KR102275295B1 - Urethane (meth)acrylate polymer - Google Patents

Abstract

〔식 중, A는 단결합, 또는 치환기를 가져도 되는 메틸렌기, 알킬렌기, -O-기, -NH-기, -S-기, -SO-기 또는 -SO₂-기를 나타낸다. R¹, R², R³ 및 R⁴는 독립적으로, 수소 원자, 알킬기, 알콕시기, 아릴기 또는 할로겐 원자를 나타낸다. R⁵ 및 R⁶은 독립적으로, 알킬렌기, 알콕실렌기, 아릴렌기를 나타낸다.〕It is an object to provide a urethane (meth)acrylate polymer from which a coating film excellent in weather resistance, scratch resistance and transparency is obtained by preventing the bleed-out of the ultraviolet absorber and a curable composition containing the same. Another object of the present invention is to provide a laminate and a decorative film having on the surface a layer containing the cured product of the urethane (meth)acrylate polymer or a curable composition containing the same. The said subject is solved by the urethane (meth)acrylate polymer which has a chemical structure represented by following formula (1).

[In the formula, A represents a single bond or a methylene group, 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 alkoxyylene group, or an arylene group.]

Description

Urethane (meth)acrylate polymer

The present invention relates to a urethane (meth)acrylate polymer excellent in transparency, weather resistance and scratch resistance after coating and curing the curable composition to a substrate, and a curable composition comprising the same. Further, the present invention relates to a cured product, a laminate, and a decorative film using the urethane (meth)acrylate polymer and the curable composition.

A radical polymerization type curable composition can be cured in a short time by irradiation with active energy rays to provide a film or molded article excellent in chemical resistance, scratch resistance, weather resistance, heat resistance, etc., so that automobiles, household appliances, and woodworking products can be provided. , is used in a paint composition for coating the surface of plastic molded articles, transfer materials, and the like.

For example, Patent Document 1 discloses a coating composition in which a bisbenzotriazolylphenol compound is added as an ultraviolet absorber.

Patent Document 2 discloses a coating composition in which an ultraviolet absorber having a specific structure is inserted into the skeleton of a polymer.

Patent Document 3 discloses a curable resin composition in which a bisbenzotriazolylphenol-based ultraviolet absorber is inserted into the skeleton of a polymer via an ester bond.

Japanese Patent Laid-Open No. 2000-017204 Japanese Patent Laid-Open No. 2000-053913 Japanese Patent Laid-Open No. 2000-109652

However, in the coating composition described in Patent Document 1, since the ultraviolet absorber is not inserted into the polymer skeleton, the ultraviolet absorber bleeds out from the coating film, and thus the transparency and weather resistance of the coating film were insufficient.

In the coating composition described in Patent Document 2, the ultraviolet absorption performance of the ultraviolet absorber was not sufficient, and thus the weather resistance was insufficient.

In the curable composition described in Patent Document 3, since the ultraviolet absorber is inserted into the backbone of the polymer through the ester bond, hydrolysis derived from the ester bond occurred, the ultraviolet absorber bleed out, and the weather resistance was insufficient.

The present invention is to provide a urethane (meth) acrylate polymer that prevents the bleed-out of the ultraviolet absorber and obtains a coating film excellent in weather resistance, abrasion resistance, and transparency, and a curable composition comprising the same.

That is, the above object of the present invention can be solved by means of the following [1] to [18]. [1] 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, 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 alkoxyylene group, or an arylene group.]

[2] The urethane (meth)acrylate polymer according to [1], wherein the formula (1) is the following formula (2).

[3] The urethane (meth)acrylate polymer according to [1] or [2], which has a chemical structure represented by the following formula (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.)

[4] A chemical structure represented by the formula (3), which contains 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), [3] The urethane (meth)acrylate polymer described in.

(In formula (4-1), (4-2) of, X ¹ has the same meaning as X ¹ in the formula (3).)

[5] The urethane (meth)acrylate polymer according to any one of [1] to [4], wherein the weight average molecular weight (Mw) is 500 to 30000.

[6] The urethane (meth)acrylate polymer according to any one of [1] to [5], wherein the ratio of the chemical structure represented by Formula (1) in the urethane (meth)acrylate polymer 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 curable composition has a solid content concentration of 5 to 90 wt%.

[10] The curable composition according to any one of [7] to [9], wherein in the polymerization component of the curable composition, the ratio of the chemical structure represented by the formula (1) is 5 to 60 wt%.

[11] A cured product of the curable composition according to any one of [7] to [10].

[12] A laminate having a cured product of the curable composition according to any one of [7] to [10] on a substrate.

[13] A head lamp lens having, on a substrate, a cured product of the curable composition according to [11].

[14] A glazing material having, on a substrate, a cured product of the curable composition according to [11].

[15] A decorative film having, on a substrate, a cured product of the curable composition according to [11].

[16] A step of applying the urethane (meth)acrylate polymer according to any one of [1] to [6] or the curable composition according to any one of [7] to [10] on a substrate, the urethane (meth) A method for producing a film, comprising: a step of irradiating an acrylate polymer or the curable composition with an active energy ray to obtain a laminate having a cured product; and a step of stretching the laminate.

[17] A method for producing a urethane (meth)acrylate polymer in which the following compound (A) and the following compound (B) are reacted to obtain a precursor of a urethane polymer, and then the following compound (C) is reacted.

Compound (A): polyisocyanate

Compound (B): a polyol represented by the following formula (5)

[In the formula, A represents a single bond or a methylene group, 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 alkoxyylene group, or an arylene group.]

Compound (C): a compound having a hydroxyl group and a (meth)acryloyl group

[18] The urethane (meth)acrylate according to [17], wherein the compound (A) and the compound (B) are further reacted with the following compound (D) to obtain a precursor of a urethane polymer, and then the compound (C) is reacted. A method of making a polymer.

Compound (D): an aliphatic polyol having a molecular weight of 500 or less

ADVANTAGE OF THE INVENTION According to this invention, the urethane (meth)acrylate polymer from which the bleed-out of a ultraviolet absorber is prevented and the coating film excellent in weather resistance, abrasion resistance, and transparency is obtained, and a curable composition containing this are obtained. In addition, it is possible to provide a laminate and a decorative film having a layer including the cured product on the surface.

In the present invention, "(meth)acrylate" is a generic term for acrylate and methacrylate, meaning one or both of acrylate and methacrylate, "(meth)acryloyl", "(meth) The same is true for 'acrylic'.

[Urethane (meth)acrylate polymer]

The urethane (meth)acrylate polymer of this invention has a chemical structure represented by following formula (1).

In Formula (1), A is a single bond, or the methylene group which may have a substituent, an alkylene group, -O- group, -NH- group, -S- group, -SO- group, or -SO ₂ - group any of these should be A methylene group and an alkylene group are preferable and a methylene group is more preferable at the point which prevents the transparency of the hardened|cured material containing the urethane (meth)acrylate polymer of this invention, and the bleed-out from the hardened|cured material of an ultraviolet absorber.

In Formula (1), R<^1> , R<^2> , R<^3>, and R<^4> should just be any independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a halogen atom. A hydrogen atom, an alkyl group, and an alkoxy group are preferable at the point of preventing the transparency of the hardened|cured material of the urethane (meth)acrylate polymer or curable composition of this invention and bleed-out from the hardened|cured material of bisbenzotriazolylphenol skeleton.

In Formula (1), R<^5> and R<^6> may be the same or different, and any of an alkylene group, an alkoxyylene group, and an arylene group may be sufficient. An alkylene group and a methylene group are preferable from the point of preventing the transparency of the hardened|cured material of the urethane (meth)acrylate polymer or curable composition of this invention, and the bisbenzotriazolyl phenol skeleton from bleeding out from the hardened|cured material.

In the urethane (meth)acrylate polymer of the present invention, a bisbenzotriazolylphenol skeleton acting as an ultraviolet absorber is inserted through a chemically stable urethane bond in the molecular chain of the polymer.

Since the bisbenzotriazolyl phenol skeleton has a structure in which benzotriazolyl phenol is dimerized, the ultraviolet absorbing power per unit weight is high, and high weather resistance can be provided in a small amount.

Further, in the present invention, since the bisbenzotriazolylphenol skeleton is inserted through a urethane bond, the bisbenzotriazolylphenol skeleton does not easily bleed out due to hydrolysis or the like, so that it has excellent long-term weather resistance.

Chemical structure represented by formula (1) in terms of preventing bleed-out from the cured product of the cured film obtained by curing the urethane (meth) acrylate polymer of the present invention and the curable composition using the same and the bisbenzotriazolyl phenol skeleton It is preferable that it is a chemical structure represented by following formula (2).

The ratio of the chemical structure represented by the formula (1) in the urethane (meth)acrylate polymer of the present invention from the viewpoint of excellent transparency, weather resistance and scratch resistance of the cured product is preferably 5 wt% or more, and 20 wt% or more This is more preferable. Moreover, 60 weight% or less is preferable, and 35 weight% or less is more preferable.

It is preferable that the urethane (meth)acrylate polymer of this invention has a chemical structure represented by following formula (3).

The urethane (meth)acrylate polymer of the present invention has a chemical structure represented by formula (3), at least among a chemical structure represented by the following formula (4-1) and a chemical structure represented by the following formula (4-2) By including one, the transparency of the cured product can be improved, and when a urethane (meth) acrylate polymer having a bisbenzotriazolyl phenol skeleton is used as a curable composition, the solubility of the urethane (meth) acrylate polymer in an organic solvent can be improved. can

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, but is 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. Moreover, X<^1> becomes like this. Preferably it is an aliphatic structure with a molecular weight of 14 or more, More preferably, it is an aliphatic structure of 28 or more. X ¹ corresponds to a residue having a hydroxyl group bonded to the aliphatic structure of the compound (B) described later, and may be a linear aliphatic structure, a branched aliphatic structure, or an alicyclic structure.

In Formula (3), although n is an integer of 2-8, n becomes like this. Preferably it is 2-6, More preferably, it is 2-4.

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 chemical structure represented by the formula (3) A chemical structure becomes following formula (4-2).

That is, more specifically, as a chemical structure represented by Formula (3), it contains 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). desirable.

The urethane (meth)acrylate polymer of the present invention has a chemical structure represented by formula (3), at least among a chemical structure represented by the following formula (4-1) and a chemical structure represented by the following formula (4-2) It is preferable to include one.

(In formula (4-1), (4-2) of, X ¹ has the same meaning as X ¹ in the formula (3).)

Moreover, the urethane (meth)acrylate polymer of this invention contains the structural unit derived from the compound which has a hydroxyl group and a (meth)acryloyl group. As a compound which has a hydroxyl group and a (meth)acryloyl group, For example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, addition reaction product of 2-hydroxyethyl (meth) acrylate and caprolactone, 4-hydroxybutyl (meth) acrylate and Addition reaction product of caprolactone, bisphenol A diglycidyl ether diacrylate, glycol mono (meth) acrylate, glycerin (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate , pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[Weight Average Molecular Weight (Mw)]

500 or more are preferable and, as for the weight average molecular weight (Mw) of the urethane (meth)acrylate polymer of this invention, 10,000 or more are more preferable. Moreover, 30,000 or less are preferable and 20,000 or less are more preferable.

When the weight average molecular weight of a urethane (meth)acrylate polymer is the said range, transparency in the solution state of a urethane (meth)acrylate polymer or a curable composition, and the abrasion resistance of a cured film become favorable.

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

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 is obtained by reacting the following compound (A) and the following compound (B) to obtain a precursor of a urethane polymer, and then reacting the following compound (C) with it.

Compound (A): polyisocyanate

Compound (B): a polyol represented by the following formula (5)

[In the formula, A represents a single bond or a methylene group, 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 alkoxyylene group, or an arylene group.]

Compound (C): a compound having a hydroxyl group and a (meth)acryloyl group

In addition, the urethane (meth)acrylate polymer of the present invention is obtained by reacting a polyol other than the compound (B) with the compound (A) and the compound (B) to obtain a precursor of the urethane polymer, and then the compound (C) may be 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, 1,14-tetradecanediol, 1,16- diols having a linear aliphatic structure such as hexadecanediol; 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 - diols having a branched aliphatic structure such as pentanediol and 1,8-nonanediol; compounds having a branched aliphatic structure such as trimethylolpropane, glycerin, sorbitol, mannitol and pentaerythritol and three or more hydroxyl groups bonded thereto; and diols having an alicyclic structure such as cyclopropanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, tricyclodecanediol, and adamantyldiol; Compound (D)) is preferred.

Further, in the present invention, when performing the reaction to obtain a precursor of a urethane polymer by reacting the compound (A) and the compound (B), a compound having two or more active hydrogens reacting with an isocyanate group may be added as a chain extender. .

[Compound (A)]

As polyisocyanate of the said compound (A), linear aliphatic polyisocyanate, aromatic polyisocyanate, alicyclic polyisocyanate, etc. are mentioned. Among these, chain|strand-shaped alicyclic polyisocyanate is preferable at the point which improves the weather resistance and hardness of the hardened|cured material obtained.

As said chain aliphatic polyisocyanate, For example, Aliphatic diisocyanate, such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, and aliphatic tris, such as tris (isocyanate hexyl) isocyanurate, isocyanate is mentioned.

It is preferable to have a C1-C6 linear or branched alkylene group from the point of improving the weather resistance and hardness of the hardened|cured material obtained.

These may be used only by 1 type, and may be used in combination of 2 or more type.

As said aromatic polyisocyanate, aromatic diisocyanate, such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, naphthalene diisocyanate, is mentioned, for example. From the viewpoint of increasing the mechanical strength of the cured film of the urethane (meth)acrylate polymer or the curable composition, the aromatic polyisocyanate is preferably tolylene diisocyanate and diphenylmethane diisocyanate. These may be used only by 1 type, and may be used in combination of 2 or more type.

Examples of the polyisocyanate having an alicyclic structure include diisocyanate having an alicyclic structure such as bis(isocyanatomethyl)cyclohexane, cyclohexanediisocyanate, bis(isocyanatecyclohexyl)methane, and isophorone diisocyanate. And triisocyanate which has alicyclic structures, such as tris (isocyanate isophorone) isocyanurate, is mentioned. Among these, as said alicyclic polyisocyanate, isophorone diisocyanate is preferable. These may be used only by 1 type, and may be used in combination of 2 or more type.

As said alicyclic structure, C5 or more is preferable and C6 or more is more preferable. Moreover, C15 or less is preferable, and C13 or less is more preferable. Moreover, as said alicyclic structure, it is preferable that it is a cycloalkylene group.

The said compound (A) may use 1 type and may use 2 or more types.

In the urethane (meth)acrylate polymer of the invention, the compound (A) is preferably 5% by weight or more, and more preferably 25% by weight or more, from the viewpoint of excellent transparency, weather resistance, and scratch resistance of the cured product. Moreover, 60 weight% or less is preferable at the point which is excellent in transparency of hardened|cured material, weather resistance, and abrasion resistance, and 50 weight% or less is more preferable.

[Compound (B)]

The said compound (B) is a polyol represented by following formula (5).

[In the formula, A represents a single bond or a methylene group, 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 alkoxyylene group, or an arylene group.]

The urethane (meth)acrylate polymer of the present invention and the compound represented by the formula (5) in terms of preventing bleed-out from the cured product of the cured product and transparency of the cured product obtained by curing the curable composition using the same (B) is preferably a polyol represented by the following formula (10).

The ratio of the chemical structure represented by the formula (5) in the urethane (meth)acrylate polymer of the present invention from the viewpoint of excellent transparency, weather resistance and scratch resistance of the cured product is preferably 5 wt% or more, and 20 wt% or more This is more preferable. Moreover, 60 weight% or less is preferable, and 35 weight% or less is more preferable.

As the compound (B), Dainsorb T-33 manufactured by Daiwa Kasei Co., Ltd. can be used as a commercial item.

5 weight% or more is preferable with respect to all the polyol components which can be used as a raw material of a urethane (meth)acrylate polymer, and, as for a compound (B) at the point of improving the weather resistance of the cured film of this invention, 25 weight% or more is more preferable Do. Moreover, 95 weight% or less is preferable at the point excellent in transparency in a solution state, transparency of a cured film, and abrasion resistance, and 90 weight% or less is more preferable.

[Compound (C)]

Since the compound having a hydroxyl group and a (meth)acryloyl group of the compound (C) has a (meth)acryloyl group, it forms a crosslinked structure with other components by irradiation with active energy rays and acts as a UV absorber. Bleed-out of triazolylphenol skeleton can be suppressed.

As said compound (C), 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl ( meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, an addition reaction product of 2-hydroxyethyl (meth) acrylate and caprolactone, an addition reaction product of 4-hydroxybutyl (meth) acrylate and caprolactone, Bisphenol A diglycidyl ether diacrylate, glycol mono (meth) acrylate, glycerin (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri ( A meth)acrylate, a dipentaerythritol penta (meth)acrylate body, etc. are mentioned.

Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy at the point of making the mechanical strength of the cured film obtained and sclerosis|hardenability of a urethane (meth)acrylate polymer favorable. Butyl (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. are preferable.

In addition, as the compound (C), an epoxy (meth)acrylate having a chain aliphatic structure having 2 to 12 carbon atoms can be used. As a raw material for synthesizing the epoxy (meth)acrylate, for example, ethylene glycol diglycidyl ether, 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1, 5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,7-heptanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9- linear aliphatic structures such as nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 1,11-undecanediol diglycidyl ether, and 1,12-dodecanediol diglycidyl ether; an epoxy compound having; Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol The epoxy compound etc. which have branched aliphatic structures, such as tetraglycidyl ether, are mentioned.

Among these, as said epoxy compound from the point of sclerosis|hardenability of a urethane (meth)acrylate polymer, 1, 4- butanediol diglycidyl ether, 1, 5- pentanediol diglycidyl ether, 1, 6- hexanediol di Epoxy compounds having a chain aliphatic structure having 4 to 6 carbon atoms, such as glycidyl ether, are preferable.

Compound (C) can be obtained by performing a ring-opening addition reaction of the compound which has a (meth)acryloyl group and a carboxyl group to the said epoxy compound. As a compound which has the said (meth)acryloyl group and a carboxyl group, the compound which has a (meth)acryloyl group and a carboxyl group can be used. As said compound, For example, (meth)acrylic acid; carboxyalkyl (meth)acrylates such as carboxymethyl (meth)acrylate, carboxyethyl (meth)acrylate, carboxypropyl (meth)acrylate, and carboxypropyl (meth)acrylate; Hydroxyalkyl (meth)acrylates, such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate, and anhydride, such as phthalic anhydride, succinic anhydride, and maleic anhydride A reaction product with carboxylic acid, etc. are mentioned. These may be used only by 1 type, and may be used in combination of 2 or more type.

Among these, as a compound which has a (meth)acryloyl group and a carboxyl group from the sclerosis|hardenability point of a urethane (meth)acrylate polymer, acrylic acid is preferable.

As an epoxy (meth)acrylate of compound (C), For example, Kayarad (trademark) R-167 (made by Nippon Kayaku Co., Ltd.), NK Oligo EA-5520, EA-5321 (made by Shin-Nakamura Chemical) etc. can be heard A compound (C) may use 1 type and may use 2 or more types.

In addition, from the viewpoint of further improving the scratch resistance of the cured film of the curable composition of the present invention and obtaining good stretchability after curing, the compound (C) is used as a raw material for the urethane (meth)acrylate polymer with respect to all polyol components that can be used. 4 weight% or more is preferable, and 8 weight% or more is more preferable. Moreover, 25 weight% or less is preferable and 18 weight% or less is more preferable.

[Compound (D)]

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

As the compound (D), for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, etc. 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 - diols having a branched aliphatic structure such as pentanediol and 1,8-nonanediol; compounds having a branched aliphatic structure such as trimethylolpropane, glycerin, sorbitol, mannitol and pentaerythritol and three or more hydroxyl groups bonded thereto; Diols having an alicyclic structure, such as cyclopropanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, tricyclodecanediol, and adamantyldiol, etc. are mentioned.

Among these, those having a linear aliphatic structure are preferable from the viewpoint of excellent scratch resistance of the cured film, and in particular, it is preferable to use at least one selected from ethylene glycol, 1,4-butanediol, and 1,12-dodecanediol. Do. Among these, ethylene glycol is preferable at the point of chemical resistance, and 1,12- dodecanediol is preferable at the point of abrasion resistance and flexibility. Moreover, in order to improve the weather resistance of a cured film more, it is necessary to introduce|transduce more compound (B) into a urethane (meth)acrylate polymer. For that purpose, the compound (D) preferably contains a diol having a branched aliphatic structure. As diols having a branched aliphatic structure, propylene glycol, 1,3-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, etc. These are more preferable, and 1,3-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, etc. are still more preferable. A compound (D) may use 1 type and may use 2 or more types.

In terms of improving the chemical resistance and scratch resistance of the cured product of the urethane (meth)acrylate polymer of the present invention, the compound (D) is 3% by weight based on the total polyol component that can be used as a raw material of the urethane (meth)acrylate polymer. More preferably, 10 weight% or more is more preferable.

Further, from the viewpoint of increasing the content of the formula (1) in the urethane (meth)acrylate polymer, the compound (D) is 99.95% by weight or less with respect to all polyol components that can be used as a raw material of the urethane (meth)acrylate polymer. is preferable, and 90 weight% or less is more preferable.

[Polyols other than the compound (B) and the compound (D)]

Examples of the polyol other than the compound (B) and the compound (D) include an aromatic polyol having a molecular weight of 500 or less, and a high molecular weight polyol having a molecular weight of more than 500.

As a polyol which has the said molecular weight 500 or less aromatic structure, bishydroxyethoxybenzene, bishydroxyethyl terephthalate, bisphenol A etc. are mentioned, for example. These may be used only by 1 type, and may be used in combination of 2 or more type.

Examples of the high molecular weight polyol having a molecular weight exceeding 500 include polyether polyol, polyester polyol, polyether ester polyol, polycarbonate polyol, polyolefin polyol, and silicone polyol. These may be used only by 1 type, and may be used in combination of 2 or more type.

When using the high molecular weight polyol, polycarbonate polyol is preferred. The polycarbonate polyol is, for example, at least one carbonate compound selected from the group consisting of alkylene carbonate, diaryl carbonate, and dialkyl carbonate, diols and polyether polyols. It can be obtained by reacting at least one of Examples of the diol include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1 ,4-cyclohexanedimethanol, 1,12-dodecanediol, diethylene glycol, dipropylene glycol, polybutadienediol, etc. are mentioned. Among these, it is preferable to include at least one selected from 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol from the viewpoint of improving scratch resistance. The polycarbonate polyol can be obtained as a commercial item. As a commercial item, Duranol (trademark) T4671 (made by Asahi Kasei Corporation), Duranol (trademark) T4691 (made by Asahi Chemical Corporation), Duranol (trademark) 5651 (made by Asahi Chemical Corporation), Dew, for example, is a commercial item, Ranol (trademark) 6001 (made by Asahi Kasei Corporation) etc. are mentioned.

[Chain Extender]

Moreover, in this invention, when carrying out the reaction which makes a compound (A) and a compound (B) react and obtains a precursor of a urethane polymer, you may add the compound which has two or more active hydrogens which react with an isocyanate group as a chain extender.

Examples of the chain extender include a low-molecular-weight diamine compound having a number average molecular weight of 500 or less, for example, 2,4- or 2,6-tolylene diamine, xylylene diamine, 4,4'-diphenyl aromatic diamines such as methanediamine; ethylenediamine, 1,2-propylenediamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, 2,2,4- or 2; aliphatic diamines such as 4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine; and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4,4'-dicyclohexylmethanediamine, isopropylidenecyclohexyl-4,4'-diamine, 1,4-diamino and alicyclic diamines such as cyclohexane, 1,3-bisaminomethylcyclohexane and tricyclodecanediamine. These may be used individually by 1 type, and may be used in combination of 2 or more type.

In addition, in the case of using a chain extender, the amount of the total polyol used is preferably 70 mol% or more with respect to the total amount of the compound (B) and the compound (C), and the compound combined with the other polyol component and the chain extender, 95 mol% or more is more preferable.

In the present invention, the compound (B) and the polyol other than the compound (B) are reacted under conditions in which an isocyanate group becomes excessive to obtain a precursor of a urethane polymer having an isocyanate terminal, and then a precursor of a urethane polymer having an isocyanate terminal, and It is preferable to react the said compound (C).

In addition, when compound (C) has two or more hydroxyl groups, it is preferable to use compound (C) in excess with respect to all the isocyanate groups of a urethane (meth)acrylate polymer.

When manufacturing a urethane (meth)acrylate polymer from the viewpoint of being able to control the molecular weight of a urethane (meth)acrylate polymer, the compound (C) and the compound containing the functional group which reacts with the isocyanate group in other raw materials 2 mol% or more is preferable and, as for the usage-amount of compound (C) with respect to the usage-amount, 10 mol% or more is more preferable. Moreover, 70 mol% or less is preferable and 50 mol% or less is more preferable. When the proportion of the compound (C) is large, the molecular weight of the urethane (meth)acrylate polymer tends to become small, and when the proportion of the compound (C) is small, the molecular weight of the urethane (meth)acrylate polymer tends to become large.

In the method for producing the urethane (meth)acrylate polymer of the present invention, an organic solvent can be used for the purpose of adjusting the viscosity. As the organic solvent, any known organic solvent can be used within the range in which the effect of the present invention is obtained. Preferred examples of the organic solvent include toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, and dimethylformamide. The said organic solvent may be used individually by 1 type, and may mix and use 2 or more types. The said organic solvent can be used normally with respect to the total mass of a urethane (meth)acrylate polymer in 300 weight% or less.

In the production of the urethane (meth)acrylate polymer, a catalyst may be used for the urethanation reaction. Examples of the catalyst include tin-based catalysts such as dibutyltin laurate, dibutyltin dioctate, dioctyltin dilaurate, and dioctyltin dioctate; Bismuth catalysts, such as bismuth tris (2-ethylhexanoate), etc. are mentioned. Among these, the catalyst is preferably dioctyltin dilaurate or bismutris(2-ethylhexanoate) from the viewpoints of environmental adaptability, catalytic activity, storage stability, and the like. A catalyst may be used individually by 1 type, and may mix and use 2 or more types. 2,000 ppm or less is preferable with respect to the total input amount of a raw material, and, as for the usage-amount of a catalyst, 1,000 ppm or less is more preferable. Moreover, 10 ppm or more is preferable, and 30 ppm or more is more preferable.

Moreover, in the case of manufacture of 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, amines such as phenothiazine and diphenylamine, and copper dibutyldithiocarbamate. copper salts, such as manganese salts, such as manganese acetate, a nitro compound, a nitroso compound, etc. are mentioned. Among these, as for the said polymerization inhibitor, phenols are preferable. The said polymerization inhibitor may be used individually by 1 type, and may mix and use 2 or more types. 3,000 ppm or less is preferable with respect to the total input amount of a raw material, and, as for the usage-amount of a polymerization inhibitor, 1,000 ppm or less is more preferable. Moreover, 50 ppm or more is preferable, and 100 ppm or more is more preferable.

Production of a urethane (meth)acrylate polymer WHEREIN: From the viewpoint of a reaction rate becoming high and manufacturing efficiency improving, 20 degreeC or more is preferable and, as for the reaction temperature of a urethanation reaction, 40 degreeC or more is more preferable. Moreover, 120 degrees C or less is preferable and, as for the reaction temperature, 120 degrees C or less is more preferable at the point that side reactions, such as an allophanation reaction, become difficult to occur. Moreover, when the said organic solvent is included in a reaction system, it is preferable that reaction temperature is below the boiling point of the organic solvent. The reaction time is usually 5 to 20 hours.

[Curable composition]

It is preferable that the curable composition of this invention contains the said 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 40% by weight or more, more preferably 60% by weight or more, based on the total amount of all components (solid content) excluding the organic solvent in the curable composition. Do. In addition, the upper limit of content of a urethane (meth)acrylate polymer is 100 weight%. Since the curing rate and surface curability of a curable composition become favorable that content of a urethane (meth)acrylate polymer is in the said range, and a tack|tack does not remain, it is preferable.

Moreover, from the point which is excellent in transparency of hardened|cured material, weather resistance, and abrasion resistance, 10 weight% or more of the structural ratio of the compound represented by the said Formula (1) among the polymerization components of a curable composition is preferable. Moreover, 25 weight% or less is preferable.

In addition, the polymerization component of a curable composition is a component which has an unsaturated double bond which has polymerizability with respect to active energy ray, The urethane (meth)acrylate polymer contained in the curable composition, an active energy ray-curable polymer, and an active energy ray-reactive monomer. means etc.

[Organic solvent]

The organic solvent can be used for adjustment of the viscosity of the coating material at the time of forming the coating film of the curable composition of this invention.

As for the solid content concentration of the said curable composition, 5-90 weight is preferable. 10 weight% or more is preferable, and 15 weight% or more is more preferable. Moreover, 80 weight% or less is preferable, and 60 weight% or less is more preferable.

As the organic solvent, a known organic solvent may be used. From the viewpoint of the solubility of the urethane (meth)acrylate polymer, the solubility parameter of the organic solvent (hereinafter, referred to as "SP value") is preferably 8.0 or more, and more preferably 11.5 or less from the viewpoint of the transparency of the solution.

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), 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), etc. have. In the present invention, the SP value is calculated by the method proposed by Fedors et al. Specifically, it is a value obtained with reference to "POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (pages 147 to 154)". In addition, when using a mixed solvent, SP value means the value as a mixture.

[Other Ingredients]

The curable composition of the present invention, as other components, an active energy ray-reactive monomer, an active energy ray-curable polymer (excluding the urethane (meth)acrylate polymer of the present invention), a polymerization initiator, a photosensitizer, an epoxy compound, and You may also contain other additives, etc.

As said active energy ray-reactive monomer, any well-known active energy ray-reactive monomer can be used in the range from which the effect of this invention is acquired. These active energy ray-reactive monomers are used for the purpose of adjusting the hydrophilicity of the urethane (meth)acrylate polymer of the present invention, the hardness of the cured product when the resulting composition is used as a cured product, and physical properties such as the elongation of the cured product. An active energy ray-reactive monomer may be used individually by 1 type, and may mix and use 2 or more types.

Examples of the active energy ray-reactive monomer include vinyl ethers, (meth)acrylamides, and (meth)acrylates, and specifically, for example, styrene, α-methylstyrene, α - Aromatic vinyl monomers, such as chlorostyrene, vinyltoluene, and divinylbenzene; vinyl ester monomers such as vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and divinyl adipate; vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; allyl compounds such as diallyl phthalate, trimethylolpropane diallyl ether, and allyl glycidyl ether; (meth)acrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl ( (meth)acrylamides, such as meth)acrylamide, Nt-butyl (meth)acrylamide, (meth)acryloylmorpholine, and methylenebis(meth)acrylamide; (meth)acrylic acid, (meth)methyl acrylate, (meth)ethyl acrylate, (meth)acrylic acid propyl, (meth)acrylic acid-n-butyl, (meth)acrylic acid-i-butyl, (meth)acrylic acid-t-butyl, (meth)acrylic acid hexyl, (meth)acrylic acid-2-ethylhexyl, (meth)acrylic acid lauryl, (meth)acrylic acid stearyl, (meth)acrylic acid tetrahydrofurfuryl, (meth)acrylic acid morpholyl, (meth)acrylic acid -2-hydroxyethyl, (meth)acrylic acid-2-hydroxypropyl, (meth)acrylic acid-4-hydroxybutyl, (meth)acrylic acid glycidyl, (meth)acrylic acid dimethylaminoethyl, (meth)acrylic acid di Ethylaminoethyl, (meth) acrylate benzyl, (meth) acrylate cyclohexyl, (meth) acrylate phenoxyethyl, (meth) acrylate tricyclodecane, (meth) acrylate dicyclopentenyl, (meth) acrylate dicyclopentenyl Monofunctional (meth)acrylates such as oxyethyl, (meth)acrylic acid dicyclopentanyl, (meth)acrylic acid allyl, (meth)acrylic acid-2-ethoxyethyl, (meth)acrylic acid isobornyl, (meth)acrylic acid phenyl ; And di(meth)acrylic acid ethylene glycol, di(meth)acrylic acid diethylene glycol, di(meth)acrylic acid triethylene glycol, di(meth)acrylic acid tetraethylene glycol, di(meth)acrylic acid polyethylene glycol (n = 5 to 14) , Di(meth)acrylic acid propylene glycol, di(meth)acrylic acid dipropylene glycol, di(meth)acrylic acid tripropylene glycol, di(meth)acrylic acid tetrapropylene glycol, di(meth)acrylic acid polypropylene glycol (n = 5 to 14) ), di(meth)acrylic acid-1,3-butylene glycol, di(meth)acrylic acid-1,4-butanediol, di(meth)acrylic acid polybutylene glycol (n=3 to 16), di(meth)acrylic acid Poly(1-methylbutylene glycol) (n=5 to 20), di(meth)acrylic acid-1,6-hexanediol, di(meth)acrylic acid-1,9-nonanediol, di(meth)acrylic acid neopentyl Glycol, hydroxypivalate neopentyl glycol di(meth)acrylic acid ester, di(meth)acrylic acid dicyclopentanediol, di(meth)acrylic acid 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-hexanediol diglycidyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethyl Allpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane trioxyethyl (meth) ) acrylate, trimethylolpropanetrioxypropyl (meth)acrylate, trimethylolpropane polyoxyethyl (meth)acrylate, trimethylolpropane polyoxypropyl (meth)acrylate, tris(2-hydroxyethyl)isocy Anurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acryl rate, propylene oxide Addition bisphenol A di(meth)acrylate, propylene oxide Addition bisphenol F di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, bisphenol A epoxydi(meth)acrylate, bisphenol F epoxydi(meth)acrylate ) polyfunctional (meth)acrylates such as acrylates; and the like.

Among these, (meth)acryloylmorpholine, (meth)acrylic acid tetrahydrofurfuryl, (meth)acrylic acid benzyl, (meth)acrylic acid cyclohexyl, (meth) Ring structures in molecules, such as trimethylcyclohexyl acrylate, phenoxyethyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, and (meth)acrylamide A monofunctional (meth)acrylate having Moreover, since the mechanical strength of the cured film obtained becomes favorable, di(meth)acrylic acid-1,4-butanediol, di(meth)acrylic acid-1,6-hexanediol, di(meth)acrylic acid-1,9- nonanediol , Di (meth) acrylic acid neopentyl glycol, di (meth) acrylic acid tricyclodecane, 1,4-cyclohexane dimethanol 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, pentaeryth Ritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Polyfunctional (meth)acrylates, such as these are preferable. Moreover, from the point which the ductility of the cured film obtained becomes favorable, di(meth)acrylic-acid polyethylene glycol (n=5-14), di(meth)acrylic-acid polypropylene glycol (n=5-14), di(meth)acrylic-acid polybutyl Polyether (meth)acrylates, such as ren glycol (n=3-16) and di(meth)acrylic acid poly(1-methylbutylene glycol) (n=5-20), are preferable.

From the viewpoint of adjusting the viscosity of the curable composition and adjusting physical properties such as hardness of the obtained cured product, the content of the active energy ray-reactive monomer relative to the total amount of all components (solid content) excluding the organic solvent of the curable composition is 50% by weight or less is preferable, and 30 weight% or less is more preferable.

Examples of the active energy ray-curable polymer include an epoxy (meth) acrylate polymer, an acrylic (meth) acrylate polymer, a polyester (meth) acrylate polymer, a polycarbonate (meth) acrylate polymer, and polybutadiene. (meth)acrylate-based polymers and polyether (meth)acrylates (except those described in the active energy ray-reactive monomers above.) are mentioned. An active energy ray-curable polymer may be used individually by 1 type, and may mix and use 2 or more types.

The said polymerization initiator is mainly used for the purpose of improving the polymerization efficiency of the polymerization reaction which advances by irradiation with active energy rays, such as an ultraviolet-ray and an electron beam. As a polymerization initiator, any well-known radical photopolymerization initiator can be used in the range from which the effect of this invention is acquired.

A polymerization initiator may be used individually by 1 type, and may mix and use 2 or more types. Moreover, you may use together a radical photopolymerization initiator and a photosensitizer.

Examples of the radical photopolymerization initiator include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis(diethylamino)benzophenone, 4-phenylbenzophenone, methylorthobenzoylbenzoate, thiok. Santhone, diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methylbenzoyl formate, 2-methyl-1- [4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2 ,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2-hydroxy-1-[4-[4] -(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl]-2-methyl-propan-1-one etc. are mentioned.

Among these, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,4 from the viewpoint that the curing rate is fast and the crosslinking density can be sufficiently increased. ,6-Trimethylbenzoyldiphenylphosphineoxide, and 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl]-2-methyl-propane -1-one is preferred, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-hydroxy-1-[4-[4-(2-hydroxy -2-methyl-propionyl)-benzyl]-phenyl]-2-methyl-propan-1-one is more preferable.

In addition, when the compound which has cationically polymerizable groups, such as an epoxy group, is contained in curable composition, the photocationic polymerization initiator may be contained together with the said radical photopolymerization initiator as a polymerization initiator. As a photocationic polymerization initiator, a well-known thing can be used in the range which does not impair the effect of this invention remarkably.

The content of the polymerization initiator is preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total weight of the polymerization component of the curable composition, from the viewpoint that the decrease in mechanical strength due to the decomposition product of the initiator does not easily occur.

The said photosensitizer can be used for the same objective as a polymerization initiator. Examples of the photosensitizer include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4 -Dimethylaminoacetophenone, etc. are mentioned. A photosensitizer may be used individually by 1 type, and may mix and use 2 or more types.

In the curable composition of the present invention, the content of the photosensitizer with respect to the total weight of the polymerization component of the curable composition is preferably 10% by weight or less, from the viewpoint that a decrease in mechanical strength due to a decrease in the crosslinking density does not easily occur, 5 weight% or less is more preferable.

Examples of the additive include fillers such as silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, talc, kaolin, metal oxide, metal fiber, iron, lead, and metal powder; carbon materials, such as fullerenes, such as carbon fiber, carbon black, graphite, carbon nanotube, and C60; Antioxidant, heat stabilizer, ultraviolet absorber, hindered amine light stabilizer (HALS), surface hydrophilic agent, antistatic agent, slippery agent, plasticizer, mold release agent, defoaming agent, leveling agent, anti-settling agent, surfactant, thixotropy imparting agent, Modifiers, such as a flame retardant, a flame-retardant auxiliary agent, a polymerization inhibitor, and a silane coupling agent; Coloring agents, such as a pigment, dye, and a color adjuster, etc. are mentioned. The said additive may be used individually by 1 type, and may mix and use 2 or more types.

In the curable composition of the present invention, since a decrease in mechanical strength due to a decrease in crosslinking density is unlikely to occur, the content of the additive is preferably 10% by weight or less, and 5% by weight based on the total weight of the polymerization component of the curable composition. % or less is more preferable.

There is no limitation in particular as a method of making the curable composition of this invention contain the said additive, A conventionally well-known mixing, dispersion method, etc. are mentioned. In addition, in order to more reliably disperse the additive in the curable composition, for example, a twin roll, a triaxial roll, a bead mill, a ball mill, a sand mill, a quartz mill, a trom mill, a sand grinder, a Segvari attritor, The method of processing with a planetary stirrer, a high-speed impeller disperser, a high-speed stone mill, a high-speed impact mill, a kneader, a homogenizer, an ultrasonic disperser, etc. is mentioned.

[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, from the viewpoints of handleability, coatability, moldability, and three-dimensional formability. Moreover, 50,000 mPa*s or less is preferable, and 10,000 mPa*s or less is more preferable.

The viscosity of the curable composition can be adjusted, for example, by the content of the urethane (meth)acrylate polymer according to the present invention, the type of the additive, the blending ratio thereof, and the like.

In addition, the viscosity measured at 25 degreeC in the E-type viscometer (rotor 1 degree 34' x 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, a curtain flow coater method, a roll coater method, a spray method, a gravure coater method, a comma coater method, a reverse roll method Known methods such as a coater method, a lip coater method, a die coater method, a slot die coater method, an air knife coater method, and a dip coater method are applicable, among which the bar coater method and the gravure coater method are preferable. The urethane (meth)acrylate polymer of this invention can also be used independently by the said coating method.

As a base material to which the urethane (meth)acrylate polymer of this invention or the curable composition of this invention is coated, For example, Polyester, such as polyethylene terephthalate and polybutylene terephthalate; polyolefins such as polypropylene and polyethylene; In addition, various plastics, such as nylon, polycarbonate, and a (meth)acrylic polymer, glass, a metal, etc. are mentioned. Among these, polyethylene terephthalate is preferable. Moreover, about the shape of these base materials, flat things, such as a film form and a sheet form, may be sufficient, and what was shape|molded into various shapes may be sufficient.

[Cured product, laminate]

The hardened|cured material of this invention is obtained by irradiating an active energy ray to the urethane (meth)acrylate polymer of this invention, or the curable composition of this invention. Examples of the active energy rays include infrared rays, visible rays, ultraviolet rays, X rays, electron rays, α rays, β rays, and γ rays. It is preferable to use an electron beam or an ultraviolet-ray from a viewpoint of apparatus cost or productivity. As the 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-state laser, a xenon lamp, a high-frequency induction mercury lamp, sunlight, etc. Can be used.

The irradiation amount of an active energy ray can be suitably selected according to the kind of active energy ray. For example, when hardening|curing by electron beam irradiation, it is preferable that the irradiation amount is 1-15 Mrad. Moreover, when hardening|curing by ultraviolet irradiation, it is preferable that it is 50-1,500 mJ/cm<2>.

When the urethane (meth)acrylate polymer of the present invention or the curable composition of the present invention is cured, any atmosphere of an inert gas such as air, nitrogen or argon may be used. Moreover, you may irradiate in the sealed space between a film or glass and a metal mold|die.

Although the thickness of hardened|cured material is suitably determined according to the intended use, 1 micrometer or more is preferable and, as for the thickness of hardened|cured material, 2 micrometers or more are preferable at the point which expression of designability and functionality after three-dimensional processing becomes favorable. Moreover, 100 micrometers or less are preferable, 50 micrometers or less are more preferable, and, as for the thickness of hardened|cured material from the point which sclerosis|hardenability and three-dimensional processing aptitude become favorable, 20 micrometers or less are still more preferable.

The laminate of the present invention can be obtained by curing the urethane (meth)acrylate polymer of the present invention or the curable composition of the present invention on a substrate. The laminate of the present invention may have a layer other than the cured product of the present invention between the base material and the cured product of the present invention, or may have it outside the laminate of the present invention. Moreover, the said laminated body may have a base material or the hardened|cured material of this invention in multiple layers.

As a method of obtaining a laminate having a multilayer cured product, all layers are laminated in an uncured state and then cured with an active energy ray, the lower layer is cured with an active energy ray or semi-cured, and then the upper layer is applied, , a method of curing with an active energy ray again, a method of applying each layer to a substrate, and then bonding the layers together in an uncured or semi-cured state can be applied. , a method of curing with an active energy ray after lamination in an uncured state is preferred. As a method of laminating in an uncured state, a known method such as sequential application in which the upper layer is applied over and over after the lower layer is applied or simultaneous multi-layer coating in which two or more layers are applied simultaneously from multiple slits can be applied. do not limit

The laminate of the present invention can be suitably used as a film for replacing paint. For example, it is possible to effectively apply to various members, such as building materials for interior/exterior use, automobiles, home appliances, and information and electronic materials. Moreover, since the weather resistance, bleed-out resistance, and abrasion resistance required for surface protection can be provided in one layer, and it becomes simple in a process, the laminated body of this invention is used suitably for a glazing member and a decorative film.

In the present invention, the decorative film is a film to which a design such as a wood grain pattern, a metal pattern, embossing, etc., various patterns, and a design such as a character, and decorations are applied by printing, painting, vapor deposition, coloring, or 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 irradiated with active energy rays to form a cured article, for use in automobile headlamp lenses , is suitably used for automotive polymer glass.

Since the hardened|cured material of this invention is excellent in stretchability, the laminated body of this invention can be extended|stretched and it can be used as a film. The manufacturing method of the said film is the process of apply|coating the urethane (meth)acrylate polymer of this invention or the curable composition of this invention on a base material, irradiating an active energy ray to this curable composition, The process of obtaining the laminated body which has a hardened|cured material It is preferable to include the process of extending|stretching the said laminated body.

In the manufacturing method of the said film, the process of apply|coating the urethane (meth)acrylate polymer of this invention or the curable composition of this invention on a base material, and irradiating an active energy ray to the said urethane (meth)acrylate polymer or the said curable composition. Each of the steps to obtain a cured product can be carried out under the conditions described above. In addition, in the manufacturing method of the said film, the process of extending|stretching a hardened|cured material is 60-200 degreeC normally, Preferably it can extend|stretch by heating under the conditions of 100-180 degreeC.

When the said film is used as a decorative film, as a shaping|molding method of a decorative film, well-known methods, such as insert molding, in-mold molding, overlay molding, blow molding, vacuum molding, can be used.

Example

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited by the Examples below.

[Method of measuring physical properties and properties]

Evaluation of a urethane (meth)acrylate polymer and a cured film was performed with the following method.

<Molecular Weight>

In GPC (“HLC-8120GPC” manufactured by Tosoh Corporation), using tetrahydrofuran (THF) as a solvent, polystyrene as a standard sample, and TSKgel superH1000+H2000+H3000 as a column, a liquid feed rate of 0.5 mL/min, a column oven temperature of 40°C , the weight average molecular weight Mw and the number average molecular weight Mn of the urethane (meth)acrylate polymer were measured.

<Transparency evaluation of curable composition>

Transparency of the curable composition was evaluated by visually confirming whether the curable composition obtained in the Example was transparent, cloudy, or insoluble about the external appearance after leaving it to stand for 1 day.

<Evaluation of cured product>

(evaluation sample)

After coating the curable aqueous substances obtained in Examples and Comparative Examples with a bar coater on a polyethylene terephthalate film, it was dried at 80° C. for 2 minutes, and UV irradiation device (US5-X1802-X1202, manufactured by Iwasaki Electric Co., Ltd.) ) was used, and was cured by irradiating ultraviolet rays with an accumulated irradiation amount of 1000 mJ/cm 2 (wavelength 315 to 380 nm) with a high-pressure mercury lamp of 160 W.

Furthermore, it cured at 23 degreeC for 1 day, and obtained the laminated body of about 5 micrometers in film thickness.

(Evaluation of coating film appearance)

The appearance of the coating film on the obtained laminate was visually confirmed whether it was transparent or cloudy, and the haze value H was measured. Haze value H was measured based on JISK7105 using the haze meter ("HAZE METER HM-65W" manufactured by Murakami Shikisai Kijutsu Genkyujo Co., Ltd.).

(weather resistance test (metal weather test))

With respect to the coating film on the laminate, by using the spectroscopic color system side (Konica Minolta Ltd., product name "Spectrophotometer CM-5") was measured for color tone b _0. Next, using a metal weather meter (manufactured by Daipla Wintes Co., Ltd., product name "Daipla Metal Weather KU-R4Ci-W"), under irradiation with an irradiation intensity of 80 mW/cm 2 , the following (1) and (2) , and (3) were conducted for 168 hours (14 cycles) and 336 hours (28 cycles) for a total of 12 hours each for a total of 4 hours as one cycle. Together with the works, the eye observation after the test with respect to the cured product, the cured product was measured hue b _1, the haze value H and after accelerated weathering test.

The color tone of the cured product was evaluated as _{b 1} -b _{0 .}

(1) Temperature 63°C, humidity 70%

(2) Temperature 70°C, humidity 90%

(3) Temperature 30°C, humidity 98% (with shower for 10 seconds before and after (3))

(Measurement of transmittance)

About the coating film on the obtained laminated body, using a spectrophotometer (manufactured by Hitachi High-Technologies Co., Ltd., product name "Recio Beam Spectrophotometer U-1900"), the baseline was made into a polyethylene terephthalate film (adhesion facilitating treatment completed). and transmittance (360 nm, 380 nm) was measured.

(Evaluation of scratch resistance)

The haze value before the abrasion test I, with respect to the coating film on the obtained laminate was measured by H _1. Next, in an atmosphere of 23 ° C., 55% RH, with an abrasion tester (manufactured by Toyo Seki Co., Ltd.), a 200 gf (per area 4 cm 2) weight was placed on steel wool #0000 and the surface of the coating film on the laminate was placed on 15 reciprocations. a haze value was measured after the H _2. The haze value H ₂ was set to be excellent in the scratch resistance is not more than 30. In addition, the said haze value was measured based on JISK7105 using the haze meter ("HAZE METER HM-65W" manufactured by Murakami Shikisai Kijutsu Genkyujo Co., Ltd.).

[Raw material, solvent]

The raw materials and solvents used in the following Examples and Comparative Examples and their abbreviations are as follows. (Compound (A))

IPDI: isophorone diisocyanate (product name "VESTANAT IPDI" manufactured by Evonik Degusa Japan)

(Compound (B))

· T-33: a polyol represented by the following formula (10) (trade name "Dainsorb T-33" manufactured by Daiwa Kasei Co., Ltd.)

T-35: polyol represented by the following formula (11) (product name "Dainsorb T-35" manufactured by Daiwa Kasei Co., Ltd.)

(Compound (C): a compound having a hydroxyl group and a (meth)acryloyl group)

·HEA: 2-hydroxyethyl acrylate (trade name "HEA" manufactured by Osaka Organic Co., Ltd.)

(Compound (D))

3MPD: 3-methyl-1,5-pentanediol

(organic solvent)

·MEK: methyl ethyl ketone (SP value: 9.0)

PGM: propylene glycol monomethyl ether (SP value: 11.3)

(polyfunctional acrylate)

V-300: A mixture (catalog value) containing 40 to 45 wt% of pentaerythritol triacrylate and 35 to 40 wt% of pentaerythritol tetraacrylate as other compounds (“bis” manufactured by Osaka Organic Co., Ltd.) Coat (registered trademark) 300”)

(radical photopolymerization initiator)

·Omn184: 1-hydroxy-cyclohexyl-phenyl-ketone ("Omnirad (registered trademark) 184" manufactured by IGM)

(Ultraviolet absorber)

TINUVIN479: Hydroxyphenyltriazine (HPT)-based UV absorber (manufactured by BASF)

(leveling agent)

・Polyflow No.75: (manufactured by Kyoesha Chemical)

[Synthesis Example 1]

In a four-neck flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 102 g of IPDI and 101 g of T-33 were put, and 203 g of methyl ethyl ketone, 0.20 g of dioctyltin dilaurate, and 0.25 g of methylhydroquinone were added. It was put and heated to 80° C. in an oil bath, and reacted for about 2 hours until the suspension became clear. After completion of the urethanization reaction, after cooling to 60° C., 0.05 g of dioctyltin dilaurate was further added, and a mixture of 297 g of V-300 and 297 g of methyl ethyl ketone was added dropwise over 1 hour to conduct a reaction. Reaction was performed for 8 hours, heating at 70 degreeC in an oil bath, the end point of the urethanation reaction was confirmed by the disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, and the urethane acrylate polymer was obtained. About the obtained urethane acrylate polymer, the weight average molecular weight and the number average molecular weight were measured. The obtained results are shown in Table-1. Hereinafter, this urethane acrylate polymer is described as "U-1".

[Synthesis Example 2]

In a four-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 247 g of IPDI and 79 g of 3MPD, 326 g of methyl ethyl ketone, and 0.10 g of dioctyltin dilaurate were added and heated to 80° C. in an oil bath. After reacting for 2 hours, 116 g of T-33, 116 g of methyl ethyl ketone, and 0.12 g of dioctyl tin dilaurate were added and reacted for about 2 hours until the suspension became transparent. After completion of the urethanation reaction, after cooling to 60° C., 0.28 g of dioctyltin dilaurate and 0.25 g of methylhydroquinone were further added, and a mixture of 57 g of HEA and 57 g of methyl ethyl ketone was added dropwise over 1 hour to conduct the reaction. initiated. Reaction was performed for 8 hours, heating at 70 degreeC in an oil bath, the end point of the urethanation reaction was confirmed by the disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, and the urethane acrylate polymer was obtained. About the obtained urethane acrylate polymer, the weight average molecular weight and the number average molecular weight were measured. The obtained results are shown in Table-1. Hereinafter, this urethane acrylate polymer is described as "U-2".

[Synthesis Example 3]

In a four-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 223 g of IPDI and 59 g of 3MPD, 282 g of methyl ethyl ketone, and 0.08 g of dioctyl tin dilaurate were added and heated to 80° C. in an oil bath. After reacting for 2 hours, 174 g of T-33, 175 g of methyl ethyl ketone, and 0.14 g of dioctyltin dilaurate were added, and reacted for about 2 hours until the suspension became transparent. After completion of the urethanation reaction, after cooling to 60° C., 0.27 g of dioctyltin dilaurate and 0.25 g of methylhydroquinone were added, and a mixture of 43 g of HEA and 43 g of methyl ethyl ketone was added dropwise over 1 hour to conduct the reaction. initiated. Reaction was performed for 8 hours, heating at 70 degreeC in an oil bath, the end point of the urethanation reaction was confirmed by the disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, and the urethane acrylate polymer was obtained. About the obtained urethane acrylate polymer, the weight average molecular weight and the number average molecular weight were measured. The obtained results are shown in Table-1. Hereinafter, this urethane acrylate polymer is described as "U-3".

[Synthesis Example 4]

In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 154 g of IPDI and 27 g of 3MPD, 181 g of methyl ethyl ketone, and 0.05 g of dioctyltin dilaurate were added and heated to 80° C. in an oil bath. After reacting for 2 hours, 258 g of T-35, 258 g of methyl ethyl ketone, and 0.17 g of dioctyltin dilaurate were added, followed by reaction for 2 hours. After completion of the urethanation reaction, after cooling to 60° C., 0.28 g of dioctyltin dilaurate and 0.25 g of methylhydroquinone were further added, and a mixture of 59 g of HEA and 59 g of methyl ethyl ketone was added dropwise over 1 hour to conduct the reaction. initiated. Reaction was performed for 8 hours, heating at 70 degreeC in an oil bath, the end point of the urethanation reaction was confirmed by the disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, and the urethane acrylate polymer was obtained. About the obtained urethane acrylate polymer, the weight average molecular weight and the number average molecular weight were measured. The obtained results are shown in Table-1. Hereinafter, this urethane acrylate polymer is described as "U-4".

[Example 1]

In a flask, 56.9 g of urethane acrylate polymer "U-1" (solid content: 50 wt%), 1.4 g of Irg 184 as a polymerization initiator, 0.1 g of Polyflow No. 75 as a leveling agent, 1.6 g of MEK, PGM was added 40.0 g, and stirred at 25°C for 1 hour to obtain a curable composition. Transparency was evaluated using the obtained curable composition. The obtained results are shown in Table-1.

[Examples 2 to 5 and Comparative Examples 1 to 7]

As shown in Table-1, it carried out similarly to Example 1 except having changed the composition of a curable composition. Table-1 shows the results obtained for each evaluation item. In Examples 2 and 3, U-2 was used, in Examples 4 and 5, U-3 was used, and in Comparative Example 1, U-4 was used instead of U-1.

Comparative Example 1, in which T-35 was introduced into the structure of urethane (meth)acrylate instead of T-33, has an ester bond in the ultraviolet absorbing backbone compared to Example 2, so that hydrolysis derived from the ester bond occurs. _{, the b 1} -b ₀ value in the metal weather test (28 cycle weather resistance) increased, and the weather resistance decreased.

Moreover, in Comparative Examples 2 and 3 in which T-33, which is a dihydroxy compound, was added to the curable composition, the solutions became cloudy, the solution appearance was unsatisfactory, and a good coating film was not obtained even as a coating film. On the other hand, Comparative Examples 4 and 5 to which T-35 was added had insufficient weather resistance. In Comparative Example 6 to which Tinuvin 479 was added, the b ₁ -b ₀ value in the metal weather test (28 cycle weather resistance) increased, and the weather resistance decreased. Comparative Example 7 had poor coating film appearance and weather resistance.

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention. This application is based on the Japanese patent application (Japanese Patent Application No. 2017-052242) for which it applied on March 17, 2017, The content is taken in here as a reference.

The hardened|cured material and laminated body obtained using the urethane (meth)acrylate polymer or curable composition of this invention can be used suitably as a film for coating replacement. For example, it is possible to effectively apply to various members, such as building materials for interior/exterior use, automobiles, home appliances, and information and electronic materials. In particular, the cured film which is an embodiment of this invention can be used suitably as a decorative film which uses this as a top coating layer.

Claims (18)

A urethane (meth)acrylate polymer having a chemical structure represented by the following formula (1) and containing at least one monomolecular polyol structure of any one of a linear aliphatic structure, a branched aliphatic structure, and an alicyclic structure.

[In the formula, A represents a single bond or a methylene group, 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 any one of an alkylene group, an alkoxyylene group, and an arylene group.] The urethane (meth)acrylate polymer according to claim 1, wherein the formula (1) is the following formula (2).

The urethane (meth)acrylate polymer according to claim 1, further having a chemical structure represented by the following formula (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 according to claim 3, wherein the urethane contains 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) as a chemical structure represented by the formula (3). (meth)acrylate polymers.

(In formula (4-1), (4-2) of, X ¹ has the same meaning as X ¹ in the formula (3).) The urethane (meth)acrylate polymer according to claim 1, wherein the weight average molecular weight (Mw) is 500 to 30000. The urethane (meth)acrylate polymer according to claim 1, wherein the proportion of the chemical structure represented by Formula (1) in the urethane (meth)acrylate polymer is 5 to 60% by weight. A curable composition comprising the urethane (meth)acrylate polymer according to claim 1 and an organic solvent. The curable composition according to claim 7, wherein the organic solvent has a solubility parameter of 8.0 to 11.5. The curable composition according to claim 7, wherein the curable composition has a solid content concentration of 5 to 90 wt%. The curable composition according to claim 7, wherein the ratio of the chemical structure represented by the formula (1) in the polymerization component of the curable composition is contained in an amount of 5 to 60% by weight. A cured product of the curable composition according to claim 7. A laminate having a cured product of the curable composition according to claim 7 on a substrate. The head lamp lens which has the hardened|cured material of the curable composition of Claim 11 on a base material. A glazing material having a cured product of the curable composition according to claim 11 on a substrate. The decorative film which has the hardened|cured material of the curable composition of Claim 11 on a base material. A step of applying the urethane (meth)acrylate polymer according to claim 1 on a substrate, a step of irradiating an active energy ray to the urethane (meth)acrylate polymer to obtain a laminate having a cured product, and stretching the laminate The manufacturing method of the film including the process of doing. Preparation of a urethane (meth)acrylate polymer by reacting the following compound (A) and the following compound (B) with the following compound (D) to obtain a precursor of a urethane polymer, and then reacting the following compound (C) with it Way.
Compound (A): polyisocyanate
Compound (B): a polyol represented by the following formula (5)

[In the formula, A represents a single bond or a methylene group, 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 any one of an alkylene group, an alkoxyylene group, and an arylene group.]
Compound (C): a compound having a hydroxyl group and a (meth)acryloyl group
Compound (D): an aliphatic polyol having a molecular weight of 500 or less delete