TW201840621A - Urethane (meth)acrylate polymer - Google Patents

Abstract

The present invention addresses the problem of providing: a urethane (meth)acrylate polymer which enables the achievement of a coating film that prevents bleeding of an ultraviolet absorbent, while having excellent weather resistance, scratch resistance and transparency; and a curable composition which contains this urethane (meth)acrylate polymer. The problems are solved by a urethane (meth)acrylate polymer which has a chemical structure represented by formula (1). (In the formula, A represents a single bond or a methylene group, an alkylene group, an -O- group, an -NH- group, an -S- group, an -SO- group or an -SO2- group, each of which may have a substituent; each of R1, R2, R3 and R4 independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom; and each of R5 and R6 independently represents an alkylene group, an alkoxylene group or an arylene group.).

Description

Urethane (meth) acrylate polymer

The present invention relates to a urethane (meth) acrylate polymer having excellent transparency, weather resistance, and abrasion resistance after a hardening composition is applied to a substrate and hardened, and hardening properties including the same组合 物。 Composition. The present invention also relates to a cured product, a laminate, and a decorative film using the urethane (meth) acrylate polymer and the curable composition.

The radical polymerizable curable composition is cured in a short period of time by irradiation with active energy rays to provide a film or a molded product having excellent chemical resistance, abrasion resistance, weather resistance, and heat resistance. Coating composition covering the surface of automobiles, home appliances, woodwork products, plastic molded products, transfer materials, etc.

For example, Patent Document 1 discloses a coating composition containing a bisbenzotriazolylphenol compound as an ultraviolet absorbent.

Patent Document 2 discloses a coating composition in which a UV absorber having a specific structure is incorporated in a polymer backbone.

Patent Document 3 discloses a curable resin composition in which a bisbenzotriazolyl-based ultraviolet absorber is incorporated into a skeleton of a polymer through an ester bond. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open No. 2000-017204 [Patent Literature 2] Japanese Patent Laid-Open No. 2000-053913 [Patent Literature 3] Japanese Patent Laid-Open No. 2000-109652

[Problems to be Solved by the Invention] However, in the coating composition described in Patent Document 1, the ultraviolet absorber is not incorporated into the polymer skeleton. Therefore, the coating film is caused by the ultraviolet absorber exuding from the coating film. Insufficient transparency and weather resistance. In the coating composition described in the said patent document 2, since the ultraviolet absorption performance of an ultraviolet absorber is inadequate, weather resistance is inadequate. In the curable composition described in Patent Document 3, since the ultraviolet absorber is incorporated into the polymer skeleton via an ester bond, hydrolysis from the ester bond occurs, the ultraviolet absorbent oozes out, and the weather resistance is not good. full.

The present invention has been made to solve the above-mentioned problems, and provides a urethane (meth) acrylate polymer which can obtain a coating film which is excellent in weather resistance, abrasion resistance, and transparency by preventing the bleeding of ultraviolet absorbers. And hardening composition containing the same. [Means for solving problems]

That is, the above-mentioned object of the present invention can be solved by the following means [1] to [18]. [1] A urethane (meth) acrylate polymer having a chemical structure represented by the following formula (1). [Chemical 1] [In the formula, A represents a single bond or a methylene group, an alkylene group, an -O- group, an -NH- group, an -S- group, an -SO- group, or an -SO ₂ -group which may have a substituent. R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom. R ⁵ and R ⁶ independently represent an alkylene group, an alkyleneoxy group, or an arylene group] [2] The urethane (meth) acrylate polymer according to [1], wherein the formula ( 1) is the following formula (2). [Chemical 2] (2) [3] The urethane (meth) acrylate polymer according to [1] or [2], which has a chemical structure represented by the following formula (3). [Chemical 3] (3) (In the formula (3), X ¹ is an aliphatic structure having a molecular weight of 500 or less, and n is an integer of 2 to 8) [4] The urethane (methyl group according to [3] ) An acrylate polymer containing at least one of the chemical structure represented by the following formula (4-1) and the chemical structure represented by the following formula (4-2) as the chemical represented by the formula (3) structure. [Chemical 4] (In the formula (4-1), (4-2), X (3) X ¹ is the same meaning as in formula ¹⁾ [5] [1] an amine according to [4] above The urethane (meth) acrylate polymer has a weight average molecular weight (Mw) of 500 to 30,000. [6] The urethane (meth) acrylate polymer according to any one of [1] to [5], wherein in the urethane (meth) acrylate polymer, the formula The ratio of the chemical structure represented by (1) is 5 to 60% by weight. [7] A curable composition comprising the urethane (meth) acrylate polymer according to any one of [1] to [6], and an organic solvent. [8] The curable composition according to [7], wherein the solubility parameter of the organic solvent is 8.0 to 11.5. [9] The curable composition according to [7] or [8], wherein the solid content concentration of the curable composition is 5 to 90% by weight. [10] The curable composition according to any one of [7] to [9], wherein the content of the chemical structure represented by the formula (1) in the polymerization component of the curable composition is 5% by weight ~ 60% by weight. [11] A cured product of a curable composition, wherein the curable composition is the curable composition according to any one of [7] to [10]. [12] A laminated body comprising a cured product of the curable composition according to any one of [7] to [10] on a substrate. [13] A headlamp lens having a cured product of the curable composition according to [11] on a substrate. [14] A glazing material having a cured product of the curable composition according to [11] on a substrate. [15] A decorative film having a cured product of the curable composition according to [11] on a substrate. [16] A method for producing a film, comprising: urethane (meth) acrylate polymer according to any one of [1] to [6] or [7] to [10] A step of applying the curable composition according to any one of the above to a substrate; irradiating an active energy ray to the urethane (meth) acrylate polymer or the curable composition to obtain A step of hardening the laminated body; and a step of extending the laminated body. [17] A method for producing a urethane (meth) acrylate polymer by reacting the following compound (A) and the following compound (B) to obtain a precursor of a urethane polymer Then, the following compound (C) is reacted with a precursor of the obtained urethane polymer. Compound (A): Polyisocyanate compound (B): Polyol represented by the following formula (5) (5) [In the formula, A represents a single bond or a methylene group, an alkylene group, an -O- group, an -NH- group, an -S- group, an -SO- group, or-which may have a substituent. SO ₂ -based. R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom. R ⁵ and R ⁶ independently represent an alkylene group, an alkyleneoxy group, or an arylene group] Compound (C): a compound having a hydroxyl group and a (meth) acrylfluorenyl group [18] An amine group as described in [17] A method for producing a formate (meth) acrylate polymer is obtained by reacting a compound (A) and a compound (B) and the following compound (D) to obtain a precursor of a urethane polymer, The compound (C) is reacted. Compound (D): aliphatic polyol having a molecular weight of 500 or less [Effect of the invention]

According to the present invention, it is possible to obtain a urethane (meth) acrylate polymer which is capable of obtaining a coating film which is excellent in weather resistance, abrasion resistance, and transparency by preventing bleeding of an ultraviolet absorber, and a hardening composition containing the same. Thing. Moreover, the laminated body which has a layer containing the said hardened | cured material on the surface, and a decorative film can be provided.

In the present invention, "(meth) acrylate" is a general term for acrylate and methacrylate, and refers to one or both of acrylate and methacrylate. "(Meth) acryl", " The same applies to "(meth) acrylic acid".

[Urethane (meth) acrylate polymer] The urethane (meth) acrylate polymer of the present invention has a chemical structure represented by the following formula (1). [Chemical 6]

In formula (1), as long as A is a single bond or a methylene group, an alkylene group, an -O- group, an -NH- group, an -S- group, an -SO- group, or -SO _2- Any one of the bases is sufficient. In terms of the transparency of the hardened product containing the urethane (meth) acrylate polymer of the present invention and the prevention of the exudation of the self-hardened product of the ultraviolet absorber, methylene and an alkylene are preferred. And more preferably methylene.

In formula (1), R ¹ , R ² , R ^3, and R ^{4 may} be any of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a halogen atom. In terms of the transparency of the cured product of the urethane (meth) acrylate polymer or the curable composition of the present invention, and the prevention of the bleeding of the self-cured product of the bisbenzotriazole phenol skeleton, Preferred are a hydrogen atom, an alkyl group and an alkoxy group.

In the formula (1), R ⁵ and R ^{6 are the} same or different, as long as they are any of an alkylene group, an alkoxy group, and an arylene group. In terms of the transparency of the cured product of the urethane (meth) acrylate polymer or the curable composition of the present invention, and the prevention of the bleeding of the self-cured product of the bisbenzotriazole phenol skeleton, Preferred are alkylene and methylene.

The urethane (meth) acrylate polymer of the present invention incorporates a bisbenzo which functions as an ultraviolet absorber through a chemically stable urethane bond in the molecular chain of the polymer. Triazolylphenol skeleton. The bisbenzotriazolyl phenol skeleton has a structure obtained by dimerizing a benzotriazolyl phenol, and therefore has high ultraviolet absorption energy per unit weight and can impart high weather resistance in a small amount. Furthermore, in the present invention, the bisbenzotriazolyl phenol skeleton is incorporated via a urethane bond, so the bisbenzotriazolyl phenol skeleton is hard to bleed out due to hydrolysis or the like, and therefore has long-term weather resistance. Also excellent.

The self-hardened product of the transparency of a cured film obtained by curing the urethane (meth) acrylate polymer of the present invention and a curable composition using the same, and a self-cured product that prevents a bisbenzotriazole phenol skeleton In terms of exudation, the chemical structure represented by the formula (1) is preferably a chemical structure represented by the following formula (2). [Chemical 7]

The ratio of the chemical structure represented by the formula (1) in the urethane (meth) acrylate polymer of the present invention in terms of excellent transparency, weather resistance, and abrasion resistance of the cured product. Preferably it is 5 weight% or more, More preferably, it is 20 weight% or more. The content is preferably 60% by weight or less, and more preferably 35% by weight or less.

The urethane (meth) acrylate polymer of the present invention preferably has a chemical structure represented by the following formula (3).

The urethane (meth) acrylate polymer of the present invention may include at least one of a chemical structure represented by the following formula (4-1) and a chemical structure represented by the following formula (4-2). The chemical structure represented by the formula (3) is used to improve the transparency of the cured product, and the urethane (meth) acrylate polymer having a bisbenzotriazolylphenol skeleton is made into a curable composition. It can improve the solubility of urethane (meth) acrylate polymers in organic solvents. [Chemical 8]

In the formula (3), X ¹ is not particularly limited as long as it has an aliphatic structure with a molecular weight of 500 or less, preferably an aliphatic structure with a molecular weight of 400 or less, and more preferably an aliphatic structure with a molecular weight of 300 or less. X ^{1 is} preferably an aliphatic structure having a molecular weight of 14 or more, and more preferably an aliphatic structure having a molecular weight of 28 or more. X ¹ corresponds to a residue obtained by removing a hydroxyl group bonded to an aliphatic structure of a compound (B) described later, and may be a linear aliphatic structure, a branched aliphatic structure, or an alicyclic ring. Family structure.

In the formula (3), n is an integer of 2 to 8, and n is preferably 2 to 6, more preferably 2 to 4.

Specifically, when the value of n is 2, the chemical structure represented by the formula (3) becomes the following formula (4-1), and when the value of n is 3, the formula (3) The chemical structure shown is the following formula (4-2).

That is, more specifically, it is preferable to include at least one of the chemical structure represented by the following formula (4-1) and the chemical structure represented by the following formula (4-2) as the formula (3). Chemical structure.

The urethane (meth) acrylate polymer of the present invention preferably contains at least one of the chemical structure represented by the following formula (4-1) and the chemical structure represented by the following formula (4-2) This is the chemical structure represented by formula (3). [Chemical 9] ????? (9) (Formula (4-1), (4-2), X with the meaning of the formula (3) is the same as X ^{1 1)}

Furthermore, the urethane (meth) acrylate polymer of the present invention includes a structural unit derived from a compound having a hydroxyl group and a (meth) acrylfluorenyl group. Examples of the compound having a hydroxyl group and a (meth) acrylfluorene group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , 6-hydroxyhexyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, addition reaction product of 2-hydroxyethyl (meth) acrylate and caprolactone, (meth) acrylic acid Addition reactant of 4-hydroxybutyl ester and caprolactone, bisphenol A diglycidyl ether diacrylate, mono (meth) acrylate of glycol, glycerol (meth) acrylate, glycerol di (methyl) ) Acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.

[Weight average molecular weight (Mw)] The weight average molecular weight (Mw) of the urethane (meth) acrylate polymer of the present invention is preferably 500 or more, and more preferably 10,000 or more. In addition, it is preferably 30,000 or less, and more preferably 20,000 or less. When the weight average molecular weight of the urethane (meth) acrylate polymer is within the above range, the transparency of the urethane (meth) acrylate polymer or the curable composition in a solution state and The scratch resistance of the cured film becomes good.

In addition, the said weight average molecular weight is measured by the gel permeation chromatography measurement (GPC measurement) by the method shown in an Example.

An example of the manufacturing method of the urethane (meth) acrylate polymer of this invention is shown below. The urethane (meth) acrylate polymer of the present invention can be obtained by reacting the following compound (A) and the following compound (B) to obtain a urethane polymer precursor, and then The compound (C) is obtained by reacting with a precursor of the obtained urethane polymer. Compound (A): Polyisocyanate compound (B): Polyol represented by the following formula (5) (5) [In the formula, A represents a single bond or a methylene group, an alkylene group, an -O- group, an -NH- group, an -S- group, an -SO- group, or-which may have a substituent. SO ₂ -based. R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom. R ⁵ and R ⁶ independently represent an alkylene group, an alkyleneoxy group, or an arylene group] Compound (C): a compound having a hydroxyl group and a (meth) acrylfluorenyl group

In addition, the urethane (meth) acrylate polymer of the present invention can also react a compound (A), a compound (B), and a polyol other than the compound (B) to obtain a urethane polymer. After the precursor, the compound (C) is reacted.

Examples of the polyol other than the compound (B) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol Alcohols, 1,14-tetradecanediol, 1,16-hexadecanediol, and other diols having a linear aliphatic structure; propylene glycol, 1,2-butanediol, 1,3-butanediol , 2,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,2-pentanediol, 3-methyl-1,5-pentanediol, 1,8- Nonanediols and other diols with branched aliphatic structures; trimethylolpropane, glycerol, sorbitol, mannitol, pentaerythritol, etc. have branched aliphatic structures and three or more hydroxyl groups bonded to them Compounds; cyclopropylene glycol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, tricyclodecanediol, adamantanediol and other diols having an alicyclic structure, preferably having a molecular weight of 500 or less Aliphatic polyol (hereinafter, referred to as compound (D)).

Furthermore, in the present invention, when the reaction of the compound (A) and the compound (B) to obtain a precursor of the urethane polymer is performed, a chain extending agent may be added as a chain extending agent. A compound of two or more active hydrogens that reacts with an isocyanate group.

[Compound (A)] Examples of the polyisocyanate of the compound (A) include a chain aliphatic polyisocyanate, an aromatic polyisocyanate, and an alicyclic polyisocyanate. Among these, a chain-like alicyclic polyisocyanate is preferable from the point of improving the weather resistance and hardness of the obtained hardened | cured material.

Examples of the chain aliphatic polyisocyanate include aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and dimer acid diisocyanate. And tris (isocyanatohexyl) isotricyanates such as aliphatic triisocyanates. In terms of improving the weather resistance and hardness of the obtained hardened material, those having a linear or branched alkylene group having 1 to 6 carbon atoms are preferred. These may be used alone or in combination of two or more.

Examples of the aromatic polyisocyanate include aromatic diisocyanates such as toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, and naphthalene diisocyanate. In terms of improving the mechanical strength of a cured film of a urethane (meth) acrylate polymer or a curable composition, the aromatic polyisocyanate is preferably toluene diisocyanate and diphenylmethane diisocyanate. . These may be used alone or in combination of two or more.

Examples of the polyisocyanate having an alicyclic structure include alicyclic groups such as bis (isocyanatemethyl) cyclohexane, cyclohexanediisocyanate, bis (isocyanatecyclohexyl) methane, and isophorone diisocyanate. A triisocyanate having an alicyclic structure such as a diisocyanate having a formula structure and a tris (isocyanate isophorone) isotricyanate. Among these, the alicyclic polyisocyanate is preferably isophorone diisocyanate. These may be used alone or in combination of two or more.

The alicyclic structure is preferably 5 or more carbon atoms, and more preferably 6 or more carbon atoms. The number of carbon atoms is preferably 15 or less, and more preferably the number of carbon atoms is 13 or less. Furthermore, the alicyclic structure is preferably a cycloalkyl group. The compound (A) may be used singly or in combination of two or more kinds.

In terms of excellent transparency, weather resistance, and abrasion resistance of the hardened material, the compound (A) is preferably 5% by weight or more in the urethane (meth) acrylate polymer of the invention, and more preferably It is 25% by weight or more. In addition, in terms of excellent transparency, weather resistance, and abrasion resistance of the cured product, it is preferably 60% by weight or less, and more preferably 50% by weight or less.

[Compound (B)] The compound (B) is a polyol represented by the following formula (5). [Chemical 11] (5) [In the formula, A represents a single bond or a methylene group, an alkylene group, an -O- group, an -NH- group, an -S- group, an -SO- group, or-which may have a substituent. SO ₂ -based. R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom. R ⁵ and R ⁶ independently represent an alkylene group, an alkyleneoxy group, or an alkylene group]

The urethane (meth) acrylate polymer of the present invention and the cured product obtained by curing the curable composition using the cured product, and the self-cured product that prevents the bisbenzotriazole phenol skeleton In terms of bleeding, the compound (B) represented by the formula (5) is preferably a polyol represented by the following formula (10). [Chemical 12] ··· (10)

The ratio of the chemical structure represented by the formula (5) in the urethane (meth) acrylate polymer of the present invention in terms of excellent transparency, weather resistance, and abrasion resistance of the cured product. Preferably it is 5 weight% or more, More preferably, it is 20 weight% or more. The content is preferably 60% by weight or less, and more preferably 35% by weight or less.

As the compound (B), Dainsorb T-33 manufactured by Daiwa Chemical Co., Ltd., which is a commercially available product, can be used.

In terms of improving the weather resistance of the cured film of the present invention, the compound (B) is preferably 5 weights relative to all the polyol components used as a raw material of the urethane (meth) acrylate polymer. % Or more, more preferably 25% by weight or more. Moreover, it is preferable that it is 95 weight% or less, and it is more preferable that it is 90 weight% or less from the point that transparency in a solution state, transparency of a cured film, and abrasion resistance are excellent.

[Compound (C)] The compound having a hydroxyl group and a (meth) acrylfluorenyl group as the compound (C) has a (meth) acrylfluorenyl group, and therefore forms a crosslinked structure with other components by active energy ray irradiation It is possible to suppress the exudation of the bisbenzotriazolylphenol skeleton which functions as an ultraviolet absorber.

Examples of the compound (C) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth) acrylic acid. 6-hydroxyhexyl ester, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate addition reaction with caprolactone, 4-hydroxybutyl (meth) acrylate and Addition reactants of caprolactone, bisphenol A diglycidyl ether diacrylate, glycol mono (meth) acrylate, glycerol (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate body, and the like.

Among these, 2-hydroxyethyl (meth) acrylate is preferred in terms of improving the mechanical strength of the obtained cured film and the hardenability of the urethane (meth) acrylate polymer. , 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate Wait.

As the compound (C), an epoxy (meth) acrylate having a chain aliphatic structure having 2 to 12 carbon atoms can be used. Examples of the raw material for synthesizing the epoxy (meth) acrylate include ethylene glycol diglycidyl ether, 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1 , 5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,7-heptanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9 -Nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 1,11-undecanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, etc. Epoxy compound with linear aliphatic structure; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, trimethylolpropane triglycidyl An epoxy compound having a branched aliphatic structure such as glyceryl ether, glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, and the like.

Among these, in terms of the hardenability of the urethane (meth) acrylate polymer, the epoxy compound is preferably 1,4-butanediol diglycidyl ether, 1,5- Epoxy compounds having a chain aliphatic structure having 4 to 6 carbon atoms, such as pentanediol diglycidyl ether and 1,6-hexanediol diglycidyl ether.

The compound (C) can be obtained by subjecting a compound having a (meth) acrylfluorenyl group and a carboxyl group to a ring-opening addition reaction with the epoxy compound. As the compound having a (meth) acrylfluorenyl group and a carboxyl group, a compound having a (meth) acrylfluorenyl group and a carboxyl group can be used. Examples of the compound include (meth) acrylic acid; carboxymethyl (meth) acrylate, carboxyethyl (meth) acrylate, carboxypropyl (meth) acrylate, and carboxypropyl (meth) acrylate Carboxyalkyl (meth) acrylate, etc .; hydroxyalkyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, etc. Reactants of carboxylic anhydrides such as phthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more.

Among these, in terms of the curability of the urethane (meth) acrylate polymer, the compound having a (meth) acrylfluorenyl group and a carboxyl group is preferably acrylic acid.

Examples of the epoxy (meth) acrylate of the compound (C) include Kayarad (registered trademark) R-167 (manufactured by Nippon Kayaku Co., Ltd.), and NK Oligo EA-5520. , EA-5321 (made by Shin Nakamura Chemical Co., Ltd.), etc. The compound (C) may be used singly or in combination of two or more kinds.

In addition, in terms of further improving the abrasion resistance of the cured film of the curable composition of the present invention and obtaining good extensibility after curing, it is better than urethane (meth) acrylate. The compound (C) is preferably 4% by weight or more, and more preferably 8% by weight or more of all the polyol components used as the raw material of the polymer. The content is preferably 25% by weight or less, and more preferably 18% by weight or less.

[Compound (D)] The compound (D) is an aliphatic polyol having a molecular weight of 500 or less.

Examples of the compound (D) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. Alcohol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,14- Tetradecanediol, 1,16-hexadecanediol and other diols having a linear aliphatic structure; propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol Glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,2-pentanediol, 3-methyl-1,5-pentanediol, 1,8-nonanediol, etc. have branches Diols having a chain-like aliphatic structure; trimethylolpropane, glycerol, sorbitol, mannitol, pentaerythritol, and other compounds having a branched aliphatic structure and three or more hydroxyl groups bonded thereto; cyclopropanediol, Cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, tricyclodecanediol, adamantanediol, and other diols having an alicyclic structure.

Among these, in terms of excellent scratch resistance of the cured film, those having a linear aliphatic structure are preferred, and it is particularly preferred to use a member selected from the group consisting of ethylene glycol, 1,4-butanediol, and 1, At least one of 12-dodecanediol. Among these, ethylene glycol is preferable in terms of chemical resistance, and 1,12-dodecanediol is preferable in terms of scratch resistance and flexibility. Furthermore, in order to further improve the weather resistance of the cured film, it is necessary to introduce a larger amount of the compound (B) into the urethane (meth) acrylate polymer. Therefore, the compound (D) preferably contains a diol having a branched aliphatic structure. In terms of replenishing the transparency of the solution and the low solubility of the ultraviolet absorbing skeleton, the diol having a branched aliphatic structure is more preferably propylene glycol, 1,3-butanediol, neopentyl glycol, and 3-formaldehyde. 1,5-pentanediol and the like, and further preferably 1,3-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol and the like. The compound (D) may be used singly or in combination of two or more kinds.

The point which improves the chemical resistance and abrasion resistance of the hardened | cured material of the urethane (meth) acrylate polymer of this invention with respect to superposition | polymerization as a urethane (meth) acrylate The compound (D) is preferably 3% by weight or more, and more preferably 10% by weight or more of all the polyol components used as raw materials of the product.

In addition, in terms of increasing the content of the formula (1) in the urethane (meth) acrylate polymer, the content of the formula (1) is higher than that of the urethane (meth) acrylate polymer. For all the polyol components used, the compound (D) is preferably 99.95% by weight or less, and more preferably 90% by weight or less.

[Polyols other than the compound (B) and the compound (D)] Examples of the polyols other than the compound (B) and the compound (D) include aromatic polyols having a molecular weight of 500 or less, and molecular weights. More than 500 high molecular weight polyols, etc.

Examples of the polyol having an aromatic structure having a molecular weight of 500 or less include bishydroxyethoxybenzene, bishydroxyethyl terephthalate, and bisphenol A. These may be used alone or in combination of two or more.

Examples of the high molecular weight polyol having a molecular weight exceeding 500 include polyether polyols, polyester polyols, polyether ester polyols, polycarbonate polyols, polyolefin polyols, and silicon polyols. These may be used alone or in combination of two or more.

When the high molecular weight polyol is used, a polycarbonate polyol is preferred. The polycarbonate polyol may be, for example, at least one carbonate compound, a diol, and a polyether polyol selected from the group consisting of an alkylene carbonate, a diaryl carbonate, and a dialkyl carbonate. At least one of the obtained by reaction. Examples of the diols include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol , 1,9-nonanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, diethylene glycol, dipropylene glycol, polybutadiene glycol, and the like. Among these, from the viewpoint that the abrasion resistance becomes good, it is preferable to include at least one selected from 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Polycarbonate polyol is available as a commercial item. Examples of commercially available products include Duranol (registered trademark) T4671 (manufactured by Asahi Kasei Corporation), Duranol (registered trademark) T4691 (manufactured by Asahi Kasei Corporation), and Duranol (registered trademark) (Registered trademark) 5651 (manufactured by Asahi Kasei Corporation), Duranol (registered trademark) 6001 (manufactured by Asahi Kasei Corporation), etc.

[Chain extender] Furthermore, in the present invention, when a reaction of the compound (A) and the compound (B) to obtain a precursor of a urethane polymer is performed, as a chain extender, an isocyanate may be added. A compound that reacts with two or more active hydrogen groups.

Examples of the chain extender include low molecular weight diamine compounds having a number average molecular weight of 500 or less, and examples thereof include 2,4- or 2,6-toluenediamine, xylene diamine, and 4,4'-diphenyl. Aromatic diamines such as methanediamine; ethylenediamine, 1,2-propanediamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl- 1,5-pentanediamine, 2,2,4- or 2,4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8- Aliphatic diamines such as octanediamine, 1,9-nonanediamine, 1,10-decanediamine; and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane , 4,4'-dicyclohexylmethyldiamine, isopropylidenecyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3-bisaminomethylcyclohexyl Alicyclic diamines such as alkane and tricyclodecanediamine. These may be used singly or in combination of two or more kinds.

When a chain extender is used, the amount of all polyols used is preferably relative to the total amount of the compound (B), compound (C), and other polyol components combined with the chain extender. Above 70 mol%, more preferably above 95 mol%.

In the present invention, the reaction is preferably performed under conditions in which an isocyanate group becomes excessive with respect to the compound (B) and a polyol other than the compound (B) to obtain an urethane polymer having an isocyanate terminal. A precursor, which in turn reacts the precursor of the urethane polymer having an isocyanate terminal with the compound (C).

When the compound (C) has two or more hydroxyl groups, the compound (C) is preferably used in excess relative to all isocyanate groups of the urethane (meth) acrylate polymer.

From the viewpoint of controlling the molecular weight of the urethane (meth) acrylate polymer, when producing the urethane (meth) acrylate polymer, the compound (C) and The total used amount of the isocyanate-reactive functional group compound in the raw material, the used amount of the compound (C) is preferably 2 mol% or more, and more preferably 10 mol% or more. The content is preferably 70 mol% or less, and more preferably 50 mol% or less. When the proportion of the compound (C) is large, the molecular weight of the urethane (meth) acrylate polymer tends to be small, and when the proportion of the compound (C) is small, the urethane (methyl) ) The molecular weight of the acrylate polymer tends to increase.

In the method for producing a urethane (meth) acrylate polymer of the present invention, an organic solvent can be used for the purpose of viscosity adjustment. As the organic solvent, any of known organic solvents may be used within the range in which the effects of the present invention are obtained. Preferable organic solvents include toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, and dimethyl Methylformamide and the like. The organic solvents may be used singly or in combination of two or more kinds. Generally, the organic solvent may be used in an amount of 300% by weight or less based on the total mass of the urethane (meth) acrylate polymer.

When producing a urethane (meth) acrylate polymer, a catalyst can be used for the urethane reaction. Examples of the catalyst include tin-based catalysts such as dibutyltin laurate, dibutyltin dicaprylate, dioctyltin dilaurate, and dioctyltin dicaprylate; bismuth tri ( 2-ethylhexanoate) and other bismuth-based catalysts. In terms of environmental adaptability, catalyst activity, storage stability, etc., the catalyst is preferably dioctyltin dilaurate and bismuth tri (2-ethylhexanoate). The catalyst may be used singly or in combination of two or more. The use amount of the catalyst is preferably 2,000 ppm or less with respect to the total input amount of the raw materials, and more preferably 1,000 ppm or less. In addition, it is preferably 10 ppm or more, and more preferably 30 ppm or more.

Moreover, when manufacturing a urethane (meth) acrylate polymer, it is preferable to use a polymerization inhibitor together. Examples of the polymerization inhibitor include phenols such as hydroquinone, methylhydroquinone, hydroquinone monoethyl ether, and dibutylhydroxytoluene; and amines such as phenothiazine and diphenylamine. , Copper salts such as copper dibutyldithiamine formate, manganese salts such as manganese acetate, nitro compounds, nitroso compounds, etc. Among these, the polymerization inhibitor is preferably a phenol. The polymerization inhibitors may be used singly or in combination of two or more kinds. The use amount of the polymerization inhibitor is preferably 3,000 ppm or less, and more preferably 1,000 ppm or less with respect to the total input amount of the raw materials. In addition, it is preferably 50 ppm or more, and more preferably 100 ppm or more.

In the production of a urethane (meth) acrylate polymer, the reaction temperature of the urethane reaction is preferably 20 ° C or higher in terms of higher reaction speed and improved production efficiency. 40 ° C or higher. The reaction temperature is preferably 120 ° C. or lower, and more preferably 100 ° C. or lower, from the viewpoint that it is difficult to generate side reactions such as an allophanate reaction. When the organic solvent is included in the reaction system, the reaction temperature is preferably equal to or lower than the boiling point of the organic solvent. The reaction time is usually 5 hours to 20 hours.

[Sclerosing Composition] The sclerosing composition of the present invention preferably contains the urethane (meth) acrylate polymer and an organic solvent.

In the curable composition of the present invention, the content of the urethane (meth) acrylate polymer is preferably based on the total amount of all components (solid content) except the organic solvent in the curable composition. 40% by weight or more, more preferably 60% by weight or more. The upper limit of the content of the urethane (meth) acrylate polymer is 100% by weight. When the content of the urethane (meth) acrylate polymer is within the above range, the hardening speed and surface hardenability of the hardenable composition will be good, and the viscosity will not remain, which is preferable.

Furthermore, in terms of excellent transparency, weather resistance, and abrasion resistance of the cured product, the structural ratio of the compound represented by the formula (1) in the polymerized component of the curable composition is preferably 10% by weight or more. . The content is preferably 25% by weight or less.

The polymerizable component of the curable composition is a component containing an unsaturated double bond that is polymerizable with respect to the active energy ray, and refers to a urethane (meth) acrylic acid contained in the curable composition. Ester polymers, active energy ray-curable polymers, and active energy ray reactive monomers.

[Organic solvent] The organic solvent can be used to adjust the viscosity of a coating material when forming a coating film of the curable composition of the present invention. The solid content concentration of the curable composition is preferably 5 to 90 weight. It is preferably 10% by weight or more, and more preferably 15% by weight or more. In addition, it is preferably 80% by weight or less, and more preferably 60% by weight or less.

As the organic solvent, a known organic solvent can be used. In terms of the solubility of the urethane (meth) acrylate polymer, the solubility parameter (hereinafter, referred to as the "SP value") of the organic solvent is preferably 8.0 or more. In terms of transparency, it is preferably 11.5 or less. Examples of the organic solvent include toluene (SP value: 9.1), xylene (SP value: 9.1), ethyl acetate (SP value: 8.7), butyl acetate (SP value: 8.7), and cyclohexanone (SP value: 9.8), methyl ethyl ketone (SP value: 9.0), methyl isobutyl ketone (SP value: 8.7), N-methylpyrrolidone (SP value: 11.2), isopropyl alcohol ( SP value: 11.5) and so on. Furthermore, in the present invention, the SP value is calculated using a method proposed by Fedors and others. Specifically, it refers to "Polymer Engineering and Science," February 14, 1974, Volume 14, Number 2, Robert F. Fedors. (Pp. 147-154) ". In addition, when using a mixed solvent, SP value means a value as a mixture.

[Other components] The curable composition of the present invention may contain an active energy ray-reactive monomer, an active energy ray-curable polymer (other than the urethane (meth) acrylate polymer of the present invention), and polymerization. Starters, photosensitizers, epoxy compounds, and other additives are used as other components.

As the active-energy-ray-reactive monomer, any known active-energy-ray-reactive monomer can be used within the range in which the effects of the present invention are obtained. These active energy ray reactive monomers can be used to adjust the hydrophilicity and hydrophobicity of the urethane (meth) acrylate polymer of the present invention, the hardness of the cured product when the obtained composition is made into a cured product, It is used for the purpose of physical properties, such as elongation of a hardened | cured material. The active energy ray reactive monomers may be used singly or in combination of two or more.

Examples of the active energy ray-reactive monomer include vinyl ethers, (meth) acrylamides, and (meth) acrylates. Specifically, for example, styrene, α -Aromatic vinyl monomers such as methylstyrene, α-chlorostyrene, vinyltoluene, and divinylbenzene; vinyl acetate, vinyl butyrate, N-vinylformamide, N-ethylene Vinyl ester monomers such as ethylacetamide, N-vinyl-2-pyrrolidone, N-vinyl caprolactam, divinyl adipate; ethyl vinyl ether, phenyl vinyl ether, etc. Vinyl ethers; allyl compounds such as diallyl phthalate, trimethylolpropane diallyl ether, allyl glycidyl ether; (meth) acrylamide, N, N -Dimethylacrylamide, N, N-dimethylmethacrylamine, N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N -Butoxymethyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, (meth) acrylfluorenylmorpholine, methylenebis (meth) acrylamide, etc. (Meth) acrylamide; (meth) acrylic acid, ( Base) methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate, Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (formyl) ) Morpholine acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, shrinking (meth) acrylate Glyceryl ester, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) Phenoxyethyl acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, bicyclic (meth) acrylate Monofunctional (methyl) esters such as amyl ester, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, isobornyl (meth) acrylate, and phenyl (meth) acrylate ) Acrylate; and ethyl di (meth) acrylate Alcohol, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (n = 5 ～ 14), propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate (n = 5 ～ 14), bis (meth) acrylic acid-1,3-butanediol, bis (meth) acrylic acid-1,4-butanediol, bis (meth) acrylic acid polybutanediol (n = 3 ～ 16) ), Di (meth) acrylic poly (1-methylbutanediol) (n = 5-20), di (meth) acrylic acid-1,6-hexanediol, di (meth) acrylic acid-1, 9-nonanediol, neopentyl glycol di (meth) acrylate, neopentyl glycol valproate di (meth) acrylate, dicyclopentanediol di (meth) acrylate, di (methyl) Acrylic tricyclodecane, bisphenol A diglycidyl ether di (meth) acrylate, 1,4-cyclohexanedimethanol diglycidyl ether di (meth) acrylate, ethylene glycol diglycidyl ether di (Meth) acrylate, 1,4-butanediol diglycidyl ether di (meth) acrylate, 1,6-hexane Alcohol diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di-trimethylol Propane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane (meth) acrylate three Ethoxyethyl ester, trimethylolpropane (meth) acrylate trioxypropyl, trimethylolpropane (meth) acrylate polyoxyethyl, trimethylolpropane (meth) acrylate polyoxypropyl , Tris (2-hydroxyethyl) iso (tris (meth) acrylate) isotricyanate, Tris (2-hydroxyethyl) di (meth) acrylic acid (tri) isocyanurate, Addition of ethylene oxide Phenol A di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate, propylene oxide addition bisphenol A di (meth) acrylate, propylene oxide addition bisphenol F di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A di (meth) acrylate epoxy, bisphenol F di (meth) acrylate epoxy, etc. official Capable of (meth) acrylate.

Among these, (meth) acrylfluorenylmorpholine, (meth) acrylic acid tetrahydrofurfuryl, and (meth) are preferable from the viewpoints of low viscosity of the curable composition and good coating properties. Benzyl acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, (meth) Dicyclopentenyl acrylate, isobornyl (meth) acrylate, and (meth) acrylamide are equal to a monofunctional (meth) acrylate having a ring structure in the molecule. In addition, in terms of improving the mechanical strength of the obtained cured film, di (meth) acrylic acid-1,4-butanediol and di (meth) acrylic acid-1,6-hexanediol are preferred. , 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane di (meth) acrylate, 1,4-cyclohexanedimethanol diglycidyl Ether di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, 1,4-butanediol diglycidyl ether di (meth) acrylate, 1,6-hexanediol Diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (methyl) Multifunctional (meth) acrylates such as acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Furthermore, in terms of the extensibility of the obtained cured film, di (meth) acrylic acid polyethylene glycol (n = 5 to 14) and di (meth) acrylic acid polypropylene glycol (n = 5) are preferred. ～ 14), poly (butyl) di (meth) acrylic acid (n = 3 ～ 16), poly (1-methylbutane diol) (n = 5 ～ 20), and other polyethers (formaldehyde) Based) acrylates.

Regarding the adjustment of the viscosity of the curable composition and the adjustment of the physical properties such as the hardness of the obtained cured product, with respect to the total amount of all components (solid content) except the organic solvent of the curable composition, the The content of the active energy ray reactive monomer is preferably 50% by weight or less, and more preferably 30% by weight or less.

Examples of the active energy ray-curable polymer include (meth) acrylic acid epoxy ester-based polymers, (meth) acrylic acid fluorenyl ester-based polymers, and polyester (meth) acrylate-based polymers. , Polycarbonate (meth) acrylate polymer, polybutadiene (meth) acrylate polymer, polyether (meth) acrylate (except those described in the active energy ray reactive monomer Except those). The active energy ray-curable polymer may be used singly or in combination of two or more kinds.

The polymerization initiator is mainly used for the purpose of improving the polymerization efficiency of the polymerization reaction by irradiation with active energy rays such as ultraviolet rays and electron beams. As the polymerization initiator, a known arbitrary photoradical polymerization initiator may be used within the range in which the effects of the present invention are obtained. The polymerization initiators may be used singly or in combination of two or more. Furthermore, a photoradical polymerization initiator and a photosensitizer may be used in combination.

Examples of the photo-radical polymerization initiator include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) benzophenone, and 4 -Phenylbenzophenone, Methyl o-benzoyl benzoate, thioanthrone, diethylthioanthone, isopropylthioanthone, chlorothioanthone, 2-ethylanthracene Quinone, third butyl anthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyldimethylketal, 1-hydroxycyclohexylbenzene Ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methylbenzyl methylformate, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinylpropane-1-one, 2,6-dimethylbenzylidene diphenylphosphine oxide, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, bis (2, 6-dimethoxybenzylidene) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzylidene) phenylphosphine oxide, and 2- Hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propanyl) -benzyl] -phenyl] -2-methyl-propane-1-one and the like.

Among these, benzophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 1 are preferred in terms of fast curing speed and sufficient increase in crosslinking density. -Hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl- (Propanyl) -benzyl] -phenyl] -2-methyl-propane-1-one, more preferably 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzyl dione Phenylphosphine oxide and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl-propane-1- ketone.

When a compound having a radically polymerizable group and a cationic polymerizable group such as an epoxy group is contained in the curable composition, the photo-radical polymerization initiator and photo may be included as the polymerization initiator. Cationic polymerization initiator. A known photocationic polymerization initiator can be used within a range that does not significantly inhibit the effect of the present invention.

From the viewpoint that it is difficult to cause a decrease in the mechanical strength due to the decomposition product of the initiator, the content of the polymerization initiator is preferably 10% by weight based on the total weight of the polymerization component of the curable composition. Hereinafter, it is more preferably 5% by weight or less.

The photosensitizer can be used for the same purpose as the polymerization initiator. Examples of the photosensitizer include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, and ethyl 4-dimethylaminobenzoate. Pentyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and the like. The photosensitizers may be used singly or in combination of two or more.

In the curable composition of the present invention, the light sensitizer is less likely to cause a decrease in mechanical strength due to a decrease in cross-linking density than the total weight of the polymerized components of the curable composition. The content of Si is preferably 10% by weight or less, and more preferably 5% by weight or less.

Examples of the additives include fillers such as silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, talc, kaolin, metal oxides, metal fibers, iron, lead, and metal powder; carbon fibers, Carbon materials such as carbon black, graphite, carbon nanotubes, fullerenes such as C60; antioxidants, heat stabilizers, ultraviolet absorbers, hindered amine light stabilizers (HALS), surface hydrophilic agents, antistatic agents, lubricants Property imparting agent, plasticizer, release agent, defoaming agent, leveling agent, anti-settling agent, surfactant, thixotropy imparting agent, flame retardant, flame retardant auxiliary, polymerization inhibitor, silane coupling agent, etc. Modifiers; pigments, dyes, hue adjusters and other colorants. These additives may be used singly or in combination of two or more.

In the curable composition of the present invention, the content of the additive is smaller than the total weight of the polymerized component of the curable composition in terms of difficulty in causing a decrease in mechanical strength due to a decrease in crosslinking density. It is preferably at most 10% by weight, more preferably at most 5% by weight.

The method of including the additive in the curable composition of the present invention is not particularly limited, and examples thereof include conventionally known methods of mixing and dispersing. Further, in order to more surely disperse the additive in the hardenable composition, for example, use of a double roll, three rolls, a bead mill, a ball mill, a sand mill, a pebble mill, and a rotary screen (Trommel), sand grinder, sand grinder, planetary mixer, high-speed impeller disperser, high-speed stone mill, high-speed impact mill, kneader, homogenizer, ultrasonic disperser, etc. Method of processing.

[Viscosity] The viscosity of the curable composition of the present invention is preferably 5 mPa · s or more, and more preferably 10 mPa · s or more in terms of operability, coatability, moldability, and three-dimensional moldability. In addition, it is preferably 50,000 mPa · s or less, and more preferably 10,000 mPa · s or less. The viscosity of the curable composition can be adjusted, for example, based on the content of the urethane (meth) acrylate polymer in the present invention, the type of the additive, or the blending ratio thereof. Moreover, the viscosity can be measured at 25 ° C in an E-type viscometer (rotor 1 ° 34 '× R24).

[Coating method] As the coating method of the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention, a bar coater method, an applicator method, and a curtain flow coating method can be applied. Cloth machine method, roll coater method, spray method, gravure coater method, notch wheel coater method, reverse roll coater method, lip coater method, die coater method, slot die coating Known methods, such as a machine method, an air knife coater method, and a dip coater method, among these, a bar coater method and a gravure coater method are preferable. The urethane (meth) acrylate polymer of the present invention may be used alone according to the coating method.

Examples of the base material for coating the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention include polyethylene terephthalate and polyethylene terephthalate. Polyesters such as succinate; polyolefins such as polypropylene and polyethylene; and various plastics, glass, and metals such as nylon, polycarbonate, and (meth) acrylic polymers. Among these, polyethylene terephthalate is preferred. The shape of these base materials may be a flat shape such as a film shape or a sheet shape, or may be formed into various shapes.

[Curable Product / Laminate] The cured product of the present invention can be obtained by irradiating an active energy ray to the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention. Examples of the active energy rays include infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, alpha rays, beta rays, and gamma rays. From the viewpoint of device cost or productivity, it is preferable to use an electron beam or ultraviolet rays. As a light source, an electron beam irradiation device, an ultra-high-pressure mercury lamp, a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an Ar laser, a He-Cd laser, a solid laser, a xenon lamp, and a high-frequency induction mercury lamp can be used. , Sunlight, etc.

The irradiation amount of the active energy ray can be appropriately selected according to the type of the active energy ray. For example, when hardening is performed by electron beam irradiation, the irradiation amount is preferably 1 Mrad to 15 Mrad. For example, when curing is performed by ultraviolet irradiation, it is preferably 50 mJ / cm ² to 1,500 mJ / cm ² .

When curing the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention, the curing can be performed in any environment of an inert gas such as air, nitrogen, or argon. In addition, irradiation may be performed in a sealed space between the film or glass and the mold.

The thickness of the cured product can be appropriately determined according to the intended use. In terms of good design or functional performance after three-dimensional processing, the thickness of the cured product is preferably 1 μm or more, and more preferably 2 μm or more. In addition, in terms of good hardenability and adaptability to three-dimensional processing, the thickness of the cured product is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 20 μm or less.

The laminated body of this invention can be obtained by hardening the urethane (meth) acrylate polymer of this invention, or the curable composition of this invention on a base material. The laminated body of this invention may have a layer other than the hardened | cured material of this invention between a base material and the hardened | cured material of this invention, and may have it on the outer side of the laminated body of this invention. Moreover, the said laminated body may have a multilayer base material or the hardened | cured material of this invention.

As a method for obtaining a laminated body having a plurality of hardened materials, there can be applied: a method of laminating all layers in an unhardened state and hardening with an active energy ray, and using an active energy ray to harden or semi-harden a lower layer and apply the coating A known method such as a method in which the upper layer is hardened again with active energy rays, a method in which each layer is coated on a substrate, and the layers are bonded to each other in an unhardened or semi-hardened state, improves the adhesion between layers. On the one hand, a method of curing with active energy rays after laminating in an uncured state is preferred. As a method of laminating in an unhardened state, a known method such as sequential coating in which an upper layer is repeatedly applied after the lower layer is applied, or simultaneous multi-layer coating in which two or more layers are repeatedly applied simultaneously from multiple slits can be applied. Is not limited to this.

The laminated body of the present invention can be preferably used as a coating replacement film. For example, it can be effectively applied to building materials for interior and exterior applications, various components such as automobiles, home appliances, and information electronic materials. In addition, the laminated body of the present invention can be preferably used for a glaze member or a glaze member or the point that the weather resistance, exudation resistance, and abrasion resistance necessary for surface protection can be imparted from one layer and the steps become simple. Decorative film. In addition, the so-called decorative film in the present invention is a film that is designed and decorated by applying uneven shapes such as wood grain, metal grain, and embossing, various patterns, and features by printing, coating, vapor deposition, coloring, and the like. The urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention is applied to the surface of a molded article such as polycarbonate, and is irradiated with active energy rays to form a cured product. The molded product can be preferably used for automotive headlamp lens applications and automotive polymer glass applications.

Since the hardened | cured material of this invention is excellent in extensibility, the laminated body of this invention can be extended and used as a film. The method for producing the film preferably includes: a step of applying the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention to a substrate; and the curable composition A step of irradiating an active energy ray with a substance to obtain a laminated body having a hardened body; and a step of extending the laminated body.

In the method for producing the film, the step of applying the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention to a substrate, and the step of applying the urethane Each of the steps of obtaining an hardened product by irradiating an active energy ray with an acid ester (meth) acrylate polymer or the hardenable composition can be performed under the conditions. In the method for producing the film, the step of stretching the cured product may be performed by heating and stretching under conditions of 60 ° C to 200 ° C, preferably 100 ° C to 180 ° C. When the film is used as a decorative film, known methods such as insert molding, in-mold molding, overlay molding, blow molding, and vacuum molding can be used as a molding method of the decorative film. [Example]

Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to the following examples.

[Measurement method of physical properties and characteristics] Evaluation of the urethane (meth) acrylate polymer and the cured film was performed by the following method. <Molecular weight> GPC ("HLC-8120GPC" manufactured by Tosoh Corporation) was used. Tetrahydrofuran (THF) was used as the solvent, polystyrene was used as the standard sample, and TSKgel superH1000 + H2000 + H3000 was used for the column. The weight average molecular weight Mw and the number average molecular weight Mn of the urethane (meth) acrylate polymer were measured at a speed of 0.5 mL / min and a column oven temperature of 40 ° C.

<Evaluation of Transparency of Curable Composition> Regarding the appearance of the curable composition obtained in the examples after being left for one day, the transparency, turbidity, or insolubility was visually confirmed to evaluate the transparency of the curable composition.

<Evaluation of hardened | cured material> (Evaluation sample) The hardenable tree product obtained by the Example and the comparative example was apply | coated to the polyethylene terephthalate film with the bar coater, and it dried at 80 degreeC 2 In a minute, an ultraviolet irradiation device (US5-X1802-X1202, manufactured by Iwasaki Electric Co., Ltd.) was used, and a 160 W high-pressure mercury lamp was used to irradiate ultraviolet rays with a cumulative irradiation amount of 1000 mJ / cm ² (wavelength 315 nm to 380 nm) and cure. Furthermore, it aged at 23 degreeC for 1 day, and obtained the laminated body with a film thickness of about 5 micrometers.

(Evaluation of coating film appearance) The coating film appearance on the obtained laminated body was visually confirmed to be transparent or cloudy, and the haze value H was measured. The haze value H is measured in accordance with JIS K7105 using a haze meter ("HAZE METER HM-65W" manufactured by Murakami Color Technology Research Institute Co., Ltd.).

(Weather resistance test (metal weather test)) The coating film on the obtained laminated body was manufactured using a spectrophotometer (Konica Minolta (Konica Minolta) Co., Ltd.), and the product name was "spectrophotometric Spectrophotometer (CM-5 ") to measure the hue b ₀ . Next, using a metal weather-resistant machine (made by Daipla wintes (stock), product name "daipla metal weather KU-R4Ci-W"), under the irradiation intensity of 80 mW / cm ² , the following The conditions of (1), (2), and (3) are each 4 hours and a total of 12 hours is set as 1 cycle, and 168 hours (14 cycles) and 336 hours (28 cycles) of the accelerated weather resistance test are performed. The cured product after the test was visually observed, and the hue b ₁ and the haze value H of the cured product after the accelerated weathering test were measured. The hue of the cured product was evaluated as b ₁ -b ₀ . (1) Temperature of 63 ° C and humidity of 70% (2) Temperature of 70 ° C and humidity of 90% (3) Temperature of 30 ° C and humidity of 98% (10 seconds spray before and after (3))

(Measurement of transmittance) Regarding the coating film on the obtained laminated body, a spectrophotometer (Hitachi High-technologies, Ltd., product name "Ratio Beam Spectrophotometer U-1900") was used. The baseline is set to a polyethylene terephthalate film (easy to be processed), and the transmittance (360 nm, 380 nm) is measured.

Haze before (Evaluation of abrasion resistance) on the coating film of the obtained laminate was measured abrasion resistance test value H _1. Next, the surface of the coating film on the laminate was measured on a steel wool # 0000 at 200 gf (area per unit area) at 23 ° C. and 55% RH using a vibration abrasion tester (manufactured by Toyo Seiki). 4 cm ² ) and the haze value H ₂ after 15 round trips. When the haze value H ₂ is 30 or less, it is excellent in abrasion resistance. The haze value is measured in accordance with JIS K7105 using a haze meter ("HAZE METER HM-65W" manufactured by Murakami Color Technology Research Institute Co., Ltd.).

[Raw materials and solvents] The raw materials and solvents used in the following Examples and Comparative Examples and their abbreviations are as follows. (Compound (A)) • IPDI: isophorone diisocyanate (manufactured by Evonik Degussa Japan, trade name "VESTANAT IPDI")

(Compound (B)) T-33: Polyol represented by the following formula (10) (trade name "Dainsorb T-33" manufactured by Yamato Chemical Co., Ltd.) [Chem. 13] (10) T-35: Polyol represented by the following formula (11) (trade name "Dainsorb T-35" manufactured by Yamato Chemical Co., Ltd.) [Chem. 14] ··· (11)

(Compound (C): a compound having a hydroxyl group and a (meth) acryl group) • HEA: 2-hydroxyethyl acrylate (trade name “HEA” manufactured by Osaka Organic Corporation) (Compound (D)) • 3MPD: 3- Methyl-1,5-pentanediol

(Organic solvents) MEK: methyl ethyl ketone (SP value: 9.0) PGM: propylene glycol monomethyl ether (SP value: 11.3)

(Multifunctional acrylate) V-300: A mixture (catalog value) containing 40% to 45% by weight of pentaerythritol triacrylate and 35% to 40% by weight of pentaerythritol tetraacrylate as a compound other than that ( "Biscoat (registered trademark) 300" manufactured by Osaka Organic Corporation)

(Photoradical polymerization initiator) · Om184: 1-hydroxy-cyclohexyl-phenyl-one ("Omnirad (registered trademark) 184" manufactured by IGM)

(Ultraviolet absorbent) TINUVIN 479: Hydroxyphenyltriazine (HPT) UV absorber (manufactured by BASF)

(Leveling agent) · Polyflow No. 75: (manufactured by Kyoeisha Chemical Co., Ltd.)

[Synthesis Example 1] In a four-necked flask equipped with a stirrer, a reflux cooler, a dropping funnel, and a thermometer, 102 g of IPDI and 101 g of T-33 were placed, and then methyl ethyl ketone 203 g, and two 0.20 g of octyltin dilaurate and 0.25 g of methyl hydroquinone were heated to 80 ° C. in oil, and reacted for about 2 hours until the suspension was transparent. After the urethane reaction was completed, the temperature was cooled to 60 ° C, and then 0.05 g of dioctyltin dilaurate was added, and a mixture of V-300: 297 g and 297 g of methyl ethyl ketone was added dropwise over 1 hour. To carry out the reaction. The reaction was heated to 70 ° C. in oil for 8 hours. The end of the urethane reaction was confirmed by the disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, thereby obtaining the aminomethyl ester. Acrylate polymer. The weight average molecular weight and number average molecular weight of the obtained urethane acrylate polymer were measured. The obtained results are shown in Table-1. Hereinafter, this urethane acrylate polymer is expressed as "U-1".

[Synthesis Example 2] A four-necked flask equipped with a stirrer, a reflux cooler, a dropping funnel, and a thermometer was charged with 247 g of IPDI and 79 g of 3MPD, and then methyl ethyl ketone 326 g and dioctyl 0.10 g of tin dilaurate, heated to 80 ° C in oil, and reacted for 2 hours, then added 116 g of T-33, 116 g of methyl ethyl ketone, and 0.12 g of dioctyltin dilaurate. The reaction was carried out for about 2 hours until the suspension was clear. After the urethane reaction was completed, the temperature was cooled to 60 ° C, and then 0.28 g of dioctyltin dilaurate and 0.25 g of methyl hydroquinone were added, and 57 g of HEA and methyl ethyl were added dropwise over 1 hour. A mixed solution of 57 g of ketone was used to start the reaction. The reaction was heated to 70 ° C. in oil for 8 hours. The end of the urethane reaction was confirmed by the disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, thereby obtaining the aminomethyl ester. Acrylate polymer. The weight average molecular weight and number average molecular weight of the obtained urethane acrylate polymer were measured. The obtained results are shown in Table-1. Hereinafter, this urethane acrylate polymer is expressed as "U-2".

[Synthesis Example 3] In a four-necked flask equipped with a stirrer, a reflux cooler, a dropping funnel, and a thermometer, 223 g of IPDI and 59 g of 3MPD were placed, and then 282 g of methyl ethyl ketone and dioctyl 0.08 g of tin dilaurate, heated to 80 ° C in oil, and reacted for 2 hours, then added 174 g of T-33, 175 g of methyl ethyl ketone, and 0.14 g of dioctyltin dilaurate. The reaction was carried out for about 2 hours until the suspension was clear. After the urethanization reaction was completed, the temperature was cooled to 60 ° C, and then 0.27 g of dioctyltin dilaurate and 0.25 g of methyl hydroquinone were added. HEA 43 g, methyl ethyl was added dropwise over 1 hour. A mixture of 43 g of ketone was used to start the reaction. The reaction was heated to 70 ° C. in oil for 8 hours. The end of the urethane reaction was confirmed by the disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, thereby obtaining the aminomethyl ester. Acrylate polymer. The weight average molecular weight and number average molecular weight of the obtained urethane acrylate polymer were measured. The obtained results are shown in Table-1. Hereinafter, this urethane acrylate polymer is expressed as "U-3".

[Synthesis Example 4] In a four-necked flask equipped with a stirrer, a reflux cooler, a dropping funnel, and a thermometer, 154 g of IPDI and 27 g of 3MPD were placed, and then methyl ethyl ketone 181 g and dioctyl 0.05 g of tin dilaurate, heated to 80 ° C in oil, and reacted for 2 hours, then added 258 g of T-35, 258 g of methyl ethyl ketone, 0.17 g of dioctyltin dilaurate, Reaction for 2 hours. After the urethanization reaction was completed, the temperature was cooled to 60 ° C, and then 0.28 g of dioctyltin dilaurate and 0.25 g of methyl hydroquinone were added. HEA 59 g, methyl ethyl was added dropwise over 1 hour. A mixed solution of 59 g of ketone was used to start the reaction. The reaction was heated to 70 ° C. in oil for 8 hours. The end of the urethane reaction was confirmed by the disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, thereby obtaining the aminomethyl ester. Acrylate polymer. The weight average molecular weight and number average molecular weight of the obtained urethane acrylate polymer were measured. The obtained results are shown in Table-1. Hereinafter, this urethane acrylate polymer is expressed as "U-4".

[Example 1] 56.9 g of a urethane acrylate polymer "U-1" (solid content: 50% by weight), 1.4 g of Irg184 as a polymerization initiator, and 0.1 g of a Polyflow No. 75 as a leveling agent, 1.6 g of MEK, and 40.0 g of PGM were stirred at 25 ° C for 1 hour to obtain a hardenable composition. The obtained curable composition was used to evaluate transparency. The obtained results are shown in Table-1.

[Example 2 to Example 5 and Comparative Example 1 to Comparative Example 7] The same procedure as in Example 1 was performed except that the composition of the curable composition was changed as shown in Table-1. The results obtained for each evaluation item are shown in Table-1. Furthermore, U-2 was used in place of U-1 in Example 2 and Example 3, U-3 was used in place of U-1 in Example 4 and Example 5, and U-4 was used in place of U in Comparative Example 1. -1.

[Table 1] Table-1

[Table 2] Table-2

Compared with Example 2, Comparative Example 1 in which T-35 was introduced into the structure of a urethane (meth) acrylate instead of T-33 had an ester bond in the ultraviolet absorbing skeleton, and therefore, it was derived from an ester. The hydrolysis of the bond and the increase in the value of b ₁ -b ₀ in the metal weathering test (28-cycle weathering resistance) increase the weathering resistance.

In addition, the solutions in Comparative Examples 2 and 3 in which T-33 as a dihydroxy compound was added to the curable composition were dirty, the appearance of the solution was unsatisfactory, and a good coating film could not be obtained even when the coating film was made. On the other hand, in Comparative Examples 4 and 5 in which T-35 was added, the weather resistance was insufficient. Furthermore, the value of b ₁ -b ₀ in the metal weathering test (28-cycle weather resistance) in Comparative Example 6 in which Tinuvin 479 was added increased, resulting in a decrease in weather resistance. In Comparative Example 7, the appearance and weatherability of the coating film were poor.

The present invention has been described in detail and with reference to specific embodiments, and it will be apparent to those skilled in the art that various changes or modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application filed on March 17, 2017 (Japanese Patent Application No. 2017-052242), the content of which is incorporated herein by reference. [Industrial availability]

The hardened | cured material and laminated body obtained using the urethane (meth) acrylate polymer or hardenable composition of this invention can be used suitably as a film for coating substitution. For example, it can be effectively applied to building materials for interior and exterior applications, various components such as automobiles, home appliances, and information electronic materials. In particular, the cured film which is an embodiment of the present invention can be suitably used as a decorative film using it as a top coat layer.

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Claims (18)

A urethane (meth) acrylate polymer having a chemical structure represented by the following formula (1), In the formula, A represents a single bond or a methylene group, an alkylene group, -O- group, -NH- group, -S- group, -SO- group, or -SO ₂ -group which may have a substituent; R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom; R ⁵ and R ⁶ independently represent an alkylene group, an alkyleneoxy group, or an alkylene group. The urethane (meth) acrylate polymer according to item 1 of the scope of patent application, wherein the formula (1) is the following formula (2), ···(2). The urethane (meth) acrylate polymer according to item 1 or item 2 of the scope of patent application, which has a chemical structure represented by the following formula (3), (3) In formula (3), X ¹ is an aliphatic structure having a molecular weight of 500 or less, and n is an integer of 2 to 8. The urethane (meth) acrylate polymer according to item 3 of the scope of patent application, which includes a chemical structure represented by the following formula (4-1) and a formula (4-2) At least one of the chemical structures of s is a chemical structure represented by the formula (3), In the formula (4-1), (4-2), the same meaning as in formula X X (2) ^{1 1.} The urethane (meth) acrylate polymer according to any one of claims 1 to 4 in the scope of the patent application, which has a weight average molecular weight (Mw) of 500 to 30,000. The urethane (meth) acrylate polymer according to any one of claims 1 to 5 in the scope of the patent application, wherein in the urethane (meth) acrylate polymer, the formula The ratio of the chemical structure represented by (1) is 5 to 60% by weight. A hardening composition comprising the urethane (meth) acrylate polymer according to any one of claims 1 to 6 of the scope of patent application, and an organic solvent. The hardenable composition according to item 7 of the scope of the patent application, wherein the solubility parameter of the organic solvent is 8.0 to 11.5. The hardenable composition according to item 7 or 8 of the scope of application for a patent, wherein the solid content concentration of the hardenable composition is 5 to 90% by weight. The hardenable composition according to any one of claims 7 to 9, in which the ratio of the chemical structure of the polymerizable component of the hardenable composition represented by the formula (1) is 5% by weight -60% by weight. A hardened composition of a hardenable composition, wherein the hardenable composition is the hardenable composition according to any one of claims 7 to 10 of the scope of patent application. A laminated body comprising, on a substrate, a cured product of the curable composition according to any one of claims 7 to 10 of the scope of patent application. A headlight lens comprising a hardened body of a hardenable composition as described in claim 11 on a base material. A glaze having a hardened body of a hardenable composition as described in claim 11 on a substrate. A decorative film having a cured product of a curable composition as described in claim 11 on a substrate. A method for manufacturing a film, comprising: applying a urethane (meth) acrylate polymer according to any one of claims 1 to 6 in the scope of patent application; The step of applying the curable composition according to any one of the tenth to a substrate; irradiating an active energy ray to the urethane (meth) acrylate polymer or the curable composition A step of obtaining a laminated body having a hardened body; and a step of extending the laminated body. A method for producing a urethane (meth) acrylate polymer by reacting the following compound (A) and the following compound (B) to obtain a precursor of a urethane polymer, and then The following compound (C) is reacted with a precursor of the obtained urethane polymer. Compound (A): polyisocyanate; compound (B): a polyol represented by the following formula (5), (5) In the formula, A represents a single bond or a methylene group, an alkylene group, an -O- group, an -NH- group, an -S- group, an -SO- group, or -SO which may have a substituent. ₂ -radical; R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom; R ⁵ and R ⁶ independently represent an alkylene group, an alkylene group And aryl groups; compound (C): a compound having a hydroxyl group and a (meth) acrylfluorenyl group. The method for producing a urethane (meth) acrylate polymer according to item 17 of the scope of patent application, which is obtained by reacting a compound (A), a compound (B), and the following compound (D) After the precursor of the urethane polymer, the compound (C) is reacted, and the compound (D): an aliphatic polyol having a molecular weight of 500 or less.