (meth) acrylate (B) not having an isocyanuric skeleton, and a single unit having an aromatic ring. A functional (meth) acrylate (C), a hindered light stabilizer (D) having a (meth) acryl group, and a photopolymerization initiator (E) are contained as essential components.

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

  In the following, a bifunctional to trifunctional (meth) acrylate (A) having an isocyanuric skeleton, a polyfunctional (meth) acrylate (B) not having an isocyanuric skeleton, a monofunctional (meth) acrylate (C) having an aromatic ring, (meta ) A hindered amine light stabilizer (D) having an acrylic group and a photopolymerization initiator (E) will be described in this order.

  The (meth) acrylate (A) having an isocyanuric skeleton in the present invention needs to have an isocyanuric skeleton and the number of (meth) acryloyl groups should be 2 to 3 from the viewpoints of hardness and adhesion to metal ink. is there. (A) may be used individually by 1 type, or may use 2 or more types together.

Specific examples of the 2- to 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). Acryloyloxyethyl] isocyanurate and ε-caprolactone-modified tris [2- (meth) acryloyloxyethyl] isocyanurate.
In the case of alkylene oxide modification, the alkylene oxide is preferably ethylene oxide, and the degree of polymerization of the alkylene oxide used is preferably 1 to 10.

  The polyfunctional (meth) acrylate (B) having no isocyanuric skeleton in the present invention needs to have at least two (meth) acryloyl groups from the viewpoint of hardness, but 3 to 6 (meth) acryloyl groups. Polyfunctional (meth) acrylates having the following are preferred.

  Specific examples of the polyfunctional (meth) acrylate (B) having no isocyanuric skeleton include di (meth) acrylate (B1), trifunctional or higher (meth) acrylate (B2), polyester (meth) acrylate (B3), Examples 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 linear or branched aliphatic dihydric alcohol having 2 to 30 carbon atoms, and 6 to 30 carbon atoms. And di (meth) acrylate of alicyclic dihydric alcohol.

  As poly (oxyalkylene glycol) di (meth) acrylate, polyoxyalkylene glycol (alkylene having 2 to 4 carbon atoms) [chemical formula weight 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) acrylate [poly (ethylene glycol (Mn400), polypropylene glycol (Mn200), polytetramethylene glycol (Mn650) di (meth) acrylate, etc.]] and the like.

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

  Examples of the di (meth) acrylate of an 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 ( And (meth) acrylate.

  The trivalent or higher (meth) acrylate (B2) is a poly (meth) acrylate having 3 to 40 carbon atoms and an AO adduct thereof [trimethylolpropane tri (meth) acrylate, tri (meth) of glycerol. Acrylate, trimethylolpropane EO3 mol or PO3 mol adduct tri (meth) acrylate, glycerin EO3 mol or PO3 mol adduct tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, tetra (meth) acrylate of pentaerythritol EO 4 mol adduct, penta (meth) acrylate of dipentaerythritol, hexa (meth) acrylate of dipentaerythritol, and the like.

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

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

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

Examples of the polyisocyanate used in (B4) include aliphatic polyisocyanate [hexamethylene diisocyanate and the like] and alicyclic polyisocyanate [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 for (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 an epoxy (meth) acrylate having a chemical formula amount and a Mn of 5,000 or less obtained by a reaction between a polyvalent (2-4 valent) epoxide and (meth) acrylic acid.

  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) acrylate having a (meth) acryloyl group in the main chain and / or side chain.

  Of these (B1) to (B7), (B2) to (B5) are preferable from the viewpoint of the hardness of the cured product, and (B2) is more preferable. (B) may be used individually by 1 type, or may use 2 or more types together.

  The monofunctional (meth) acrylate (C) having an aromatic ring in the present invention is particularly a compound having an aromatic ring skeleton such as a phenyl group and a substituted phenyl group and having only one (meth) acryloyl group. Without limitation, the compound (C1) represented by the following general formula (1), the compound (C2) represented by the general formula (2), and a monofunctional (meta) having an aromatic ring other than (C1) and (C2) ) Acrylate (C3) and the like.

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 added moles of ethylene oxide, 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. Examples include benzyl (meth) acrylate, o-, m- or p-methylbenzyl (meth) acrylate and o-, m- or p-hydroxybenzyl (meth) acrylate.

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. Is mentioned.
(C) may be used alone or in combination of two or more.

  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 substituents having a steric hindrance function are bonded to two carbon atoms adjacent to a nitrogen atom and having a (meth) acryl group in the molecule . Examples of the substituent having such steric hindrance include a methyl group.

Aside from the presence or absence of a (meth) acryl group, so-called hindered amine light stabilizers are compounds having light-stabilizing effects and actions, and specific examples are described in, for example, Japanese Patent No. 5283485.
(D) that can be used in the present invention has at least one (meth) acryl group in the molecule. For example, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate [ADEKA ADK STAB LA-87], 2,2,6,6-tetramethyl-4-piperidinyl methacrylate [ADEKA K.K., ADK STAB LA-82], bis (1,2,2,6) , 6-pentamethyl-4-piperidinyl) p-methoxybenzylidene malonate [manufactured by Clariant Chemical Co., Ltd., Hostavin PR-31].
(D) may be used individually by 1 type, or may use 2 or more types together.

  As the photopolymerization initiator (E) in the present invention, phosphine oxide compound (E1), benzoylformate compound (E2), thioxanthone compound (E3), oxime ester compound (E4), hydroxybenzoyl compound (E5), benzophenone A compound (E6), a ketal compound (E7), an α-aminoalkylphenone compound (E8) and the like can be mentioned.

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 formate compound (E2) include methyl benzoyl formate.
Examples of the thioxanthone compound (E3) include isopropyl thioxanthone.
Examples of the oxime ester compound (E4) include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and ethanone, 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

Examples of the hydroxybenzoyl compound (E5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and benzoin alkyl ether.
Examples of the benzophenone compound (E6) include benzophenone.
Examples of the ketal compound (E7) include benzyl dimethyl ketal.
As the α-aminoalkylphenone compound (E8), 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.

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

  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 the metal ink. More preferably, it is 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 based on the total weight of (A) to (E) from the viewpoint of adhesion to the substrate, and more preferably Preferably it is 10 to 30% by weight.

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

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

The composition of the present invention can be diluted with a solvent as necessary in order to adjust the viscosity to be suitable for coating or to improve the substrate adhesion.
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. Further, the viscosity of the paint is a temperature at the time of use (preferably 5 to 60 ° C.) from the viewpoint of coatability, preferably 5 to 5,000 mPa · s, 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, monomethyl ether of propylene glycol and monoethyl ether of diethylene glycol), 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 If dimethylformamide, dimethylacetamide, N- methylpyrrolidone), sulfoxides (e.g., dimethyl sulfoxide), and water and 2 or more kinds mixed solvents thereof.

Among these solvents, esters, ketones and alcohols having a boiling point of 70 to 100 ° C. are preferable from the viewpoint of the smoothness of the coating film and the efficiency of solvent removal, more preferably ethyl acetate, methyl ethyl ketone, i-propanol, and these. It is a mixture.
A solvent may be used individually by 1 type, or may use 2 or more types together.

The active energy ray-curable resin composition of the present invention is diluted with a solvent as necessary, applied to at least a part of at least one side of the substrate, dried as necessary, and then cured by irradiation with light. A resin coating having a cured film can be obtained.
In 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 viewpoints of drying properties and curability, and a further preferable lower limit is 1 μm from the viewpoints of wear resistance, solvent resistance, and contamination resistance.

  As said base material, what consists of resin, such as a polycarbonate, a methylmethacrylate (co) polymer, a polyethylene terephthalate, a polypolytriacetylcellulose, a polycycloolefin, is mentioned.

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

The active energy ray-curable resin composition of the present invention may contain various additives (F) as necessary within a range that does not impair the effects of the present invention.
Additives (F) include plasticizers, organic solvents, dispersants, antifoaming agents, thixotropic agents (thickeners), slip agents, leveling agents, antioxidants, hindered amines that do not have (meth) acrylic groups Examples include light stabilizers and ultraviolet absorbers. For example, polyether-modified polysiloxane and polyether-modified fluorine compound are useful because they have both a slip agent and a leveling agent.
One additive may be used alone, or two or more additives may be used in combination.

When the active energy ray-curable resin composition of the present invention is cured with ultraviolet rays, various ultraviolet irradiation devices [for example, ultraviolet irradiation devices [model number “VPS / I600”, manufactured by Fusion UV Systems Co., Ltd.] can be used.
Examples of the lamp to be 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, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, a part shows a weight part.

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 Toagosei Co., Ltd.], dipentaerythritol hexaacrylate ( B-1) [Product Name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.] 40.0 parts, Bisphenolfluorene EO 2 mol adduct diacrylate (B-3) [Product Name: Ogsol EA-0200, Osaka Gas Chemical Co., Ltd.] 10.0 parts, benzyl acrylate (C-1) [trade name: Biscote # 160, Osaka Organic Chemical Industry Co., Ltd.] 30.0 parts, 2,2,6,6-tetramethyl -4-piperidyl methacrylate (D-1) [trade name: ADK STAB LA-87, manufactured by ADEKA Corporation] 10.0 parts and 2-methyl-1- [4- ( Tilthio) phenyl] -2-morpholinopropan-1-one (E-1) [trade name: Irgacure 907, manufactured by BASF Corp.] 5.0 parts is added and mixed and stirred at 70 ° C. until uniform, active energy A linear curable composition was obtained.

Examples 2-11 and Comparative Examples 1-7
It carried out similarly to Example 1, and mixed uniformly with the raw material and number of parts which are shown in Table 1, and obtained the active energy ray curable composition of Examples 2-11 and Comparative Examples 1-7.

The raw materials used in Table 1 are as follows.
(A-1): Isocyanuric acid EO-modified diacrylate [trade name: Aronix M-215, manufactured by Toagosei Co., Ltd.]
(A-2): Isocyanuric acid EO-modified triacrylate [trade 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 [trade name: Light acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.]
(B-2): Pentaerythritol tetraacrylate [Brand name: Neomer EA-300, manufactured by Sanyo Chemical Industries, Ltd.]
(B-3): Diacrylate of bisphenol fluorene ethylene oxide (EO) 2 mol adduct [trade name: Ogsol EA-0200, manufactured by Osaka Gas Chemical Co., Ltd.]
(C-1): benzyl acrylate [Brand name: Biscote # 160, manufactured by Osaka Organic Chemical Industry Co., Ltd.]
(C-2): Phenoxyethyl acrylate [Brand name: Light acrylate PO-A, manufactured by Kyoeisha Chemical Co., Ltd.]
(C-3): m-phenoxybenzyl acrylate [trade name: Light acrylate POB-A, manufactured by Kyoeisha Chemical Co., Ltd.]
(C′-1): Isobornyl acrylate [trade name: IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.]
(D-1): 2,2,6,6-tetramethyl-4-piperidyl methacrylate [trade name: ADK STAB LA-87, manufactured by ADEKA Corporation, one methacryl group]
(D-2): 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate [trade name: ADK STAB LA-82, manufactured by ADEKA Corporation, one methacryl group]
(D′-1): Triethylamine [manufactured by Tokyo Chemical Industry Co., Ltd.]
(D′-2): Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate [trade name: ADK STAB LA-77Y, manufactured by ADEKA Corporation]
(E-1): 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one [trade name: Irgacure 907, manufactured by BASF Corporation]
(E-2): 1-hydroxycyclohexyl phenyl ketone [trade name: Irgacure 184, manufactured by BASF Corporation]
(F-1): Alkylene oxide modified polydimethylsiloxane [Brand name: BYK-333, manufactured by Big Chemie Japan Co., Ltd.]
(F-2): Fluorine atom-containing nonionic surfactant having a (meth) acryl group [trade name: MegaFac RS-90, manufactured by DIC Corporation]

  About 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, the initial method and the polycarbonate substrate after the hydrothermal treatment were used in the following manner. Performance evaluation of adhesion, scratch resistance, and adhesion to metal ink was performed. The results are shown in Table 1.

[Evaluation of adhesion]
<Curing film production method>
After applying the active energy ray-curable composition to one side of a polycarbonate resin substrate having a thickness of 0.8 mm using a bar coater so that the film thickness after curing is 5 μm, the temperature is adjusted at 60 ° C. for 90 seconds. Then, ultraviolet rays were irradiated at 400 mJ / cm ^{2 in} a nitrogen atmosphere using an ultraviolet irradiation device [model number “VPS / I600”, manufactured by Fusion UV Systems Co., Ltd.] to prepare a cured film.

<Evaluation of initial adhesion>
This was performed according to JIS K5600-5-6. That is, the cured film was allowed to stand for 24 hours in an environment of 23 ° C. and 50% relative humidity, and then cut into a 1 mm width with a cutter knife to produce a grid (10 × 10 pieces).
A cellophane adhesive tape was affixed on the grid, peeled 90 degrees, and the peeled state of the cured product from the polycarbonate resin substrate was visually observed. The number of squares in close contact without peeling in 100 squares 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 free from 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.
The cured film was dipped in hot water at 90 ° C. for 10 minutes and then pulled up, and then the moisture on the surface was wiped off and 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 adhered without peeling in 100 squares was counted and evaluated in the same manner as the evaluation of the initial adhesion. In terms of adhesion after immersion in hot water, it is preferable that the number of grids that are in close contact without peeling is 90 or more.

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

[Evaluation of adhesion to metal ink]
Using a 300-mesh screen printer on the resin surface of the cured film, a metal ink (mirror surface ink 700CX silver, manufactured by Seiko Advance Co., Ltd.) was applied so that the thickness after drying was 5 μm, at 25 ° C. Dried for 1 hour at 80 ° C. for 5 hours. The cured film was allowed to stand for 24 hours in an environment of 23 ° C. and 50% relative humidity, and then cut into a 1 mm width with a cutter knife to produce a grid (10 × 10 pieces). A cellophane adhesive tape was affixed on the grid, peeled by 90 degrees, and the peeled state of the mirror ink from the cured film surface was visually observed. The number of squares in 100 squares that did not peel and adhered was counted and evaluated.
The adhesion of the metal ink to the active energy ray-curable composition of the present invention is preferably free from peeling from the substrate.

From the results in Table 1, the cured films obtained by curing the active energy ray-curable compositions of Examples 1 to 11 of the present invention have initial adhesion to the polycarbonate resin substrate, adhesion after hot water immersion treatment, and resistance to resistance. It can be seen that the film is excellent in scratch resistance and adhesion to the metal ink.
On the other hand, the composition of Comparative Example 1 that does not contain a 2-3 functional polyfunctional (meth) acrylate (A) having an isocyanuric skeleton has insufficient scratch resistance of the cured product and insufficient adhesion to metal. It is. Moreover, the composition of Comparative Example 2 that does not contain the polyfunctional (meth) acrylate (B) having no isocyanuric skeleton has insufficient scratch resistance of the cured product.
Furthermore, the composition of Comparative Example 3 using a monofunctional (meth) acrylate (C′-1) having no aromatic ring skeleton and the 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 the hot water immersion treatment.
The composition of Comparative Example 5 using an amine compound (D′-1) that is not a hindered amine skeleton and the composition of Comparative Example 7 that does not use a hindered amine light stabilizer (D) having a (meth) acrylic group include a metal ink and The composition of Comparative Example 6 using the hindered amine light stabilizer (D′-2) having no (meth) acrylic group has poor scratch resistance in addition to the adhesion to the metal ink. It becomes.

  The cured product obtained by curing the active energy ray-curable composition of the present invention is excellent in initial adhesion with a polycarbonate resin substrate, adhesion after hot water immersion treatment, and scratch resistance, and adhesion with metal ink. Excellent optical properties, such as plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle improvement lenses, etc.), optical compensation films, retardation films, and other optical members, electrical and electronic materials, and decorative films It is also useful.

Claims (5)

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