JP2018203946A - Urethane (meth) acrylate resin - Google Patents

Abstract

To provide a curable composition that secures all of hardness, elongation, and chemical resistance, and is excellent in other performances, and a laminate film prepared therewith.SOLUTION: A urethane (meth) acrylate resin has a polyisocyanate compound (A), a polyester diol compound (B), and a monohydroxy (meth) acrylate compound (C) as essential reaction raw materials. At least 70 mass% of the polyisocyanate compound (A) is an aromatic group-containing polyisocyanate compound (A1).SELECTED DRAWING: None

Description

  The present invention relates to a urethane (meth) acrylate resin, a curable composition containing the same, a cured product thereof, and a laminated film having a layer made of the cured product.

  Urethane (meth) acrylate resins are generally known to have cured products having toughness, high extensibility, high hardness, etc., and are applied to a wide range of applications such as hard coat agents, adhesives, and pressure-sensitive adhesives. Yes. In general, it is known that the physical properties of urethane (meth) acrylate resins can be adjusted by controlling the molecular structure. For example, the hardness of the obtained cured product can be controlled by appropriately changing the number of (meth) acryloyl groups. Moreover, about the urethane bond, the toughness etc. of the hardened | cured material obtained can be controlled by changing the number suitably. In addition, for example, by introducing a polyol-derived structure or the like into the molecule of the urethane (meth) acrylate resin, the extensibility and the like of the obtained cured product can be controlled.

  For example, in Patent Document 1, 400 parts by mass of isophorone diisocyanate, 470 parts by mass of tolylene diisocyanate, 4886 parts by mass of a polyester polyol with a molecular weight of 2030, 565 parts by mass of a polyester polyol with a molecular weight of 490, and 232 parts by mass of 2-hydroxyethyl acrylate are reacted. It is described that the urethane acrylate compound obtained in this way is excellent in both surface hardness and elongation in a cured coating film.

  The required performance for urethane (meth) acrylate resins varies widely depending on each application, but recently, chemical resistance for cosmetics and the like is required as a new market requirement. Although the urethane acrylate compound described in Patent Document 1 exhibits relatively excellent performance in terms of hardness and elongation, chemical resistance is not sufficient.

Japanese Patent Laid-Open No. 2002-3560

  Therefore, the problem to be solved by the present invention is to provide a curable composition that has both hardness, elongation and chemical resistance in a cured coating film and is excellent in other performances, and a laminated film using the same. It is in.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, it has been found that the above problem can be solved by using 70% by mass or more of the polyisocyanate raw material of the urethane (meth) acrylate resin as an aromatic group-containing polyisocyanate compound and using polyester diol as the polyol raw material. It came to complete.

  That is, the present invention uses polyisocyanate compound (A), polyester diol compound (B), and monohydroxy (meth) acrylate compound (C) as essential reaction raw materials, and is 70% by mass or more of the polyisocyanate compound (A). Relates to a urethane (meth) acrylate resin which is an aromatic group-containing polyisocyanate compound (A1).

  The present invention further relates to a curable composition containing the urethane (meth) acrylate resin.

  The present invention further relates to a cured product of the curable composition.

  The present invention further relates to a laminated film having a layer made of the cured product.

  ADVANTAGE OF THE INVENTION According to this invention, the curable composition which has the hardness in a cured coating film, elongation, and chemical resistance, and is excellent also in other various performances, and a laminated film using the same are provided.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
<Urethane (meth) acrylate resin>
The urethane (meth) acrylate resin according to the present embodiment uses the polyisocyanate compound (A), the polyester diol compound (B), and the monohydroxy (meth) acrylate compound (C) as essential reaction raw materials. 70% by mass or more of the aromatic group-containing polyisocyanate compound (A1). In the present specification, “(meth) acrylate” means methacrylate, acrylate, or both. Further, “(meth) acryl” means methacryl, acryl, or both. Furthermore, “(meth) acryloyl” means methacryloyl, acryloyl, or both.

<Aromatic group-containing polyisocyanate compound (A1)>
One feature of the present invention is that 70% by mass of the polyisocyanate compound (A) is an aromatic group-containing polyisocyanate compound (A1). Furthermore, 90% by mass of the polyisocyanate compound (A) is more preferably an aromatic group-containing polyisocyanate compound (A1) because the urethane (meth) acrylate resin is more excellent in chemical resistance in the cured coating film.

In this specification, an “aromatic group” is a group having a structure in which atoms having π electrons are arranged in a ring, and at this time, π electrons of at least a part of the ring structure satisfy the Hückel rule (4n + 2) It means that.
Such an aromatic group is not particularly limited, but benzene, naphthalene, anthracene, thiophene, phenylthiophene, diphenylthiophene, imidazole, oxazole, thiazole, pyrrole, furan, benzimidazole, benzoxazole, rhodanine, pyrazolone, imidazolone, Examples thereof include those derived from an aromatic ring such as pyran, pyridine, and fluorene. Further, it may be a combination of a plurality of these aromatic rings, for example, aromatics such as biphenyl, terphenyl, fluorenyl, bithiophene, thienylphenyl, diphenylstyryl, stilbene, triphenylethylene, phenylpyridine, styrylthiophene, etc. The thing derived from a ring is mentioned. Among these, the aromatic group is preferably derived from benzene, naphthalene, anthracene, or fluorene, and more preferably derived from benzene from the viewpoint of achieving both high hardness and high flexibility. In addition, the said aromatic group may be contained independently in the compound, or 2 or more types may be contained.

  The term “polyisocyanate compound” means that the compound has two or more isocyanate groups, and the number of isocyanate groups in the compound is preferably 2 to 6, more preferably 2 to 3, and the flexibility is increased. From the viewpoint, it is particularly preferably 2.

  The structure of the aromatic group-containing polyisocyanate compound is generally represented by the following chemical formula (1).

上記式（１）中、Ａｒは置換または非置換の芳香族基である。

In the above formula (1), Ar is a substituted or unsubstituted aromatic group.

  The aromatic group is as described above. The substituent when the aromatic group has a substituent is not particularly limited, but is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an alkenyl having 2 to 20 carbon atoms. A group having 3 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, and 2 to 2 carbon atoms. 20 alkylcarbonyloxy groups and the like.

  The alkyl group having 1 to 20 carbon atoms is not particularly limited, but is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, Examples include n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, n-nonyl group, n-decyl group and the like.

  The cycloalkyl group having 3 to 20 carbon atoms is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.

  The alkenyl group having 2 to 20 carbon atoms is not particularly limited, but vinyl group, allyl group, propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-hexenyl group. 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like.

  Although it does not restrict | limit especially as said C3-C20 cycloalkenyl group, A cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group etc. are mentioned.

  Although it does not restrict | limit especially as said C2-C20 alkynyl group, An ethynyl group, 2-propynyl group, 2-butynyl group, etc. are mentioned.

  The alkoxy group having 1 to 20 carbon atoms is not particularly limited, but is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group. Group, nonyloxy group, decyloxy group and the like.

  The alkyloxycarbonyl group having 2 to 20 carbon atoms is not particularly limited, but is a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, an n-butyloxycarbonyl group. , Isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxycarbonyl group and the like.

  The alkylcarbonyloxy group having 2 to 20 carbon atoms is not particularly limited, but a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, an n-butylcarbonyloxy group. , Isobutylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group and the like.

  Among the above, the substituent is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. The above substituents may be used alone or in combination of two or more.

  Examples of A in Formula (1) include a single bond, alkylene having 1 to 20 carbon atoms, alkenylene having 2 to 20 carbon atoms, and alkynylene having 2 to 20 carbon atoms. Examples of the alkylene having 1 to 20 carbon atoms include, but are not limited to, methylene, ethylene, propylene, isobutylene, sec-butylene, tert-butylene, pentylene, iso-pentylene, hexylene and the like. Although it does not restrict | limit especially as said C2-C20 alkenylene, Vinylene, 2-butenylene, 1-butenylene, etc. are mentioned. The alkynylene having 2 to 20 carbon atoms is not particularly limited, and examples thereof include ethynylene and 1,3-butadiyne-1,4-diyl. Furthermore, n is an integer greater than or equal to 2, Preferably it is an integer of 2-6, More preferably, it is an integer of 2-4, More preferably, it is an integer of 2-3 from a viewpoint of maintaining a softness | flexibility.

  Of the above-described aromatic group-containing polyisocyanate compound (A1), a preferred aromatic group-containing polyisocyanate compound (A1) is represented by the following chemical formula (2).

上記式中、Ａおよびｎは、上述の通りである。
また、Ｒ^１は置換基である。その具体例については、上述の通りである。
ｍは、０〜４の整数である。この際、ｎおよびｍの和は６以下の整数である。

In the above formula, A and n are as described above.
R ¹ is a substituent. Specific examples thereof are as described above.
m is an integer of 0-4. At this time, the sum of n and m is an integer of 6 or less.

  Specific examples of the aromatic group-containing polyisocyanate compound (A1) represented by the above formula (2) include o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, toluene-2,3-diisocyanate. , Toluene-2,4-diisocyanate, toluene-2,5-diisocyanate, toluene-2,6-diisocyanate, toluene-3,4-diisocyanate, toluene-3,5-diisocyanate, diphenylmethane diisocyanate, m-phenylenebisisopropylisocyanate And a compound represented by the following chemical formula: These aromatic group-containing polyisocyanate compounds (A1) may be isocyanurate-modified products, biuret-modified products, allophanate-modified products, and the like.

  Of the above-mentioned aromatic group-containing polyisocyanate compounds (A1), o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,5-diisocyanate, toluene -2,6-diisocyanate, toluene-3,5-diisocyanate, diphenylmethane diisocyanate, m-phenylenebisisopropyl isocyanate, and a compound represented by the following chemical formula are more preferable, m-xylylene diisocyanate, toluene-2 , 4-diisocyanate, toluene-2,6-diisocyanate, diphenylmethane diisocyanate, and m-phenylenebisisopropyl isocyanate are more preferable.

  Moreover, the above-mentioned aromatic group-containing polyisocyanate compound (A1) may be used alone or in combination of two or more.

<Aromatic group-free polyisocyanate compound (A2)>
In one embodiment of the present invention, the urethane (meth) acrylate can be used in combination with an aromatic group-free polyisocyanate compound (A2) that does not contain an aromatic group as long as the effects of the present invention are not impaired. Although it does not restrict | limit especially as an aromatic group non-containing polyisocyanate compound (A2), An aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, etc. are mentioned.

  The aliphatic polyisocyanate compound is not particularly limited, but is a substituted or unsubstituted alkane having 1 to 20 carbon atoms, a substituted or unsubstituted alkene having 2 to 20 carbon atoms, or a substituted or unsubstituted carbon atom. The thing by which the at least 2 hydrogen atom of the alkyne of several 2-20 is substituted by the isocyanate group is mentioned. The alkane having 2 to 20 carbon atoms is not particularly limited, but includes methane, ethane, propane, butane, 2-methylpropane, heptane, 2-methylbutane, 3-methylbutane, 2-ethylpropane, hexane, decane, and the like. Can be mentioned. The alkene having 2 to 20 carbon atoms is not particularly limited, and examples thereof include ethylene, propene, 1-butene, 2-butene, 1,3-butadiene, 1,3,5-hexatriene and the like. The alkyne having 2 to 20 carbon atoms is not particularly limited, and examples thereof include acetylene, methylacetylene, 1-butyne, 2-butyne, and 1-pentyne.

  The substituent in the case where the alkane having 1 to 20 carbon atoms, the alkene having 2 to 20 carbon atoms, or the alkyne having 2 to 20 carbon atoms has a substituent is not particularly limited. Examples include 20 alkoxy groups, alkyloxycarbonyl groups having 2 to 20 carbon atoms, and alkylcarbonyloxy groups having 2 to 20 carbon atoms. In addition, since at least two hydrogen atoms of an alkane having 1 to 20 carbon atoms, an alkene having 2 to 20 carbon atoms, and an alkyne having 2 to 20 carbon atoms become an isocyanate group, the number of substituents that can be included The limit is obtained by subtracting 2 from the hydrogen atoms of alkanes having 1 to 20 carbon atoms, alkenes having 2 to 20 carbon atoms, and alkynes having 2 to 20 carbon atoms.

  The alicyclic polyisocyanate compound is not particularly limited, and examples thereof include substituted or unsubstituted cycloalkanes having 3 to 20 carbon atoms, and substituted or unsubstituted cycloalkenes having 3 to 20 carbon atoms. The cycloalkane having 3 to 20 carbon atoms is not particularly limited, but is cyclopropane, cyclobutane, cyclopentane, cyclohexane, 1-methylcyclohexane, 1,1,3,3-tetramethylcyclohexane, cycloheptane, cyclooctane. , Cyclononane, cyclodecane, bicyclohexyl and the like. The cycloalkene having 3 to 20 carbon atoms is not particularly limited, and examples thereof include cyclopentene, cyclohexene, and cyclooctene.

  The substituent in the case where the cycloalkane having 3 to 20 carbon atoms and the cycloalkene having 3 to 20 carbon atoms has a substituent is not particularly limited, but the above-described alkoxy group having 1 to 20 carbon atoms, carbon atom Examples thereof include an alkyloxycarbonyl group having 2 to 20 carbon atoms and an alkylcarbonyloxy group having 2 to 20 carbon atoms. In addition, since at least two hydrogen atoms of the cycloalkane having 3 to 20 carbon atoms and the cycloalkene having 3 to 20 carbon atoms are isocyanate groups, the limit of the number of substituents that can be included is 3 to 3 carbon atoms. 2 is subtracted from the hydrogen atom of 20 cycloalkane, 3 to 20 carbon alkene.

  Specific examples of the aromatic group-free polyisocyanate compound (A2) are not particularly limited, but include hexamethylene diisocyanate and dimer acid diisocyanate (10- [5,6-dihexyl-2- (8-isocyanatooctyl) -3. -Cyclohexen-1-yl] -9-decenyl isocyanate), lysine diisocyanate (methyl 2,6-diisocyanatohexanoate), isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, 1,3-bis ( (Isocyanatomethyl) cyclohexane, nerbonene diisocyanate and the like. The above-mentioned aromatic group-free polyisocyanate compound (A2) may be used alone or in combination of two or more. These aromatic group-free polyisocyanate compounds (A2) may be isocyanurate-modified products, biuret-modified products, allophanate-modified products, and the like.

<Polyesterdiol compound (B)>
Although it does not restrict | limit especially as a polyester diol compound (B), The reaction product of dicarboxylic acid and diol is mentioned.

  The dicarboxylic acid is not particularly limited, but malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1 Aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; aromatic group-containing dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid; and these acids Anhydrides are mentioned. These dicarboxylic acids may be used alone or in combination of two or more.

  The diol is not particularly limited, but ethylene glycol, propylene glycol, 1,3-tetramethylene diol, 1,4-tetramethylene diol, 2-methyl-1,3-trimethylene diol, 1,5-pentamethylene diol Neopentyl glycol, 1,6-hexamethylenediol, 1,9-nonanediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, 1,2- Fats such as cyclobutanediol, 1,3-cyclopentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bicyclo [4,3,0] -nonanediol, diethylene glycol, dipropylene glycol, trimethylene glycol Diols; catechol, reso Shinoru, hydroquinone, bisphenol A, and aromatic group-containing diols such as naphthalene diol. These diols may be used alone or in combination of two or more.

  Any combination of the above-mentioned dicarboxylic acid and diol may be adopted. Especially, since it becomes urethane (meth) acrylate resin which is further excellent in the chemical resistance in hardened | cured material, it is preferable that a polyester diol compound (B) contains an aromatic group. That is, at least one of the dicarboxylic acid and the diol is preferably an aromatic group-containing dicarboxylic acid, an aromatic group-containing dicarboxylic acid anhydride, or an aromatic group-containing polyol. A specific combination of polycarboxylic acid and polyol is preferably a combination of an aromatic group-containing dicarboxylic acid or an acid anhydride thereof and an aliphatic diol, such as phthalic acid, isophthalic acid, terephthalic acid, or these acids. Anhydride, ethylene glycol, propylene glycol, 1,3-tetramethylene diol, 1,4-tetramethylene diol, 2-methyl-1,3-trimethylene diol, 1,5-pentamethylene diol, neopentyl glycol It is more preferable that it is a combination.

  In one embodiment, specific examples of the polyester diol compound (B) include poly [(ethylene glycol) -alt- (phthalic acid)], poly [(ethylene glycol) -alt- (isophthalic acid)], poly [( Ethylene glycol) -alt- (terephthalic acid)], poly [(1,4-butanediol) -alt- (phthalic acid)], poly [(1,4-butanediol) -alt- (isophthalic acid)], Poly [(1,4-butanediol) -alt- (terephthalic acid)], poly [(1,6-hexanediol) -alt- (phthalic acid)], poly [(1,6-hexanediol) -alt -(Isophthalic acid)], poly [(1,6-hexanediol) -alt- (terephthalic acid)], poly [(3-methyl-1,5, -pentanediol) -alt (Phthalic acid)], poly [(3-methyl-1,5-pentanediol) -alt- (isophthalic acid)], poly [(3-methyl-1,5-pentanediol) -alt- (terephthalate) Acid)], poly [(catechol) -alt- (adipic acid)], poly [(resorcinol) -alt- (adipic acid)], poly [(hydroquinone) -alt- (adipic acid)], poly [(bisphenol A) -alt- (adipic acid)] and the like.

  Among these, from the viewpoint of increasing the hardness of the coating film, poly [(3-methyl-1,5-pentanediol) -alt- (isophthalic acid)], poly [(3-methyl-1,5) , -Pentanediol) -alt- (terephthalic acid)], poly [(ethylene glycol) -alt- (isophthalic acid)], poly [(ethylene glycol) -alt- (terephthalic acid)], and resin From the viewpoint of controlling the crystallinity of poly ((3-methyl-1,5-pentanediol) -alt- (isophthalic acid)], poly [(ethylene glycol) -alt- (isophthalic acid)]. Is more preferable

Since the polyester diol compound (B) is a urethane (meth) acrylate resin having an excellent balance of hardness, elongation, chemical resistance and the like in the cured product, the weight average molecular weight (Mw) is in the range of 450 to 5,000. It is preferable that it is, and it is more preferable that it is the range of 450-1200. In the present invention, the molecular weight of each compound is a value measured by each manufacturer's published value or gel permeation chromatograph (GPC) under the following conditions.
Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Tosoh Corporation guard column HXL-H
+ Tosoh Corporation TSKgel G5000HXL
+ Tosoh Corporation TSKgel G4000HXL
+ Tosoh Corporation TSKgel G3000HXL
+ Tosoh Corporation TSKgel G2000HXL
Detector: RI (differential refractometer)
Data processing: Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 1.0 ml / min Standard: Polystyrene sample: 0.4 mass% tetrahydrofuran solution filtered in terms of resin solids with a microfilter (100 μl)

<Other polyol compounds (B ′)>
In the present invention, other polyol compound (B ′) may be used in combination with the polyester diol compound (B). When other polyol compound (B ′) is used, it becomes a urethane (meth) acrylate resin having an excellent balance of hardness, elongation, chemical resistance, etc. in the cured product, so that all polyols of urethane (meth) acrylate resin It is preferable to use 70 mass% or more of the said polyester diol compound (B) with respect to a raw material, and it is preferable to use 90 mass% or more. Examples of the other polyol compound (B ′) include an aliphatic polyol compound, an aromatic group-containing polyol compound, a polyether polyol compound, a tri- or higher functional polyester polyol compound, and a polycarbonate polyol compound.

  The aliphatic polyol compound includes aliphatic triols such as glycerin, 1,2,4-butanetriol, trimethylolethane, and trimethylolpropane, as well as the aliphatic diol exemplified as the raw material of the polyester diol compound (B); penta Examples include aliphatic tetraols such as erythritol.

  Examples of the aromatic polyol compound include aromatic group-containing triols such as hydroxyquinol, phloroglucinol, and pyrogallol in addition to the aromatic group-containing diol exemplified as the raw material of the polyester diol compound (B).

  In the polyether polyol compound, a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of the various polyol compounds ( And poly) oxyalkylene modified products.

  Examples of the trifunctional or higher functional polyester polyol compound include those obtained by replacing part of the raw material of the polyester diol compound (B) with a trifunctional or higher functional polyol or polycarboxylic acid. Examples of the tri- or higher functional polycarboxylic acid include aliphatic tricarboxylic acids such as 1,2,3-propanetricarboxylic acid, aconitic acid, and citric acid; 1,2,3,4-butanetetracarboxylic acid, ethylenetetracarboxylic acid Aliphatic tetracarboxylic acids such as 1,3,5-benzenetricarboxylic acid, aromatic group-containing tricarboxylic acids such as trimellitic acid; 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, And aromatic group-containing tetracarboxylic acids such as 4,4′-biphenyltetracarboxylic acid; and acid anhydrides thereof.

  Examples of the polycarbonate polyol compound include those obtained by condensation reactions of various polyol compounds and carbonylating agents.

<Monohydroxy (meth) acrylate compound (C)>
Specific examples of the monohydroxy (meth) acrylate compound (C) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth). Monohydroxy mono (meth) acrylate compound (C1) such as acrylate; Lactone (caprolactone, etc.) adduct or alkylene oxide (methylene oxide, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the compound (C1); Glycerin di ( (Meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate Monohydroxy poly (meth) acrylate compounds (C2) such as carbonates; lactone (caprolactone etc.) adducts or alkylene oxides (methylene oxide, ethylene oxide, propylene oxide, butylene oxide etc.) adducts of the compound (C2), etc. It is done. Among these, the monohydroxy mono (meth) acrylate compound (C1) is preferable because it becomes a urethane (meth) acrylate resin excellent in the balance between hardness and elongation in the cured product. Moreover, it is preferable that the ratio of the said monohydroxy mono (meth) acrylate compound (C1) in the said monohydroxy (meth) acrylate compound (C) is 70 mass% or more, and it is more preferable that it is 90 mass% or more. . In addition, the above-mentioned monohydroxy (meth) acrylate compound (C) may be used independently, or may be used in combination of 2 or more type.

<Manufacture of urethane (meth) acrylate resin>
The method for producing the urethane (meth) acrylate resin of the present invention is not particularly limited, and may be produced in any way. For example, it may be produced by a method (method 1) in which all reaction raw materials of urethane (meth) acrylate resin are reacted together, or the polyisocyanate compound (A) and the polyester diol compound (B) are reacted. After obtaining the intermediate, the method of reacting the monohydroxy (meth) acrylate compound (C) (Method 2) or the reaction of the polyisocyanate compound (A) with the monohydroxy (meth) acrylate compound (C) After obtaining the intermediate, the polyester diol compound (B) may be reacted by a method (method 3). When using the said other polyol compound (B '), it is preferable to make it react at the same timing as the said polyester diol compound (B). Among these, the method 2 is preferable because the reaction can be easily controlled.

  About the said method 2, the reaction ratio of the said polyisocyanate compound (A) and the said polyester diol compound (B) is in the said polyester diol compound (B) with respect to 1 mol of isocyanate groups in the said polyisocyanate compound (A). It is preferable that the hydroxyl group has a ratio of 0.5 to 0.9 mol. When using the said other polyol compound (B '), it is preferable to make the sum total of the hydroxyl group which the said compound (B) and compound (B') contain into the range of 0.5-0.9 mol. Examples of the reaction conditions include a method of using a known and usual urethanization catalyst as necessary under a temperature condition of about 20 to 120 ° C.

  Subsequently, the obtained intermediate and the monohydroxy (meth) acrylate compound (C) can be carried out under the same conditions as the reaction of the polyisocyanate compound (A) and the polyester diol compound (B). The reaction ratio between the two is preferably such that the hydroxyl group in the monohydroxy (meth) acrylate compound (C) is 0.095 to 1.05 mol with respect to 1 mol of the isocyanate group in the intermediate.

  Since the urethane (meth) acrylate resin of the present invention is a urethane (meth) acrylate resin having an excellent balance of hardness, elongation, chemical resistance and the like in the cured product, the weight average molecular weight (Mw) is 1,000 to 20%. , Preferably in the range of 1,000, more preferably in the range of 1,000 to 10,000. The said value is a value measured by the gel permeation chromatograph (GPC) of the said conditions.

  The urethane (meth) acrylate resin having the above-described configuration has high hardness, excellent flexibility, and high chemical resistance. The reason for this is not always clear, but the structure derived from the polyester diol compound (B) is introduced into the urethane (meth) acrylate resin, so that it is sufficient even after the (meth) acrylate group has advanced the crosslinking reaction by ultraviolet irradiation. Flexibility is ensured. In addition to this, by suppressing the decrease in hardness that was in a trade-off relationship due to stacking of aromatic rings, aggregation of ester bonds and urethane bonds, a cured product having flexibility, high hardness, and chemical resistance is obtained. A urethane (meth) acrylate resin can be obtained. In addition, the said mechanism is a presumed thing to the last, and even if it is a case where the effect of this invention is show | played by another mechanism, it is contained in the technical scope of this invention.

<Curable composition>
The curable composition of the present invention may contain other components in addition to the urethane (meth) acrylate resin. Examples of the other components include other resin components other than the urethane (meth) acrylate resin, inorganic fine particles, photopolymerization initiators, solvents, ultraviolet absorbers, antioxidants, silicon-based additives, and fluorine-based additives. , Antistatic agents, organic beads, quantum dots (QD), rheology control agents, defoaming agents, antifogging agents, coloring agents and the like.

<Other resin components>
Other resin components include, for example, (meth) acryloyl group-containing acrylic resin (X1), dendrimer type (meth) acrylate resin (X2), epoxy (meth) acrylate resin (X3), mono (meth) acrylate compound, and modifications thereof Body (X4), aliphatic hydrocarbon type poly (meth) acrylate compound and modified product (X5), alicyclic poly (meth) acrylate compound and modified product (X6), aromatic poly (meth) acrylate compound and The modified body (X7) etc. are mentioned. These may be used alone or in combination of two or more.

  The (meth) acryloyl group-containing acrylic resin (X1) is obtained by polymerizing, for example, a (meth) acrylate monomer (α) having a reactive functional group such as a hydroxyl group, a carboxy group, an isocyanate group, or a glycidyl group as an essential component. What can be obtained by introducing a (meth) acryloyl group by further reacting the resulting acrylic resin intermediate with a (meth) acrylate monomer (β) having a reactive functional group capable of reacting with these functional groups. It is done.

  The (meth) acrylate monomer (α) having a reactive functional group is, for example, a hydroxyl group-containing (meth) acrylate monomer such as hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate; a carboxy such as (meth) acrylic acid Group-containing (meth) acrylate monomer; isocyanate group-containing (meth) acrylate monomer such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate; glycidyl (meth) acrylate And glycidyl group-containing (meth) acrylate monomers such as 4-hydroxybutyl acrylate glycidyl ether. These may be used alone or in combination of two or more.

  In addition to the (meth) acrylate monomer (α), the acrylic resin intermediate may be obtained by copolymerizing another polymerizable unsaturated group-containing compound as necessary. Examples of the other polymerizable unsaturated group-containing compound include (meth) methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. Acrylic acid alkyl ester; Cyclo ring-containing (meth) acrylate such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl acrylate Aromatic ring-containing (meth) acrylates; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene . These may be used alone or in combination of two or more.

  When the acrylic resin intermediate is obtained by copolymerizing the (meth) acrylate monomer (α) and the other polymerizable unsaturated group-containing compound, the reaction ratio of both is excellent in curability. Since it becomes (meth) acryloyl group containing acrylic resin (X1), it is preferable that the ratio of the said (meth) acrylate monomer ((alpha)) with respect to the sum total of both is the range of 20-70 mass%, and is 30-60 mass. More preferably, it is in the range of part%.

  The said acrylic resin intermediate body can be manufactured by the method similar to a general acrylic resin. As an example of manufacturing conditions, it can manufacture by polymerizing various monomers in the temperature range of 60 degreeC-150 degreeC, for example in presence of a polymerization initiator. Examples of the polymerization method include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Examples of the polymerization mode include random copolymers, block copolymers, and graft copolymers. When the solution polymerization method is used, for example, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, or a glycol ether solvent such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether is preferably used. Can do.

  The (meth) acrylate monomer (β) is not particularly limited as long as it can react with the reactive functional group of the (meth) acrylate monomer (α), but is the following combination from the viewpoint of reactivity. Is preferred. That is, when the hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), it is preferable to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate monomer (β). When the carboxy group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), it is preferable to use the glycidyl group-containing (meth) acrylate as the (meth) acrylate monomer (β). When the isocyanate group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), the hydroxyl group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer (β). When the glycidyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), the carboxy group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer (β).

  The reaction between the acrylic resin intermediate and the (meth) acrylate monomer (β) is, for example, an esterification catalyst such as triphenylphosphine in a temperature range of 60 to 150 ° C. when the reaction is an esterification reaction. Can be used as appropriate. Moreover, when this reaction is a urethanation reaction, the method of making it react, dripping a compound ((alpha)) to an acrylic resin intermediate body in the temperature range of 50-120 degreeC etc. is mentioned.

  The (meth) acryloyl group-containing acrylic resin (X1) preferably has a weight average molecular weight (Mw) in the range of 5,000 to 80,000. The (meth) acryloyl group equivalent is preferably in the range of 200 to 500 g / equivalent.

  The dendrimer type (meth) acrylate resin (X2) is a resin having a regular multi-branched structure and having a (meth) acryloyl group at the end of each branched chain. It is called a mold or a star polymer. Examples of such compounds include those represented by the following chemical formulas (3-1) to (3-8), but are not limited thereto, and have a regular multi-branched structure. Any resin having a (meth) acryloyl group at the end of each branched chain can be used.

（式中Ｒ^２は水素原子又はメチル基であり、Ｒ^３は炭素原子数１〜４の炭化水素基である。）

(In the formula, R ² is a hydrogen atom or a methyl group, and R ³ is a hydrocarbon group having 1 to 4 carbon atoms.)

  As such a dendrimer type (meth) acrylate resin (X2), “Viscoat # 1000” manufactured by Osaka Organic Chemical Co., Ltd. [weight average molecular weight (Mw) 1,500 to 2,000, average (meth) acryloyl per molecule Radix 14], “Biscoat 1020” [weight average molecular weight (Mw) 1,000 to 3,000], “SIRIUS501” [weight average molecular weight (Mw) 15,000 to 23,000], “SP-1106 manufactured by MIWON [Weight average molecular weight (Mw) 1,630, average number of (meth) acryloyl groups 18 per molecule], “CN2301”, “CN2302” [average number of (meth) acryloyl groups 16 per molecule] manufactured by SARTOMER, “ CN2303 ”[average number of (meth) acryloyl groups 6 per molecule],“ CN2304 ”[one Average (meth) acryloyl radical number per child 18], “Esdrimer HU-22” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “A-HBR-5” manufactured by Shin-Nakamura Chemical Co., Ltd., “New Frontier R” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. -1150 "," Hypertech UR-101 "manufactured by Nissan Chemical Co., Ltd. may be used.

  The dendrimer type (meth) acrylate resin (X2) preferably has a weight average molecular weight (Mw) in the range of 1,000 to 30,000. Moreover, what is the range whose average (meth) acryloyl group number per molecule is 5-30 is preferable.

    As for the said epoxy (meth) acrylate resin (X3), what is obtained by making (meth) acrylic acid or its anhydride react with an epoxy resin is mentioned, for example. Examples of the epoxy resin include diglycidyl ethers of dihydric phenols such as hydroquinone and catechol; diglycidyl ethers of biphenol compounds such as 3,3′-biphenyldiol and 4,4′-biphenyldiol; bisphenol A type epoxy resins; Bisphenol type epoxy resins such as bisphenol B type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin; 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalene Polyglycidyl ethers of naphthol compounds such as diols, 2,7-naphthalenediol, binaphthol, bis (2,7-dihydroxynaphthyl) methane; triglycidyl ethers such as 4,4 ′, 4 ″ -methylidynetrisphenol A novolak type epoxy resin such as a phenol novolak type epoxy resin or a cresol novolak resin; a molecular structure of the various epoxy resins such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, a (poly) oxytetramethylene chain, etc. (Poly) oxyalkylene chain-modified (poly) oxyalkylene-modified products; lactone-modified products in which (poly) lactone structures are introduced into the molecular structures of the various epoxy resins.

  The mono (meth) acrylate compound and the modified product (X4) are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, propyl (meth) acrylate, hydroxypropyl (meth) acrylate, Aliphatic mono (meth) acrylate compounds such as butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; alicyclic mono (meta) such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate ) Acrylate compounds; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenylphenol (meth) acrylate, phenylphenol alkyl (meth) acrylate, phenylbenzyl Aromatic mono (meth) acrylate compounds such as (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl (meth) acrylate, phenylphenoxyethyl (meth) acrylate, paracumylphenol (meth) acrylate; chemical formula (4)

（式中Ｒ^４は水素原子又はメチル基である。）
で表される化合物等のモノ（メタ）アクリレート化合物：前記各種のモノ（メタ）アクリレート化合物の分子構造中に（ポリ）オキシエチレン鎖、（ポリ）オキシプロピレン鎖、（ポリ）オキシテトラメチレン鎖等の（ポリ）オキシアルキレン鎖を導入した（ポリ）オキシアルキレン変性体；前記各種のモノ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性体等が挙げられる。

(In the formula, R ⁴ is a hydrogen atom or a methyl group.)
Mono (meth) acrylate compounds such as compounds represented by: (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc. in the molecular structure of the various mono (meth) acrylate compounds (Poly) oxyalkylene-modified products in which a (poly) oxyalkylene chain is introduced; lactone-modified products in which a (poly) lactone structure is introduced into the molecular structure of the various mono (meth) acrylate compounds.

  The aliphatic hydrocarbon type poly (meth) acrylate compound and the modified product (X5) are, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di Aliphatic di (meth) acrylate compounds such as (meth) acrylate and neopentyl glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylol Aliphatic tri (meth) acrylate compounds such as propane tri (meth) acrylate and dipentaerythritol tri (meth) acrylate; pentaerythritol tetra (meth) acrylate and ditrimethylol group Tetra- or higher functional aliphatic poly (meth) acrylate compounds such as pantetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; (Poly) oxyalkylene chains such as (poly) oxyethylene chain, (poly) oxypropylene chain, and (poly) oxytetramethylene chain are introduced into the molecular structure of the aliphatic hydrocarbon type poly (meth) acrylate compound (poly ) Oxyalkylene modified products; lactone modified products in which a (poly) lactone structure is introduced into the molecular structure of the above-mentioned various aliphatic hydrocarbon type poly (meth) acrylate compounds.

  The alicyclic poly (meth) acrylate compound and the modified product (X6) are, for example, 1,4-cyclohexanedimethanol di (meth) acrylate, norbornane di (meth) acrylate, norbornane dimethanol di (meth) acrylate, Alicyclic di (meth) acrylate compounds such as dicyclopentanyl di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate; in the molecular structure of the various alicyclic poly (meth) acrylate compounds ( (Poly) oxyalkylene chain such as (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc.) (poly) oxyalkylene modified product; various alicyclic poly (meth) acrylates described above Lactone modification by introducing (poly) lactone structure into the molecular structure of the compound Etc. The.

  Examples of the aromatic poly (meth) acrylate compound and the modified product (X7) include biphenol di (meth) acrylate, bisphenol di (meth) acrylate, and the following chemical formula (5).

［式中Ｒ^５はそれぞれ独立に（メタ）アクリロイル基、（メタ）アクリロイルオキシ基、（メタ）アクリロイルオキシアルキル基の何れかである。］
で表されるビカルバゾール化合物、下記構造式（６−１）又は（６−２）

[In the formula, each R ⁵ independently represents any of a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloyloxyalkyl group. ]
A bicarbazole compound represented by the following structural formula (6-1) or (6-2)

［式中Ｒ^６はそれぞれ独立に（メタ）アクリロイル基、（メタ）アクリロイルオキシ基、（メタ）アクリロイルオキシアルキル基の何れかである。］
で表されるフルオレン化合物等の芳香族ジ（メタ）アクリレート化合物；前記各種の芳香族ポリ（メタ）アクリレート化合物の分子構造中に（ポリ）オキシエチレン鎖、（ポリ）オキシプロピレン鎖、（ポリ）オキシテトラメチレン鎖等の（ポリ）オキシアルキレン鎖を導入した（ポリ）オキシアルキレン変性体；前記各種の芳香族ポリ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性体等が挙げられる。

[In the formula, each R ⁶ is independently a (meth) acryloyl group, a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group. ]
An aromatic di (meth) acrylate compound such as a fluorene compound represented by: (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) in the molecular structure of the various aromatic poly (meth) acrylate compounds (Poly) oxyalkylene modified products in which (poly) oxyalkylene chains such as oxytetramethylene chains are introduced; lactone modified products in which (poly) lactone structures are introduced into the molecular structures of the various aromatic poly (meth) acrylate compounds Etc.

  Although the addition amount in the case of using these other resin components is not specifically limited, since the effect of this invention is fully exhibited, the urethane (meth) acrylate of this invention with respect to the total mass of the resin component in a curable composition The proportion of the resin is preferably 50% by mass or more, and more preferably 70% by mass or more.

<Inorganic fine particles>
The inorganic particles have a function of increasing the hardness of the cured product of the resin composition. At this time, a decrease in flexibility that is in a trade-off relationship is relatively less likely to occur, and the hardness and flexibility can be increased overall.

The inorganic particles may be subjected to surface treatment. Introducing a functional group or the like by the surface treatment is preferable because inorganic particles can be more suitably dispersed in the resin composition.
Although it does not restrict | limit especially as a surface treating agent used for the surface treatment of an inorganic particle, It is preferable that it is a silane coupling agent. The silane coupling agent is not particularly limited, but vinyl silane coupling agent, epoxy silane coupling agent, (meth) acryloyloxy silane coupling agent, amino silane coupling agent, ureido silane cup. Examples thereof include a ring agent, a mercapto silane coupling agent, a sulfide silane coupling agent, and an isocyanate silane coupling agent.

  The vinyl silane coupling agent is not particularly limited, but vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, p-styryltrimethoxysilane, N- (vinylbenzyl) ) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, diethoxymethylvinylsilane and the like.

  The epoxy silane coupling agent is not particularly limited, but is diethoxy (glycidyloxypropyl) methylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and 3-glycidyloxy. Examples thereof include propylmethyldiethoxysilane and 3-glycidyloxypropyltriethoxysilane.

  The (meth) acryloyloxy-based silane coupling agent is not particularly limited, but 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyl Examples thereof include oxypropylmethyldiethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane.

The amino silane coupling agent is not particularly limited, but N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N -(2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) ) Propylamine, N-phenyl-3-aminopropyltrimethoxysilane and the like.
Although it does not restrict | limit especially as said ureido type | system | group silane coupling agent, 3-ureidopropyl triethoxysilane etc. are mentioned.

  Although it does not restrict | limit especially as said mercapto type | system | group silane coupling agent, 3-mercaptopropyl methyl dimethoxysilane, (3-mercaptopropyl) trimethine silane, etc. are mentioned.

  The sulfide-based silane coupling agent is not particularly limited, and examples thereof include bis [3- (triethoxysilyl) propyl)] tetrasulfide.

  Although it does not restrict | limit especially as said isocyanate type silane coupling agent, (3-isocyanatopropyl) triethoxysilane etc. are mentioned. In addition, the above-mentioned silane coupling agent may be used independently or may be used in combination of 2 or more type.

  The inorganic particles are not particularly limited, and examples thereof include silica, alumina, zirconia, titania, barium titanate, and antimony trioxide. These may be used alone or in combination of two or more. The average particle diameter of these inorganic fine particles is preferably in the range of 95 to 250 nm, and more preferably in the range of 100 to 180 nm. Further, when these inorganic fine particles are contained, a dispersion aid may be further used. Examples of the dispersion aid include phosphate esters such as isopropyl acid phosphate, triisodecyl phosphite, and ethylene oxide-modified phosphate dimethacrylate. Compounds and the like. These may be used alone or in combination of two or more. Examples of commercially available dispersion aids include “Kayamar PM-21” and “Kayamer PM-2” manufactured by Nippon Kayaku Co., Ltd., “Light Ester P-2M” manufactured by Kyoeisha Chemical Co., Ltd., and the like.

In the present invention, the average particle size of the inorganic fine particles is a value obtained by measuring the particle size in the composition under the following conditions.
Particle size measuring device: “ELSZ-2” manufactured by Otsuka Electronics Co., Ltd.
Particle size measurement sample: A composition in which the composition is a methyl isobutyl ketone solution having a nonvolatile content of 1% by mass.

  As content of an inorganic particle, it is preferable that it is 3-30 mass% with respect to the total mass of the component except the organic solvent in a curable composition, and it is 5-5 from a viewpoint from which higher hardness and a high softness | flexibility are obtained. More preferably, it is 15 mass%. When the content of the inorganic particles is 3% by mass or more, the hardness of the composition can be further increased, and when the content of the inorganic particles is 30% by mass or less, sufficient flexibility can be maintained. .

<Photopolymerization initiator>
In one embodiment, the resin composition may further contain a polymerization initiator. The polymerization initiator has a function of suitably curing the resin composition. The polymerization initiator is not particularly limited, but is a benzophenone polymerization initiator, a xanthone / thioxanthone polymerization initiator, a benzoin / benzoyl polymerization initiator, a ketal polymerization initiator, an acetophenone polymerization initiator, a triazine polymerization initiator. , Lophine dimer polymerization initiators, phosphine oxide polymerization initiators, and the like.

  The benzophenone-based polymerization initiator is not particularly limited, but is benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone. 4,4′-dichlorobenzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and the like.

  The xanthone / thioxanthone polymerization initiator is not particularly limited, and examples thereof include diethylthioxanthone, diisopropylthioxanthone, isopropylthioxanthone, 2-chlorothioxanthone, and 2,4-diethylthioxanthen-9-one.

  The benzoin / benzoyl polymerization initiator is not particularly limited, and examples thereof include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  The ketal polymerization initiator is not particularly limited, and examples thereof include benzyldimethyl ketal and benzyl-β-methoxyethyl acetal.

  The acetophenone-based polymerization initiator is not particularly limited, but 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, α, α-dichloro-4′-phenoxyacetophenone 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 2-hydroxy-2-methyl-1- (4-isopropylphenyl) -1-propan-1-one, 2-benzyl-2- (dimethylamino) -4′-morpholinobutyrophenone, 1- [4- (2 -Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, etc. Is mentioned.

  The triazine polymerization initiator is not particularly limited, but 2,4-bis (trichloromethyl) -6- (p-methoxyphenyl) -S-triazine, 2,4-bis (trichloromethyl) -6- ( p-ethoxyphenyl) -S-triazine, 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -S-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) ) -S-triazine, 2,4-bis (trichloromethyl) -6-[[N, N-di (ethoxycarbonylmethyl) amino] phenyl] -S-triazine, 2,4-bis (trichloromethyl) -6 -[(3-bromo-4-ethoxy) phenyl] -S-triazine, 2,4-bis (trichloromethyl) -6-biphenyl-S-triazine, etc.

  The lophine dimeric polymerization initiator is not particularly limited, but 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer. Examples thereof include 2-mer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, and the like.

  The sphinoxide-based polymerization initiator is not particularly limited, and examples thereof include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. The above polymerization initiators may be used alone or in combination of two or more.

<Solvent>
In one embodiment, the resin composition may further contain a solvent. The solvent has a function of adjusting the viscosity of the resin composition. The solvent is not particularly limited, but a ketone solvent such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; an ether solvent such as tetrahydrofuran and dioxolane; an ester solvent such as methyl acetate, ethyl acetate, and butyl acetate; toluene, xylene, dibutylhydroxytoluene, and the like Aromatic solvents: alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether; glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether And system solvents. These solvents may be used alone or in combination of two or more.

<Method for producing curable composition>
The manufacturing method in particular of a resin composition is not restrict | limited, It can manufacture by a well-known method. For example, when the curable composition contains inorganic particles, the inorganic particles may be sequentially added to and mixed with the urethane (meth) acrylate resin, or the urethane (meth) acrylate resin may be sequentially added to the inorganic particles. You may add and mix and manufacture. When the curable composition contains other resin components, a solvent, a polymerization initiator, other additives, and the like, the order of addition is not particularly limited. For example, when other resin components are included, the resin composition may be mixed with urethane (meth) acrylate resin and other resin components, and then added and mixed with inorganic particles, or urethane (meth) acrylate resin. After adding and mixing the inorganic particles sequentially, other resin components may be added and mixed sequentially. The mixing conditions are not particularly limited, and may be dry or wet. Further, the mixing temperature, the mixing pressure and the like are not particularly limited and can be appropriately determined.

  For the production of curable compositions, high-speed flow mixer, Henschel mixer, Shugy mixer, double-arm kneader, paddle mixer, turbuler mixer, horizontal cylindrical mixer, V-type mixer, double-cone mixer, vibration Rotary type mixer, Ribbon type mixer, Paddle type mixer, Screw type (Nauta type) mixer, High speed stirring type mixer, Rotating cone type mixer, Rotary container type mixer with roller, Rotary container type mixing with stirring Mixing devices such as a mixing machine, a high-speed elliptical rotor type mixer, an airflow stirring type mixer, an unstirred type mixer, etc .; a grinding device such as a ball mill, a rod mill, a bead mill, and a jet mill can be used.

  In one embodiment, the curable composition is preferably produced under wet conditions using a ball mill. In this case, the ball mill includes a vessel filled with media therein, a rotating shaft, a rotating shaft coaxially with the rotating shaft, and a stirring blade that is rotated by rotational driving of the rotating shaft, and the vessel It is preferable to have a supply port installed, a discharge port installed in the vessel, and a shaft seal device disposed at a portion where the rotating shaft passes through the vessel. In this case, the shaft seal device preferably has two mechanical seal units, and the seal portions of the two mechanical seal units are preferably sealed with an external seal liquid. When a ball mill having such a configuration is used, urethane (meth) acrylate and inorganic particles are supplied to the vessel from the supply port, and the rotating shaft and the stirring blade are rotated in the vessel so that the medium and the supply are supplied. Stir and mix. Thereby, the grinding | pulverization of an inorganic particle and the dispersion | distribution to the urethane (meth) acrylate of the said inorganic particle can be performed, and a curable composition can be manufactured efficiently.

<Hardened product>
According to one form of this invention, hardened | cured material is provided.
In one Embodiment, the said hardened | cured material hardens | cures the curable composition containing the above-mentioned urethane (meth) acrylate resin. The cured product has a high surface hardness, scratch resistance, and is excellent in flexibility, is easy to decorate and form, and is a display member for imparting excellent design to home appliance casings and automobile interior parts. It can be suitably used for various applications such as surface protection films for various electronic devices, home appliances, furniture, etc., plating substitution, painting substitution, etc., as well as automotive parts and building materials. Since the cured product according to the present embodiment has high hardness and excellent flexibility, the decorative formability is easy, and excellent design properties can be imparted to home appliance housings, automobile interior parts, and the like. Excellent scratch resistance.

In addition, hardened | cured material can be normally obtained by apply | coating a solution and irradiating an active energy ray to the obtained coating film. In this case, the coating method is not particularly limited, and known methods such as bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing method, etc. Can be adopted. Moreover, it does not restrict | limit especially about the active energy ray irradiated, An ultraviolet-ray, an electron beam, etc. are mentioned. The light source used is not particularly limited, and examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp. Examples of the electron beam light source include a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type electron beam accelerator. Integrated light quantity of the active energy ray is not particularly limited, is preferably from 100~5000mJ / cm ^2, more preferably 300~2000mJ / cm ^2. It is preferable for the integrated light amount to be in the above-mentioned range because the generation of uncured portions can be prevented or suppressed. Note that the irradiation with active energy rays may be performed in one stage or may be performed in two or more stages.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not restrict | limited to description of an Example.

[Example 1]
<Manufacture of urethane (meth) acrylate resin (1)>
Takenate 500 (m-xylylene diisocyanate (XDI), manufactured by Mitsui Chemicals) 376.4 parts by mass, 0.1 parts by mass of zinc octate as a catalyst, 0.3 parts by mass of methoquinone as a polymerization inhibitor, Then, 3.3 parts by mass of dibutylhydroxytoluene was added to the four-necked flask and heated until the internal temperature of the flask reached 50 ° C. Next, 492.1 parts by mass of Kuraray polyol P-530 (poly [(3-methyl-1,5, -pentanediol) -alt- (isophthalic acid)], weight average molecular weight: 500, manufactured by Kuraray Co., Ltd.) The solution was added in portions over time and reacted at 80 ° C. for 2 hours. Next, 241.5 parts of 2-hydroxypropyl acrylate was dividedly added over 1 hour and reacted at 80 ° C. for 3 hours to synthesize a urethane (meth) acrylate resin (1). The reaction completion was judged by confirming the disappearance of the isocyanate group in the infrared absorption spectrum. The weight average molecular weight (Mw) of the urethane (meth) acrylate resin (1) was 3,650.

[Example 2]
<Manufacture of urethane (meth) acrylate resin (2)>
A urethane (meth) acrylate resin (2) was synthesized in the same manner as in Example 1 except that 348.4 parts by mass of toluene diisocyanate (TDI) was used instead of XDI. The weight average molecular weight (Mw) of the urethane (meth) acrylate resin (2) was 2,560.

[Example 3]
<Manufacture of urethane (meth) acrylate resin (3)>
Instead of Kuraray polyol P-530, Kuraray polyol P-1020 (poly [(3-methyl-1,5-pentanediol) -alt- (terephthalic acid)], weight average molecular weight: 1000, manufactured by Kuraray Co., Ltd.) A urethane (meth) acrylate resin (3) was synthesized in the same manner as in Example 1 except that 996.5 parts by mass were used. The weight average molecular weight (Mw) of the urethane (meth) acrylate resin (3) was 7,100.

[Comparative Example 1]
<Manufacture of urethane (meth) acrylate resin (1 ')>
A urethane (meth) acrylate resin (1 ′) was synthesized in the same manner as in Example 1 except that 366 parts by mass of hexamethylene diisocyanate (HDI) was used instead of XDI.

[Production Example 1]
<Production of (meth) acryloyl group-containing acrylic resin>
A reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube was charged with 453 parts by mass of methyl isobutyl ketone and heated while stirring until the system temperature reached 110 ° C. A mixed liquid consisting of 720 parts by mass of glycidyl methacrylate, 480 parts by mass of methyl methacrylate and 48 parts by mass of t-butyl peroxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Emulsifier Co., Ltd.) was dropped over 3 hours. After dropping from the funnel, the reaction was carried out at 110 ° C. for 15 hours. The mixture was cooled to 90 ° C., 1.6 parts by mass of methoquinone and 367 parts by mass of acrylic acid were added, and 7.8 parts by mass of triphenylphosphine was further added. The mixture was heated to 100 ° C. and reacted for 8 hours to obtain 3000 parts by mass (non-volatile content: 50% by mass) of a methyl isobutyl ketone solution of a (meth) acryloyl group-containing acrylic resin. The weight average molecular weight (Mw) of the (meth) acryloyl group-containing acrylic resin is 20,000, the theoretical value of (meth) acryloyl group equivalent calculated from the raw material charge ratio is 309 g / equivalent, and the hydroxyl value is 182 mgKOH / g. there were.

[Examples 4 to 8 and Comparative Example 2]
<Manufacture of curable compositions (1) to (3) and (1 ')>
Each component was mix | blended in the ratio shown in Table 1, ethyl acetate was added, and it adjusted to 40 mass% of non volatile matters, and obtained the curable composition. As a photopolymerization initiator, “Irgacure # 184” manufactured by BASF was used.
<Manufacture of curable composition (4)>
82 parts by mass of urethane (meth) acrylate resin (1) and 10 parts by mass of inorganic particles R7200 (hydrophobic fumed silica having a (meth) acryloyl group on the particle surface, average primary particle size: 12 nm, manufactured by Aerosil) And 8 parts by mass (resin solid content) of the (meth) acryloyl group-containing acrylic resin, and a slurry having a non-volatile content of 50% by mass using methyl isobutyl ketone, is a wet ball mill (manufactured by Ashizawa Corporation “ The mixture was dispersed using a star mill LMZ015 ”) to obtain a dispersion. Furthermore, 2 parts by mass of a photopolymerization initiator (“Irgacure # 184” manufactured by BASF) was added, and methyl isobutyl ketone was added to adjust the nonvolatile content to 40% by mass to obtain a curable composition (4).

Each condition of dispersion by the wet ball mill is as follows.
Media: Zirconia beads having a median diameter of 100 μm Filling ratio of resin composition with respect to the inner volume of the mill: 70% by volume
Peripheral speed of the tip of the stirring blade: 12 m / sec
Flow rate of resin composition: 200 ml / min
Dispersion time: 60 minutes

<Manufacture of curable composition (5)>
In the production of the curable composition (4), the urethane (meth) acrylate resin (1) is 64 parts by mass, the inorganic particles R7200 is 20 parts by mass, and the (meth) acryloyl group-containing acrylic resin is 16 parts by mass ( A curable composition (5) was produced in the same manner as the curable composition (4) except that the resin solid content was changed.

<Performance evaluation of resin composition>
Various performance evaluation was performed about curable composition (1)-(5) and (1 '). The results are shown in Table 1.

[Tensile elongation test]
The curable composition was applied to a polyethylene terephthalate (PET) film having a thickness of 125 μm with a bar coater and dried at 80 ° C. for 1 minute. Next, ultraviolet rays were irradiated with a high-pressure mercury lamp in an air atmosphere (300 mJ / cm ² ) to obtain a laminated film in which a cured product having a film thickness of 5 μm was laminated on the PET film.
The laminated film was cut out to be a test piece having a width of 10 mm and a length of 100 mm.
A tensile test was performed on the obtained test piece under the following conditions.
Tensile speed: 10 mm / min Distance between chucks: 40 mm
Temperature: 25 ° C
The elongation until the test piece surface cracked or the test piece broke was measured and evaluated according to the following criteria.
A: More than 100% B: More than 60% and less than 100% C: More than 20% and less than 60% D: Less than 20%

[Pencil hardness test]
A laminated film was obtained in the same manner as in the tensile elongation test.
Based on JIS K 5400: 1990, a pencil scratch test with a load of 750 g was performed on the surface of the laminated film. At this time, the pencil scratch test was performed five times, and the hardness one degree lower than the hardness at which scratches were made once or more was judged as the pencil strength of the cured product. The evaluation was performed according to the following criteria.
A: F-9H
B: B to HB
C: 3B-2B
D: 6B-4B

[Chemical resistance test]
A laminated film was obtained in the same manner as in the tensile elongation test.
A sunscreen cream (“Neutrogena Ultra Shear Sunscreen” manufactured by Johnson & Johnson Consumer Inc.) was applied to the laminated film to a concentration of 0.1 g / cm ² and left in an oven at 80 ° C. for 6 hours. After taking out from oven and returning to normal temperature, the sunscreen emulsion was wiped off with a cloth, and the state of the coating film surface after wiping was evaluated.
A: No change compared with the laminated film before the test B: After wiping or fogging occurs C: Peeling or cracking occurs in the coating film

  From the results in Table 1, it can be seen that the curable compositions (1) to (5) have high hardness, excellent flexibility, and high chemical resistance.

Claims (6)

  The polyisocyanate compound (A), the polyester diol compound (B), and the monohydroxy (meth) acrylate compound (C) are essential reaction raw materials, and 70% by mass or more of the polyisocyanate compound (A) contains aromatic group-containing poly Urethane (meth) acrylate resin which is an isocyanate compound (A1). The urethane (meth) acrylate resin according to claim 1, wherein the polyester diol compound (B) has a weight average molecular weight (Mw) in the range of 450 to 1200. The urethane (meth) acrylate resin according to claim 1, wherein monohydroxy mono (meth) acrylate (C1) is used as the previous monohydroxy (meth) acrylate compound (C). The curable composition containing the urethane (meth) acrylate resin as described in any one of Claims 1-3. A cured product of the curable composition according to claim 4. A laminated film having a layer comprising the cured product according to claim 5.