WO2018169031A1 - 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 present invention also addresses the problem of providing a laminate and a decorative film, each of which has a layer that is formed of a cured product of the above-described urethane (meth)acrylate polymer or a curable composition containing the above-described urethane (meth)acrylate polymer on the surface. 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 excellent in transparency, weather resistance, and scratch resistance after coating and curing a curable composition on a substrate, and a curable composition containing the same. Moreover, this invention relates to the hardened | cured material, laminated body, and decorating film using this urethane (meth) acrylate polymer and a curable composition.

The radical polymerization type curable composition can be cured in a short time by irradiation with active energy rays, and can provide a film or a molded product excellent in chemical resistance, scratch resistance, weather resistance, heat resistance, etc. Therefore, it is used in coating compositions for coating the surfaces of automobiles, home appliances, woodwork products, plastic molded products, 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 a UV absorber having a specific structure is incorporated into a polymer skeleton.

Patent Document 3 discloses a curable resin composition in which a bisbenzotriazolylphenol ultraviolet absorber is incorporated into a polymer skeleton via an ester bond.

JP 2000-017204 A JP 2000-053913 A JP 2000-109652 A

However, in the coating composition described in Patent Document 1, since the ultraviolet absorber is not incorporated in the polymer skeleton, the transparency and weather resistance of the coating film are caused by bleeding out of the ultraviolet absorber from the coating film. Was insufficient.
The coating composition described in Patent Document 2 has insufficient weather resistance since the ultraviolet absorbing performance of the ultraviolet absorber is not sufficient.
Since the curable composition described in Patent Document 3 incorporates an ultraviolet absorber into the polymer skeleton via an ester bond, hydrolysis resulting from the ester bond occurs, and the ultraviolet absorber bleeds out. The weather resistance was insufficient.

The present invention solves the above-described problems, and includes a urethane (meth) acrylate polymer that prevents bleeding out of an ultraviolet absorber and provides a coating film excellent in weather resistance, scratch resistance, and transparency, and the same. The object is to provide a curable composition.

That is, the above 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).

[In the formula, A represents a single bond or an optionally substituted methylene group, alkylene group, —O— group, —NH— group, —S— group, —SO— group or —SO ₂ — group. To express. 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 alkoxylene 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] The chemical structure represented by the formula (3) includes 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 [3].

(Formula (4-1), (4-2) in, 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], which has a weight average molecular weight (Mw) of 500 to 30,000.
[6] The urethane (meth) according to any one of [1] to [5], wherein the ratio of the chemical structure represented by the formula (1) in the urethane (meth) acrylate polymer is 5 to 60% by weight. Acrylate polymer.
[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 curability according to any one of [7] to [9], wherein the polymerization component of the curable composition contains 5 to 60% by weight of the chemical structure represented by the formula (1). Composition.
[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 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 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 manufacturing method of a film including the process of irradiating an active energy ray to the said urethane (meth) acrylate polymer or the said curable composition, obtaining the laminated body which has hardened | cured material, and the process of extending | stretching the said laminated body.
[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 urethane polymer precursor, and then the following compound (C) is reacted therewith.
Compound (A): Polyisocyanate compound (B): Polyol represented by the following formula (5)

[In the formula, A represents a single bond or an optionally substituted methylene group, alkylene group, —O— group, —NH— group, —S— group, —SO— group or —SO ₂ — group. To express. 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 alkoxylene group, or an arylene group. ]
Compound (C): Compound [18] having hydroxyl group and (meth) acryloyl group [18] In addition to compound (A) and compound (B), the following compound (D) was reacted to obtain a urethane polymer precursor, The method for producing a urethane (meth) acrylate polymer according to [17], wherein the compound (C) is reacted.
Compound (D): aliphatic polyol having a molecular weight of 500 or less

ADVANTAGE OF THE INVENTION According to this invention, the urethane (meth) acrylate polymer which prevents the bleeding out of a ultraviolet absorber, and the coating film excellent in a weather resistance, an abrasion resistance, and transparency is obtained, and a curable composition containing this are obtained. . Moreover, the laminated body and decorating film which have the layer which consists of the said hardened | cured material on the surface can be provided.

In the present invention, “(meth) acrylate” is a general term for acrylate and methacrylate, and means one or both of acrylate and methacrylate. The same applies to “(meth) acryloyl” and “(meth) acryl”. It is.

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

In formula (1), A is a single bond or may have a substituent, a methylene group, an alkylene group, an —O— group, an —NH— group, an —S— group, an —SO— group, or —SO _2. It may be any group. From the viewpoint of transparency of the cured product containing the urethane (meth) acrylate polymer of the present invention and prevention of bleeding out of the cured product of the ultraviolet absorbent, a methylene group and an alkylene group are preferable, and a methylene group is more preferable.

In the formula (1), R ¹ , R ² , R ³ and R ⁴ may independently be any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom. A hydrogen atom, an alkyl group, or an alkoxy group is preferable from the viewpoint of preventing transparency of the cured product of the urethane (meth) acrylate polymer or curable composition of the present invention and bleeding out from the cured product of the bisbenzotriazolylphenol skeleton. .

In Formula (1), R ⁵ and R ⁶ are the same or different and may be any one of an alkylene group, an alkoxylene group, and an arylene group. An alkylene group and a methylene group are preferred from the viewpoint of transparency of the cured product of the urethane (meth) acrylate polymer or curable composition of the present invention and prevention of bleeding out from the cured product of the bisbenzotriazolylphenol skeleton.

In the urethane (meth) acrylate polymer of the present invention, a bisbenzotriazolylphenol skeleton that acts as an ultraviolet absorber is incorporated into the molecular chain of the polymer via a chemically stable urethane bond.
Since the bisbenzotriazolylphenol skeleton has a structure in which benzotriazolylphenol is dimerized, it has a high ultraviolet-absorbing ability per unit weight and can impart high weather resistance even in a small amount.
Furthermore, in the present invention, since the bisbenzotriazolylphenol skeleton is incorporated through a urethane bond, the bisbenzotriazolylphenol skeleton is difficult to bleed out due to hydrolysis or the like, so that it has long-term weather resistance. Also excellent.

The formula of the urethane (meth) acrylate polymer of the present invention and the transparency of the cured film obtained by curing the curable composition using the same and the prevention of bleedout from the cured product of the bisbenzotriazolylphenol skeleton. The chemical structure represented by (1) is preferably a chemical structure represented by the following formula (2).

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

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

In formula (3), X ¹ is not particularly limited as long as it is an aliphatic structure having a molecular weight of 500 or less, but is preferably an aliphatic structure having a molecular weight of 400 or less, more preferably an aliphatic structure having a molecular weight of 300 or less. . X ¹ is preferably an aliphatic structure having a molecular weight of 14 or more, more preferably an aliphatic structure having 28 or more. X ¹ corresponds to a residue from which a hydroxyl group is bonded to the aliphatic structure of the compound (B) described later, and is a linear aliphatic structure or a branched aliphatic structure. It may be a cyclic structure.

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

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

That is, more specifically, as the chemical structure represented by the formula (3), 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) It is preferable to contain.

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

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

Furthermore, the urethane (meth) acrylate polymer of the present invention contains a structural unit derived from a compound having a hydroxyl group and a (meth) acryloyl group. Examples of the compound having a hydroxyl group and a (meth) acryloyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. Cyclohexanedimethanol mono (meth) acrylate, addition reaction product of 2-hydroxyethyl (meth) acrylate and caprolactone, 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 (meth) a Relate, 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 is preferable and 20,000 or less is more preferable.
When the weight average molecular weight of the urethane (meth) acrylate polymer is in the above range, the transparency of the urethane (meth) acrylate polymer or the curable composition in the solution state and the scratch resistance of the cured film are improved.

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

An example of the method for producing the urethane (meth) acrylate polymer of the present 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 this. can get.
Compound (A): Polyisocyanate compound (B): Polyol represented by the following formula (5)

[In the formula, A represents a single bond or an optionally substituted methylene group, alkylene group, —O— group, —NH— group, —S— group, —SO— group or —SO ₂ — group. To express. 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 alkoxylene group, or an arylene group. ]
Compound (C): Compound having a hydroxyl group and a (meth) acryloyl group

In addition to the compound (A) and the compound (B), the urethane (meth) acrylate polymer of the present invention is reacted with a polyol other than the compound (B) to obtain a urethane polymer precursor, and then the compound ( C) may be reacted.

Examples of polyols 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-hexadecanediol, etc. A diol having a linear aliphatic structure of: 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-nona Diols having a branched aliphatic structure such as diols; Compounds having a branched aliphatic structure such as trimethylolpropane, glycerin, sorbitol, mannitol, pentaerythritol and three or more hydroxyl groups bonded thereto; cyclopropanediol Diols having an alicyclic structure such as cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, tricyclodecanediol, adamantyldiol, and the like, and aliphatic polyols having a molecular weight of 500 or less (hereinafter referred to as compound (D)). .) Is preferred.

Furthermore, in this invention, when performing reaction which makes a compound (A) and a compound (B) react, and obtains the precursor of a urethane polymer, two or more active hydrogen which reacts with an isocyanate group is used as a chain extension agent. You may add the compound which has.

[Compound (A)]
Examples of the polyisocyanate of the compound (A) include chain aliphatic polyisocyanate, aromatic polyisocyanate, and alicyclic polyisocyanate. Among these, a chain alicyclic polyisocyanate is preferable from the viewpoint of enhancing the weather resistance and hardness of the cured product obtained.

Examples of the chain aliphatic polyisocyanate include aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and dimer acid diisocyanate, and aliphatic triisocyanates such as tris (isocyanatohexyl) isocyanurate. Can be mentioned.
From the viewpoint of increasing the weather resistance and hardness of the resulting cured product, 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 tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, and naphthalene diisocyanate. Tolylene diisocyanate and diphenylmethane diisocyanate are preferable as the aromatic polyisocyanate from the viewpoint of increasing the mechanical strength of the urethane (meth) acrylate polymer or the cured film of the curable composition. These may be used alone or in combination of two or more.

Examples of the polyisocyanate having an alicyclic structure include diisocyanates having an alicyclic structure such as bis (isocyanate methyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, and isophorone diisocyanate, and tris (isocyanate isophorone) isocyanurate. And triisocyanate having an alicyclic structure. Among these, the alicyclic polyisocyanate is preferably isophorone diisocyanate. These may be used alone or in combination of two or more.

The alicyclic structure preferably has 5 or more carbon atoms, more preferably 6 or more carbon atoms. Moreover, carbon number 15 or less is preferable and carbon number 13 or less is more preferable. Furthermore, the alicyclic structure is preferably a cycloalkylene group.
As the compound (A), one type may be used, or two or more types may be used.

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

[Compound (B)]
The compound (B) is a polyol represented by the following formula (5).

[In the formula, A represents a single bond or an optionally substituted methylene group, alkylene group, —O— group, —NH— group, —S— group, —SO— group or —SO ₂ — group. To express. 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 alkoxylene group, or an arylene group. ]

From the point which prevents the bleedout from the transparency of the hardened | cured material obtained by hardening | curing the urethane (meth) acrylate polymer of this invention, and a curable composition using the same, and the hardened | cured material of a bisbenzotriazolylphenol skeleton. The compound (B) represented by the formula (5) is preferably a polyol represented by the following formula (10).

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

As the compound (B), Dinesorb T-33 manufactured by Daiwa Kasei Co., Ltd. can be used as a commercially available product.

In view of improving the weather resistance of the cured film of the present invention, the compound (B) is preferably 5% by weight or more, more preferably 25% by weight or more based on the total polyol component used as a raw material for the urethane (meth) acrylate polymer. More preferred. Moreover, 95 weight% or less is preferable and 90 weight% or less is more preferable from the point which is excellent in transparency in a solution state, transparency of a cured film, and abrasion resistance.

[Compound (C)]
Since the compound having a hydroxyl group and a (meth) acryloyl group in the compound (C) has a (meth) acryloyl group, a bisbenzotria which acts as an ultraviolet absorber by forming a crosslinked structure with other components by irradiation with active energy rays. Bleed-out of the zolylphenol skeleton can be suppressed.

Examples of the compound (C) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and cyclohexanedimethanol mono (Meth) acrylate, addition reaction product of 2-hydroxyethyl (meth) acrylate and caprolactone, addition reaction product of 4-hydroxybutyl (meth) acrylate and caprolactone, bisphenol A diglycidyl ether diacrylate, mono (meta) of glycol ) Acrylate, glycerin (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Rupenta (meth) acrylate and the like can be mentioned.

Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4 from the viewpoint of improving the mechanical strength of the resulting cured film and the curability of the urethane (meth) acrylate polymer. -Hydroxybutyl (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like 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. 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, epoxy compound having a linear aliphatic structure such as 1,12-dodecanediol diglycidyl ether; propylene glycol diglycidyl ether, neopentyl glycol Epoxy compounds having a branched aliphatic structure such as diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, etc. Can be mentioned.

Among these, from the viewpoint of curability of the urethane (meth) acrylate polymer, the epoxy compound includes 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diester. Epoxy compounds having a chain aliphatic structure having 4 to 6 carbon atoms such as glycidyl ether are preferred.

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

Among these, acrylic acid is preferable as the compound having a (meth) acryloyl group and a carboxyl group from the viewpoint of curability of the urethane (meth) acrylate polymer.

Examples of the epoxy (meth) acrylate of the compound (C) include Kayrad (registered trademark) R-167 (manufactured by Nippon Kayaku Co., Ltd.), NK oligo EA-5520, EA-5321 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like. It is done. As the compound (C), one type may be used, or two or more types may be used.

In addition, the compound (C) is used as a raw material for the urethane (meth) acrylate polymer 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 total polyol component is preferably 4% by weight or more, more preferably 8% by weight or more. 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.

Examples of the compound (D) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Linear fat such as octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, etc. Diols having a family structure: propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,2-pentane Branched chain such as diol, 3-methyl-1,5-pentanediol, 1,8-nonanediol Diols having an aliphatic structure; compounds having a branched aliphatic structure such as trimethylolpropane, glycerin, sorbitol, mannitol, pentaerythritol and three or more hydroxyl groups bonded thereto; cyclopropanediol, cyclohexanediol, cyclohexanedi Examples include diols having an alicyclic structure such as methanol, hydrogenated bisphenol A, tricyclodecanediol, and adamantyldiol.

Among these, those having a linear aliphatic structure are preferred from the viewpoint of excellent scratch resistance of the cured film, and particularly at least one selected from ethylene glycol, 1,4-butanediol, and 1,12-dodecanediol. It is preferable to use one. Among these, ethylene glycol is preferable from the viewpoint of chemical resistance, and 1,12-dodecanediol is preferable from the viewpoint of scratch resistance and flexibility. In order to further improve the weather resistance of the cured film, it is necessary to introduce more compound (B) into the urethane (meth) acrylate polymer. For this purpose, the compound (D) preferably contains a diol having a branched aliphatic structure. As the diol having a branched aliphatic structure, propylene glycol, 1,3-butanediol, neopentyl glycol, 3-methyl-1,5 can be complemented with the solution transparency and the low solubility of the ultraviolet absorption skeleton. -Pentanediol and the like are more preferable, and 1,3-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol and the like are more preferable. As the compound (D), one type may be used, or two or more types may be used.

From the point 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 based on the total polyol component used as a raw material for the urethane (meth) acrylate polymer. It is preferably 3% by weight or more, and more preferably 10% by weight or more.

Moreover, from the point which makes content of said Formula (1) in a urethane (meth) acrylate polymer high, a compound (D) is 99 with respect to all the polyol components used as a raw material of a urethane (meth) acrylate polymer. .95% by weight or less is preferable, and 90% by weight or less is more preferable.

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

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 polyol, polyester polyol, polyether ester polyol, polycarbonate polyol, polyolefin polyol, and silicon polyol. These may be used alone or in combination of two or more.

When using the high molecular weight polyol, polycarbonate polyol is preferable. The polycarbonate polyol can be obtained, for example, by reacting at least one carbonate compound selected from the group consisting of alkylene carbonate, diaryl carbonate, and dialkyl carbonate with at least one of diols and polyether polyols. Examples of the diols 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, polybutadiene diol and the like. Among these, it is preferable to contain at least one selected from 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol from the viewpoint of good scratch resistance. Polycarbonate polyol can be obtained as a commercial product. Examples of commercially available products include DURANOL (registered trademark) T4671 (manufactured by Asahi Kasei Co., Ltd.), DURANOL (registered trademark) T4691 (manufactured by Asahi Kasei Co., Ltd.), DURANOL (registered trademark) 5651 (manufactured by Asahi Kasei Corporation), and DURANOL (registered trademark) 6001 (registered trademark). Asahi Kasei Co., Ltd.).

[Chain extender]
Furthermore, in this invention, when performing reaction which makes a compound (A) and a compound (B) react, and obtains the precursor of a urethane polymer, it has two or more active hydrogens which react with an isocyanate group as a chain extension agent Compounds may be added.

Examples of the chain extender include low molecular weight diamine compounds having a number average molecular weight of 500 or less, and examples include aromatic compounds such as 2,4- or 2,6-tolylenediamine, xylylenediamine, and 4,4′-diphenylmethanediamine. Group diamine; ethylenediamine, 1,2-propylenediamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, 2,2,4- or Aliphatic diamines such as 2,4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine; 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4,4′-dicyclohexylmeta Diamine, isopropylidene cyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3-bis-aminomethyl cyclohexane, alicyclic diamines such as tricyclodecane diamine. These may be used alone or in combination of two or more.

In addition, when using a chain extender, the usage-amount of all the polyols is 70 mol% with respect to the total usage-amount of the compound which combined the compound (B) and the compound (C), and other polyol components and chain extension agents. The above is preferable, and 95 mol% or more is more preferable.

In the present invention, a polyol other than the compound (B) and the compound (B) is reacted under a condition that the isocyanate group becomes excessive to obtain a precursor of a urethane polymer having an isocyanate terminal, It is preferable to react the urethane polymer precursor having an isocyanate terminal with the compound (C).

In addition, when the compound (C) has two or more hydroxyl groups, the compound (C) is preferably used in an excess amount with respect to all isocyanate groups of the urethane (meth) acrylate polymer.

When producing a urethane (meth) acrylate polymer in terms of controlling the molecular weight of the urethane (meth) acrylate polymer, the total amount of the compound containing a functional group that reacts with an isocyanate group in the compound (C) and other raw materials On the other hand, the amount of the compound (C) used is preferably 2 mol% or more, more preferably 10 mol% or more. 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 be small, and when the proportion of the compound (C) is small, the molecular weight of the urethane (meth) acrylate polymer tends to be large.

In the method for producing a 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 as long as the effects of the present invention are obtained. Preferred organic solvents include toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, dimethylformamide and the like. The said organic solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it. The said organic solvent can be normally used at 300 weight% or less with respect to the total mass of a urethane (meth) acrylate polymer.

In the production of the urethane (meth) acrylate polymer, a catalyst can be used for the urethanization reaction. Examples of the catalyst include tin-based catalysts such as dibutyltin laurate, dibutyltin dioctate, dioctyltin dilaurate, and dioctyltin dioctate; and bismuth-based catalysts such as bismuth tris (2-ethylhexanoate). . Of these, dioctyltin dilaurate and bismuth tris (2-ethylhexanoate) are preferable from the viewpoint of environmental adaptability, catalytic activity, storage stability, and the like. A catalyst may be used individually by 1 type and may be used in mixture of 2 or more types. The amount of the catalyst used is preferably 2,000 ppm or less, more preferably 1,000 ppm or less, based on the total amount of raw materials charged. Moreover, 10 ppm or more is preferable and 30 ppm or more is more preferable.

In addition, it is preferable to use a polymerization inhibitor in combination with the production of the urethane (meth) acrylate polymer. Examples of the polymerization inhibitor include phenols such as hydroquinone, methylhydroquinone, hydroquinone monoethyl ether, and dibutylhydroxytoluene, amines such as phenothiazine and diphenylamine, copper salts such as copper dibutyldithiocarbamate, and manganese salts such as manganese acetate. , Nitro compounds, nitroso compounds and the like. Of these, the polymerization inhibitor is preferably a phenol. The said polymerization inhibitor may be used individually by 1 type, and may mix and use 2 or more types. The amount of the polymerization inhibitor used is preferably 3,000 ppm or less, more preferably 1,000 ppm or less, based on the total amount of raw materials charged. Moreover, 50 ppm or more is preferable and 100 ppm or more is more preferable.

In the production of a urethane (meth) acrylate polymer, the reaction temperature of the urethanization reaction is preferably 20 ° C. or higher and more preferably 40 ° C. or higher from the viewpoint of increasing the reaction rate and improving the production efficiency. In addition, the reaction temperature is preferably 120 ° C. or less, more preferably 100 ° C. or less from the viewpoint that side reactions such as allophanatization reaction do not easily 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)
The curable 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 40% by weight or more based on the total amount of all components (solid content) excluding the organic solvent in the curable composition. More preferably, it is more than wt%. In addition, the upper limit of content of a urethane (meth) acrylate polymer is 100 weight%. It is preferable for the content of the urethane (meth) acrylate polymer to be in the above range since the curing rate and surface curability of the curable composition will be good and no tack will remain.

Furthermore, the structural ratio of the compound represented by the formula (1) in the polymerization component of the curable composition is preferably 10% by weight or more from the viewpoint of excellent transparency, weather resistance and scratch resistance of the cured product. Moreover, 25 weight% or less is preferable.

The polymerization component of the curable composition is a component having an unsaturated double bond that is polymerizable with respect to active energy rays, and is a urethane (meth) acrylate polymer contained in the curable composition, active energy. It means a line curable polymer and an active energy ray reactive monomer.

[Organic solvent]
The organic solvent can be used for adjusting the viscosity of the coating material when forming the coating film of the curable composition of the present invention.
The solid content concentration of the curable composition is preferably 5 to 90 wt. 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.

A known organic solvent can be used as the organic solvent. The solubility parameter of the organic solvent (hereinafter referred to as “SP value”) is preferably 8.0 or more from the viewpoint of the solubility of the urethane (meth) acrylate polymer, and 11.5 from the viewpoint of the transparency of the solution. The following is preferred.
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). In the present invention, the SP value is calculated by the method proposed by Fedors et al. Specifically, it is a value obtained by referring to "POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147 to 154)". Moreover, SP value means the value as a mixture, when using a mixed solvent.

[Other ingredients]
The curable composition of the present invention includes, 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, and a photosensitizer. Sensitizers, epoxy compounds and other additives may also be included.

Any known active energy ray-reactive monomer can be used as the active energy ray-reactive monomer as long as the effects of the present invention are obtained. These active energy ray reactive monomers adjust the physical properties such as the hydrophilicity / hydrophobicity of the urethane (meth) acrylate polymer of the present invention, the hardness of the cured product when the resulting composition is cured, and the elongation of the cured product. Used for purposes such as An active energy ray reactive monomer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

Examples of the active energy ray-reactive monomer include vinyl ethers, (meth) acrylamides, and (meth) acrylates. Specific examples include styrene, α-methylstyrene, α-chlorostyrene, and vinyl. Aromatic vinyl monomers such as toluene 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) acrylamide, Nt-butyl (meth) acrylamide, (meth) acryloylmorpholine, methylenebis (Meth) acrylamides such as (meth) acrylamide; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylate-n-butyl, ( (Meth) acrylic acid-i-butyl, (meth) acrylic acid-t-butyl, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (Meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic Morpholyl acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, dimethylamino (meth) acrylate Ethyl, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, (Meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid allyl, (meth) acrylic acid-2-ethoxyethyl, (meth) acrylic acid isobornyl, (meth) acrylic Monofunctional (meth) acrylates such as phenyl acid And ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate ( n = 5 to 14), propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, di (meth) Polypropylene glycol acrylate (n = 5-14), 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, neopentyl di (meth) acrylate Glycol, hydroxypivalate neopentyl glycol di (meth) acrylate, di (meth) acrylate dicyclopentanediol, di (meth) acrylate 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 (Meta) ak Rate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, trimethylolpropane trioxypropyl (meth) acrylate, trimethylolpropane polyoxyethyl (meth) acrylate, trimethylolpropane poly Oxypropyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate , Tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, propylene Examples thereof include polyfunctional (meth) acrylates such as oxide-added bisphenol F di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A epoxy di (meth) acrylate, and bisphenol F epoxy di (meth) acrylate.

Among these, (meth) acryloylmorpholine, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid benzyl, (meth) acrylic acid cyclohexyl, because the viscosity of the curable composition is low and the coating property is good. , Molecules such as trimethylcyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylamide, etc. A monofunctional (meth) acrylate having a ring structure therein is preferred. In addition, since the mechanical strength of the resulting cured film is good, di (meth) acrylic acid-1,4-butanediol, di (meth) acrylic acid-1,6-hexanediol, di (meth) acrylic Acid-1,9-nonanediol, 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 Tet (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyfunctional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate. Furthermore, from the point that the stretchability of the obtained cured film is good, di (meth) acrylic acid polyethylene glycol (n = 5 to 14), di (meth) acrylic acid polypropylene glycol (n = 5 to 14), di (meth) Polyether (meth) acrylates such as polybutylene glycol acrylate (n = 3 to 16) and poly (1-methylbutylene glycol) di (meth) acrylate (n = 5 to 20) are preferred.

From the viewpoint of adjusting the viscosity of the curable composition and adjusting the physical properties such as hardness of the resulting cured product, the active energy ray reactivity with respect to the total amount of all components (solid content) excluding the organic solvent of the curable composition. The content of the 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 epoxy (meth) acrylate polymers, acrylic (meth) acrylate polymers, polyester (meth) acrylate polymers, polycarbonate (meth) acrylate polymers, polybutadiene (meth ) Acrylate polymer, polyether (meth) acrylate (excluding those described in the active energy ray-reactive monomer). The active energy ray-curable polymer may be used alone or in combination of two or more.

The polymerization initiator is mainly used for the purpose of improving the polymerization efficiency of a polymerization reaction that proceeds by irradiation with active energy rays such as ultraviolet rays and electron beams. As the polymerization initiator, any known radical photopolymerization initiator can be used as long as the effects of the present invention are obtained.
A polymerization initiator may be used individually by 1 type, and 2 or more types may be mixed and used for it. Furthermore, you may use together 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, thioxanthone, diethylthioxanthone, isopropylthioxanthone, chloro Thioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl benzoyl 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 and the like.

Among these, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6, since the curing speed is high and the crosslinking density can be sufficiently increased. -Trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one 1-hydroxycyclohexyl phenyl 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 preferred.

Further, when the curable composition contains a compound having a cationically polymerizable group such as an epoxy group together with a radically polymerizable group, a photocationic polymerization initiator is included as a polymerization initiator together with the photoradical polymerization initiator. It may be. A well-known thing can be used for a photocationic polymerization initiator in the range which does not inhibit the effect of this invention remarkably.

The content of the polymerization initiator is preferably 10% by weight or less, based on the total weight of the polymerization components of the curable composition, because the mechanical strength is not easily lowered by the initiator decomposition product. The following is more preferable.

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, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4 -Dimethylaminoacetophenone and the like. A photosensitizer may be used individually by 1 type and may be used in mixture of 2 or more types.

In the curable composition of the present invention, the content of the photosensitizer is 10 with respect to the total weight of the polymerization component of the curable composition, since the mechanical strength is not easily lowered due to the reduction of the crosslinking density. % By weight or less is preferable, and 5% by weight or less is more preferable.

Examples of the additive include silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, talc, kaolin, metal oxide, metal fiber, iron, lead, metal powder and other fillers; carbon fiber, carbon black , Graphite, carbon nanotubes, carbon materials such as C60 fullerenes; antioxidants, heat stabilizers, UV absorbers, hindered amine light stabilizers (HALS), surface hydrophilizing agents, antistatic agents, slipperiness imparting agents Modifiers such as plasticizers, mold release agents, antifoaming agents, leveling agents, anti-settling agents, surfactants, thixotropy imparting agents, flame retardants, flame retardant aids, polymerization inhibitors, silane coupling agents; Examples thereof include colorants such as pigments, dyes, and hue adjusting agents. The said additive may be used individually by 1 type, and 2 or more types may be mixed and used for it.

In the curable composition of the present invention, the content of the additive is 10% by weight with respect to the total weight of the polymerization component of the curable composition, because the mechanical strength is not easily lowered due to the reduced crosslinking density. The following is preferable, and 5% by weight or less is more preferable.

The method of adding the additive to the curable composition of the present invention is not particularly limited, and examples thereof include conventionally known mixing and dispersing methods. In order to more reliably disperse the additive in the curable composition, for example, a two-roll, three-roll, bead mill, ball mill, sand mill, pebble mill, tron mill, sand grinder, seg barrier striker, planetary type Examples of the processing method include a stirrer, a high-speed impeller disperser, a high-speed stone mill, a high-speed impact mill, a kneader, a homogenizer, and an ultrasonic disperser.

[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. Further, 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 by, for example, 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.
The viscosity was measured at 25 ° C. in an E-type viscometer (rotor 1 ° 34 ′ × R24).

[Coating method]
As a 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, reverse roll coater method, lip coater method, die coater method, slot die coater method, air knife coater method, dip coater method, etc., among which the bar coater method and the gravure coater method are applicable. preferable. The urethane (meth) acrylate polymer of the present invention can be used alone by the coating method.

Examples of the substrate on which the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention is applied include, for example, polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyolefins such as polypropylene and polyethylene; Examples include various plastics such as polycarbonate and (meth) acrylic polymers, glass, and metals. Among these, polyethylene terephthalate is preferable. Moreover, about the shape of these base materials, even if it is flat things, such as a film form and a sheet form, and what was shape | molded in various shapes may be sufficient.

[Hardened 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 beams, α rays, β rays, and γ rays. From the viewpoint of apparatus cost and productivity, it is preferable to use an electron beam or ultraviolet rays. Light sources include electron beam irradiation equipment, ultra high pressure mercury lamp, high pressure mercury lamp, medium pressure mercury lamp, low pressure mercury lamp, metal halide lamp, Ar laser, He-Cd laser, solid state laser, xenon lamp, high frequency induction mercury lamp, solar Light or the like can be used.

The irradiation amount of the active energy ray can be appropriately selected according to the type of the active energy ray. For example, when curing by electron beam irradiation, the irradiation amount is preferably 1 to 15 Mrad. In the case of curing by ultraviolet irradiation, it is preferably 50 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, it may be in any atmosphere of air, an inert gas such as nitrogen or argon. Moreover, you may irradiate in the sealed space between a film or glass, and a metal metal mold | die.

The thickness of the cured product is appropriately determined according to the intended use, but the thickness of the cured product is preferably 1 μm or more from the viewpoint of good design and functional expression after three-dimensional processing, 2 μm or more is preferable. In addition, 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 from the viewpoint of good curability and three-dimensional processability.

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 substrate and the cured product of the present invention, or may be disposed outside the laminate of the present invention. . Moreover, the said laminated body may have multiple layers of the base material and the hardened | cured material of this invention.

As a method of obtaining a laminate having a multi-layered cured product, all layers are laminated in an uncured state and then cured with active energy rays, and the lower layer is cured with active energy rays or semi-cured. A known method such as a method of applying an upper layer and curing again with active energy rays, a method of bonding each layer to an uncured state or a semi-cured state after applying each layer to a substrate can be applied. From the viewpoint of improving the adhesion between layers, a method of curing with active energy rays after laminating in an uncured state is preferable. As a method of laminating in an uncured state, a known method such as sequential coating in which the upper layer is applied after the lower layer is applied or simultaneous multilayer coating in which two or more layers are simultaneously applied from multiple slits is applied. Yes, but not necessarily.

The laminate of the present invention can be suitably used as a coating substitute film. For example, the present invention can be effectively applied to interior and exterior building materials and various members such as automobiles, home appliances, and information electronic materials. In addition, the laminated body of the present invention is suitable for a glazing member or a decorative film from the viewpoint that the weather resistance, bleed-out resistance, and scratch resistance necessary for surface protection can be imparted in a single layer and the process is simple. used.
In the present invention, the decorative film is a film to which irregularities such as wood grain, metal tone, embossing, various designs, designs such as characters, and decoration are added by printing, painting, vapor deposition, coloring, and the like.
The molded article formed by applying the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention to the surface of a molded article such as polycarbonate and irradiating an active energy ray is an automobile head. It is suitably used for lamp lenses and automotive polymer glass.

Since the cured product of the present invention is excellent in stretchability, the laminate of the present invention can be stretched and used as a film. The method for producing the film includes a step of applying the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention on a substrate, and irradiating the curable composition with active energy rays to form a cured product. It is preferable to include the process of obtaining the laminated body which has, and the process of extending | stretching the said laminated body.

In the film production method, the step of applying the urethane (meth) acrylate polymer of the present invention or the curable composition of the present invention on a substrate and the urethane (meth) acrylate polymer or the curable composition are active. Each of the steps of obtaining a cured product by irradiating energy rays can be performed under the above-described conditions. In the method for producing a film, the step of stretching the cured product can be usually performed by heating at 60 to 200 ° C., preferably 100 to 180 ° C.
When using the said film as a decorating film, as a shaping | molding method of a decorating film, well-known methods, such as insert molding, in-mold shaping | molding, overlay shaping | molding, blow molding, vacuum forming, can be used.

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

[Measurement methods of physical properties and characteristics]
The urethane (meth) acrylate polymer and the cured film were evaluated by the following methods.
<Molecular weight>
Using GPC (“HLC-8120GPC” manufactured by Tosoh Corporation), tetrahydrofuran (THF) as a solvent, polystyrene as a standard sample, TSKgel superH1000 + H2000 + H3000 as a column, a liquid feeding speed of 0.5 mL / min, and 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>
The transparency of the curable composition was evaluated by visually confirming whether the curable composition obtained in the example was transparent, cloudy or insoluble with respect to the appearance after standing for 1 day.

<Evaluation of cured product>
(Evaluation sample)
The curable resin obtained in Examples and Comparative Examples was coated on a polyethylene terephthalate film with a bar coater, dried at 80 ° C. for 2 minutes, and then irradiated with an ultraviolet irradiation device (US5-X1802-X1202, manufactured by Iwasaki Electric Co., Ltd.). ) Was irradiated with an ultraviolet ray with an integrated irradiation amount of 1000 mJ / cm ² (wavelength 315 to 380 nm) with a 160 W high-pressure mercury lamp and cured.
The film was further cured at 23 ° C. for 1 day to obtain a laminate having a thickness of about 5 μm.

(Evaluation of coating film appearance)
The appearance of the coating film on the obtained laminate was visually confirmed to be transparent or cloudy, and the haze value H was measured. The haze value H was measured according to JIS K7105 by using a haze meter (“HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory Co., Ltd.).

(Weather resistance test (metal weather test))
The color tone b ₀ of the coating film on the obtained laminate was measured using a spectrocolorimeter (manufactured by Konica Minolta, product name “Spectrophotometer CM-5”). Next, using a metal weather meter (product name “Daipura Metal Weather KU-R4Ci-W” manufactured by Daipura Wintes Co., Ltd.) under the irradiation intensity of 80 mW / cm ² , the following (1), (2) The accelerated weathering test was conducted for 168 hours (14 cycles) and 336 hours (28 cycles), with the conditions of (3) being 4 hours each for a total of 12 hours. The cured product after the test was visually observed, and the color tone b ₁ and haze value H of the cured product after the accelerated weather resistance test were measured.
The color tone of the cured product was evaluated by 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))

(Transmittance measurement)
Using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, product name “ratio beam spectrophotometer U-1900”), the base line was made of polyethylene terephthalate film (with easy adhesion treatment). ), Transmittance (360 nm, 380 nm) was measured.

(Evaluation of scratch resistance)
The coating on the resulting laminate, the haze value before abrasion test was measured H _1. Next, in an atmosphere of 23 ° C. and 55% RH, a surface of the coating film on the laminate was coated with steel wool # 0000 with a weight of 200 gf (per 4 cm ² area) using a Gakushin Abrasion Tester (manufactured by Toyo Seiki). The haze value H ₂ after placing and reciprocating 15 times was measured. When the haze value H ₂ was 30 or less, the scratch resistance was considered excellent. The haze value was measured according to JIS K7105 using a haze meter (“HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory Co., Ltd.).

[Raw materials / solvents]
The raw materials and solvents and their abbreviations used in the following Examples and Comparative Examples are as follows. (Compound (A))
・ IPDI: Isophorone diisocyanate (Evonik Degussa Japan, trade name “VESTANAT IPDI”)

(Compound (B))
T-33: polyol represented by the following formula (10) (trade name “Dynesorb T-33” manufactured by Daiwa Kasei Co., Ltd.)

T-35: polyol represented by the following formula (11) (trade name “Dynesorb T-35” manufactured by Daiwa Kasei Co., Ltd.)

(Compound (C): Compound having a hydroxyl group and a (meth) acryloyl group)
・ HEA: 2-hydroxyethyl acrylate (trade name “HEA” manufactured by Osaka Organic Chemicals)

(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 containing 40 to 45% by weight of pentaerythritol triacrylate and 35 to 40% by weight of pentaerythritol tetraacrylate as other compounds (catalog value) (“Biscoat (registered trademark) 300 manufactured by Osaka Organic Chemical Co., Ltd.) ")

(Photo radical polymerization initiator)
・ Omn184: 1-hydroxy-cyclohexyl-phenyl-ketone ("OMNIRAD (registered trademark) 184" manufactured by IGM)

(UV absorber)
TINUVIN479: hydroxyphenyltriazine (HPT) ultraviolet absorber (manufactured by BASF)

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

[Synthesis Example 1]
A 4-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 102 g of IPDI and 101 g of T-33, and further with 203 g of methyl ethyl ketone, 0.20 g of dioctyltin dilaurate, and 0.25 g of methyl hydroquinone. While being heated to 80 ° C. in an oil bath, the reaction was continued for about 2 hours until the suspension became transparent. After completion of the urethanization reaction, the mixture was cooled to 60 ° C., and 0.05 g of dioctyltin dilaurate was further 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 carried out for 8 hours while heating to 70 ° C. in an oil bath, and the end point of the urethanization reaction was confirmed by the disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum to obtain a urethane acrylate polymer. It was. 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 referred to as “U-1”.

[Synthesis Example 2]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 247 g of IPDI and 79 g of 3MPD were added, and 326 g of methyl ethyl ketone and 0.10 g of dioctyltin dilaurate were added, and 80 ° C. in an oil bath. Then, 116 g of T-33, 116 g of methyl ethyl ketone, and 0.12 g of dioctyltin dilaurate were added, and the reaction was continued for about 2 hours until the suspension became clear. After completion of the urethanization reaction, the reaction mixture was cooled to 60 ° C., and further 0.28 g of dioctyltin dilaurate and 0.25 g of methyl hydroquinone were added, and a mixture of 57 g of HEA and 57 g of methyl ethyl ketone was added dropwise over 1 hour to initiate the reaction. The reaction was carried out for 8 hours while heating to 70 ° C. in an oil bath, and the end point of the urethanization reaction was confirmed by the disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum to obtain a urethane acrylate polymer. It was. 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 referred to as “U-2”.

[Synthesis Example 3]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 223 g of IPDI and 59 g of 3MPD were added, and 282 g of methyl ethyl ketone and 0.08 g of dioctyltin dilaurate were added, and 80 ° C. in an oil bath. Then, 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 clear. After completion of the urethanization reaction, the mixture was cooled to 60 ° C., 0.27 g of dioctyltin dilaurate and 0.25 g of methyl hydroquinone were further added, and a mixture of 43 g of HEA and 43 g of methyl ethyl ketone was added dropwise over 1 hour to initiate the reaction. The reaction was carried out for 8 hours while heating to 70 ° C. in an oil bath, and the end point of the urethanization reaction was confirmed by the disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum to obtain a urethane acrylate polymer. It was. 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 referred to 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 were added, and 181 g of methyl ethyl ketone and 0.05 g of dioctyltin dilaurate were added, and 80 ° C. in an oil bath. Then, 258 g of T-35, 258 g of methyl ethyl ketone and 0.17 g of dioctyltin dilaurate were added and reacted for 2 hours. After completion of the urethanization reaction, the mixture was cooled to 60 ° C., and then 0.28 g of dioctyltin dilaurate and 0.25 g of methyl hydroquinone were added, and a mixture of 59 g of HEA and 59 g of methyl ethyl ketone was added dropwise over 1 hour to initiate the reaction. The reaction was carried out for 8 hours while heating to 70 ° C. in an oil bath, and the end point of the urethanization reaction was confirmed by the disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum to obtain a urethane acrylate polymer. It was. 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 referred to as “U-4”.

[Example 1]
In a flask, 56.9 g of urethane acrylate polymer “U-1” (solid content: 50% by weight), 1.4 g of Irg184 as a polymerization initiator, and Polyflow No. 1 as a leveling agent. 0.1 g of 75, 1.6 g of MEK, and 40.0 g of PGM were added 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]
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. 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.

Since Comparative Example 1 in which T-35 was introduced into the urethane (meth) acrylate structure instead of T-33 had an ester bond in the ultraviolet absorption skeleton compared to Example 2, hydrolysis derived from the ester bond was not performed. As a result, the b ₁ -b ₀ value in the metal weather test (28 cycle weather resistance) increased and the weather resistance decreased.

In Comparative Examples 2 and 3, in which T-33, which is a dihydroxy compound, was added to the curable composition, the solution was cloudy, the solution appearance was unacceptable, and a good coating film could not be obtained. On the other hand, Comparative Examples 4 and 5 to which T-35 was added had insufficient weather resistance. Further, 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 was poor in coating film appearance and weather resistance.

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

A cured product and a laminate obtained by using the urethane (meth) acrylate polymer or the curable composition of the present invention can be suitably used as a coating substitute film. For example, the present invention can be effectively applied to interior and exterior building materials and various members such as automobiles, home appliances, and information electronic materials. Especially the cured film which is embodiment of this invention can be used suitably as a decorating film which uses this as a topcoat layer.

Claims (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 an optionally substituted methylene group, alkylene group, —O— group, —NH— group, —S— group, —SO— group or —SO ₂ — group. To express. 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 alkoxylene group, or an arylene group. ]
2. The urethane (meth) acrylate polymer according to claim 1, wherein the formula (1) is the following formula (2).
   

   
3. The urethane (meth) acrylate polymer according to claim 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. The chemical structure represented by the formula (3) includes 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 urethane (meth) acrylate polymer described.
   

   

   (Formula (4-1), (4-2) in, X ¹ has the same meaning as X ¹ in the formula (2).)
5. The urethane (meth) acrylate polymer according to any one of claims 1 to 4, having a weight average molecular weight (Mw) of 500 to 30,000.
6. The urethane (meth) acrylate polymer according to any one of claims 1 to 5, wherein the ratio of the chemical structure represented by the 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 claims 1 to 6 and an organic solvent.
8. The curable composition according to claim 7, wherein the solubility parameter of the organic solvent is 8.0 to 11.5.
9. The curable composition according to claim 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 claims 7 to 9, wherein a proportion of the chemical structure represented by the formula (1) is contained in the polymerization component of the curable composition in an amount of 5 to 60% by weight.
11. A cured product of the curable composition according to any one of claims 7 to 10.
12. A laminate having a cured product of the curable composition according to any one of claims 7 to 10 on a substrate.
13. A headlamp lens having a cured product of the curable composition according to claim 11 on a substrate.
14. A glazing material having a cured product of the curable composition according to claim 11 on a substrate.
15. A decorative film having a cured product of the curable composition according to claim 11 on a substrate.
16. A step of applying the urethane (meth) acrylate polymer according to any one of claims 1 to 6 or the curable composition according to any one of claims 7 to 10 on a substrate; The manufacturing method of a film including the process of irradiating an active energy ray to a meth) acrylate polymer or the said curable composition, obtaining the laminated body which has hardened | cured material, and the process of extending | stretching the said laminated body.
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 urethane polymer precursor, and then the following compound (C) is reacted therewith.
    Compound (A): Polyisocyanate compound (B): Polyol represented by the following formula (5)
    

    

    [In the formula, A represents a single bond or an optionally substituted methylene group, alkylene group, —O— group, —NH— group, —S— group, —SO— group or —SO ₂ — group. To express. 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 alkoxylene group, or an arylene group. ]
    Compound (C): Compound having a hydroxyl group and a (meth) acryloyl group
18. 18. The urethane (meth) acrylate according to claim 17, wherein in addition to the compound (A) and the compound (B), the following compound (D) is reacted to obtain a urethane polymer precursor, and then the compound (C) is reacted. A method for producing a polymer.
    Compound (D): aliphatic polyol having a molecular weight of 500 or less