JP2014015559A - Active energy ray-curable composition, method for forming cured film, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition capable of rapidly forming an inorganic coating excellent in appearance, hardness, scratch resistance and adhesion to a base material with good reproducibility, and to provide a laminate that forms a cured coating on a surface of the base material by using the composition.SOLUTION: An active energy ray-curable composition contains: a polysiloxane compound obtained by hydrolysis and condensation of at least one kind of compound selected from an organosilane compound and an alkyl silicate compound; and an active energy ray-sensitive base-generating agent.

Description

  The present invention relates to an active energy ray-curable composition capable of forming a transparent cured film excellent in surface hardness in a short time, and a laminate having a cured film formed on the surface of a substrate.

In recent years, transparent plastic materials such as acrylic resin and polycarbonate resin, which are excellent in impact resistance and light weight, have been widely used as an alternative to transparent glass. However, since the transparent plastic material has a lower surface hardness than glass, it has a problem that the surface is easily damaged.
Thus, various attempts have been made so far to improve the scratch resistance of plastic materials. For example, a method of forming an inorganic cured film having good scratch resistance and weather resistance on the surface of a plastic material using a sol-gel reaction is widely performed. For example, Patent Document 1 discloses a method of forming an inorganic coating by photocuring a siloxane oligomer in the presence of a photoacid generator. In this method, a film having excellent cured properties can be formed in a low temperature process and in a short time. However, strong acids generated from photoacid generators are very active and unstable, and they are easily deactivated by trace amounts of metal ions, acidic substances, basic substances, etc. in the system, affecting the curing behavior. There was a possibility of affecting. On the other hand, Patent Document 2 discloses a technique for forming a fine pattern by performing a sol-gel reaction using amines generated from a photobase generator as a catalyst. In this method, since the amines which are curing catalysts are stable, pattern formation can be performed with good reproducibility. However, no mention is made of the cured properties in bulk.
On the other hand, in Patent Document 3, Non-Patent Document 1, and Non-Patent Document 2, synthesis is easy and photobase generators with high quantum yield are proposed one after another, and the range of material selection is expanding. .

JP 2005-89697 A JP 2010-117439 A JP2009-280785A

J.Photopolym.Sci.Technol., Vol.22, No.5 (2009) Polymer Preprints, Japan Vol. 60, No. 1 (2011)

  An object of the present invention is to use an optical base generator to form an inorganic cured coating excellent in appearance, hardness, scratch resistance and adhesion to a substrate in a short time with good reproducibility. The object is to provide an active energy ray-curable composition. Moreover, it is providing the laminated body which formed the cured film in the surface of the base material using this composition.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have made organosilane compounds or alkylsilicate compounds hydrolyzed / condensed (hereinafter referred to as polysiloxane compounds) in the presence of a specific photobase generator. The present invention finds that an inorganic cured film having a good appearance, surface hardness, scratch resistance, and adhesion to a substrate can be formed with good reproducibility by rapidly irradiating with active energy rays. It reached.

（式中、Ｒ³は炭素数１〜４のアルキル基を示し、ｎは平均４〜２０の整数を示す） That is, the first invention for solving the above problems is an organosilane compound (a-1) represented by the following general formula (1) and an alkyl silicate compound (a-2) represented by the following general formula (2). An active energy ray-curable composition containing a polysiloxane compound (A) obtained by hydrolyzing and condensing a compound selected from (2) and an active energy ray-sensitive base generator (B).
R ¹ _m Si (OR ² ) _4-m (1)
(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group, a carbon-carbon unsaturated bond-containing group, or a cyclic ether-containing group. R ² represents an alkyl group having 1 to 4 carbon atoms. M represents an integer of 1 to 2).

(In the formula, R ³ represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 4 to 20 on average)

  In the second invention, the polysiloxane compound (A) hydrolyzes at least one compound selected from the above (a-1) and at least one compound selected from the above (a-2). -It is an active energy ray-curable composition obtained by condensation.

  The active energy ray-curable base generator (B) is a compound having a benzophenone structure, a 2-allylbenzoic acid structure, an anthracene structure, or an anthraquinone structure in the molecule. Composition.

（式中、Ｒ⁴，Ｒ⁵は各々独立に水素原子、炭素数１〜４のアルキル基、または水酸基を示す。） Moreover, 4th invention is an active energy ray curable composition whose said active energy ray sensitive base generator (B) is a compound which has a structure selected from following (i)-(iv) in a molecule | numerator. It is.
(i) a compound having a benzophenone structure represented by the following general formula (3);

(In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyl group.)

（式中、Ｒ⁶、Ｒ⁷は各々独立に水素原子、または炭素数１〜４のアルコキシ基を示す。） (ii) a compound having a 2-allylbenzoic acid structure represented by the following general formula (4);

(In the formula, R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.)

（式中、Ｒ⁸、Ｒ⁹、Ｒ¹⁰は各々独立に水素原子、炭素数１〜８の環状または非環状アルキル基、または炭素数５〜１２のアリール基を示し、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴は、各々独立に水素原子、炭素数１〜６のアルキル基、または炭素数６〜１２のアリール基を示し、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹は、各々独立に水素原子、炭素数１〜８の環状または非環状のアルキル基、または炭素数６〜１２のアリール基を示す。） X ⁺ in the above formulas (3) and (4) is represented by general formulas (5a) to (5d),

(Wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a cyclic or non-cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group having 5 to 12 carbon atoms, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are Each independently represents a hydrogen atom, a cyclic or acyclic alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)

(iii) a compound having an anthracene structure represented by the following general formula (6);

(iv) a compound having an anthraquinone structure represented by the following general formula (7);

（Ｒ²⁰、Ｒ²¹は、各々独立に炭素数１〜４のアルキル基を表し、Ｒ²²、Ｒ²³、Ｒ²⁴は各々独立に水素原子、炭素数１〜６のアルキル基、または炭素数６〜１２のアリール基、Ｒ²⁵、Ｒ²⁶、Ｒ²⁷、Ｒ²⁸は各々独立に水素原子、炭素数１〜８のアルキル環状または非環状基、または炭素数６〜１２のアリール基を示す。） Y in the above formulas (6) and (7) is represented by general formulas (8a) to (8c).

(R ²⁰ and R ²¹ each independently represents an alkyl group having 1 to 4 carbon atoms, and R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 6 carbon atoms. -12 aryl groups, R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ each independently represent a hydrogen atom, an alkyl cyclic or acyclic group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)

Moreover, 5th invention is a formation method of the cured film including the process of irradiating active energy ray to said active energy ray curable composition, generating a base, and hardening | curing a composition.
Furthermore, 6th invention is a laminated body which has the cured film of said active energy ray curable composition on the surface of a base material.

  INDUSTRIAL APPLICABILITY According to the present invention, an active energy ray-curable composition capable of forming an inorganic cured film excellent in appearance, hardness, scratch resistance, and adhesion to a substrate in a short time by a low temperature process with good reproducibility is obtained. . In addition, by applying this composition to a desired substrate and irradiating it with active energy rays, a cured film excellent in appearance, hardness, scratch resistance and adhesion to the substrate is short on the substrate. Formed in time.

  In the following description, the active energy ray-curable composition of the present invention is referred to as “the composition of the present invention”, the organosilane compound represented by the general formula (1) is “silane (a-1)”, and the general formula (2). ) Obtained by hydrolyzing and condensing at least one compound selected from “silicate (a-2)”, silane (a-1) and silicate (a-2). The siloxane compound is referred to as “siloxane (A)”, and the active energy ray-sensitive base generator (B) is referred to as “base generator (B)”.

Siloxane (A)
Siloxane (A) is obtained by hydrolyzing and condensing at least one compound selected from silane (a-1) and silicate (a-2).
Silane (a-1) is represented by the following general formula.
R ¹ _m Si (OR ² ) _4-m (1)
(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydrocarbon group having at least one carbon-carbon unsaturated bond, and a carbon group having at least one cyclic ether group. A hydrogen group, R ² represents an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 1 to 2)
Each group of R ¹ may have a substituent. Examples of the substituent include at least one group selected from the group consisting of an amino group, a halogen, an isocyanate, a hydroxyl group, and a mercapto group. More preferably, the number of substituents is one.
Examples of the “hydrocarbon group having at least one carbon-carbon unsaturated bond” exemplified as R ¹ include groups selected from the group consisting of alkenyl groups, acryloyl groups, methacryloyl groups, vinyl groups, and styryl groups. .
Examples of the “hydrocarbon group having at least one cyclic ether group” mentioned as R ¹ include an epoxy group-containing hydrocarbon group, and more preferably an epoxycyclohexyl group or a glycidoxypropyl group.
Preferable R ¹ includes an alkyl group having 1 to 4 carbon atoms or a phenyl group which may have a substituent.

  Specific examples of silane (a-1) include methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy. Silane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, p-styryltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3- Socyanate propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, 2- (3,4-epoxycyclohexyl) Examples include ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyltrimethoxysilane. These organosilanes can be used alone or in combination of two or more.

  Among these, methyltrimethoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2 in that good scratch resistance can be imparted to the cured film. -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyltrimethoxysilane are preferred.

Silicate (a-2) is represented by the following general formula.

(In the formula, R ³ represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 4 to 20 on average)
Specific examples of silicate (a-2) include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, isobutyl silicate and n-butyl silicate. Among them, methyl silicate in which R ³ is a methyl group or ethyl silicate in which an ethyl group is an ethyl group is preferable in that the hydrolysis / condensation reaction is fast. N is an integer representing the degree of polymerization. For example, if n = 4, it represents a tetramer. In the present invention, n is preferably 4 or more and 20 or less. In addition, these silicates (a-2) may have a linear structure or a branched structure.

Siloxane (A) can be obtained by hydrolyzing and condensing at least one compound selected from silane (a-1) and silicate (a-2).
In addition, (a-1) and (a-2) can each be used individually or in mixture of 2 or more types. Although not particularly limited, it is preferable to use (a-1) and (a-2) in combination from the viewpoint of improving the hardness of the resulting cured film.
As a method of hydrolysis / condensation, for example, silane (a-1) and / or silicate (a-2) is mixed with a polar solvent, and further, the total of silane (a-1) and silicate (a-2). The method of adding and stirring about 1-100 mol of water with respect to 1 mol is mentioned. At that time, a mineral acid such as hydrochloric acid or acetic acid or an organic acid can be added as a catalyst. Moreover, the temperature of a solution can be adjusted to 0-100 degreeC. Furthermore, the alcohol generated upon hydrolysis can be distilled out of the reaction system.
As the polar solvent used for the hydrolysis / condensation, a solvent arbitrarily mixed with water, for example, alcohols is preferably used.
The siloxane (A) obtained by hydrolyzing and condensing at least one compound selected from the silicate (a2) has a mass average molecular weight (by GPC) of 500 to 100,000, more preferably 1,000 to 50,000.

Base generator (B)
The base generator (B) used in the present invention is a compound that generates a base upon irradiation with active energy rays such as visible light, ultraviolet rays, heat rays, electron beams, and serves as a catalyst for the polycondensation reaction of siloxane (A). . The base generator (B) of the present invention has a benzophenone structure, a 2-allylbenzoic acid structure, an anthracene structure, or an anthraquinone structure in the molecule.
Among these, a photo-sensitive base generator that generates a base by irradiation with visible light or ultraviolet light, and a heat-sensitive base generator that generates a base by heat rays are preferable. Furthermore, a photosensitive base generator capable of generating a base even at a low temperature is more preferable.

（式中、Ｒ⁴，Ｒ⁵は各々独立に水素原子、炭素数１〜４のアルキル基、または水酸基を示す。Ｘ⁺は遊離して塩基となる対カチオンである。） The active energy ray-sensitive base generator having a benzophenone structure in the molecule is preferably a compound represented by the general formula (3).

(In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyl group. X ⁺ is a counter cation that is liberated to become a base.)

（式中、Ｒ⁶、Ｒ⁷は各々独立に水素原子、または炭素数１〜４のアルコキシ基を示す。Ｘ⁺は遊離して塩基となる対カチオンである。） The active energy ray-sensitive base generator having a 2-allylbenzoic acid structure in the molecule is preferably a compound represented by the general formula (4).

(In the formula, R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms. X ⁺ is a counter cation which is liberated to become a base.)

（式中、Ｒ⁸、Ｒ⁹、Ｒ¹⁰は各々独立に水素原子、炭素数１〜８の環状または非環状アルキル基、または炭素数５〜１２のアリール基を示し、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴は、各々独立に水素原子、炭素数１〜６のアルキル基、または炭素数６〜１２のアリール基を示し、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹は、各々独立に水素原子、または炭素数１〜８の環状または非環状アルキル基、または炭素数６〜１２のアリール基を示す。） X ⁺ in the above formulas (3) and (4) is not particularly limited, but general formulas (5a) to (5d) are preferable.

(Wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a cyclic or non-cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group having 5 to 12 carbon atoms, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are Each independently represents a hydrogen atom, a cyclic or acyclic alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)

Among the base generators represented by the general formulas (3) and (4), in particular, R ⁴ and R ⁵ are hydrogen atoms, ketoprofen having a methyl group, and R ⁶ and R ⁷ are hydrogen atoms. Acid is preferred.

In general formula (3), amine compound X is liberated by decarboxylation, and in general formula (4), amine compound (X) is liberated by ring closure reaction.
The amine compound (X) can be selected from widely known compounds and is not particularly limited, but examples suitable for the present invention include general formulas (5a) to (5d). More specifically, examples of (5a) include dimethylamine, diethylamine, dipropylamine, dibutylamine, n-hexylamine, cyclohexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine and the like.
(5b) includes imidazole, 1-methylimidazole, 1-phenylimidazole, 2-methylimidazole, 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 2-ethyl-4-methylimidazole, 4-methyl -2-phenylimidazole and the like.
(5c) includes guanidine, 1-methylguanidine, 2-methylguanidine, 1-ethylguanidine, 1-phenylguanidine, 1,1-dimethylguanidine, 1,3-dimethylguanidine, 1,3-dimethylguanidine, 1 1,3,3-tetramethylguanidine and the like.
(5d) includes {1,8-diazabicyclo [5,4,0] -undecene-7} (DBU) and {1,5-diazabicyclo [4,3,0] -nonene-5} (DBN). Can be mentioned.

式中、Ｙは遊離して塩基となる有機基である。 In addition, base generators represented by the general formulas (6) and (7) are also preferably used.
That is, the active energy ray-sensitive base generator having an anthracene structure in the molecule is preferably a compound represented by the general formula (6).

In the formula, Y is an organic group which is liberated to become a base.

式中、Ｙは遊離して塩基となる有機基である。 The active energy ray-sensitive base generator having an anthraquinone structure in the molecule is preferably a compound represented by the general formula (7).

In the formula, Y is an organic group which is liberated to become a base.

（Ｒ²⁰、Ｒ²¹は、各々独立に炭素数１〜４のアルキル基を表し、Ｒ²²、Ｒ²³、Ｒ²⁴は各々独立に水素原子、炭素数１〜６のアルキル基、または炭素数６〜１２のアリール基を表し、Ｒ²⁵、Ｒ²⁶、Ｒ²⁷、Ｒ²⁸は各々独立に水素原子、炭素数１〜８の環状または非環状アルキル基、または炭素数６〜１２のアリール基を示す。） Y in the above formulas (6) and (7) is not particularly limited, but preferred examples include (8a) to (8c).

(R ²⁰ and R ²¹ each independently represents an alkyl group having 1 to 4 carbon atoms, and R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 6 carbon atoms. Represents an aryl group having ˜12, and R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ each independently represent a hydrogen atom, a cyclic or acyclic alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. .)

More specifically, examples of (8a) include dimethylamine, diethylamine, dipropylamine, dibutylamine and the like. (8b) is the same as X described for (5b) above, and (8c) is the same as X described for (5c) above.
These base generators can be used alone or in admixture of two or more.
The addition amount of the base generator (B) is preferably 0.01 to 30 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass (in terms of solid content) of the siloxane (A).
An acid generator can be cited as a technique for comparing with a base generator. However, when a base generator is used, there is a possibility that a corrosive problem that is a concern particularly in a metal protective coating may be avoided. Conceivable.

Composition of the Present Invention The composition of the present invention can contain an organic solvent for the purpose of adjusting the solid content concentration, improving dispersion stability, improving coatability, improving adhesion to a substrate, and the like. Examples of the organic solvent include alcohols, ketones, ethers, esters, cellosolves, and aromatic compounds.
Specific examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, benzyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxy Methoxy) ethanol, 2-butoxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, di Propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene group Cole monomethyl ether, diacetone alcohol, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, acetophenone, diethyl ether, di Propyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, anisole, phenetole, tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol dibutyl ether, glycerin ether, methyl acetate, ethyl acetate, acetate Pill, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, methyl propionate, ethyl propionate, butyl propionate Γ-butyrolactone, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzene, toluene and xylene. These organic solvents can be used alone or in combination of two or more.

The content of the organic solvent is preferably 50 to 1000 parts by mass with respect to 100 parts by mass in total of the solid content of the siloxane (A) and the base generator (B).
The composition of the present invention can contain an epoxy compound that can be polymerized with an amine, a vinyl compound having a radical polymerizable double bond in the molecule, an active energy ray-sensitive radical polymerization initiator, and the like without departing from the object. An epoxy compound polymerizable by an amine contains an epoxy group in the molecule. Specific examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol. Diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, diglycerin tetraglycidyl ether, trimethylolpropane triglycidyl ether, 2,6-diglycidyl phenyl ether, sorbitol triglycidyl ether, triglycidyl isocyanurate , Diglycidyl phthalate, bisphenol A diglycidyl ether, butadiene Dioxide, dicyclopentadiene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate Bis (3,4-epoxycyclohexylmethyl) adipate, pentaerythritol polyglycidyl ether, adducts of bisphenol A type epoxy resin and ethylene oxide, phenol novolac type epoxy resin, cresol novolac type epoxy resin.

A vinyl compound having a radically polymerizable double bond in the molecule has one or more polymerizable double bonds in the molecule. The vinyl compound is preferably a monofunctional or polyfunctional (meth) acrylate compound containing a (meth) acryloyl group in the molecule from the viewpoint of a high polymerization rate.
Examples of monofunctional (meth) acrylate compounds include phenyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, paracumylphenol ethylene oxide modified (meth) acrylate, and isobornyl. (Meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl ( (Meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethyl Sil (meth) acrylate, n-hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples include tetrahydrofurfuryl (meth) acrylate and phosphoethyl (meth) acrylate.

  Examples of the polyfunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and tripropylene glycol di (meth). ) Acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meta) ) Acrylate, 2,2-bis [4- (meth) acryloyloxyphenyl] -propane, 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] -propane, 2,2-bis [4- (Meth) acryloyloxydiethoxyphenyl] -propane, 2,2-bis [4- (meth) acryloyloxypentaethoxyphenyl] -propane, 2,2-bis [4- (meth) acryloyloxyethoxy-3-phenylphenyl ] -Propane, bis [4- (meth) acryloylthiophenyl] sulfide, bis [4- (meth) acryloyloxyphenyl] sulfone, bis [4- (meth) acryloyloxyethoxyphenyl] sulfone, bis [4- (meth) ) Acryloyloxydiethoxyphenyl] sulfone, bis [4- (meth) acryloyloxypentaethoxyphenyl] sulfone, bis [4- (meth) acryloyloxyethoxy-3-phenylphenyl] sulfone, bis [4- (meth) acryloyl Oxyethoxy 3,5-dimethylphenyl] sulfone, bis [4- (meth) acryloyloxyphenyl] sulfide, bis [4- (meth) acryloyloxyethoxyphenyl] sulfide, bis [4- (meth) acryloyloxypentaethoxyphenyl] sulfide Bis [4- (meth) acryloyloxyethoxy-3-phenylphenyl] sulfide, bis [4- (meth) acryloyloxyethoxy-3,5-dimethylphenyl] sulfide, 2,2-bis [4- (meth) Acryloyloxyethoxy-3,5-dibromophenylpropane], trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate and dipentaerythritol hexa (meth) Acrylate, and the like. The vinyl compound having a radical polymerizable double bond in the molecule can be used alone or in combination of two or more.

  Examples of the active energy ray-sensitive radical polymerization initiator include 3,3-dimethyl-4-methoxy-benzophenone, benzyldimethyl ketal, isoamyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, benzophenone, p- Methoxybenzophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy 2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2,4,6-trimethylbenzoyldiphenylphosphine oxide Can be mentioned.

  In addition, the composition of the present invention may be a polymer, a polymer fine particle, an inorganic fine particle, a dye, a pigment, a pigment dispersant, a flow regulator, a leveling agent, an antifoaming agent, an ultraviolet absorber, and a light stabilizer, as necessary. Further, an antioxidant and the like can be contained.

The substrates used in the laminate of the substrate present invention, for example, plastic, metal, cans, paper, wood materials, inorganic materials, and include those to form a primer layer on these substrates. Among these, plastic substrates such as polymethyl methacrylate, polycarbonate, polystyrene, and a copolymer resin of methyl methacrylate and styrene are preferable.

Formation of Cured Film A cured film can be formed by applying the composition of the present invention to a substrate and irradiating active energy rays. Application to a substrate or the like can be performed by a known method. Examples include dip coating, spray coating, bar coating, roll coating, gravure printing, flexographic printing, screen printing, spin coating, flow coating, and electrostatic coating.

Examples of active energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, incandescent lamps, xenon lamps, halogen lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, gallium lamps and excimer lasers. Examples include light rays used as a light source, electron beams, β rays, and γ rays. The active energy rays can be used alone or in combination of two or more. When a plurality of types of active energy rays are used, they can be irradiated simultaneously or sequentially.
In the present invention, not only irradiation with active energy rays but also heat treatment using radiant heat from an electric furnace or the like can be used in combination as required. The heat treatment can be performed simultaneously with the active energy ray irradiation or before and after the active energy ray irradiation.
About 0.1-50 micrometers is suitable for the film thickness of the cured film formed in the surface of a base material.

Laminated body The composition of this invention is apply | coated to the surface of a base material, and then hardens | cures by irradiation of an active energy ray, and the laminated body in which the cured film was formed on the surface of the base material is obtained.
Since the cured film is excellent in transparency, scratch resistance and adhesion to the substrate, the laminate having the cured film is a flat panel display film / front plate, a transparent sound insulation board such as a highway, a headlamp. It is suitable for various uses such as automobile parts such as lenses, plastic window materials for vehicles, and the like.

  The present invention will be described below with reference to examples. In the following, “%” means “mass%”. In addition, the solid content of the condensate in the examples is based on the theoretical value when the hydrolysis / condensation reaction with the alkyl silicate and / or the organosilane is completed.

[Synthesis Example 1] Synthesis of Siloxane Oligomer (A1) In a 200 ml glass reaction vessel equipped with a stirrer, a condenser and a temperature controller, in a reaction vessel equipped with a stirrer, methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) , 25.3 g of molecular weight 136), 2.8 g of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 198) and 22.0 g of isopropyl alcohol were added and stirred to obtain a uniform solution. Next, 21.6 g of water was added to the reaction vessel, and hydrolysis and condensation were carried out by heating at 80 ° C. for 9 hours while stirring to obtain a solution of siloxane oligomer A1 having a solid content concentration of 20%. When the mass average molecular weight by GPC of the siloxane oligomer (A1) was measured, the mass average molecular weight in terms of polystyrene was about 1,500.

  In addition, in this invention, solid content concentration means the mass fraction computed with respect to the whole solution of the amount of the siloxane oligomer obtained when fully hydrolyzing and condensing.

[Synthesis Example 2] Synthesis of Siloxane Oligomer (A2) In a reaction vessel equipped with a stirrer, methyl silicate having a silica conversion concentration of 53% (manufactured by Colcoat Co., average heptamer, molecular weight (average value) 788, trade name: 10.0 g of methyl silicate 53A), 17.2 g of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 136.2) and 10.0 g of isopropyl alcohol were added and stirred to obtain a uniform solution. Next, 10.5 g of water was added to the reaction vessel, and hydrolysis and condensation were performed by heating at 80 ° C. for 3 hours while stirring. Further, isopropyl alcohol was added to the reaction vessel to make 84.3 g as a whole, and a solution of a siloxane oligomer (A2) having a solid concentration of 20% was obtained. When the mass average molecular weight by GPC of the siloxane oligomer (A2) was measured, the mass average molecular weight in terms of polystyrene was about 15,000.

[Example 1]
<Preparation of active energy ray-curable composition>
10.0 g (2.0 g in terms of solid content) of a 20% solution of siloxane oligomer A1 obtained in Synthesis Example 1, and guanidinium-2- (3-benzoylphenyl) propionate (Wako Pure Chemical Industries, Ltd.) as base generator B ), Trade name: WPBG-082) 0.1 g and γ-butyrolactone 2.0 g were blended and stirred to prepare composition C1.

<Formation of cured film>
An appropriate amount of the composition C1 is dropped with a dropper onto an acrylic resin plate (Mitsubishi Rayon Co., Ltd., trade name: Acrylite L) having a length of 15 cm, a width of 10 cm, and a thickness of 3 mm, which is a base material. It was applied so that a cured film having a thickness of 3 to 4 μm was obtained, and prebaked at 100 ° C. for 5 minutes in a dryer. Furthermore, using a 120 W / cm high-pressure mercury lamp equipped with a conveyor (manufactured by Oak Manufacturing Co., Ltd., ultraviolet irradiation device, trade names: Handy UV-1200, QRU-2161 type), an ultraviolet ray with an integrated light quantity of 5000 mJ / cm ² . To obtain a laminate (L1) having a cured coating. The time required for UV curing was about 5 minutes.
The amount of ultraviolet irradiation was measured with an ultraviolet light meter (trade name: UV-351, manufactured by Oak Manufacturing Co., Ltd., peak sensitivity wavelength 360 nm).
The following evaluation was implemented about the cured film of the surface of the laminated body L1. The results are shown in Table 1.

<Evaluation of cured film>
(1) Film thickness The cross section of the acrylic board in which the cured film was formed was observed with the scanning electron microscope, and the film thickness of the cured film was measured.
(2) Appearance The transparency of the cured film and the presence or absence of cracks and whitening were visually observed, and the appearance was evaluated according to the following criteria.
“◯”: Transparent and free from cracks and whitening defects.
“X”: An opaque part or a crack or whitening defect.
(3) Pencil hardness Pencil hardness was evaluated according to a pencil scratch test (JIS-K-5600).
(4) Scratch resistance A rubbing tester (manufactured by Imoto Seisakusho Co., Ltd., trade name: A1566) was used, and the surface of the cured layer was # 0000 steel wool and a load of 9.8 × 10 ⁴ Pa per cm ² And rubbed back and forth 10 times. Next, a haze value (ΔHz (%)) was obtained by measuring the haze value of the scratched portion with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name: NDH2000), and subtracting the haze value before the test. ) Was evaluated as follows.
A: ΔHz is less than 5% B: ΔHz is 5% or more and less than 10% C: ΔHz is 10% or more

(5) Adhesiveness A total of 25 squares were made on the surface of the cured coating of each laminate by cutting 6 vertical and horizontal cuts at 1 mm intervals with a razor blade. Next, after the cellophane tape was well adhered on the 25 grids, it was peeled off rapidly 45 degrees forward, and the number of grids remaining on the laminate without peeling the cured film was measured. The adhesion between the cured film and the substrate was evaluated according to the criteria.
“Good”: Good adhesion (no peeled squares)
"△": Medium adhesion (1-5 peeled cells)
“×”: poor adhesion (6 or more peeled cells)

[Examples 2 and 3, Comparative Examples 1 and 2]
A composition C2 was prepared in the same manner as in Example 1 except that A2 was used in place of the siloxane oligomer A1, and the cured film L2 was formed. Then, the cured film was evaluated. The results are shown in Table 1.

[Comparative Examples 1-2]
In Examples 1 and 2, except that the base generator was not used, compositions C3 to C4 were prepared in the same manner as in Example 1 and cured films L3 to L4 were formed, and then the cured film was evaluated. did. The results are shown in Table 1.

  As is apparent from Table 1, when the active energy ray-curable composition of the present invention is used, the obtained cured film is very excellent in all of appearance, high degree, scratch resistance and adhesion, Particularly high scratch resistance was exhibited (Examples 1 and 2). On the other hand, when a composition containing no base generator was used, the appearance and adhesiveness were almost the same as those of the present invention, but the results were clearly inferior in terms of altitude and scratch resistance. (Comparative Examples 1 and 2).

Claims (6)

Polysiloxane obtained by hydrolyzing and condensing a compound selected from the organosilane compound (a-1) represented by the following general formula (1) and the alkyl silicate compound (a-2) represented by the following general formula (2) A siloxane compound (A), and an active energy ray-sensitive base generator (B),
An active energy ray-curable composition containing
R ¹ _m Si (OR ² ) _4-m (1)
(In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydrocarbon group having at least one carbon-carbon unsaturated bond, and a hydrocarbon having at least one cyclic ether group. R ² represents an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 1 to 2).

(In the formula, R ³ represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 4 to 20 on average)   The polysiloxane compound (A) is obtained by hydrolyzing and condensing at least one compound selected from the above (a-1) and at least one compound selected from the above (a-2). The active energy ray-curable composition according to claim 1.   The active energy ray according to claim 1 or 2, wherein the sexual energy ray-sensitive base generator (B) is a compound having a benzophenone structure, a 2-allylbenzoic acid structure, an anthracene structure, or an anthraquinone structure in the molecule. Curable composition. The activity according to any one of claims 1 to 3, wherein the sexual energy ray-sensitive base generator (B) is a compound having a structure selected from the following (i) to (iv) in the molecule. Energy ray curable composition.
(i) a compound having a benzophenone structure represented by the following general formula (3);

(In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyl group.)
(ii) a compound having a 2-allylbenzoic acid structure represented by the following general formula (4);

(In the formula, R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.)
X ⁺ in the above formulas (3) and (4) is represented by general formulas (5a) to (5d),

(Wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a cyclic or acyclic alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are Each independently represents a hydrogen atom, a cyclic or acyclic alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)
(iii) a compound having an anthracene structure represented by the following general formula (6);

(iv) a compound having an anthraquinone structure represented by the following general formula (7);

Y in the above formulas (6) and (7) is represented by general formulas (8a) to (8c).

(R ²⁰ and R ²¹ each independently represents an alkyl group having 1 to 4 carbon atoms, and R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 6 carbon atoms. Represents an aryl group having ˜12, and R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ each independently represent a hydrogen atom, a cyclic or acyclic alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. .)   The formation method of a cured film including the process of generating a base by irradiating an active energy ray curable composition as described in any one of Claims 1-4 with an active energy ray, and hardening this composition.   The laminated body which has a cured film of the active energy ray curable composition as described in any one of Claims 1-4.