JP2017114976A - Urethane (meth)acrylate oligomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an urethane (meth)acrylate oligomer excellent in curability during active energy ray irradiation, coated film appearance after curing, stain resistance, scratch resistance and abrasion resistance as well as excellent in stretchability after curing for deformation of three dimensional processing, and a curable composition, a laminate and a cured film using the same.SOLUTION: There is provided an aliphatic urethane (meth)acrylate oligomer represented by the formula (1) and the formula (2).SELECTED DRAWING: None

Description

  The present invention is excellent in curability when irradiated with active energy rays, excellent in coating film appearance after curing, stain resistance, scratch resistance, abrasion resistance, etc., after curing to follow the deformation of three-dimensional processing The present invention relates to a urethane (meth) acrylate oligomer excellent in stretchability and a curable composition using the same. Moreover, this invention relates to the hardened | cured material and laminated body using this urethane (meth) acrylate oligomer and a curable composition.

  Radical polymerization type curable composition is cured in a short time by irradiation with active energy rays, and has excellent chemical resistance, stain resistance, scratch resistance, abrasion resistance, weather resistance, heat resistance, etc. Since a molded product can be provided, it is widely used in various surface processing fields and cast molded product applications. Among such curable compositions, from the viewpoint of curability and work efficiency, a cured product obtained by previously curing a curable composition containing a urethane (meth) acrylate oligomer with an active energy ray is manufactured. A method of performing three-dimensional processing at room temperature or under heating conditions after surface processing or the like is used. In this case, the cured product has stretchability after curing to follow deformation during three-dimensional processing. Necessary.

  Patent Document 1 discloses at least selected from diisocyanate compounds, polyether diols, polyester diols, and polycarbonate diols as having excellent transparency, low curing shrinkage, light transmittance, recording film protection performance, and low viscosity. A curable composition of a urethane (meth) acrylate oligomer that is a reaction product of one diol compound, an epoxy di (meth) acrylate compound, and a hydroxy group-containing (meth) acrylic acid ester is disclosed.

  Patent Document 2 describes a diisocyanate compound, a compound having two hydroxyl groups in the molecule and a molecular weight of 50 to 500, and a diepoxy compound having a cyclic skeleton in the molecule, as having excellent surface hardness and moldability. A curable composition of a urethane (meth) acrylate oligomer synthesized from a (meth) acrylic acid derivative and a reaction product of an epoxy (meth) acrylate having two hydroxyl groups in the molecule is disclosed.

  Patent Document 3 contains polyisocyanate, polycarbonate diol, and two hydroxyl groups and two ethylenically unsaturated groups in the molecule as having excellent curing performance, cured film flexibility, and elongation. A curable composition of a urethane (meth) acrylate oligomer that is a reaction product of a bifunctional epoxy (meth) acrylate is disclosed.

  Patent Document 4 describes a polyisocyanate having an alicyclic structure, a chain fatty acid having 8 to 16 carbon atoms, which has stretchability and is excellent in coating film appearance, scratch resistance, stain resistance, and abrasion resistance. A curable composition of a urethane (meth) acrylate oligomer that is a reaction product of a group diol and a hydroxyalkyl (meth) acrylate is disclosed.

JP 2004-35715 A JP 2010-275339 A JP 2008-127475 A JP 2014-214270 A

  According to the detailed study by the present inventors, the curable compositions described in Patent Documents 1 to 3 have a problem that the wear resistance and the stain resistance are particularly insufficient. It was done. Further, the active energy ray-curable oligomer described in Patent Document 4 has a problem that the curability is low and the obtained cured product has insufficient scratch resistance. That is, the object of the present invention is excellent in curability when irradiated with active energy rays, appearance of the coating film after curing, stain resistance, scratch resistance, abrasion resistance, and the like, and curing for following the deformation of three-dimensional processing. An object of the present invention is to provide a urethane (meth) acrylate oligomer excellent in later stretchability, and a curable composition, a laminate and a cured film using the same.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a urethane (meth) acrylate oligomer obtained using a specific raw material, and a curable composition containing this and an organic solvent. The present inventors have found that the problem can be solved and have reached the present invention. That is, the gist of the present invention resides in the following [1] to [13].

[1] A urethane (meth) acrylate oligomer having a chemical structure represented by the following formula (1) and a chemical structure represented by the formula (2).

(In formula (1), X ¹ is an aliphatic hydrocarbon structure having a molecular weight of 500 or less, and n is an integer of 2 to 8. In formula (2), R ¹ and R ² are each independently a hydrogen atom. or a methyl group, X ² is a linear aliphatic hydrocarbon structure having 2 to 12 carbon atoms.)

[2] The urethane (meth) acrylate oligomer according to [1], wherein the weight average molecular weight (Mw) is 1,500 to 30,000.

[3] The chemical structure represented by the formula (1) includes a chemical structure represented by the following formula (1-1) and / or a chemical structure represented by the following formula (1-2), [1] Or the urethane (meth) acrylate oligomer as described in [2].

[4] A method for producing a urethane (meth) acrylate oligomer, in which the following compound (A) and the following compound (B) are reacted to obtain a urethane prepolymer, and then the following compound (C) is reacted therewith.
Compound (A): Polyisocyanate compound (B): Aliphatic polyol compound having 2 to 8 hydroxyl groups and a molecular weight of 500 or less (C): Epoxy di (meth) having a chain aliphatic hydrocarbon structure having 2 to 12 carbon atoms Acrylate

[5] Compound (C) is obtained by reacting a diepoxy compound having a chain aliphatic hydrocarbon structure having 2 to 12 carbon atoms with a compound having a (meth) acryloyl group and a carboxyl group, and two hydroxyl groups And the method for producing a urethane (meth) acrylate oligomer according to [4], which is a compound having at least one (meth) acryloyl group.

[6] A curable composition comprising the urethane (meth) acrylate oligomer according to any one of [1] to [3] and an organic solvent.

[7] The curable composition according to [6], wherein the solubility parameter of the organic solvent is 8.0 to 11.5.

[8] The curable composition according to [6] or [7], wherein the solid content concentration is 5 to 90% by weight.

[9] A cured product obtained by curing the curable composition according to any one of [6] to [8].

[10] A laminate in which the curable composition according to any one of [6] to [8] is cured on a substrate.

[11] A cured film obtained by stretching the cured product according to [9].

[12] The urethane (meth) acrylate oligomer according to any one of [1] to [3] or the curable composition according to any one of [6] to [8] is applied onto a substrate. The manufacturing method of the cured film which passes through the process to perform, the process of irradiating an active energy ray to this curable composition, obtaining the hardened | cured material, and the process of extending | stretching this hardened | cured material.
[13] A decorative film comprising the cured product according to [9].

According to the present invention, the curability at the time of active energy ray irradiation, the coating appearance after curing, the stain resistance, the scratch resistance, the wear resistance, etc. are excellent, and the curing for following the deformation of the three-dimensional processing. There are provided a urethane (meth) acrylate oligomer excellent in later stretchability and a curable composition using the same. Moreover, according to this invention, the hardened | cured material, laminated body, and cured film using this urethane (meth) acrylate oligomer or this curable composition are provided.

  Embodiments of the present invention will be described in detail below, but the following descriptions are representative examples of embodiments of the present invention, and the present invention is not limited to these contents. In the present invention, “(meth) acrylate” is a general term for acrylate and methacrylate, and means one or both of acrylate and methacrylate. About “(meth) acryloyl” and “(meth) acryl” Is the same. Further, in the present invention, “to” is used in the sense of including numerical values described before and after it as a lower limit value and an upper limit value.

[Urethane (meth) acrylate oligomer]
The urethane (meth) acrylate oligomer of the present invention has a chemical structure represented by the following formula (1) and a chemical structure represented by the formula (2).

(In formula (1), X ¹ is an aliphatic hydrocarbon structure having a molecular weight of 500 or less, and n is an integer of 2 to 8. In formula (2), R ¹ and R ² are each independently a hydrogen atom. or a methyl group, X ² is a linear aliphatic hydrocarbon structure having 2 to 12 carbon atoms.)

  The urethane (meth) acrylate oligomer of the present invention and the curable composition of the present invention to be described later are curable at the time of irradiation with active energy rays, coating appearance after curing, stain resistance, scratch resistance, abrasion resistance, etc. It is also excellent in stretchability after curing for following the deformation of three-dimensional processing. In particular, the abrasion resistance and stain resistance are remarkably superior to those of the curable compositions described in Patent Documents 1 to 3, and the curability and scratch resistance are described in Patent Document 4. It is remarkably superior as compared with the curable composition.

The reason why the curable composition of the present invention exhibits the excellent effects as described above is not clear, but the stain resistance and wear resistance are considered to be due to the following reasons. That is, the urethane (meth) acrylate oligomer of the present invention has the chemical structure of X ¹ in the formula (1), so that the distance between the urethane bonds in the molecule is shortened, and the strongness derived from the urethane bond between the molecules. This is considered to be due to the formation of a proper hydrogen bond and the hardness and rigidity of the cured film. In the urethane (meth) acrylate oligomers described in Patent Documents 1 to 3, since a high-molecular diol having a long chain length is used, the amount of urethane bonds is low although hydrogen bonds are formed. It is estimated that the rigidity is insufficient and the contamination resistance and wear resistance are insufficient.

Moreover, about the sclerosis | hardenability at the time of active energy ray irradiation, and scratch resistance, it is estimated that the chemical structure of Formula (2) in the urethane (meth) acrylate oligomer of this invention has favorable curability. The chemical structure represented by the formula (2) has a good curability because the hydroxyl group in the formula (2) is electronically unstable and thus easily radicalized, and the adjacent (meth) acryloyl group It is presumed to be due to promoting curing. The urethane (meth) acrylate oligomer described in Patent Document 4 does not have the chemical structure represented by the formula (2) in the present invention, and compared with the urethane (meth) acrylate oligomer of the present invention, It is estimated that curability is low and scratch resistance is insufficient.

  In the urethane (meth) acrylate of the present invention, the chemical structure represented by the formula (1) is usually a reaction between a polyisocyanate of the compound (A) described below and an aliphatic polyol having a molecular weight of 500 or less of the compound (B). It is formed by. Moreover, in the urethane (meth) acrylate of the present invention, the chemical structure represented by the formula (2) is usually that of the product obtained by the reaction between the compound (A) and the compound (B) and the compound (C). It is formed by reaction with epoxy di (meth) acrylate having a chain aliphatic structure having 2 to 12 carbon atoms.

In formula (1), X ¹ is not particularly limited as long as it is an aliphatic hydrocarbon structure having a molecular weight of 500 or less, preferably an aliphatic hydrocarbon structure having a molecular weight of 400 or less, more preferably an aliphatic hydrocarbon structure having a molecular weight of 300 or less. Group hydrocarbon structure. On the other hand, X ¹ is an aliphatic hydrocarbon structure having a molecular weight of 14 or more, and preferably an aliphatic hydrocarbon structure having 28 or more.

  In the formula (1), n is an integer of 2 to 8, and n is preferably 2 to 6, and more preferably 2 to 4. Specifically, when n is 2, the chemical structure represented by the formula (1) is represented by the following formula (1-1). When n is 3, the chemical structure represented by the formula (1) The structure is represented by the following formula (1-2).

In the formula (2), X ² is not particularly limited as long as it is a chain aliphatic hydrocarbon structure having 2 to 12 carbon atoms, and even if it is a linear aliphatic hydrocarbon structure, a branched chain aliphatic hydrocarbon Although it may be a structure, it is preferably a linear aliphatic hydrocarbon structure. X ² is preferably a chain aliphatic hydrocarbon structure having 2 to 10 carbon atoms, more preferably a chain aliphatic hydrocarbon structure having 2 to 8 carbon atoms, from the viewpoint of curability of the urethane (meth) acrylate oligomer. More preferably, it is a 4-8 chain aliphatic hydrocarbon structure.

  The urethane (meth) acrylate of the present invention has a chemical structure represented by the formula (1), and has a chemical structure represented by the formula (2) as a terminal structure. In addition, if the urethane (meth) acrylate oligomer of the present invention has the chemical structure represented by the above formula (1) and the chemical structure represented by the formula (2), the effect of the present invention is not significantly impaired. It may have another chemical structure. Other chemical structures can be introduced by using “other raw material compounds” described later.

[Compound (A)]
The compound (A) used in the present invention is a polyisocyanate. Polyisocyanate is
It is a compound having a total of two or more isocyanate groups and / or substituents containing isocyanate groups in one molecule. As the compound (A), one type may be used, or two or more types may be used. In the present invention, the isocyanate group and the substituent containing the isocyanate group may be collectively referred to as “isocyanate groups”. In the compound (A), the isocyanate groups may be the same or different.

  As a substituent containing an isocyanate group, a C1-C5 alkyl group, a C1-C5 alkenyl group, or a C1-C5 alkoxyl group containing 1 or more isocyanate groups is mentioned, for example. Among these, an alkyl group having 1 to 5 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is particularly preferable.

  The type of polyisocyanate is not particularly limited, but examples thereof include chain aliphatic polyisocyanate, aromatic polyisocyanate, alicyclic polyisocyanate, etc. Even if one of these is used, two or more are combined. May be used. Among these, the component (A) preferably contains an alicyclic polyisocyanate from the viewpoint of enhancing the weather resistance and hardness of the resulting cured product.

  A chain aliphatic polyisocyanate is a compound having a chain aliphatic structure and two or more isocyanate groups bonded thereto. A chain aliphatic polyisocyanate is preferable from the viewpoint of enhancing the weather resistance of a cured film obtained by curing the curable composition and imparting stretchability. The chain aliphatic structure in the chain aliphatic polyisocyanate is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 6 carbon atoms. Examples of such chain aliphatic polyisocyanates include aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and dimer acid diisocyanate, and aliphatic triisocyanates such as tris (isocyanatehexyl) isocyanurate. Isocyanates. These may be used alone or in combination of two or more.

  An aromatic polyisocyanate is a compound having an aromatic structure and two or more isocyanate groups bonded thereto. Although the aromatic structure in aromatic polyisocyanate is not specifically limited, It is preferable that it is a C6-C13 aromatic structure. Examples of such aromatic polyisocyanates include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, and naphthalene diisocyanate. The aromatic polyisocyanate is preferable from the viewpoint of increasing the mechanical strength of a cured film obtained by curing the curable composition. Examples of such aromatic polyisocyanate include tolylene diisocyanate and diphenylmethane diisocyanate. These may be used alone or in combination of two or more.

  An alicyclic polyisocyanate is a compound having an alicyclic structure and two or more isocyanate groups. Although the alicyclic structure in a compound (A) is not specifically limited, It is preferable that it is C5-C15, and it is more preferable that it is C6 or more. Moreover, it is more preferable that it is C14 or less, and it is especially preferable that it is C13 or less. Furthermore, the alicyclic structure is preferably a cycloalkylene group. 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, it is preferable to contain isophorone diisocyanate.

[Compound (B)]
The compound (B) used in the present invention is an aliphatic polyol having 2 to 8 hydroxyl groups and having a molecular weight of 500 or less. An aliphatic polyol is a compound having an aliphatic structure and 2 to 8 hydroxyl groups bonded thereto. The aliphatic structure in the compound (B) may be a linear aliphatic structure, a branched aliphatic structure, or an alicyclic structure. The number of hydroxyl groups in the compound (B) is preferably 6 or less, more preferably 4 or less.

  Examples of the compound (B) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Linear aliphatic such as octanediol, 1,9-nonanediol, 1-10 decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol Diol having a hydrocarbon structure: propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,2- Branching of pentanediol, 3-methyl-1,5-pentanediol, 1,8-nonanediol, etc. A diol having a linear aliphatic hydrocarbon structure; a compound having a branched aliphatic hydrocarbon structure such as trimethylolpropane, glycerin, sorbitol, mannitol, pentaerythritol and three or more hydroxyl groups bonded thereto; cyclopropanediol, Examples include diols having an alicyclic structure such as cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, tricyclodecanediol, and adamantyldiol. Among these, those having a linear aliphatic hydrocarbon structure are preferable, and particularly containing at least one selected from ethylene glycol, 1,4-butanediol, and 1,12-dodecanediol is scratch-resistant after curing. It is preferable because it can provide a curable composition excellent in adhesion, abrasion resistance and stain resistance. Among these, ethylene glycol is most preferable in terms of stain resistance, and in terms of scratch resistance and wear resistance. In this case, it is most preferable to contain 1,12-dodecanediol.

  In the present invention, the compound (B) is used in an amount of 5% by weight or more based on the total diol component used as a raw material for the urethane (meth) acrylate oligomer, so that the stain resistance, scratch resistance, and abrasion resistance after curing. From the viewpoint of improving the ratio. In order to further enhance this effect, the compound (B) is more preferably 10% by weight or more, further preferably 20% by weight or more, particularly preferably 30% by weight or more, while the upper limit. Is usually 100% by weight.

[Compound (C)]
The compound (C) used in the present invention is an epoxy di (meth) acrylate having a chain aliphatic hydrocarbon structure having 2 to 12 carbon atoms. With the compound (C), the curability of the urethane (meth) acrylate oligomer can be improved. The chain aliphatic hydrocarbon structure may be a straight chain aliphatic hydrocarbon structure or a branched chain aliphatic hydrocarbon structure.

  Compound (C) is an epoxy di (meth) acrylate having a chain aliphatic hydrocarbon structure having 2 to 12 carbon atoms, preferably a diepoxy compound having a chain aliphatic hydrocarbon structure having 2 to 12 carbon atoms, A compound obtained by reacting a compound having a (meth) acryloyl group and a carboxyl group (in the present invention, containing (meth) acrylic acid) and having two hydroxyl groups and at least one (meth) acryloyl group. is there.

Examples of the diepoxy compound having a chain aliphatic hydrocarbon structure having 2 to 12 carbon atoms include 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-nonanediol diglycidyl ether, 1, An epoxy compound having a linear aliphatic hydrocarbon structure such as 10-decanediol diglycidyl ether, 1,11-undecanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether; propylene glycol diglycidyl ether Branched chain aliphatic hydrocarbon structures such as tereline, neopentylglycol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether An epoxy compound having

  Among these, a chain aliphatic hydrocarbon structure having 4 to 6 carbon atoms such as 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc. The epoxy compound having is preferable from the viewpoint of curability of the urethane (meth) acrylate oligomer.

  Examples of the compound having the (meth) acryloyl group and the carboxyl group include (meth) acrylic acid; carboxymethyl (meth) acrylate, carboxyethyl (meth) acrylate, carboxypropyl (meth) acrylate, and carboxypropyl (meth). Carboxyalkyl (meth) acrylates such as acrylate; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, phthalic anhydride, succinic anhydride, maleic anhydride Examples thereof include a reaction product with a carboxylic anhydride such as an acid. These may be used alone or in combination of two or more. Among these, from the viewpoint of curability of the urethane (meth) acrylate oligomer from which a compound having an acryloyl group is obtained, acrylic acid is particularly preferable.

  The epoxy di (meth) acrylate of the compound (C) can be obtained as a commercial product. Examples of the commercially available products include Kayalad R-167 (manufactured by Nippon Kayaku Co., Ltd.), NK oligo EA-5520, EA-5321 (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

[Other raw material compounds]
In the raw material compound of the urethane (meth) acrylate oligomer of the present invention, other raw material compounds other than the compound (A), the compound (B) and the compound (C) may be used as long as the effects of the present invention are not significantly inhibited. Good. Examples of such other raw material compounds include, for example, a polyol having an aromatic structure having a molecular weight of 500 or less, a high molecular weight polyol having a molecular weight higher than 500, a compound having a hydroxyl group other than the compound (C) and a (meth) acryloyl group, A chain extender etc. are mentioned.

  Examples of the diol having an aromatic structure having a molecular weight of 500 or less include bishydroxyethoxybenzene, bishydroxyethyl terephthalate, and bisphenol A.

  Examples of the high molecular weight polyol having a molecular weight higher than 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 the above polymer polyol is used, polycarbonate polyol is preferable. This polycarbonate polyol is obtained, for example, by reacting at least one carbonate compound selected from the group consisting of alkylene carbonate, diaryl carbonate, and dialkyl carbonate with diols and / or polyether polyols. Examples of diols as a raw material for polycarbonate polyol 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, at least one selected from 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol is preferable from the viewpoint of scratch resistance and wear resistance. Polycarbonate polyol can be obtained as a commercial product. Examples of the commercially available products include DURANOL (registered trademark) T4671, T4691, 5651, 6001 (manufactured by Asahi Kasei).

  Examples of the compound having a hydroxyl group and a (meth) acryloyl group other than the compound (C) include 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, 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, pentaerythrito Rutori (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like can be mentioned. Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol A hydroxyalkyl (meth) acrylate having an alkylene group having 2 to 4 carbon atoms between a (meth) acryloyl group such as penta (meth) acrylate and a hydroxyl group is particularly preferable from the viewpoint of mechanical strength of the resulting cured film. In particular, hydroxyalkyl poly (meth) having two or more (meth) acryloyl groups such as pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Acrylate is particularly preferred.

  A chain extender is a compound having two or more active hydrogens that react with isocyanate groups. Examples of the chain extender include low molecular weight diamine compounds having a number average molecular weight of 500 or less, and examples include aromatics such as 2,4- or 2,6-tolylenediamine, xylylenediamine, 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; And 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4,4′-dicyclohexylmethane Amine, 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.

The weight average molecular weight (Mw) of the urethane (meth) acrylate oligomer is preferably 1,500 or more, more preferably 3,000 or more, while 30,000.
Or less, more preferably 25,000 or less, and even more preferably 20,000 or less. When the weight average molecular weight of the urethane (meth) acrylate oligomer is not less than the above lower limit value, the three-dimensional processability of the resulting cured film tends to be good. When the number average molecular weight of the urethane (meth) acrylate oligomer is not more than the above upper limit, the stain resistance of the cured film obtained from the curable composition tends to be good. The weight average molecular weight of the urethane (meth) acrylate oligomer is related to the distance between the crosslink points in the network structure and the three-dimensional processability and stain resistance of the cured film obtained by using this, and the smaller the weight average molecular weight, the more the crosslink point The distance between them is short, and the distance between the crosslinking points tends to be longer as the weight average molecular weight is larger. The reason why the weight average molecular weight affects the three-dimensional processing suitability and stain resistance is that the longer the distance between the cross-linking points, the more flexible and easy-to-extend structure, the better the three-dimensional workability, while the shorter the distance, the stronger the network structure. It is presumed that the structure is improved and the scratch resistance, contamination resistance, and wear resistance are improved. In addition, the weight average molecular weight of a urethane (meth) acrylate oligomer can be calculated | required by a gel permeation chromatography measurement (GPC measurement), and a more detailed measuring method is shown in the below-mentioned Example.

[Method for producing urethane (meth) acrylate oligomer]
The method for producing the urethane (meth) acrylate oligomer of the present invention is not particularly limited. Usually, the compound (A) is urethanated with the compound (B), and the resulting product, the compound (C), and Can be made to react. Further, the charging ratio of each raw material compound at that time is usually substantially the same as or the same as the composition of the target urethane (meth) acrylate oligomer.

  More specifically, usually, the compound (A) and the compound (B) are reacted under conditions such that the isocyanate group becomes excessive to obtain a urethane prepolymer having an isocyanate terminal, and then the isocyanate terminal It can manufacture by the method with which the urethane prepolymer which has this, and the said compound (C) are made to react.

  According to said manufacturing method, the said urethane prepolymer is obtained by making a compound (A) and a compound (B) urethanate. A chemical structure represented by the formula (1) is formed by this urethanization reaction. The target urethane (meth) acrylate oligomer can be obtained by reacting a urethane prepolymer having an isocyanate group at the terminal with the compound (C). According to this production method, the molecular weight can be easily controlled, and the chemical structure represented by the formula (2) can be introduced at the terminal, so that a cured film can be easily obtained. .

  The amount of all isocyanate groups in the urethane (meth) acrylate oligomer and the amount of all functional groups that react with isocyanate groups such as hydroxyl groups and amino groups are usually theoretically equimolar. However, when the compound (C) has two or more hydroxyl groups, it is preferable to use an excessive amount of the compound (C) in order to avoid a decrease in handling properties due to an increase in viscosity accompanying the increase in the molecular weight. . For this reason, the amount of the compound (A), compound (B), compound (C) and other raw material compounds used as raw materials is the amount of all isocyanate groups in the urethane (meth) acrylate oligomer and the total functional groups that react with it. The amount is equivalent to 50% to 300% by equivalent weight or equivalent% of all functional groups relative to isocyanate groups.

  When producing a urethane (meth) acrylate oligomer, the amount of the compound (C) used is 5 moles relative to the total amount of the compound containing functional groups that react with isocyanate groups in the compound (C) and other raw materials. % Or more, preferably 10 mol% or more, and more preferably 70 mol% or less, and particularly preferably 50 mol% or less. By this ratio, the molecular weight of the obtained urethane (meth) acrylate oligomer can be controlled. When the proportion of the compound (C) is large, the molecular weight of the urethane (meth) acrylate oligomer tends to be small, and when the proportion is small, the molecular weight tends to be large.

  Further, in the case of using a chain extender, the amount of all polyols used is 70 mol with respect to the total amount of the compound (B) and the total amount of compounds other than the compound (B) and the polyol component and the chain extender. % Or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 95 mol% or more.

  In addition, said raw material ratio becomes a standard at the time of manufacturing a urethane (meth) acrylate oligomer. Actually, it is preferable to finely adjust the raw material blending ratio in the above range depending on the desired physical properties.

  In the production of the urethane (meth) acrylate oligomer, an organic solvent can be used for the purpose of adjusting the viscosity. An organic solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it. 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 organic solvent can be used usually at 300 parts by weight or less with respect to 100 parts by weight of the solid content in the reaction system.

  In the production of the urethane (meth) acrylate oligomer, the total content of the urethane (meth) acrylate oligomer to be produced and its raw material compound is preferably 20% by weight or more, more preferably 40% by weight or more based on the total amount of the reaction system. More preferably. The upper limit of the total content is usually 100% by weight. It is preferable for the total content of the urethane (meth) acrylate oligomer and its raw material compounds to be at least the above lower limit value because the reaction rate tends to increase and the production efficiency tends to improve.

  A catalyst can be used in the production of the urethane (meth) acrylate oligomer. This catalyst can be selected from the range in which the effects of the present invention can be obtained. For example, tin-based catalysts such as dibutyltin laurate, dibutyltin dioctate, dioctyltin dilaurate, and dioctyltin dioctate; bismuth tris (2- Examples thereof include bismuth-based catalysts such as ethyl hexanate 9. One type of catalyst may be used alone, or two or more types may be mixed and used, among which dioctyltin dilaurate, Bismuth tris (2-ethylhexanate) is preferable from the viewpoints of environmental adaptability, catalytic activity, storage stability, etc. The upper limit of the amount of the catalyst used is usually 2 with respect to the total content of the raw material compounds. 1,000 ppm or less, preferably 1,000 ppm or less, and the lower limit is usually 10 ppm or more, preferably 30 ppm or more. In addition, in the case of producing by the above method, in particular, the reaction of obtaining a urethane prepolymer by reacting the compound (A) with the compound (B), and the reaction of the compound (C) with respect to the urethane prepolymer. It is preferable to use the above-mentioned catalyst in both of the reactions.

Moreover, when using the compound which contains a (meth) acryloyl group like a compound (C) at the time of manufacture of a urethane (meth) acrylate oligomer, it is preferable to use a polymerization inhibitor together. Examples of such a polymerization inhibitor include phenols such as hydroquinone, methylhydroquinone, hydroquinone monoethyl ether, dibutylhydroxytoluene, amines such as phenothiazine and diphenylamine, copper salts such as copper dibutyldithiocarbamate, and manganese acetate. Manganese salts, nitro compounds, nitroso compounds and the like can be mentioned. A polymerization inhibitor may be used individually by 1 type, and 2 or more types may be mixed and used for it. Of these, phenols are preferable as the polymerization inhibitor. The amount of the polymerization inhibitor used is usually 3,000 ppm or less, preferably 1,000 ppm or less, particularly preferably 500 ppm or less, while the lower limit is usually 50 ppm, based on the total content of the raw material compounds. Above, preferably 100 ppm or more.

  In the production of the urethane (meth) acrylate oligomer, the reaction temperature is preferably 20 ° C. or higher, preferably 40 ° C. or higher, and more preferably 60 ° C. or higher. It is preferable for the reaction temperature to be at least the above lower limit value because the reaction rate increases and the production efficiency tends to improve. The reaction temperature is preferably 120 ° C. or lower, more preferably 100 ° C. or lower. It is preferable for the reaction temperature to be not more than the above upper limit value because side reactions such as allophanatization reaction are less likely to occur. When the reaction system contains an organic solvent, the reaction temperature is preferably not higher than the boiling point of the organic solvent. When a compound having a (meth) acryloyl group such as compound (C) is contained, ) From the viewpoint of preventing the acryloyl group from reacting excessively, it is preferably 70 ° C or lower. The reaction time is usually 5 to 20 hours.

(Curable composition)
The curable composition of the present invention contains at least the urethane (meth) acrylate oligomer of the present invention and an organic solvent.

<Organic solvent>
The curable composition of the present invention contains an organic solvent. By using an organic solvent, the urethane (meth) acrylate oligomer is dissolved well, and the viscosity for forming a coating film when the urethane (meth) acrylate oligomer is cured by irradiation with active energy rays as described later. And a uniform cured film can be obtained.

Any known organic solvent can be used as the organic solvent as long as the effects of the present invention are obtained. The organic solvent preferably has a solubility parameter (hereinafter referred to as “SP value”) of 8.0 to 11.5. An SP value of 8 or more is preferable from the viewpoint of the solubility of the urethane (meth) acrylate oligomer, and an SP value of 11.5 or less is preferable from the viewpoint of the transparency of the solution. Examples of the organic solvent in the above range 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), and 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 represents a solubility parameter, and the value is calculated by the method proposed by Fedors et al. Specifically, "POLYMER ENGINEERING"
AND SCIENCE, FEBRUARY, 1974, Vol. 14, no. 2, ROBERT F.R. FEDORS. (Pages 147 to 154) ". The SP value is a physical property value determined by the content of the hydrophobic group or hydrophilic group of the molecule, and means a value as a mixture when a mixed solvent is used.

  The organic solvent can usually be used at a solid content concentration of 5 to 90% by weight of the curable composition, the solid content concentration is preferably 10% by weight or more, more preferably 15% by weight or more, On the other hand, it is preferably 80% by weight or less, more preferably 70% by weight or less, and further preferably 60% by weight or less. The term “solid content” as used herein means not only urethane acrylate (meth) acrylate oligomers but also all components excluding solvents, and not only solids but also semi-solids and viscous liquids. Shall be included.

<Other ingredients>
The curable composition of the present invention may be further referred to as a component other than the urethane (meth) acrylate oligomer and the organic solvent (in the present invention, “other components”) as long as the effects of the present invention are not significantly impaired. May be included). Examples of other components include an active energy ray reactive monomer, an active energy ray curable oligomer (excluding the urethane (meth) acrylate oligomer of the present invention), a polymerization initiator, a photosensitizer, an epoxy compound, and other components. An additive etc. are mentioned.

  In the curable composition of the present invention, the content of the urethane (meth) acrylate oligomer is 40% by weight or more based on the total amount of all components excluding the solvent in the curable composition such as the active energy ray reactive component. It is preferable that it is 60% by weight or more. If the content of the urethane (meth) acrylate oligomer is not less than the above lower limit value, the curability will be good, and the three-dimensional workability tends to be improved without excessively increasing the mechanical strength when used as a cured film. Therefore, it is preferable. In addition, the upper limit of content of a urethane (meth) acrylate oligomer is 100 weight%.

  Further, in the curable composition of the present invention, the total content of the active energy ray-reactive component including the urethane (meth) acrylate oligomer is excellent in the curing speed and surface curability as the composition, and no tack remains. In view of the above, it is preferably 60% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and 95% by weight or more based on the total amount of the composition. It is particularly preferred. In addition, the upper limit of this content is 100 weight%.

  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 are used for the purpose of adjusting the hydrophilicity / hydrophobicity of the urethane (meth) acrylate oligomer and the physical properties such as hardness and elongation of the cured film when the resulting composition is a cured film. The 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 such active energy ray reactive monomers include vinyl ethers, (meth) acrylamides, and (meth) acrylates. Specific examples include styrene, α-methylstyrene, α-chlorostyrene. Aromatic vinyl monomers such as vinyltoluene and divinylbenzene; vinyl such as vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam and divinyl adipate Ester monomers; 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 (Meth) acrylamides such as methylenebis (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, (meth) acrylic acid hexyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic acid Stearyl, tetrahydrofurfuryl (meth) acrylate, (meth) a Morpholyl laurate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, 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) Monofunctional (meth) acyl such as phenyl acrylate 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 = 5-14), 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 = 3-16), di (meth) acrylic acid poly Li (1-methylbutylene glycol) (n = 5-20), 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) acrylate, di (meth) acrylate dicyclopentanediol, di (meth) acrylate tricyclodecane, bisphenol A diglycidyl ether diacrylate, 1,4 -Cyclohexanedimethanol diglycidyl ether diacrylate, ethylene glycol diglycidyl ether diacrylate, 1,4-butanediol diglycidyl ether diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, trimethylolpropane triacrylate (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 polyoxypropyl (meth) acrylate, Tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) i Cyanurate 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 oxide-added bisphenol F di (meth) acrylate, And polyfunctional (meth) acrylates such as tricyclodecane dimethanol di (meth) acrylate, bisphenol A epoxy di (meth) acrylate, and bisphenol F epoxy di (meth) acrylate.

Among these, in particular, in applications where coating properties are required for the composition of the present invention, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate , 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 in the inside is preferred. On the other hand, in applications where mechanical strength of the resulting cured film is required, di (meth) acrylic acid-1,4-butanediol, di (meth) ) Acrylic acid-1,6-hexanediol, di (meth) acrylic acid-1,9-nonane , Neopentyl glycol di (meth) acrylate, tricyclodecane di (meth) acrylate, 1,4-cyclohexanedimethanol diglycidyl ether diacrylate, ethylene glycol diglycidyl ether diacrylate, 1,4-butanediol Diglycidyl ether diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) Preferred are polyfunctional (meth) acrylates such as acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. In applications where stretchability of the cured film is required, polyethylene glycol di (meth) acrylate (n = 5-14), polypropylene glycol di (meth) acrylate (n = 5-14), di (meth) acrylic acid Polyether (meth) acrylates such as polybutylene glycol (n = 3 to 16) and poly (1-methylbutylene glycol) di (meth) acrylate (n = 5 to 20) are preferred.

  In the curable composition of the present invention, the content of the active energy ray-reactive monomer is based on the total amount of the composition from the viewpoint of adjusting the viscosity of the composition and adjusting physical properties such as hardness and elongation of the cured film obtained. Thus, it is preferably 50% by weight or less, more preferably 30% by weight or less, further preferably 20% by weight or less, and further more preferably 10% by weight or less.

  The active energy ray-curable oligomer may be used alone or in combination of two or more. Examples of the active energy ray-curable oligomer include epoxy (meth) acrylate oligomers, acrylic (meth) acrylate oligomers, polyester (meth) acrylate oligomers, polycarbonate (meth) acrylate oligomers, and polybutadiene (meth) acrylate oligomers. And polyether (meth) acrylate (excluding those described in the active energy ray-reactive monomer). In the curable composition of the present invention, the content of the active energy ray-reactive oligomer is 50% by weight or less based on the total amount of the composition from the viewpoint of adjusting physical properties such as hardness and elongation of the obtained cured film. It is preferably 30% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less.

  The polymerization initiator is mainly used for the purpose of improving the initiation efficiency of a polymerization reaction that proceeds by irradiation with active energy rays such as ultraviolet rays and electron beams. As the polymerization initiator, a photoradical polymerization initiator which is a compound having a property of generating radicals by light is generally used, and any known photoradical polymerization initiator can be used as long as the effects of the present invention can be obtained. It is. 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 photo radical polymerization initiator include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) benzophenone, 4-phenylbenzophenone, methyl orthobenzoylbenzoate, 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, methylbenzoylformate, 2-methyl-1- [4- ( Tilthio) 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.

  In addition, 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 above-mentioned radical photopolymerization initiator. It may be. Any known cationic photopolymerization initiator may be used as long as it does not significantly impair the effects of the present invention.

  The content of these polymerization initiators in the curable composition of the present invention is preferably 10 parts by weight or less, preferably 5 parts by weight or less with respect to 100 parts by weight of the total of the active energy ray reactive components. More preferably. It is preferable for the content of the photopolymerization initiator to be equal to or lower than the above upper limit value because the mechanical strength is not easily lowered by the initiator decomposition product.

The photosensitizer can be used for the same purpose as the polymerization initiator. A photosensitizer may be used individually by 1 type and may be used in mixture of 2 or more types. As the photosensitizer, any known photosensitizer can be used as long as the effects of the present invention are obtained. Examples of such photosensitizers include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, And 4-dimethylaminoacetophenone.

  In the curable composition of the present invention, the content of the photosensitizer is preferably 10 parts by weight or less, preferably 5 parts by weight or less, with respect to 100 parts by weight as a total of the active energy ray reactive components. It is more preferable that It is preferable for the content of the photosensitizer to be not more than the above upper limit value because it is difficult for the mechanical strength to decrease due to a decrease in the crosslinking density.

  The additive is optional as long as the effects of the present invention are obtained, and various materials added to a composition used for the same application can be used as the additive. An additive may be used individually by 1 type, and 2 or more types may be mixed and used for it. Examples of such additives include glass fiber, glass bead, silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, mica, talc, kaolin, metal oxide, metal fiber, iron, lead, and metal powder. Fillers such as carbon fibers, carbon black, graphite, carbon nanotubes, carbon materials such as fullerenes such as C60 (fillers and carbon materials may be collectively referred to as “inorganic components”); Agent, heat stabilizer, ultraviolet absorber, hindered amine light stabilizer (HALS), anti-fingerprint agent, surface hydrophilizing agent, antistatic agent, slipperiness imparting agent, plasticizer, mold release agent, antifoaming agent, leveling agent, Anti-settling agents, surfactants, thixotropy imparting agents, lubricants, flame retardants, flame retardant aids, polymerization inhibitors, fillers, silane coupling agents and other modifiers; pigments, dyes, hue adjustments Colorants and the like; and, monomer and / or oligomer thereof, or a curing agent required for the synthesis of inorganic components, catalysts, curing accelerators like; and the like.

  In the curable composition of the present invention, the content of the additive is preferably 10 parts by weight or less, and preferably 5 parts by weight or less, with respect to 100 parts by weight of the total of the active energy ray reactive components. It is more preferable. It is preferable for the content of the additive to be equal to or less than the above upper limit value because it is difficult for the mechanical strength to decrease due to a decrease in the crosslinking density.

There are no particular limitations on the method of incorporating the optional components such as the aforementioned additives into the curable composition of the present invention, and conventionally known mixing and dispersion methods and the like can be mentioned. In addition, in order to disperse | distribute the said arbitrary component more reliably, it is preferable to perform a dispersion | distribution process using a disperser. Specifically, for example, two rolls, three rolls, bead mill, ball mill, sand mill, pebble mill, tron mill, sand grinder, seg barrier striker, planetary stirrer, high speed impeller disperser, high speed stone mill, high speed impact mill , A kneader, a homogenizer, an ultrasonic disperser and the like.

  The viscosity of the curable composition of the present invention can be adjusted as appropriate according to the use and usage of the curable composition. From the viewpoints of handleability, coatability, moldability, three-dimensional formability, etc., the E type The viscosity at 25 ° C. in the viscometer (rotor 1 ° 34 ′ × R24) is preferably 5 mPa · s or more, more preferably 10 mPa · s or more, while it is 50,000 mPa · s or less. It is preferably 10,000 mPa · s or less, more preferably 5,000 mPa · s or less, and particularly preferably 2,000 mPa · s or less. The viscosity of the curable composition can be adjusted by, for example, the content of the urethane (meth) acrylate oligomer according to the present invention, the type of the optional component, the blending ratio thereof, and the like.

  As a coating method of 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 coater method, a lip coater method, Known methods such as a die coater method, a slot die coater method, an air knife coater method, and a dip coater method can be applied. Among them, a bar coater method and a gravure coater method are preferable.

[Hardened product / Laminate]
A cured product can be obtained by irradiating the above-described curable composition of the present invention with active energy rays (hereinafter sometimes referred to as “cured product of the present invention”). Examples of the active energy ray used for curing the curable composition include infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, and γ rays. It is preferable to use an electron beam or an ultraviolet ray from the viewpoint of apparatus cost and productivity. As a light source, an electron beam irradiation apparatus, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, Ar A laser, a He—Cd laser, a solid laser, a xenon lamp, a high frequency induction mercury lamp, sunlight, or the like is suitable.

The irradiation amount of the active energy ray can be appropriately selected according to the type of the active energy ray. For example, when it hardens | cures by electron beam irradiation, it is preferable that the irradiation amount is 1-15 Mrad. Moreover, when hardening by ultraviolet irradiation, it is preferable that it is 50-1,500 mJ / cm < ² >.
When curing, any atmosphere of air, inert gas such as nitrogen or argon may be used. Moreover, you may irradiate in the sealed space between a film or glass, and a metal metal mold | die.

  In the present invention, the thickness of the cured film is appropriately determined according to the intended use, but the lower limit is preferably 1 μm, more preferably 2 μm. The upper limit is preferably 100 μm, more preferably 50 μm, and particularly preferably 20 μm. If the film thickness is equal to or greater than the above lower limit value, the appearance of design and functionality after three-dimensional processing tends to be favorable. On the other hand, if the film thickness is equal to or less than the upper limit value, internal curability and three-dimensional workability are suitable. Tends to be good.

Moreover, a laminated body can be obtained by hardening the curable composition of this invention on a base material (henceforth "the laminated body of this invention" may be called). The laminate of the present invention is not particularly limited as long as the cured product of the present invention is formed on the substrate, and a layer other than the substrate and the cured product of the present invention is interposed between the substrate and the cured product of the present invention. You may have, and you may have on the outer side. 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. Apply a known method such as applying the upper layer and curing again with active energy rays, or applying each layer to the release film or base film and then laminating the layers in an uncured or semi-cured state. Although possible, a method of curing with an active energy ray after laminating in an uncured state is preferable from the viewpoint of improving adhesion between layers. 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.

  Examples of the substrate include polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyolefins such as polypropylene and polyethylene; various plastics such as nylon, polycarbonate, and (meth) acrylic resin, 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.

  In the present invention, since the obtained cured product is excellent in stretchability, it is preferable to stretch the cured product to obtain a cured film, and it is particularly preferable to produce a cured film by the following method. A preferable method for producing a cured film includes a step of applying the curable composition of the present invention on a substrate, a step of irradiating the curable composition with active energy rays to obtain a cured product, and a step of stretching the cured product. It is by going through. Since the urethane (meth) acrylate oligomer of the present invention has stretchability after curing capable of following deformation during three-dimensional processing, it exhibits good stretchability in the step of stretching the cured product. The obtained cured film has particularly good suitability for deformation during three-dimensional processing.

  In the present invention, in the method for producing the cured film, each of the step of applying the curable composition onto the substrate and the step of obtaining a cured product by irradiating the curable composition with active energy rays. Can be performed under the aforementioned conditions. Moreover, in the manufacturing method of this cured film, the process of extending | stretching hardened | cured material can be normally extended by heating on the conditions of 60-200 degreeC, Preferably 100-180 degreeC. As the stretching method, a known method can be used. For example, any of methods such as insert molding, in-mold molding, overlay molding, blow molding, and vacuum molding can be used.

  The cured product and laminate obtained by using the urethane (meth) acrylate oligomer and 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. In particular, the cured film of the present invention is useful as a decorative film using this as a top coat layer.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by the following example. In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

[Measurement method of physical properties]
The measurement / evaluation method of the physical properties of the urethane (meth) acrylate oligomer and the cured film in the following Examples and Comparative Examples is as follows.

<Physical properties of urethane (meth) acrylate oligomer>
1-1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of urethane (meth) acrylate oligomer
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 and number average molecular weight (GPC measurement value) of the urethane (meth) acrylate oligomer were measured.

<Physical properties of cured film>
2-1) Evaluation of coating film appearance The coating film appearance of the cured film laminated on the polyethylene terephthalate obtained by the film forming method I described later was visually evaluated according to the following criteria.
○: Uniform film thickness, no abnormalities such as foreign matter, wrinkles, and skin on the surface of the coating. Abnormalities such as dirt skin are observed ×: Abnormalities such as foreign matter, wrinkles, and skin are observed on the surface of the coating film

2-2) Evaluation of scratch resistance (nail scratch) For the cured film laminated on the polyethylene terephthalate obtained by the film forming method I described later, the index finger, middle finger of the dominant hand under an atmosphere of 23 ° C. and 55% RH, It was made to reciprocate 10 times with the fingernail. The degree of damage of the cured film was visually evaluated according to the following criteria.
○: No change in appearance ○-: Slight dents are present △: Clear dents are present △-: The paint film is shaved and whitened ×: The paint film is shaved as white powder appears

2-3) About film forming methods cured film laminated on a polyethylene terephthalate obtained in the I evaluation described later abrasion resistance (cloth), the haze value measured before the scratch test was H _1. On the other hand, under an atmosphere of 23 ° C. and 55% RH, a weight of 200 gf or 500 gf (per area of 4 cm ² ) is placed on a dry cloth (for cotton-JIS L 0803 compliant dyeing fastness test), and the cured film surface is subjected to a Gakusei abrasion tester 100 times of reciprocating rubbing (manufactured by Toyo Seiki Co., Ltd.) and the haze value measured immediately after that was H ₂ . The difference (ΔH (ΔH = H ₂ −H ₁ )) between H ₂ and H ₁ was determined and evaluated according to the following criteria. In the above, the haze value was measured in accordance with JIS K7105 using a haze meter (“HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory Co., Ltd.).
○: ΔH ≦ 2.5
○-: 2.5 <ΔH ≦ 5.0
Δ: 5.0 <ΔH ≦ 10.0
Δ-: 10.0 <ΔH ≦ 15.0
×: 15.0 <ΔH

2-4) Evaluation of stain resistance Using a cured film obtained by the film-forming method I described later, red water-based ink (Pilot Inc. cartridge ink / red / IRF-12S-R), 10% by weight hydrochloric acid aqueous solution, 10 A 0.04 g / cm ² contact with a weight% aqueous sodium hydroxide solution (hereinafter referred to as a contaminant),
After standing for 30 hours in an atmosphere of 55% RH, the degree of contamination after wiping off contaminants with absorbent cotton containing water was visually evaluated. The evaluation criteria for each pollutant are as follows.
<Red water-based ink>
○: No change in appearance ○-: Orange is visible on white paper △: Orange is visible in any state Δ-: Light red on the whole x: Red on the whole <10 wt% hydrochloric acid aqueous solution>
○: No change in appearance ○-: Marks remain on the ridges of the contact part Δ: The whole is slightly white Δ-: The whole is slightly yellow ×: The whole is yellow <10 wt% sodium hydroxide aqueous solution>
○: No change in appearance ○-: Marks remain on the wrinkles of the contact part Δ: Fine cracks appear in the wrinkles of the contact part Δ-: Fine cracks appear in the whole x: The whole is white

2-5) Evaluation of curability (curing rate) An uncured film of the film forming method I described later is measured by an ATR method using an infrared spectrophotometer ("Spectrum 100" (number of scans: 4 times) manufactured by Perkin Elmer). in measured, the value obtained by dividing the peak intensity at around 1,720 cm ^-1 derived from a carbonyl group a peak intensity at around 810 cm ^-1 derived from C = C double bond was _{P 0.} A cured film obtained by curing in a film forming method I of the method described below, ATR method determined in the same manner, the calculated value was defined as P _5. From the obtained value, the curing rate (%) = 100− (P ₅ / P ₀ ) × 100 was calculated.

2-6) Evaluation of stretchability A cured film of the film formation method II described later is cut into a width of 10 mm, and a tensile load measuring machine (“MX2-500N” manufactured by Imada Co., Ltd.) is used. The elongation at break was measured under the conditions of 40 mm / min and the distance between chucks of 40 mm, and evaluated according to the following criteria.
A: Elongation 100% or more B: Elongation 50% or more and less than 100% X: Elongation less than 50%

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

(Compound (B))
EG: ethylene glycol 1,4-BD: 1,4-butanediol 1,12-DD: 1,12-dodecanediol

(Compound (B) (for Comparative Example))
T4691: Polycarbonate polyol "Duranol (registered trademark) T4691" manufactured by Asahi Kasei Corporation
1,4-butanediol / 1,6-hexanediol = 9/1 (mass ratio)
Number average molecular weight: 1,000
Hydroxyl value: 119.4 mg KOH / g
・ T5651: Polycarbonate polyol “Duranol (registered trademark) T5651” manufactured by Asahi Kasei Corporation
1,5-pentanediol / 1,6-hexanediol = 5/5 (mass ratio)
Number average molecular weight: 1,000
Hydroxyl value: 110.0 mgKOH / g

(Compound (C))
R-167: “Kayarad (registered trademark) R-167” manufactured by Nippon Kayaku Co., Ltd.
1,6-hexanediol diglycidyl ether diacrylate

(Compound (C) (for Comparative Example))
3000A: “Epoxy ester (registered trademark) 3000A” manufactured by Kyoeisha Chemical Co., Ltd.
Bisphenol A diglycidyl ether diacrylate V-300: “Biscoat (registered trademark) 300” manufactured by Osaka Organic Chemical Co., Ltd.
Mixture of 40 to 45% by weight of pentaerythritol triacrylate and 35 to 40% by weight of pentaerythritol tetraacrylate (catalog value)
Hydroxyl value: 120 mgKOH / g

(Organic solvent)
MEK: methyl ethyl ketone (SP value: 9.0)
IPA: isopropyl alcohol (SP value: 11.5)

[Example 1]
Into a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 166 g of IPDI and 41 g of ethylene glycol were added, and 207 g of methyl ethyl ketone and 0.02 g of bismuth tris (2-ethylhexanoate) were added. The mixture was allowed to react for 9 hours while heating to 80 ° C. in an oil bath. After completion of the urethanization reaction, the mixture was cooled to 60 ° C., 0.25 g of bismuth tris (2-ethylhexanoate), 0.15 g of methylhydroquinone and 93 g of methyl ethyl ketone were added, and 93 g of R-167 was added dropwise to start the reaction. I let you. The reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath. After confirming the end point of the urethanization reaction by disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, 400 g of methyl ethyl ketone was added and cured. A functional resin composition was obtained. About the urethane acrylate oligomer in the obtained curable composition, the weight average molecular weight and the number average molecular weight were measured by the method of said 1-1). The obtained results are shown in Table-1.

  The curable composition was formed into a film by the following film forming method I and film forming method II, and the evaluations of the above 2-1) to 2-6) were performed. These results are shown in Table-1.

(Film forming method I)
The curable composition was coated on a polyethylene terephthalate film with a bar coater to form a coating film, then dried at 60 ° C. for 1 minute, and an accelerating voltage using an electron beam irradiation apparatus (CB175, manufactured by Eye Graphic). A dried film was irradiated with an electron beam under the conditions of 165 kV and an irradiation dose of 5 Mrad, and further cured at 23 ° C. for one day to obtain a laminate (cured film) in which a cured film having a thickness of about 5 μm was laminated on polyethylene terephthalate. It was.

(Film Formation Method II)
The curable composition was coated on a polyethylene terephthalate film with a bar coater to form a coating film, then dried at 60 ° C. for 1 minute, and an accelerating voltage using an electron beam irradiation apparatus (CB175, manufactured by Eye Graphic). After irradiating the dried coating film with an electron beam under the conditions of 165 kV and an irradiation dose of 5 Mrad, and further curing at 23 ° C. for one day to form a cured film, the cured film is peeled off from the polyethylene terephthalate film and cured to a thickness of about 30 μm. A membrane was obtained.

[Example 2]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 135 g of IPDI, 115 g of 1,12-dodecanediol, and 250 g of methyl ethyl ketone and 0.03 g of dioctyltin dilaurate The reaction was conducted for 9 hours while heating to 80 ° C. in a bath. After completion of the urethanization reaction, the mixture was cooled to 60 ° C., 0.07 g of dioctyltin dilaurate, 0.15 g of methyl hydroquinone and 50 g of methyl ethyl ketone were further added, and 50 g of R-167 was added dropwise to initiate the reaction. Except the above operation, it implemented similarly to Example 1 and obtained the urethane acrylate oligomer and the curable composition. Each evaluation was performed in the same manner as in Example 1.

[Example 3]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 106 g of IPDI, 81 g of 1,12-dodecanediol, 183 g of methyl ethyl ketone and 0.02 g of dioctyltin dilaurate were added and oiled. The reaction was conducted for 9 hours while heating to 80 ° C. in a bath. After completion of the urethanization reaction, the mixture was cooled to 60 ° C., 0.07 g of dioctyltin dilaurate, 0.15 g of methyl hydroquinone and 113 g of methyl ethyl ketone were further added, and 113 g of R-167 was added dropwise to initiate the reaction. Except the above operation, it implemented similarly to Example 1 and obtained the urethane acrylate oligomer and the curable composition. Each evaluation was performed in the same manner as in Example 1.

[Example 4]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 79 g of IPDI, 16 g of 1,4-butanediol, and 146 g of T-4691 were added, and 241 g of methyl ethyl ketone, dioctyltin dilaurate 0 0.02 g was added and reacted for 9 hours while heating to 80 ° C. in an oil bath. After completion of the urethanization reaction, the mixture was cooled to 60 ° C., 0.07 g of dioctyltin dilaurate, 0.15 g of methyl hydroquinone and 59 g of methyl ethyl ketone were further added, and 59 g of R-167 was added dropwise to initiate the reaction. Except the above operation, it implemented similarly to Example 1 and obtained the urethane acrylate oligomer and the curable composition. Each evaluation was performed in the same manner as in Example 1.

[Comparative Example 1]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 152 g of IPDI and 38 g of ethylene glycol were added, and 190 g of methyl ethyl ketone and 0.02 g of bismuth tris (2-ethylhexanoate) were added. The mixture was allowed to react for 9 hours while heating to 80 ° C. in an oil bath. After completion of the urethanization reaction, the reaction mixture was cooled to 60 ° C., 0.25 g of bismuth tris (2-ethylhexanoate), 0.15 g of methylhydroquinone and 110 g of methyl ethyl ketone were added, and 110 g of 3000A was added dropwise to initiate the reaction. . The reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath, and after confirming the end point of the urethanation reaction by disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, 250 g of methyl ethyl ketone and 150 g of isopropyl alcohol were obtained. Was added to obtain a curable resin composition. Each evaluation was performed in the same manner as in Example 1.

[Comparative Example 2]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 164 g of IPDI and 40 g of ethylene glycol were added, and 204 g of methyl ethyl ketone and 0.02 g of bismuth tris (2-ethylhexanoate) were added. The mixture was allowed to react for 9 hours while heating to 80 ° C. in an oil bath. After completion of the urethanization reaction, the mixture was cooled to 60 ° C., 0.25 g of bismuth tris (2-ethylhexanoate), 0.15 g of methylhydroquinone and 96 g of methyl ethyl ketone were added, and 96 g of V-300 was added dropwise to start the reaction. I let you. Except the above operation, it implemented similarly to Example 1 and obtained the urethane acrylate oligomer and the curable composition. Each evaluation was performed in the same manner as in Example 1.

[Comparative Example 3]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 128 g of IPDI, 110 g of 1,12-dodecanediol, 238 g of methyl ethyl ketone, and 0.02 g of dioctyltin dilaurate are added. The reaction was conducted for 9 hours while heating to 80 ° C. in a bath. After completion of the urethanization reaction, the reaction mixture was cooled to 60 ° C., 0.06 g of dioctyltin dilaurate, 0.15 g of methylhydroquinone and 62 g of methyl ethyl ketone were further added, and 62 g of 3000A was added dropwise to initiate the reaction. Except the above operation, it implemented similarly to Example 1 and obtained the urethane acrylate oligomer and the curable composition. Each evaluation was performed in the same manner as in Example 1.

[Comparative Example 4]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 142 g of IPDI, 121 g of 1,12-dodecanediol, 263 g of methyl ethyl ketone and 0.01 g of dioctyltin dilaurate were added and oiled. The reaction was conducted for 9 hours while heating to 80 ° C. in a bath. After completion of the urethanization reaction, the mixture was cooled to 60 ° C., 0.08 g of dioctyltin dilaurate, 0.15 g of methyl hydroquinone and 37 g of methyl ethyl ketone were further added, and 37 g of V-300 was added dropwise to initiate the reaction. Except the above operation, it implemented similarly to Example 1 and obtained the urethane acrylate oligomer and the curable composition. Each evaluation was performed in the same manner as in Example 1.

[Comparative Example 5]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 117 g of IPDI and 89 g of 1,12-dodecanediol were added, and 206 g of methyl ethyl ketone and bismuth tris (2-ethylhexanoate) were added. 0.02 g was added and reacted for 9 hours while heating to 80 ° C. in an oil bath. After completion of the urethanization reaction, the mixture was cooled to 60 ° C., 0.25 g of bismuth tris (2-ethylhexanoate), 0.15 g of methylhydroquinone and 94 g of methyl ethyl ketone were added, and 94 g of V-300 was added dropwise to start the reaction. I let you. Except the above operation, it implemented similarly to Example 1 and obtained the urethane acrylate oligomer and the curable composition. Each evaluation was performed in the same manner as in Example 1.

[Comparative Example 6]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 57 g of IPDI and 195 g of T-5651, and 252 g of methyl ethyl ketone and 0.02 g of dioctyltin dilaurate were added in an oil bath. The reaction was conducted for 9 hours while heating to 80 ° C. After completion of the urethanization reaction, the reaction mixture was cooled to 60 ° C., 0.13 g of dioctyltin dilaurate, 0.15 g of methyl hydroquinone and 48 g of methyl ethyl ketone were further added, and 48 g of R-167 was added dropwise to initiate the reaction. Except the above operation, it implemented similarly to Example 1 and obtained the urethane acrylate oligomer and the curable composition. Each evaluation was performed in the same manner as in Example 1.

[Comparative Example 7]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, put 58 g of IPDI and 177 g of T-5651, and further add 235 g of methyl ethyl ketone and 0.02 g of dioctyltin dilaurate in an oil bath. The reaction was conducted for 9 hours while heating to 80 ° C. After completion of the urethanization reaction, the reaction mixture was cooled to 60 ° C., 0.13 g of dioctyltin dilaurate, 0.15 g of methyl hydroquinone and 65 g of methyl ethyl ketone were further added, and 65 g of R-167 was added dropwise to initiate the reaction. Except the above operation, it implemented similarly to Example 1 and obtained the urethane acrylate oligomer and the curable composition. Each evaluation was performed in the same manner as in Example 1.

[Evaluation results]
From the results shown in Table 1, the following can be seen when Example 1 and Comparative Examples 1 and 2, Example 2 and Comparative Examples 3 and 4, and Example 3 and Comparative Example 5 are compared. First, Comparative Examples 1 and 3 are examples that do not have the chemical structure represented by Formula (2) because “3000A” was used instead of Compound (C). The curability was low as compared with each of 1 and 2, and accordingly the scratch resistance and wear resistance were poor. Comparative Examples 2, 4 and 5 are examples that do not have the chemical structure represented by the above formula (2) because the compound (C) was not used and “V-300” was used instead. As in the example using “3000A”, the curability was low as compared with each of Examples 1 to 3, and accordingly the scratch resistance and wear resistance were poor.

  Further, Comparative Examples 6 and 7 are examples in which the compound (B) was not used and “T4691” and “T5651” were used instead, and thus the chemical structure represented by the formula (1) was not present. However, compared with Examples 1-4, abrasion resistance and stain resistance were bad.

  The cured product and laminate obtained by using the urethane (meth) acrylate oligomer and 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. In particular, the cured product of the present invention is useful as a decorative film using this as a top coat layer.

Claims (13)

A urethane (meth) acrylate oligomer having a chemical structure represented by the following formula (1) and a chemical structure represented by the formula (2).

(In formula (1), X ¹ is an aliphatic hydrocarbon structure having a molecular weight of 500 or less, and n is an integer of 2 to 8. In formula (2), R ¹ and R ² are each independently a hydrogen atom. or a methyl group, X ² is a linear aliphatic hydrocarbon structure having 2 to 12 carbon atoms.)   The urethane (meth) acrylate oligomer according to claim 1, wherein the weight average molecular weight (Mw) is 1,500 to 30,000. The chemical structure represented by the formula (1) includes a chemical structure represented by the following formula (1-1) and / or a chemical structure represented by the following formula (1-2). The urethane (meth) acrylate oligomer described.

A method for producing a urethane (meth) acrylate oligomer, in which the following compound (A) and the following compound (B) are reacted to obtain a urethane prepolymer, and then the following compound (C) is reacted therewith.
Compound (A): Polyisocyanate compound (B): Aliphatic polyol compound having 2 to 8 hydroxyl groups and a molecular weight of 500 or less (C): Epoxy di (meth) acrylate having a chain aliphatic structure having 2 to 12 carbon atoms   The compound (C) is obtained by reacting a diepoxy compound having a chain aliphatic structure having 2 to 12 carbon atoms with a compound having a (meth) acryloyl group and a carboxyl group, two hydroxyl groups and at least one ( The method for producing a urethane (meth) acrylate oligomer according to claim 4, which is a compound having a (meth) acryloyl group.   A curable composition comprising the urethane (meth) acrylate oligomer according to any one of claims 1 to 3 and an organic solvent.   The curable composition of Claim 6 whose solubility parameter of the said organic solvent is 8.0-11.5.   The curable composition of Claim 6 or 7 whose solid content concentration is 5-90 weight%.   Hardened | cured material which the curable composition of any one of Claims 6 thru | or 8 hardened | cured.   The laminated body which the curable composition of any one of Claim 6 thru | or 8 hardened | cured on the base material.   A cured film obtained by stretching the cured product according to claim 9.   The process of apply | coating the urethane (meth) acrylate oligomer of any one of Claims 1 thru | or 3, or the curable composition of any one of Claims 6 thru | or 8 on a base material, this curable composition The manufacturing method of a cured film which passes through the process of irradiating an active energy ray to a thing, obtaining the hardened | cured material, and extending the hardened | cured material.   A decorative film comprising the cured product according to claim 9.