WO2019182155A1 - Curable composition, cured product, method for producing cured product, and method for repairing damage of cured product - Google Patents

Abstract

The present invention provides: a hard cured product which has excellent three-dimensional processability, while exhibiting excellent chemical resistance and/or excellent damage repairability; a method for producing this cured product; a curable composition which enables the achievement of this cured product; and a method for repairing damage of a cured product. A cured product which contains a compound (1) represented by formula (1), a compound (2) represented by formula (2), a compound (3) represented by formula (3) and a urethane (meth)acrylate, and which is configured such that the sum of the number of moles of the compound (1) contained in 1g of the cured product and the number of moles of either the compound (2) or the compound (3) contained in 1g of the cured product, said number of moles being lower than the other, is 0.05 mmol or more. (In formulae (1)-(3), each of R¹-R⁴, R⁷ and R⁸ represents a substituent; each of X¹ and X² represents a divalent group; at least one of R¹-R⁴ and X¹ represents a group having an electron-donating group; and at least one of R⁷, R⁸ and X² represents a group having an electron-withdrawing group.)

Description

Curable composition, cured product, method for producing cured product, and method for repairing scratches on cured product

The present invention relates to a curable composition, a cured product, a method for producing a cured product, and a method for repairing scratches on the cured product.
The present application is filed on March 23, 2018, Japanese Patent Application No. 2018-057022 filed in Japan, March 23, 2018, Japanese Patent Application No. 2018-057023 filed in Japan, and March 23, 2018. Claims priority based on Japanese Patent Application No. 2018-057025 filed in Japan, the contents of which are incorporated herein by reference.

The Diels-Alder (DA) reaction, in which a ring structure is formed by the reaction of a conjugated diene and dienophile (parent diene), is a thermoreversible equilibrium reaction, and the retro Diels-Alder (rDA) reaction occurs at a relatively high temperature. It is known to dissociate into conjugated dienes and dienophiles.

An adhesive using a thermoreversible Diels Alder (DA) network composed of such a conjugated diene and dienophile has been proposed (Patent Documents 1 and 2).
In addition, it has been proposed to use a hybrid polymer network in which a thermoreversible DA network and another polymer network are combined (Non-Patent Documents 1 and 2).

Non-Patent Document 1 proposes a self-healing hybrid polymer network that combines a DA network and a polyurethane network. When a film made of this hybrid polymer network is damaged, only the DA network is decomposed by the rDA reaction by heating the film and dissociates into the original conjugated diene and dienophile. Since the polyurethane network remains, the conjugated diene and dienophile ooze out into the wound area and fill the wound while maintaining the shape of the film. When the film is cooled, a DA network is formed again by the DA reaction, and the wound is repaired.

Non-Patent Document 2 proposes a photoresist by two-stage curing in which a DA network and an acrylate network are combined. By heating, the conjugated diene and dienophile react with each other to form a DA network, and the DA network forms a solid photoresist in which the acrylate is supported. When this is irradiated with light, an acrylate network is formed. The DA network is decomposed by the rDA reaction, dissociated into the original conjugated diene and dienophile, and then removed by development together with the unexposed acrylate.

JP 2003-183348 A Japanese Unexamined Patent Publication No. 2016-027116

However, according to the study of the inventor of the present invention, the hybrid polymer network described in Non-Patent Document 1 includes a polyurethane network, so that the cured product is soft and is not suitable for a hard coat film. Moreover, since it contains a polyurethane network, the chemical resistance of the cured product was insufficient.
Moreover, since the hybrid polymer network described in Non-Patent Document 2 contains an acrylate network having a high crosslink density, the wound repairability of the cured product was insufficient.

Also, the cured product may be required to have a three-dimensional workability after the curable composition is cured once and then deformed to be processed into a three-dimensional shape. However, the inventors of the present invention have found that the hybrid polymer network described in Non-Patent Document 2 has insufficient stretchability and is not suitable for three-dimensional processing.

The present invention is a curable composition capable of obtaining a cured product that is hard and excellent in three-dimensional processability, and has excellent chemical resistance and / or scratch repairability; hard, excellent in three-dimensional processability, chemical resistance and / or A cured product excellent in scratch repairability and a method for producing the cured product; and a method for repairing scratches on the cured product are provided.

The first aspect of the present invention is a curable composition that can form a thermoreversible DA network and can obtain a hardened cured product having excellent three-dimensional processability and chemical resistance; thermoreversible DA network And a cured product that is hard and excellent in three-dimensional processability and chemical resistance, and a method for producing the same.
The second aspect of the present invention is a curable composition capable of obtaining a hardened cured product excellent in three-dimensional workability and scratch repairability; a hardened cured product excellent in three-dimensional workability and scratch repairability and production thereof And a method for repairing a wound of a cured product.
The third aspect of the present invention is a curable composition capable of obtaining a hard and cured product excellent in three-dimensional workability, chemical resistance and scratch repairability; hard and three-dimensional workability, chemical resistance and scratch repair The present invention provides a cured product having excellent properties and a method for producing the same; and a method for repairing scratches on the cured product.

The present invention has the following aspects.
[1] A compound (1) represented by the following formula (1), a compound (2) represented by the following formula (2), which is a precursor of the compound (1), and a formula (3) A cured product containing a compound (3) which is a precursor of the compound (1) and urethane (meth) acrylate, and the number of moles of the compound (1) contained in 1 g of the cured product, among the compounds (2) and the compound (3), the sum N ₁ of the moles of the compound towards moles contained in the cured product 1g is small, not less than 0.05Mmol, cured product.

[In Formula (1), R ¹ to R ⁴ , R ⁷ and R ⁸ are substituents, X ¹ is a divalent group, and at least one of R ¹ to R ⁴ and X ¹ is an electron donor. X ² is a divalent group, and at least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group.
In formula (2), R ¹ to R ⁴ are substituents, X ¹ is a divalent group, and at least one of R ¹ to R ⁴ and X ¹ is a group having an electron donating group.
In formula (3), R ⁷ and R ⁸ are substituents, X ² is a divalent group, and at least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group. ]
[2] The compound (1) is a compound (4) represented by the following formula (4), the compound (2) is a compound (5) represented by the following formula (5), and The cured product of [1], wherein the compound (3) is the compound (6) represented by the following formula (6).

[In the formula (4), R ¹ to R ⁴ , R ⁷ and R ⁸ are substituents, R ¹¹ is an oxygen atom or —NR ¹² —, R ¹² is a substituent, and X ³ is an oxygen atom , A nitrogen atom or an alkylene group which may have a substituent, Y and Z are an oxygen atom or a sulfur atom,
At least one of R ¹ to R ⁴ and X ³ is a group having an electron donating group, and at least one of R ⁷ , R ⁸ and R ¹¹ is a group having an electron withdrawing group.
In the formula (5), R ¹ to R ⁴ are substituents, X ³ is an oxygen atom, a nitrogen atom or an alkylene group which may have a substituent, and R ¹ to R ⁴ and X ³ At least one is a group having an electron donating group.
In formula (6), R ⁷ and R ⁸ are substituents, R ¹¹ is an oxygen atom or —NR ¹² —, R ¹² is a substituent, and Y and Z are oxygen atoms or sulfur atoms, At least one of R ⁷ , R ⁸ and R ¹¹ is a group having an electron withdrawing group. ]
[3] The cured product according to [1] or [2], wherein the glass transition point measured by dynamic viscosity measurement is 20 ° C. or higher.
[4] The cured product according to any one of [1] to [3], wherein the haze value measured according to JIS K 7105 is 10% or less.
[5] The urethane (meth) acrylate is a reaction product of polyisocyanate, a polyol containing a chain aliphatic diol having 2 to 12 carbon atoms, and a polyfunctional (meth) acrylate having a hydroxyl group. [1] A cured product of any one of [4].
[6] The cured product according to any one of [1] to [5], which has scratch repair properties.
[7] The compound (2) represented by the following formula (2), the compound (3) represented by the following formula (3), the following formula (1), the compound (2) and the compound Compound (1) that is a reaction product of (3) and urethane (meth) acrylate, and among the solid content of the composition, the number of moles of the conjugated diene structure that compound (2) has The curable composition wherein the sum N ₂ of the smaller number of moles of the dienophile structure of the compound (3) and the number of moles of the compound (1) is 0.05 mmol / g or more.

[In Formula (1), R ¹ to R ⁴ , R ⁷ and R ⁸ are substituents, X ¹ is a divalent group, and at least one of R ¹ to R ⁴ and X ¹ is an electron donor. X ² is a divalent group, and at least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group.
In formula (2), R ¹ to R ⁴ are substituents, X ¹ is a divalent group, and at least one of R ¹ to R ⁴ and X ¹ is a group having an electron donating group.
In formula (3), R ⁷ and R ⁸ are substituents, X ² is a divalent group, and at least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group. ]
[8] The compound (1) is a compound (4) represented by the following formula (4):
The compound (2) is a compound (5) represented by the following formula (5),
The curable composition according to [7], wherein the compound (3) is a compound (6) represented by the following formula (6).

[In the formula (4), R ¹ to R ⁴ , R ⁷ and R ⁸ are substituents, R ¹¹ is an oxygen atom or —NR ¹² —, R ¹² is a substituent, and X ³ is an oxygen atom , A nitrogen atom or an alkylene group which may have a substituent, Y and Z are an oxygen atom or a sulfur atom,
At least one of R ¹ to R ⁴ and X ³ is a group having an electron donating group,
At least one of R ⁷ , R ⁸ and R ¹¹ is a group having an electron withdrawing group.
In the formula (5), R ¹ to R ⁴ are substituents, X ³ is an oxygen atom, a nitrogen atom or an alkylene group which may have a substituent, and R ¹ to R ⁴ and X ³ At least one is a group having an electron donating group.
In formula (6), R ⁷ and R ⁸ are substituents, R ¹¹ is an oxygen atom or —NR ¹² —, R ¹² is a substituent, and Y and Z are oxygen atoms or sulfur atoms,
At least one of R ⁷ , R ⁸ and R ¹¹ is a group having an electron withdrawing group. ]
[9] The curable composition according to [7] or [8], wherein the compound (2), the compound (3), and the urethane (meth) acrylate do not have an acid group.
[10] The curable composition according to any one of [7] to [9], which does not contain a photopolymerization initiator.
[11] The curable composition according to any one of [7] to [10], wherein the compound (3) includes a compound having two or more dienophile structures.
[12] The urethane (meth) acrylate is a reaction product of polyisocyanate, a polyol containing a chain aliphatic diol having 2 to 12 carbon atoms, and a polyfunctional (meth) acrylate having a hydroxyl group. [7] The curable composition according to any of [11].
[13] A composition comprising a compound (2) represented by the following formula (2), a compound (3) represented by the following formula (3), and a urethane (meth) acrylate, the compound (2) ) And the compound (3) above the temperature at which the Diels-Alder reaction is performed, the semi-cured product is obtained by heating at a temperature below the temperature at which the compound (2) and the compound (3) are dissociated by the retro Diels-Alder reaction, A method for producing a cured product, wherein a semi-cured product is irradiated with active energy rays to obtain a cured product.

[In Formula (2), R ¹ to R ⁴ are substituents, X ¹ is a divalent group, and at least one of R ¹ to R ⁴ and X ¹ is a group having an electron donating group. .
In formula (3), R ⁷ and R ⁸ are substituents, X ² is a divalent group, and at least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group. ]
[14] The compound (2) is a compound (5) represented by the following formula (5), and the compound (3) is a compound (6) represented by the following formula (6). 13] The manufacturing method of the hardened | cured material.

[In the formula (5), R ¹ to R ⁴ are substituents, X ³ is an oxygen atom, a nitrogen atom or an alkylene group which may have a substituent, and R ¹ to R ⁴ and X ³ At least one of them is a group having an electron donating group.
In formula (6), R ⁷ and R ⁸ are substituents, R ¹¹ is an oxygen atom or —NR ¹² —, R ¹² is a substituent, and Y and Z are oxygen atoms or sulfur atoms,
At least one of R ⁷ , R ⁸ and R ¹¹ is a group having an electron withdrawing group. ]
[15] A method for repairing a scratch generated in a cured product according to any one of [1] to [6], wherein the cured product having a scratch is treated with Diels of the compound (2) and the compound (3). A method for repairing scratches on a cured product, in which a Diels Alder network formed by an Alder reaction is heated to a temperature at which it is dissociated into the Compound (2) and the Compound (3) by a Retro Diels Alder reaction and then cooled.

The first aspect of the present invention relates to the following <1> to <10>.
<1> Component (A): a compound having a conjugated diene structure, Component (B): a compound having a dienophile structure (excluding component (C)), and component (C): urethane (meth) acrylate A curable composition comprising.
<2> Component (D): The curable composition according to <1>, further including a polymerization initiator.
<3> The curable composition according to <1> or <2>, wherein the component (A), the component (B), and the component (C) do not have an acid group.
<4> The curable composition according to any one of <1> to <3>, wherein the conjugated diene structure in the component (A) is a furan skeleton, and the dienophile structure in the component (B) is a maleimide skeleton. .
<5> The curable composition according to any one of <1> to <4>, wherein the component (A) comprises a compound having two or more conjugated diene structures.
<6> The curable composition according to any one of <1> to <5>, wherein the component (B) includes a compound having two or more dienophile structures.
<7> The above <1>, wherein the component (C) is a reaction product of a polyisocyanate, a polyol containing a chain aliphatic diol having 2 to 5 carbon atoms, and a polyfunctional (meth) acrylate having a hydroxyl group. The curable composition according to any one of <6>.
<8> A cured product obtained by curing the curable composition according to any one of <1> to <7>.
<9> The cured product of <8>, which is a hard coat film.
<10> The curable composition according to any one of <1> to <7> is subjected to a retro Diels-Alder reaction at a temperature equal to or higher than a temperature at which the component (A) and the component (B) react with each other. ) And the component (B) at a temperature lower than the dissociation temperature to obtain a semi-cured product, and the semi-cured product is irradiated with active energy rays to obtain a cured product.

The second aspect of the present invention relates to the following << 1 >> to << 13 >>.
<< 1 >> Component (A): Compound having conjugated diene structure, Component (B): Compound having dienophile structure (excluding component (C)), and Component (C): urethane (meth) acrylate A curable composition containing a cured film formed by the following method having a breaking elongation at 23 ° C. of 50% or more.
(Method for forming cured film)
The curable composition was applied to the surface of the 100 μm-thick polyethylene terephthalate film that had been subjected to the release treatment with an applicator so that the thickness after curing was 35 μm, and the coating film was heated at 70 ° C. for 30 minutes. Then, the coating film is irradiated with ultraviolet rays using a high-pressure mercury lamp under the condition of an integrated light quantity of 500 mJ / cm ² and cured at 23 ° C. for 1 day to form a cured film.
<< 2 >> The curable composition according to << 1 >>, wherein the component (C) has a mass average molecular weight of 3000 or more.
<< 3 >> The curable composition according to << 1 >> or << 2 >>, in which the component (A), the component (B), and the component (C) do not have an acid group.
<< 4 >> The ratio of the total mass of the component (A) and the component (B) to the total mass of the component (A), the component (B) and the component (C) is 1 to 95% by mass. The curable composition according to any one of << 1 >> to << 3 >>.
<< 5 >> The curable composition according to any one of the above << 1 >> to << 4 >>, wherein the conjugated diene structure in the component (A) is a furan skeleton.
<< 6 >> The curable composition according to any one of the above << 1 >> to << 5 >>, wherein the dienophile structure in the component (B) is a maleimide skeleton.
<< 7 >> The curable composition according to any one of the above << 1 >> to << 6 >>, wherein the component (A) has a urethane bond or a urea bond.
<< 8 >> The curable composition according to any one of the above << 1 >> to << 7 >>, wherein the component (A) includes a compound having two or more conjugated diene structures.
<< 9 >> The curable composition according to any one of the above << 1 >> to << 8 >>, wherein the component (B) includes a compound having two or more dienophile structures.
<< 10 >> The above-mentioned << 1 >>, wherein the component (C) is a reaction product of polyisocyanate, a polyol containing a chain aliphatic diol having 2 to 5 carbon atoms, and a polyfunctional (meth) acrylate having a hydroxyl group. A curable composition of any one of <9>.
<< 11 >> A cured product obtained by curing the curable composition according to any one of the above << 1 >> to << 10 >>.
<< 12 >> The cured product of the above << 11 >>, which is a hard coat film.
<< 13 >> The curable composition according to any one of the above << 1 >> to << 10 >> is subjected to a retro Diels Alder reaction at a temperature equal to or higher than a temperature at which the above component (A) and the above component (B) are subjected to a Diels Alder reaction. ) And the component (B) at a temperature lower than the dissociation temperature to obtain a semi-cured product, and the semi-cured product is irradiated with active energy rays to obtain a cured product.

A third aspect of the present invention relates to the following [1] to [17].
[1] Component (A): a compound having a conjugated diene structure, Component (B): a compound having a dienophile structure (excluding component (C)), and component (C): urethane (meth) acrylate A curable composition containing a cured film formed by the following method having a tensile elastic modulus at 23 ° C of 1 MPa or more.
(Method for forming cured film)
The curable composition was applied to the surface of the 100 μm-thick polyethylene terephthalate film that had been subjected to the release treatment with an applicator so that the thickness after curing was 35 μm, and the coating film was heated at 70 ° C. for 30 minutes. Then, the coating film is irradiated with ultraviolet rays using a high-pressure mercury lamp under the condition of an integrated light quantity of 500 mJ / cm ² and cured at 23 ° C. for 1 day to form a cured film.
[2] The curable composition according to [1], wherein the component (C) is a urethane (meth) acrylate having a tensile elastic modulus at 23 ° C. of 3000 MPa or less of a cured film formed by the following method.
(Method for forming cured film)
A mixture of component (C) dissolved in a solvent was applied to the surface of the 100 μm-thick polyethylene terephthalate film on which the release treatment had been performed with an applicator so that the thickness after curing was 35 μm. Heat at 70 ° C. for 30 minutes, irradiate the coating film with ultraviolet rays under a condition of an integrated light quantity of 500 mJ / cm ² using a high pressure mercury lamp, and cure at 23 ° C. for 1 day to form a cured film.
[3] The combination of [1] or [2], wherein the component (A) and the component (B) are combinations in which the tensile elastic modulus at 23 ° C. of the cured film formed by the following method is 0.1 MPa or more. Curable composition.
(Method for forming cured film)
A mixture in which component (A) and component (B) are dissolved in a solvent so that the molar ratio of the conjugated diene structure in component (A) to the dienophile structure in component (B) (conjugated diene structure / dienophile structure) is 1. The surface of the peeled side of the 100 μm thick polyethylene terephthalate film was coated with an applicator so that the thickness after curing was 40 μm, and the coating film was heated at 70 ° C. for 30 minutes, at 23 ° C. Cured for 1 day to form a cured film.
[4] The curable composition according to any one of [1] to [3], wherein the content of the conjugated diene structure in the component (A) is more than 2 mmol / g.
[5] The curable composition according to any one of [1] to [4], wherein the component (C) has a mass average molecular weight of 3000 or more.
[6] The curable composition according to any one of [1] to [5], wherein the component (A), the component (B), and the component (C) do not have an acid group.
[7] The ratio of the total mass of the component (A) and the component (B) to the total mass of the component (A), the component (B) and the component (C) is 20 to 99% by mass. The curable composition according to any one of [1] to [6].
[8] The curable composition according to any one of [1] to [7], wherein the conjugated diene structure in the component (A) is a furan skeleton.
[9] The curable composition according to any one of [1] to [8], wherein the dienophile structure in the component (B) is a maleimide skeleton.
[10] The curable composition according to any one of [1] to [9], wherein the component (A) has a urethane bond or a urea bond.
[11] The curable composition according to any one of [1] to [10], wherein the component (A) includes a compound having two or more conjugated diene structures.
[12] The curable composition according to any one of [1] to [11], wherein the component (B) includes a compound having two or more dienophile structures.
[13] The component (C) is a reaction product of a polyisocyanate, a polyol containing a chain aliphatic diol having 2 to 5 carbon atoms, and a polyfunctional (meth) acrylate having a hydroxyl group. -The curable composition in any one of [12].
[14] A cured product obtained by curing the curable composition according to any one of [1] to [13].
[15] The cured product according to [14], which is a hard coat film.
[16] The curable composition according to any one of [1] to [13] is mixed with the component (A) by a retro Diels-Alder reaction at a temperature equal to or higher than a Diels-Alder reaction between the component (A) and the component (B). ) And the component (B) at a temperature lower than the dissociation temperature to obtain a semi-cured product, and the semi-cured product is irradiated with active energy rays to obtain a cured product.
[17] A method for repairing a scratch produced in the cured product of [14] or [15], wherein the cured product having a scratch is treated with a Diels-Alder reaction between the compound (A) and the compound (B). A method for repairing scratches on a cured product, wherein the Diels Alder network formed by heating is heated to a temperature at which it is dissociated into the component (A) and the component (B) by a retro Diels Alder reaction and then cooled.

The cured product of the present invention is hard and excellent in three-dimensional processability, and excellent in chemical resistance and / or scratch repairability.
According to the curable composition of the present invention, it is possible to obtain a cured product that is hard and excellent in three-dimensional processability and excellent in chemical resistance and / or scratch repairability.
According to the method for producing a cured product of the present invention, it is possible to produce a cured product that is hard and excellent in three-dimensional processability and excellent in chemical resistance and / or scratch repairability.
According to the method for repairing a scratch on a cured product of the present invention, a scratch generated on the cured product can be sufficiently repaired.

According to the curable composition of the first aspect of the present invention, a thermoreversible DA network can be formed, and a cured product that is hard and excellent in three-dimensional processability and chemical resistance can be obtained.
The cured product of the first aspect of the present invention has a thermoreversible DA network and is hard and excellent in three-dimensional processability and chemical resistance.
According to the manufacturing method of the hardened | cured material of the 1st aspect of this invention, while having a thermoreversible DA network, it can manufacture hardened | cured hardened | cured material which is hard and excellent in three-dimensional workability and chemical resistance.

According to the curable composition of the 2nd aspect of this invention, the hardened | cured material which is hard and excellent in three-dimensional workability and a wound repairability can be obtained.
The cured product of the second aspect of the present invention is hard and excellent in three-dimensional processability and scratch repairability.
According to the manufacturing method of the hardened | cured material of the 2nd aspect of this invention, the hardened | cured material which is hard and excellent in three-dimensional workability and a wound repairability can be manufactured.
According to the method for repairing scratches on the cured product according to the second aspect of the present invention, it is possible to sufficiently repair the scratches generated on the cured product.

According to the curable composition of the 3rd aspect of this invention, the hardened | cured material which is hard and is excellent in three-dimensional workability, chemical resistance, and flaw repairability can be obtained.
The hardened | cured material of the 3rd aspect of this invention is hard, and is excellent in three-dimensional workability, chemical resistance, and flaw repairability.
According to the manufacturing method of the hardened | cured material of the 3rd aspect of this invention, the hardened | cured material which is hard and excellent in three-dimensional workability, chemical-resistance, and a flaw repair property can be manufactured.
According to the method for repairing a scratch on a cured product according to the third aspect of the present invention, a scratch generated on the cured product can be sufficiently repaired.

The following definitions of terms apply throughout this specification and the claims.
The compound represented by the formula (1) is referred to as “compound (1)”. The compounds represented by other formulas are also described in the same manner.
“(Meth) acrylate” is a general term for acrylate and methacrylate.
“(Meth) acryloyl group” is a general term for an acryloyl group and a methacryloyl group.
“(Meth) acrylamide” is a general term for acrylamide and methacrylamide.
“DA reaction” means Diels Alder reaction.
“RDA reaction” means Retro Diels Alder reaction.
“Active energy rays” means ultraviolet rays, electron rays, visible rays, heat rays (infrared rays, etc.), X rays, α rays, β rays, γ rays and the like.
“Content of conjugated diene structure in component (A)” is obtained by calculating the number of moles of conjugated diene from the result of ¹ H-NMR analysis.
The content of each compound in the cured product or cured film, as an index ratio of the peak intensity C-O-C stretching vibration and 1200 cm ^-1 and the benzene ring derived from ^{1600 cm} -1 to be estimated, the 830 cm ^-1 as a reference To calculate and obtain.
“Mass average molecular weight of component (C)” is determined by gel permeation chromatography measurement (GPC measurement).
The “tensile modulus of the cured film at 23 ° C.” is obtained as follows.
A cured film peeled off from a polypropylene plate and cut to a width of 10 mm was obtained by performing a tensile test using a tensile tester under the conditions of a temperature of 23 ° C., a humidity of 55% RH, a tensile speed of 50 mm / min, and a distance between chucks of 50 mm. The straight line connecting the stress at 0% elongation and the stress at 0.5% elongation of the stress-strain curve is extended, and the stress converted at 100% elongation is taken as the tensile modulus.
The “storage elastic modulus of the cured film at 23 ° C. or 150 ° C.” is measured as follows.
About the cured film which peeled from the polypropylene plate and cut | disconnected to 4 mm width, the storage elastic modulus from the temperature 23 degreeC to 200 degreeC was used for the temperature increase rate 2 using the dynamic viscoelasticity measuring apparatus (For example, SSI company make, DMS6100). Measured under the conditions of ° C / min and frequency of 0.1 Hz.
“˜” indicating a numerical range means that numerical values described before and after that are included as a lower limit value and an upper limit value.

<Hardened product>
The cured product of the present invention comprises a compound (1), a compound (2) that is a precursor of the compound (1), a compound (3) that is a precursor of the compound (1), and a urethane (meth) acrylate. And a cured product containing
The number of moles of the compound (1) contained in 1 g of the cured product and the number of moles of the compound having the smaller number of moles contained in the cured product 1 g out of the compound (2) and the compound (3). sum _{N 1} is greater than or equal to 0.05mmоl.

[In the formula (1), R ¹ to R ⁴ , R ⁷ , R ⁸ are substituents, X ¹ is a divalent group,
At least one of R ¹ to R ⁴ and X ¹ is a group having an electron donating group,
X ² is a divalent group,
At least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group.
In the formula (2), R ¹ to R ⁴ are substituents, X ¹ is a divalent group,
At least one of R ¹ to R ⁴ and X ¹ is a group having an electron donating group.
In formula (3), R ⁷ and R ⁸ are substituents, X ² is a divalent group,
At least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group. ]

In the cured product of the present invention, formation of a hybrid polymer network combining a DA network and a urethane (meth) acrylate network and decomposition of the DA network occur by the mechanism shown in the following reaction formula. Here, the DA network includes the compound (1) and a repeating unit derived from the compound (1).

When the cured product of the present invention is heated above the temperature at which the rDA reaction of the DA network occurs, the DA network is dissociated into the compound (2) and the compound (3). When the DA network is dissociated into the component (2) and the compound (3) and then cooled to a temperature below the dissociation between the compound (2) and the compound (3) by the rDA reaction, the compound (2) and the compound (3) reacts with DA, and a DA network is formed again.

The reason why the cured product of the present invention exhibits the effects of the present invention is as follows.
The cured product of the present invention forms a thermoreversible DA network as described above. Further, the cured product of the present invention forms a urethane (meth) acrylate network in which urethane (meth) acrylate is cured and reacted. The hybrid polymer network in which the DA network having covalent crosslinks and the urethane (meth) acrylate network are combined has a higher elastic modulus than the cured product of the urethane (meth) acrylate network alone, and is a hard cured product. There is a tendency.
When a cured product composed of a hybrid polymer network combining a DA network and a urethane (meth) acrylate network is damaged, only the DA network is decomposed by the rDA reaction by heating the cured product, and the original compound (2) And compound (3). On the other hand, since the polyurethane network remains, the compound (2) and the compound (3) ooze out into the scratched part and fill the wound while maintaining the shape of the cured product. When the cured product is cooled, a DA network is formed again by the DA reaction, and the flaw is repaired. At this time, the sum of the number of moles of the compound (1) contained in the cured product and the smaller number of moles contained in 1 g of the cured product in the compounds (2) and (3) is 0.05 mmol or more. Thus, there is sufficient DA network in the cured product, and the wound can be filled by oozing out into the scratched part. Therefore, the wound repairability of the cured product of the present invention is improved.
In addition, since the ratio of the DA network in the cured product is sufficient, at a temperature lower than the temperature at which the rDA reaction occurs, strong cross-linking due to carbon-carbon bonds is formed, and chemical resistance is improved. In addition, when the tensile elastic modulus at 23 ° C. of the cured product is sufficiently high, the hard coat property is excellent, the cured product is difficult to be damaged, and the elastic recovery force tends to repair the scratch.

(Compound (1))
Compound (1) is represented by the following formula (1).

In the formula (1), R ¹ to R ⁴ , R ⁷ and R ⁸ are substituents, X ¹ is a divalent group, and at least one of R ¹ to R ⁴ and X ¹ is an electron donating group. X ² is a divalent group, and at least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group.

R ¹ to R ⁴ , R ⁷ and R ⁸ are not particularly limited. R ¹ to R ⁴ , R ⁷ and R ⁸ may be, for example, a hydrogen atom, an alkyl group which may have a substituent, an aryl which may have a substituent, or a substituent. Good heteroaryl, alkoxy group and the like can be mentioned. R ¹ to R ⁴ , R ⁷ and R ⁸ are mutually independent substituents, and may be the same or different from each other.

The alkyl group which may have a substituent may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more, more preferably 2 or more. The number of carbon atoms of the alkyl group is preferably 20 or less, more preferably 10 or less. Accordingly, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms. When the carbon number of the alkyl group is within the above range, the solubility of the compound (1) in an organic solvent tends to be improved, which can be advantageous in processes such as coating and film formation.

The aryl group which may have a substituent is not particularly limited. Examples of the aryl group which may have a substituent include groups derived from a single ring or a plurality of rings. The number of rings contained in the groups derived from a plurality of rings is not particularly limited, but is usually 2 to 4 and preferably 3 or less. The number of carbon atoms of the aryl group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 15. When the carbon number of the aryl group is within the above range, the solubility of the compound (1) in an organic solvent tends to be improved, which can be advantageous in processes such as coating and film formation.

Examples of the heteroaryl group which may have a substituent include groups derived from a single ring or a plurality of rings. The number of rings contained in the group derived from a plurality of rings is not particularly limited, but is usually 2 to 4, and 2 or 3 is preferable. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 15. Specific examples include thienyl group, furyl group, pyridyl group, pyrazyl group, triazyl group, thiazolyl group, thiadiazolyl group, carbazolyl group, imidazolyl group and the like. Preferably a thienyl group, a furyl group, etc. are mentioned. If the number of carbon atoms of the heteroaryl group is within the above range, the effect of increasing the reaction point of the DA reaction tends to be obtained.

Of these, R ¹ to R ⁴ , R ⁷ and R ⁸ are each a hydrogen atom or an alkyl optionally having a substituent because the DA reaction tends to proceed and the raw material is easily procured. Groups are preferred.
The substituent that R ¹ to R ⁴ , R ⁷ and R ⁸ may have is not particularly limited. Examples of the substituent that R ¹ to R ⁴ , R ⁷ and R ⁸ may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, and an alkylcarbonyl. Group, ester group and the like. When it has a plurality of substituents, these substituents may be connected to each other to form a ring.

X ¹ is not particularly limited as long as it is a divalent group. Specific examples of X ¹ include, for example, an oxygen atom, a nitrogen atom, a sulfur atom, an alkylene group which may have a substituent; a phenylene group which may have a substituent; —Si (R ³¹ ) R Organic groups such as ^32- groups are mentioned. Here, R ³¹ and R ³² are each independently an alkyl group having 1 to 20 carbon atoms. Among these, oxygen atoms are preferable as R ³¹ and R ³² from the viewpoint of small steric hindrance and ease of raw material procurement.

The carbon number of the alkylene group which may have a substituent is preferably 1 or more, and more preferably 2 or more. The alkylene group which may have a substituent has preferably 20 or less, more preferably 10 or less. Therefore, the alkylene group which may have a substituent preferably has 1 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. When the number of carbon atoms of the alkylene group which may have a substituent is within the above range, the solubility of the compound (1) in an organic solvent tends to be improved, which can be advantageous in processes such as coating and film formation.

The substituent that the alkylene group may have is not particularly limited. Specific examples of the substituent that the alkylene group may have include a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylcarbonyl group, and an ester group. . When the alkylene group has a plurality of substituents, the plurality of substituents may be linked to each other with adjacent substituents to form a ring.

At least one of R ¹ to R ⁴ and X ¹ has an electron donating group. R ¹ to R ⁴ and X ¹ may be an electron donating group. Further, the position of the electron donating group in R ¹ to R ⁴ and X ¹ is not particularly limited.
The electron donating group is a group that has an effect of increasing the electron density at a specific position of the molecule. Specific examples of the electron donating group include an alkyl group, amino group, hydroxyl group, alkoxyl group, alkylene group, phenylene group, alkalkyl group, alkylamino group, dialkylamino group and the like. Among these, alkoxyalkyl groups, alkylamino groups, and dialkylamino groups are preferable because the solubility of the compound (1) in an organic solvent tends to be improved and can be advantageous in processes such as coating and film formation.
When at least one of R ¹ to R ⁴ and X ¹ has an electron donating group, the HOMO level of the compound (2) (diene) is increased and the reactivity of the DA reaction is improved.

X ² is not particularly limited as long as it is a divalent group. Specific examples of X ² include an oxygen atom, a nitrogen atom, an alkylene group which may have a substituent; an imide group; an —NR ¹² — group; a combination of these groups, and the like. R ¹² is preferably an alkyl group having 1 to 20 carbon atoms.
Alkylene group which may have a substituent has the same meaning as the alkylene group which may have a substituent at X ¹ of the above. The details and preferred embodiments of the alkylene group for X ² are the same as the alkylene group which may have a substituent for X ¹ .
Among these, X ² is preferably an imide group from the viewpoint of stability of compound (1), heat resistance, and ease of procurement of raw materials.

At least one of R ⁷ , R ⁸ and X ² has an electron withdrawing group. R ⁷ , R ⁸ and X ² may be an electron withdrawing group. Moreover, the position of the electron withdrawing group in R ⁷ , R ⁸ and X ² is not particularly limited.
The electron withdrawing group is a group that has an effect of reducing the electron density at a specific position of the molecule. Specific examples of the electron withdrawing group include, for example, an imide group, an amide group, a carboxyl group, a carbonyl group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoro group, a cyano group, a nitro group, a sulfoxide group, and a sulfone group. Etc. Among these, an imide group is preferable from the viewpoints of stability of compound (1), heat resistance, ease of procurement of raw materials, and the like.
When at least one of R ⁷ , R ⁸ and X ² has an electron withdrawing group, the LUMO level of the compound (3) (dienophile) is lowered, and the reactivity of the DA reaction is improved.

As the compound (1), the following compound (4) is preferable.

In the formula (4), R ¹ to R ⁴ , R ⁷ and R ⁸ are substituents, R ¹¹ is an oxygen atom or —NR ¹² —, R ¹² is a substituent, X ³ is an oxygen atom, An alkylene group which may have a nitrogen atom or a substituent, Y and Z are an oxygen atom or a sulfur atom,
At least one of R ¹ to R ⁴ and X ³ is a group having an electron donating group,
At least one of R ⁷ , R ⁸ and R ¹¹ is a group having an electron withdrawing group.

As the compound (1), the following compound (7) or compound (10) is more preferable, and the following compound (13) is more preferable.

In formula (7), formula (10) or formula (13),
R ¹ to R ⁴ and R ¹⁴ are substituents, and at least one of R ¹ to R ⁴ and R ¹⁴ is a group having an electron donating group;
R ⁷ and R ⁸ are substituents;
R ¹² is a substituent, and at least one of R ⁷ , R ⁸ and R ¹² is a group having an electron withdrawing group.
Here, Equation (7), equation (10) or formula (13) ^R 1 ^~ R ⁴ in, ^{R 7,} R ^{8, R 12} has the formula (1) or ^R 1 ^{~ R} 4 in formula (4), It is synonymous with R < ⁷ >, R < ⁸ >, R < ¹² >.

(Compound (2), Compound (3))
Compound (2) is represented by the following formula (2). Compound (3) is represented by the following formula (3).

In formula (2), R ¹ to R ⁴ are substituents, X ¹ is a divalent group, and at least one of R ¹ to R ⁴ and X ¹ is a group having an electron donating group.
In formula (3), R ⁷ and R ⁸ are substituents, X ² is a divalent group, and at least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group.

^R 1 ^~ R ⁴ in Formula (2) or Formula ^{(3), R 7, R} 8, X 1, X 2 is, ^R 1 ^{~ R 4} in the formula ^{(1), R 7, R} 8, X 1, X ² is synonymous with each other.

As the compound (2), the following compound (5) is preferable. As the compound (3), the following compound (6) is preferable.

In the formula (5), R ¹ to R ⁴ are substituents, X ³ is an oxygen atom, a nitrogen atom or an alkylene group which may have a substituent, and R ¹ to R ⁴ and X ³ At least one is a group having an electron donating group.
In formula (6), R ⁷ and R ⁸ are substituents, R ¹¹ is an oxygen atom or —NR ¹² —, R ¹² is a substituent, and Y and Z are oxygen atoms or sulfur atoms,
At least one of R ⁷ , R ⁸ and R ¹¹ is a group having an electron withdrawing group.
R ¹ to R ⁴ , R ⁷ , R ⁸ , X ³ , R ¹¹ , Y and Z in formula (5) or formula (6) are the same as R ¹ to R ⁴ , R ⁷ , R ⁸ , X ³ , R ¹¹ , Y and Z have the same meanings.

As the compound (5), the following compound (8) is preferable, the following compound (11) is more preferable, and the following compound (14) is more preferable.
As the compound (6), the following compound (9) is preferable, the following compound (12) is more preferable, and the following compound (15) is more preferable.

In formula (8), (9), (11), (12), (14) or (15),
R ¹ to R ⁴ and R ¹⁴ are substituents, and at least one of R ¹ to R ⁴ and R ¹⁴ is a group having an electron donating group;
R ⁷ and R ⁸ are substituents;
R ¹² is a substituent, and at least one of R ⁷ , R ⁸ and R ¹² is a group having an electron withdrawing group.
R ¹ to R ⁴ , R ⁷ , R ⁸ , R ¹² , R ¹⁴ in formula (8), (9), (11), (12), (14) or (15) are represented by formula (1), formula It is synonymous with R ¹ to R ⁴ , R ⁷ , R ⁸ , R ¹² , R ^{14 in} (4) or Formula (13).

Similarly to the DA network containing the compound (1), the rDA reaction and DA reaction of the DA network containing each of the compound (4), the compound (7) and the compound (10) are expressed as follows.

Further, in the compound (2), when the core part is nurate, the wound repair property of the cured product is particularly remarkably improved. Although the reason is not clear, it is possible to improve compatibility with urethane (meth) acrylate and improve affinity with compound (3) when rDA reaction occurs. As an example of the compound (2) when the core site is nurate, the following compound (2-1) can be mentioned.

In the formula (2-1), R ¹⁰¹ to R ¹⁰³ are n-valent organic groups, R ¹⁰⁴ to R ¹⁰⁶ are single bonds or alkylene groups having 1 to 10 carbon atoms, and R ¹⁰⁷ to R ¹¹⁵ are A hydrogen atom or an alkylene group having 1 to 20 carbon atoms. X ¹⁰ is preferably an oxygen atom or a sulfur atom. R ¹⁰¹ to R ¹⁰³ have the same meaning as Q ¹ described later.

In the compound (2), when the core part is biuret, the chemical resistance of the cured product is particularly improved. The reason for this is not clear, but the fact that the core part is biuret-type, the furan part spreads in the three-dimensional direction, the degree of crosslinking tends to be higher, and a dense DA network is formed. . As an example of the compound (2) when the core site is biuret, the following compound (2-2) may be mentioned.

In the formula (2-2), R ¹¹⁶ to R ¹¹⁸ are n-valent organic groups, R ¹¹⁹ , R ¹²³ , and R ¹²⁷ are single bonds or alkylene groups having 1 to 10 carbon atoms, and R ¹²⁰ to R ¹²² , R ¹²⁴ to R ¹²⁶ , R ¹²⁸ to R ¹³⁰ are each a hydrogen atom or an alkylene group having 1 to 20 carbon atoms, and X ²⁰ is preferably an oxygen atom or a sulfur atom. R ¹¹⁶ ~ ^{R 118} has the same meaning as to ^{Q 1} below.

In the cured product of the present invention, it can be said that the compound (2) is the following component (A). Moreover, in the hardened | cured material of this invention, it can be said that a compound (3) is the following component (B). Hereinafter, the component (A) and the component (B) will be described.
Component (A): Compound having a conjugated diene structure.
Component (B): Compound having a dienophile structure (excluding urethane (meth) acrylate).

(Ingredient (A))
Component (A): The compound having a conjugated diene structure is a component that forms a thermoreversible DA network by DA reaction with the component (B).
A component (A) may be used individually by 1 type, and may use 2 or more types together.

Examples of the conjugated diene structure include a cyclic conjugated diene structure and a chain conjugated diene structure. A cyclic conjugated diene structure is preferable because the diene structure is chemically stable and easily causes an rDA reaction. A cyclic conjugated diene structure having a hetero atom is more preferable, and a furan skeleton is particularly preferable.
Specific examples of the conjugated diene structure include the following structures.

Some hydrogen atoms of the conjugated diene structure may be substituted with one or both of other atoms and other atomic groups constituting the compound. Examples of other atoms include halogen atoms. Examples of the other atomic group include a monovalent organic group or a divalent or higher organic group that links two or more conjugated diene structures.

The content of the conjugated diene structure in component (A) is preferably more than 2 mmol / g, more preferably 2.2 mmol / g or more. Moreover, 10 mmol / g or less is preferable and 7.5 mmol / g or less is more preferable. The combination of the upper and lower limits is not particularly limited, but is preferably more than 2 mmol / g and not more than 10 mmol / g, more preferably not more than 2.2 to 7.5 mmol / g. If the content of the conjugated diene structure is not less than the lower limit of the above range, a DA network can be sufficiently formed. If the content of the conjugated diene structure is not more than the upper limit of the above range, the density of the DA network does not become excessively dense and the brittleness of the cured product can be reduced. Moreover, if content of a conjugated diene structure is in the said range, it exists in the tendency which can provide a wound repair property to the hardened | cured material of the curable composition of this invention.

Component (A) preferably does not have an acid group from the viewpoint of obtaining a cured product having excellent chemical resistance. Examples of the acid group include a carboxy group, a phenolic hydroxyl group, a phosphonic acid group, and a sulfonic acid group.

Component (A) preferably contains a compound having two or more conjugated diene structures from the viewpoint of easily forming a DA network. The number of conjugated diene structures is preferably an integer of 2 to 4 from the viewpoint of easy availability of raw materials.
The component (A) preferably has a urethane bond or a urea bond from the viewpoint that the compatibility with the component (C) is good and a transparent cured product is obtained.
The component (A) preferably has no sulfur atom in the molecule from the viewpoints of odor and storage stability. Specifically, it is preferable not to use a compound having a sulfur-containing group such as a thiol group (furfuryl mercaptan or the like) as a raw material for the component (A).

Component (A) is a compound represented by the following formula (I) from the point of easily forming a DA network, the point of obtaining a cured product excellent in chemical resistance, the point of obtaining a transparent cured product and the point of odor. It is preferable that (I) is included.

In the formula (I),
Q ¹ is an n-valent organic group, R ²⁰¹ is a single bond or an alkylene group having 1 to 10 carbon atoms, n is an integer of 2 or more, and R ²⁰² to R ²⁰⁴ are any groups. is there.
Q ¹ preferably has no acid group and no sulfur atom. X ³⁰ is preferably an oxygen atom or a sulfur atom. R ²⁰¹ is preferably an alkylene group having 1 to 6 carbon atoms, more preferably a methylene group, from the viewpoint of easy availability of raw materials. n is preferably an integer of 2 to 4 from the viewpoint of easy availability of raw materials. Specific examples of Q ¹ include the following groups.

However, * is a bond, R ²¹⁰ is a divalent hydrocarbon group, R ²¹¹ is a trivalent hydrocarbon group, and a plurality of R ²¹⁰ are the same or different. May be.
Examples of the divalent hydrocarbon group include an alkylene group, a cycloalkylene group, and an arylene group. The alkylene group, cycloalkylene group, arylene group and the like are not particularly limited, and may have a substituent.
Although carbon number of an alkylene group is not specifically limited, 1 or more are preferable and 2 or more are more preferable. The alkylene group preferably has 20 or less carbon atoms, more preferably 10 or less. The alkylene group may be linear or branched.
Although carbon number of a cycloalkylene group is not specifically limited, 3 or more are preferable and 4 or more are more preferable. The carbon number of the cycloalkylene group is preferably 20 or less, and more preferably 10 or less.
The arylene group is not particularly limited, and examples thereof include a group derived from a single ring or a plurality of rings. The number of rings contained in the groups derived from a plurality of rings is not particularly limited, but is usually 2 to 4 and preferably 3 or less. Although carbon number of an arylene group is not specifically limited, It is 6 or more, 20 or less are preferable and 15 or less are more preferable.
Examples of the substituent that the alkylene group, cycloalkylene group, and arylene group may have include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a cyano group, a carboxy group, and a halogen atom. Is mentioned.
The trivalent hydrocarbon group may contain an aromatic or alicyclic structure, and may have an alkyl group, a hydroxyl group or the like as a branch. The trivalent hydrocarbon group may have an ether bond, an ester bond, a carbonate bond, a urethane bond, a urea bond, an amide bond, a ketone group, and the like. Although carbon number of a trivalent hydrocarbon group is not specifically limited, It is 1 or more, 50000 or less are preferable and 40000 or less are more preferable.

The compound represented by the formula (I) can be obtained, for example, by reacting a polyisocyanate with a furan compound having a hydroxyl group or an amino group (furfuryl alcohol, furfurylamine, etc.).
The compound represented by the formula (I) is preferably a reaction product of polyisocyanate and furfuryl alcohol from the viewpoint of easy availability of raw materials.

(Ingredient (B))
Component (B): A compound having a dienophile structure (excluding component (C)) is a component that forms a thermoreversible DA network by DA reaction with component (A).
A component (B) may be used individually by 1 type, and may use 2 or more types together.

As the dienophile structure, a maleimide skeleton is particularly preferable because the dienophile structure is chemically stable and easily causes an rDA reaction.
Specific examples of the dienophile structure include the following structures.

Some hydrogen atoms having a dienophile structure may be substituted with one or both of other atoms and other atomic groups constituting the compound. Examples of other atoms include halogen atoms. Examples of the other atomic group include a monovalent organic group or a divalent or higher valent organic group that connects two or more dienophile structures.

Component (B) preferably has no acid group from the viewpoint of obtaining a cured product having excellent chemical resistance. Examples of the acid group include a carboxy group, a phenolic hydroxyl group, a phosphonic acid group, and a sulfonic acid group.

Component (B) preferably contains a compound having two or more dienophile structures from the viewpoint of easily forming a DA network. In view of easy availability of raw materials, the number of dienophile structures is preferably 2.

Component (B) is a compound (II) represented by the following formula (II) from the viewpoint of easily forming a DA network, a cured product having further excellent chemical resistance, and the availability of raw materials. ) Is preferably included.

However, ^{Q 2} is a divalent organic group. Q ² preferably has no acid group.
Specific examples of Q ² include the following groups.

However, * is a bond, p is an integer of 1 or more, q is an integer of 1 or more, and r is an integer of 1 or more.
As the compound represented by the formula (II), phenylene bismaleimide, 4,4′-bismaleimide diphenylmethane, polyphenylmethane maleimide, 3,3′-dimethyl-5,5 ′ are preferable in view of availability. -Diethyl-4,4'-diphenylmethane bismaleimide is preferred.

(Urethane (meth) acrylate)
Urethane (meth) acrylate is a component that forms an irreversible urethane (meth) acrylate network by a curing reaction with active energy rays.
In the cured product of the present invention, the urethane (meth) acrylate forms a urethane (meth) acrylate network. Urethane (meth) acrylate may be used individually by 1 type, and may use 2 or more types together.

Urethane (meth) acrylate preferably has no acid group from the viewpoint of excellent chemical resistance. Examples of the acid group include a carboxy group, a phenolic hydroxyl group, a phosphonic acid group, and a sulfonic acid group.

The mass average molecular weight (Mw) of urethane (meth) acrylate is not particularly limited. The mass average molecular weight (Mw) of the urethane (meth) acrylate is preferably 1500 or more, more preferably 3000 or more, and still more preferably 4000 or more. Moreover, 300000 or less is preferable, 200000 or less is more preferable, 100000 or less is further more preferable, 50000 or less is more preferable, 40000 or less is especially preferable. If the mass average molecular weight (Mw) is not less than the lower limit of the above range, the three-dimensional processability of the cured product tends to be good. If a mass average molecular weight (Mw) is below the upper limit of the said range, it exists in the tendency for a viscosity to be appropriate and for paintability to become favorable.
From the above, the mass average molecular weight (Mw) of the urethane (meth) acrylate is preferably 1500 to 300000, more preferably 3000 to 200000, further preferably 4000 to 100000, particularly preferably 4000 to 50000, and most preferably 4000 to 40000. .
The mass average molecular weight (Mw) can be determined by gel permeation chromatography measurement (GPC measurement).

The urethane (meth) acrylate preferably has a storage elastic modulus at 23 ° C. of the cured film III formed by the following method of 5 × 10 ⁴ Pa or more, and more preferably 1 × 10 ⁵ Pa or more.
The storage elastic modulus at 23 ° C. of the cured film III is preferably 5 × 10 ¹² Pa or less, more preferably 5 × 10 ¹⁰ Pa or less, and further preferably 1 × 10 ⁹ Pa or less. If the storage elastic modulus at 23 ° C. of the cured film III is not less than the lower limit of the above range, in addition to the wound repair by dissociation of the DA network by the rDA reaction into the compound (2) and the compound (3), Repair can also be expected. If the storage elastic modulus at 23 ° C. of the cured film III is not more than the upper limit of the above range, the wound repair by the dissociation into the compound (2) and the compound (3) by the rDA reaction of the DA network and the wound repair by the elastic recovery force There is no hindrance and the cured product of the curable composition of the present invention tends to have excellent wound repairability.
From the above, the storage elastic modulus of the cured film III at 23 ° C. is preferably 5 × 10 ⁴ to 5 × 10 ¹² Pa, more preferably 5 × 10 ⁴ to 5 × 10 ¹⁰ Pa, and 5 × 10 ⁴ to 1 × 10. ¹⁰ Pa is more preferable.

The storage elastic modulus at 23 ° C. of the cured film III is appropriately adjusted depending on the hydrogen bond density of the urethane bond and the covalent bond density of the (meth) acryloyl group. When the hydrogen bond density of the urethane bond is high, the storage elastic modulus is high, and when the covalent bond density of the (meth) acryloyl group is high, the storage elastic modulus is high. If necessary, the storage elastic modulus of the cured film III can be adjusted by adding another polyol to the urethane (meth) acrylate raw material in addition to the chain aliphatic diol having 2 to 12 carbon atoms.

Method for forming cured film III:
Thickness after curing is 35 μm on the surface of the peel-treated side of a 100 μm-thick polyethylene terephthalate film obtained by removing a mixture of urethane (meth) acrylate dissolved in a solvent (methyl ethyl ketone, butyl acetate, cyclohexanone, etc.) The film is applied with an applicator, heated at 70 ° C. for 30 minutes, irradiated with ultraviolet rays under a condition of an integrated light quantity of 500 mJ / cm ² using a high pressure mercury lamp, and cured at 23 ° C. for 1 day. Form III.

As urethane (meth) acrylate, publicly known urethane (meth) acrylate can be used.
The urethane (meth) acrylate has both hardness and stretchability (flexibility), and is capable of obtaining a cured product having excellent chemical resistance and shape retention of the cured product at high temperatures. A reaction product of a polyol containing 12 to 12 chain aliphatic diols and a polyfunctional (meth) acrylate having a hydroxyl group (hereinafter also referred to as component (C1)) is preferred.

Examples of the polyisocyanate include chain aliphatic polyisocyanate, aromatic polyisocyanate, and alicyclic polyisocyanate.
It is preferable that polyisocyanate contains alicyclic polyisocyanate from the point which raises the hardness of hardened | cured material.

Examples of chain aliphatic polyisocyanates include aliphatic diisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, etc.), aliphatic triisocyanates (tris (isocyanatohexyl) isocyanurate, etc.), and the like. .

Examples of the aromatic polyisocyanate include aromatic diisocyanates (tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, naphthalene diisocyanate, etc.).

Examples of alicyclic polyisocyanates include alicyclic diisocyanates (bis (isocyanatemethyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, isophorone diisocyanate, etc.), alicyclic triisocyanates (tris (isocyanate isophorone) isocyanurate, etc.) Isophorone diisocyanate is preferable.

Specific examples of the chain aliphatic diol having 2 to 12 carbon atoms include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,2-butane. Examples thereof include diol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,5-pentanediol and the like. The chain aliphatic diol having 2 to 12 carbon atoms is preferably ethylene glycol or 1,4-butanediol from the viewpoint of stain resistance of the cured product, wear resistance, and handling properties of the curable composition. Is particularly preferred.
Here, it can be said that these specific examples are chain aliphatic diols having 2 to 5 carbon atoms.

The proportion of the chain aliphatic diol having 2 to 12 carbon atoms is preferably 40% by mass or more of the total diol component from the viewpoint of stain resistance of the cured product, wear resistance, and handleability of the curable composition. More preferably, it is more preferably 80% by weight or more, and particularly preferably 90% by weight or more. The upper limit of the proportion of the chain aliphatic diol having 2 to 12 carbon atoms is usually 100% by mass.
Here, the chain aliphatic diol having 2 to 12 carbon atoms is a concept including a chain aliphatic diol having 2 to 5 carbon atoms.

Examples of the polyfunctional (meth) acrylate having a hydroxyl group include bisphenol A diglycidyl ether diacrylate, 1,4-cyclohexanedimethanol diglycidyl ether diacrylate, ethylene glycol diglycidyl ether diacrylate, 1,4-butanediol diglycidyl ether. Examples include diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

As the polyfunctional (meth) acrylate having a hydroxyl group, from the viewpoint of the mechanical strength of the cured film, (meth) acrylate such as pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. ) A hydroxyalkyl poly (meth) acrylate having an alkylene group having 2 to 4 carbon atoms between an acryloyl group and a hydroxyl group is preferred.

The molecular weight of the polyfunctional (meth) acrylate having a hydroxyl group is preferably 100 or more, and more preferably 200 or more. The molecular weight of the polyfunctional (meth) acrylate having a hydroxyl group is preferably 800 or less, and more preferably 500 or less, from the viewpoint of the mechanical strength of the cured film.
From the above, the molecular weight of the polyfunctional (meth) acrylate having a hydroxyl group is preferably from 100 to 800, more preferably from 200 to 500.
Here, when the polyfunctional (meth) acrylate having a hydroxyl group is an addition reactant or a polymer, the molecular weight is a number average molecular weight by GPC measurement.

As a raw material for the component (C1), other than polyisocyanate, a chain aliphatic diol having 2 to 12 carbon atoms, and a polyfunctional (meth) acrylate having a hydroxyl group, as long as the effects of the present invention are not impaired. These raw materials may be used. Other raw materials include C6-C16 chain aliphatic diol, polyester polyol, polyether polyol, polycarbonate polyol, polyacryl polyol, alicyclic diol, polyalkylene glycol, high molecular weight polyol (excluding polyalkylene glycol) .), Hydroxyalkyl mono (meth) acrylates, chain extenders and the like.

The urethane bond amount of the component (C1) is preferably 0.1 × 10 ⁻³ to 10.0 × 10 ⁻³ eq / g, and is preferably 0.2 × 10 ⁻³ eq / g to 9.0 × 10 ⁻³ eq / G is more preferable, 0.5 × 10 ⁻³ to 9.0 × 10 ⁻³ eq / g is more preferable, and 1.0 × 10 ⁻³ to 8.0 × 10 ⁻³ eq / g is particularly preferable. When the urethane bond amount is at least the lower limit of the above range, the stain resistance of the cured product and the handleability of the curable composition are improved. If the amount of urethane bonds is less than or equal to the upper limit of the above range, the solution stability and handling properties of the curable composition are improved.
The amount of urethane bonds in component (C1) is the number of urethane bonds (the total number of isocyanate groups (the total value of the number of moles of polyisocyanate multiplied by the number of isocyanate group functional groups)) and isocyanate groups such as hydroxyl groups and amino groups. The smaller of the total number of equivalents of all functional groups to be reacted) is the total amount of the constituent components of component (C1) (the total amount of each raw material component excluding the amount of components added in excess (not the amount charged). ) Divided by.

The amount of the (meth) acryloyl group of the component (C1) is preferably 0.2 × 10 ⁻³ to 3.0 × 10 ⁻³ eq / g, and 0.4 × 10 ⁻³ to 2.7 × 10 ⁻³ eq / G is more preferable, and 0.5 × 10 ⁻³ to 2.5 × 10 ⁻³ eq / g is more preferable. If the amount of (meth) acryloyl group is not less than the lower limit of the above range, the stain resistance and wear resistance of the cured product will be improved. If the amount of the (meth) acryloyl group is not more than the upper limit of the above range, the stretchability of the cured product is improved.
The amount of the (meth) acryloyl group of the component (C1) is the number of (meth) acryloyl groups (the number of (meth) acryloyl group functional groups is added to the number of moles of the polyfunctional (meth) acrylate having a hydroxyl group excluding the excessively added component amount. The sum of the multiplied values) is divided by the total amount of the constituent components of the component (C1) (the total amount of each raw material component excluding the excessively added component amount (not the charged amount)).

Component (C1) can be produced by subjecting polyisocyanate to a polyfunctional (meth) acrylate having a chain aliphatic diol having 2 to 12 carbon atoms and a hydroxyl group. Specifically, it can be produced by the method described in JP 2016-186039 A.

The amount of all isocyanate groups in component (C1) and the amount of all functional groups that react with isocyanate groups such as hydroxyl groups and amino groups are usually equimolar. Therefore, the polyisocyanate used as the raw material, the chain aliphatic diol having 2 to 12 carbon atoms, the polyfunctional (meth) acrylate having a hydroxyl group, and the other raw materials are used in an amount equal to the amount of all isocyanate groups in the component (C1). The amount of the total functional group reacting with it is an equivalent amount or an amount which is 50 to 200 equivalent% in terms of the equivalent percentage of the total functional group reacting with it relative to the isocyanate group.

The amount of the polyfunctional (meth) acrylate having a hydroxyl group is preferably 3 to 70 mol%, more preferably 5 to 50 mol%, of the total amount of the compound having a functional group that reacts with an isocyanate group. 30 mol% or less is more preferable. The molecular weight of the component (C1) can be controlled by the amount of the polyfunctional (meth) acrylate having a hydroxyl group.

In the production of component (C1), an organic solvent may be used for the purpose of adjusting the viscosity. Examples of the organic solvent include toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, N, N-dimethylformamide and the like.

In the production of component (C1), a catalyst may be used. Examples of the catalyst include tin-based catalysts (such as dibutyltin laurate, dibutyltin dioctate, dioctyltin dilaurate, and dioctyltin dioctate), bismuth-based catalysts (such as bismuth tris (2-ethylhexanate)), and the like.

In the production of the component (C1), a polymerization inhibitor may be used. Polymerization inhibitors include phenols (hydroquinone, methylhydroquinone, hydroquinone monoethyl ether, dibutylhydroxytoluene, etc.), amines (phenothiazine, diphenylamine, etc.), copper salts (such as copper dibutyldithiocarbamate), manganese salts (manganese acetate, etc.) ), Nitro compounds, nitroso compounds and the like.

In the production of component (C1), the reaction temperature is preferably 20 to 120 ° C, more preferably 40 to 100 ° C, and further preferably 60 to 100 ° C. When using 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 a polyfunctional (meth) acrylate having a hydroxyl group is included, the reaction temperature is preferably 70 ° C. or less from the viewpoint of preventing the (meth) acryloyl group from reacting excessively.
The reaction time is usually 5 to 20 hours.

(Ratio of each compound)
The number of moles of compound (1) contained in 1 g of the cured product of the present invention,
Of the compound (2) and the compound (3), the sum N ₁ with the number of moles of the compound having the smaller number of moles contained in 1 g of the cured product is 0.05 mmol or more.
For example, for 1 g of the cured product, the number of moles of compound (1) is n ₁₁ mol / g, the number of moles of compound (2) is n ₂₁ mmol / g, and the number of moles of compound (3) is n _31. When mm / g and n ₂₁ > n ₃₁ , the sum N ₁ is n ₁₁ + n ₃₁ . In this case, the cured product of the present invention satisfies n ₁₁ + n ₃₁ ≧ 0.05 mmol / g.
The sum _{N 1} is based on the cured product 1g, is preferably at least 0.1Mmol, more 0.3mmоl is more preferable. Also, especially when emphasizing wound-healing properties, the sum _{N 1} is preferably more than 0.3Mmol, more 0.5mmоl is more preferable. Further, the upper limit value of the sum N ₁ is not particularly limited, and may be adjusted as appropriate according to the application. When using the cured product of the present invention workability film or the like, the sum _{N 1} is preferably at most 10Mmol, more preferably less 5Mmol, 3 mmol or less is more preferable.
From the above, the sum N ₁ is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 10 mmol / g, further preferably 0.3 to 10 mmol / g, and particularly preferably 0.5 to 10 mmol / g. 0.5 to 5 mmol / g is most preferable.

In the cured product of the present invention, the number of moles (n ₁₁ mole) of the compound (1) in 1 g of the cured product, the number of moles (n ₂₁ mole) of the compound (2) in 1 g of the cured product, and the compound in 1 g of the cured product. The total number of moles (n ₁₁ mole) of compound (1) in 1 g of the cured product is preferably 25 mol% or more, more preferably 40 mol% or more, with respect to 100 mol% in total with the number of moles (n ₃₁ mole) of (3). 50 mol% or more is more preferable. If the number of moles (n ₁₁ mole) is equal to or greater than the above lower limit with respect to the total of 100 mole% of the number of moles (n ₁₁ mole), the number of moles (n ₂₁ mole), and the number of moles (n ₃₁ mole), curing is achieved. Even if the reaction is sufficiently advanced, the cured product has sufficient hardness, and the effect of the cured product of the present invention is easily obtained.
The upper limit of the total number of moles (n ₁₁ moles), the number of moles (n ₁₁ moles), the number of moles (n ₂₁ moles), and the number of moles (n ₃₁ moles) is not particularly limited. For example, it may be 99 mol% or less, 90 mol% or less, or 80 mol% or less with respect to the total 100 mol% of the number of moles (n ₁₁ mole), the number of moles (n ₂₁ mole), and the number of moles (n ₃₁ mole). .

Moreover, the magnitude | size, ratio, etc. of content of the compound (2) and the compound (3) in the hardened | cured material of this invention are not specifically limited. The ratio (n ₂₁ / n ₃₁ ) of the number of moles (n ₂₁ mole) of compound (2) to the number of moles (n ₃₁ mole) of compound (3) in 1 g of the cured product is preferably 1 to 10. 5 to 10 is more preferable, 1.5 to 5 is more preferable, 1.5 to 3 is further preferable, and 1.5 to 2 is particularly preferable. If the ratio (n ₂₁ / n ₃₁ ) is within the above range, the elongation at break of the cured product tends to be improved. In addition, the molecular weight of the DA network is lowered, the cured product is soft, and when it is made into a film, it tends to be a flexible film.
When the ratio (n ₂₁ / n ₃₁ ) is, for example, 1 to 1.5, the elastic modulus of the cured product tends to be improved. Within these ranges, the molecular weight of the DA network is high, and there is a tendency that damage repairability, chemical resistance, and a decrease in elastic modulus during heating tend to occur, especially for applications that require chemical resistance. Become. In addition, when the ratio (n ₂₁ / n ₃₁ ) is, for example, 1.5 to 2, there is a tendency to easily exhibit flaw repairability, chemical resistance, and a decrease in elastic modulus during heating. Tend to be useful for certain applications.

How to the sum _{N 1 0.05mmоl} more it is not particularly limited. For example, when producing a composition for obtaining a cured product, the sum of the number of moles of compound (1) and the smaller number of moles of compound (2) and compound (3) is The method etc. which mix a compound (2), a compound (3), and urethane (meth) acrylate so that it may become 0.05 mmol or more at the time of solid content 1g conversion are mentioned. Further, when increasing the ratio of the compound (1) in the cured product, there is a method of performing a heating treatment for 1 to 100 minutes at a temperature lower than the temperature at which the rDA reaction occurs after application of the composition or the like. Can be mentioned.

The proportions of urethane (meth) acrylate, compound (1), compound (2), and compound (3) in the cured product of the present invention may be appropriately adjusted depending on the application.
Ratio of the total mass of compound (1), compound (2) and compound (3) with respect to the total mass (100 mass%) of urethane (meth) acrylate, compound (1), compound (2) and compound (3) W is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 80% by mass or less, and particularly preferably 75% by mass or less. If the said ratio W is below the said upper limit, it is excellent in the dryness to the touch of the surface of hardened | cured material, and three-dimensional moldability is favorable.
The ratio W is preferably 4% by mass or more, and more preferably 10% by mass or more. If the ratio W is greater than or equal to the lower limit, dissociation of the compound (1) into the compound (2) and the compound (3) occurs due to the rDA reaction of the compound (1) in the molding temperature range, and the elastic modulus decreases, thereby reducing the urethane (meta ) Three-dimensional processability is better than the cured acrylate alone.
From the above, the proportion W is preferably 4 to 95% by mass, more preferably 4 to 90% by mass, further preferably 4 to 80% by mass, particularly preferably 4 to 75% by mass, and most preferably 10 to 75% by mass. preferable. If the ratio W is within the above range, a cured product that is hard and excellent in three-dimensional formability, chemical resistance, and shape retention at high temperatures tends to be obtained.

For example, in the case where the cured product of the present invention contains the compounds 2-0, 2-1, and 2-3 shown in the examples as the compound (2), the ratio of urethane (meth) acrylate from the viewpoint of wound repairability Is preferably 99% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and particularly preferably 70% by mass or less with respect to 100% by mass of the cured product. Moreover, 30 mass% or more is preferable and, as for the ratio of urethane (meth) acrylate, 50 mass% or more is more preferable.
In this case, the proportion of urethane (meth) acrylate is preferably 30 to 99% by mass, more preferably 30 to 80% by mass, still more preferably 30 to 75% by mass, and more preferably 30 to 70% by mass with respect to 100% by mass of the cured product. % Is particularly preferable, and 50 to 70% by mass is most preferable.

In addition, when the cured product of the present invention includes compound 2-2 shown in the examples as compound (2), the ratio of urethane (meth) acrylate is 100% by mass of cured product from the viewpoint of wound repairability. 75 mass% or less is preferable, 70 mass% or less is more preferable, 65 mass% or less is more preferable, 60 mass% or less is especially preferable. Moreover, 10 mass% or more is preferable with respect to 100 mass% of hardened | cured materials, and, as for the ratio of urethane (meth) acrylate, 30 mass% or more is more preferable.
In this case, the proportion of urethane (meth) acrylate is preferably 10 to 75% by mass, more preferably 10 to 70% by mass, further preferably 10 to 65% by mass, with respect to 100% by mass of the cured product. % Is particularly preferable, and 30 to 60% by mass is most preferable.

(Other ingredients)
The hardened | cured material of this invention may further have other components other than a compound (1), a compound (2), a compound (3), and urethane (meth) acrylate. What is necessary is just to adjust suitably the kind and ratio of another component according to a use etc. Specific examples of the other components include the same components as those described for the curable composition of the present invention described later.

(Shape retention at high temperatures)
The cured product of the present invention is excellent in shape retention at high temperatures. The cured product of the present invention preferably has shape retention at 80 ° C or higher, more preferably has shape retention at 90 ° C or higher, and shape retention at 100 ° C or higher. Further preferred. The fact that the cured product has a high-temperature shape-retaining property means that it does not drip (no fluidity) after holding the cured product (standing upright so that the film surface is vertical if it is a film) in a high-temperature environment. )

(Glass transition point)
The glass transition point (Tg) of the cured product of the present invention is preferably 20 ° C. or higher. The glass transition point (Tg) is, for example, preferably 20 to 200 ° C., more preferably 25 to 160 ° C. When the glass transition point (Tg) is within the above range, the compound (2) or the compound (3) tends to migrate during the rDA reaction.
The glass transition point (Tg) of the cured product can be measured by a method such as dynamic viscosity measurement (DMA measurement).

(Haze value)
The haze value of the cured product of the present invention is preferably 10% or less, and more preferably 5% or less. The lower limit of the haze value of the cured product is not particularly limited, and when the cured product is applied to a use requiring transparency, the haze value is preferably as small as possible. The lower limit value of the haze value of the cured product is, for example, 0.001% or more.
The haze value of the cured product can be measured according to JIS K 7105 using a haze meter (for example, Haze Computer HZ-2 manufactured by Suga Test Instruments Co., Ltd.).

(Tensile modulus)
The tensile elasticity modulus in 23 degreeC of the hardened | cured material of this invention is not specifically limited. The tensile elastic modulus at 23 ° C. of the cured product is preferably 20 MPa or more, and more preferably 30 MPa or more. Although the upper limit of the tensile elasticity modulus in 23 degreeC of hardened | cured material is not specifically limited, 3000 MPa or less is preferable and 2000 MPa or less is more preferable.
From the above, the tensile elastic modulus at 23 ° C. of the cured product is preferably 20 to 3000 MPa, more preferably 30 to 2000 MPa. When the tensile elastic modulus at 23 ° C. of the cured product is within the above range, the cured product is further excellent in scratch repairability and the hardness is further improved.
If the tensile elastic modulus at 23 ° C. of the cured product is equal to or higher than the lower limit value, stickiness of the cured film surface and an increase in friction coefficient tend to be suppressed. Further, if the tensile modulus of the cured product at 23 ° C. is not more than the above upper limit value, it is difficult to prevent migration during the rDA reaction of each compound (2) and compound (3), and further excellent wound repair properties are obtained. Tend to be obtained. The tensile elastic modulus at 23 ° C. of the cured product can be measured by a method using a Tensilon tensile tester.

(Storage modulus)
The storage elastic modulus at 150 ° C. of the cured product of the present invention is preferably 5 × 10 ⁴ Pa or more, and more preferably 1 × 10 ⁵ Pa or more. Further, the storage elastic modulus of the cured product at 150 ° C. is preferably 5 × 10 ¹² Pa or less, and more preferably 1 × 10 ¹⁰ Pa or less. If the storage elastic modulus at 150 ° C. of the cured product is equal to or higher than the lower limit, in addition to the flaw repairability by dissociation of the DA network into the compound (2) and the compound (3) by the rDA reaction, flaw repair by elastic recovery force is also possible. It tends to be expected. If the storage elastic modulus at 150 ° C. of the cured product is less than or equal to the above upper limit, scratch repairability due to dissociation of compound (2) and compound (3) during the rDA reaction of the DA network, and wound repair due to elastic recovery force are hindered. There is a tendency to be difficult to be.

The storage elastic modulus at 150 ° C. of the cured product of the present invention can be adjusted by the ratio between the urethane (meth) acrylate network density and the DA network density. When the storage modulus of a single cured product of urethane (meth) acrylate is higher than that of a cured product of DA network alone, a method of decreasing the proportion of urethane (meth) acrylate, storage of a single cured product of urethane (meth) acrylate In the case where the elastic modulus is lower than the cured product of the DA network alone, a method of increasing the proportion of urethane (meth) acrylate can be considered.

(Method for repairing scratches on cured products)
The method for repairing scratches on the cured product of the present invention is a method for repairing scratches generated on the cured product of the present invention. According to the method for repairing a wound of a cured product of the present invention, a DA network formed by a DA reaction between the compound (2) and the compound (3) is converted into a compound ( In this method, the mixture is heated to a temperature at which it is dissociated into 2) and the compound (3) and then cooled.

<Method for producing cured product>
In the method for producing a cured product of the present invention,
Compound (2) represented by the following formula (2),
Compound (3) represented by the following formula (3),
Urethane (meth) acrylate,
The composition containing is heated at a temperature above the temperature at which the compound (2) and the compound (3) undergo a Diels-Alder reaction and below the temperature at which the compound (2) and the compound (3) are dissociated by a retro Diels-Alder reaction. Thus, a semi-cured product is obtained, and the semi-cured product is irradiated with active energy rays to obtain a cured product.

In formula (2), R ¹ to R ⁴ are substituents, X ¹ is a divalent group, and at least one of R ¹ to R ⁴ and X ¹ is a group having an electron donating group.
In formula (3), R ⁷ and R ⁸ are substituents, X ² is a divalent group, and at least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group.

The details and preferred embodiments of the compound (2), the compound (3) and the urethane (meth) acrylate are the same as those described for the cured product of the present invention.
It can also be said that the compound (2) is the above-mentioned component (A). Similarly, it can be said that the compound (3) is the above-mentioned component (B). The details and preferred embodiments of the component (A) and the component (B) are the same as those described for the cured product of the present invention.

First, a composition containing compound (2), compound (3) and urethane (meth) acrylate is converted into a compound by retro Diels-Alder reaction at a temperature equal to or higher than the Diels-Alder reaction between compound (2) and compound (3). The semi-cured product is heated at a temperature lower than the temperature at which it dissociates into (2) and compound (3) (first stage reaction).
Next, active energy rays are irradiated to the semi-cured product to form a urethane (meth) acrylate network by urethane (meth) acrylate curing reaction (polymerization reaction of urethane (meth) acrylate), DA network and urethane (meth) A cured product having a hybrid polymer network combined with an acrylate network is obtained (second stage reaction).

<Curable composition>
The curable composition of the present invention comprises:
Compound (2) represented by the following formula (2),
Compound (3) represented by the following formula (3),
A compound (1) represented by the following formula (1), which is a reaction product of the compound (2) and the compound (3);
Urethane (meth) acrylate,
A composition comprising
Of the solid content of the composition, the smaller number of moles of the number of moles of the conjugated diene structure possessed by the compound (2) and the number of moles of the dienophile structure possessed by the compound (3), and the number of moles of the compound (1) Of N ₂ is 0.05 mmol / g or more.

In the formula (1), R ¹ to R ⁴ , R ⁷ and R ⁸ are substituents, X ¹ is a divalent group,
At least one of R ¹ to R ⁴ and X ¹ is a group having an electron donating group,
X ² is a divalent group,
At least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group.
In the formula (2), R ¹ to R ⁴ are substituents, X ¹ is a divalent group,
At least one of R ¹ to R ⁴ and X ¹ is a group having an electron donating group.
In formula (3), R ⁷ and R ⁸ are substituents, X ² is a divalent group,
At least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group.

In the curable composition of the present invention, the details and preferred embodiments of the compound (1), the compound (2), the compound (3) and the urethane (meth) acrylate are the contents described for the above-described cured product of the present invention. It is the same.
Moreover, also in the curable composition of this invention, it can be said that a compound (2) is the above-mentioned component (A) similarly to the hardened | cured material of this invention. It can also be said that the compound (3) is the above-mentioned component (B). The details and preferred embodiments of the component (A) and the component (B) are the same as those described for the cured product of the present invention.
In the following description, urethane (meth) acrylate is described as component (C),
Compound (1) may be referred to as component (D). Here, component (C) is synonymous with urethane (meth) acrylate, and component (D) is synonymous with compound (1).

In the curable composition of the present invention, for example, formation of a hybrid polymer network combining a DA network and a urethane (meth) acrylate network and decomposition of the DA network occur by a mechanism shown in the following reaction formula. Here, the formation of the hybrid polymer network and the decomposition of the DA network in the curable composition of the present invention are not limited to the embodiments and compounds shown in the following reaction formula.

First, the curable composition of the present invention is heated at a temperature equal to or higher than the temperature at which the component (A) and the component (B) react with each other and less than the temperature at which the rDA reacts to form a DA network to obtain a semi-cured product (1 Step reaction).
Next, active energy rays are irradiated to the semi-cured product to form a urethane (meth) acrylate network by curing reaction of component (C) (polymerization reaction of (meth) acrylate), and DA network and urethane (meth) acrylate network To obtain a cured product having a hybrid polymer network in combination with (second stage reaction).

When the cured product obtained from the curable composition of the present invention is heated to a temperature at which the rDA reaction of the DA network occurs, the DA network is dissociated into the component (A) and the component (B). After the DA network is dissociated into the component (A) and the component (B) and then cooled below the temperature at which it is dissociated into the component (A) and the component (B) by the rDA reaction, the component (A) and the component (B) DA reacts to form a DA network again (third stage reaction).

A cured product having a hybrid polymer network combining such a thermoreversible DA network and a urethane (meth) acrylate network is a self-repairable hard coat film, a two-step cured photoresist, and a reworkable cured product. Can be used as etc.

The reason why the curable composition of the present invention exhibits the effects of the present invention is as follows.
In the curable composition of the present invention, since component (A): a compound having a conjugated diene structure and component (B): a compound having a dienophile structure are included, component (A) and component (B) Can react with DA to form a thermoreversible DA network. In addition, since component (C): urethane (meth) acrylate is included, component (C) can be cured to form a urethane (meth) acrylate network. Since the cured product containing the urethane (meth) acrylate network has a higher elastic modulus than the cured product containing the polyurethane network or the acrylate network, a hard cured product can be obtained.
When a cured product composed of a hybrid polymer network combining a DA network and a urethane (meth) acrylate network is damaged, only the DA network is decomposed by the rDA reaction by heating the cured product, and the original component (A) And component (B). Since the polyurethane network remains, the component (A) and the component (B) ooze out into the scratched part and fill the wound while maintaining the shape of the cured product. When the cured product is cooled, a DA network is formed again by the DA reaction, and the flaw is repaired.

In the curable composition of the present invention, among the solid content of the composition, the smaller number of moles of the number of moles of the conjugated diene structure possessed by the compound (2) and the number of moles of the dienophile structure possessed by the compound (3) The sum of the number of moles of compound (1) is 0.05 mmol / g or more. Therefore, there is a sufficient DA network in the cured product obtained from the curable composition, and when the cured product is scratched, it can ooze out into the scratched portion and fill the scratch. In addition, since there is sufficient DA network in the cured product, chemical resistance is improved at a temperature lower than the temperature at which the rDA reaction occurs, because strong cross-linking is formed by carbon-carbon bonds.

The curable composition of the present invention may further contain component (E): a polymerization initiator.
The curable composition of the present invention may further contain component (F): a liquid medium.
The curable composition of the present invention further contains components other than the components (A) to (F) (hereinafter also referred to as “other components”) as necessary within the range not impairing the effects of the present invention. You may go out.

(Ingredient (E))
Component (E): The polymerization initiator is a component that improves the initiation efficiency of the polymerization reaction of the (meth) acryloyl group of component (C) that proceeds by irradiation with active energy rays.
When the active energy ray used for the polymerization reaction of the (meth) acryloyl group is an electron beam, the curable composition of the present invention may not contain the component (E).

Examples of the component (E) include a photo radical polymerization initiator that generates radicals by light.
As photo radical polymerization initiators, benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) benzophenone, 4-phenylbenzophenone, methyl orthobenzoylbenzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, 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, methylbenzoyl formate, 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholinopropan-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4 -Trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] And -2-methyl-propan-1-one.

As radical photopolymerization initiators, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, , 4,6-Trimethylbenzoyldiphenylphosphine oxide, 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, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl 2-methyl-propan-1-one is more preferred.

When the curable composition contains a compound having a cationic polymerizable group such as an epoxy group, the curable composition may contain a photocationic polymerization initiator as a polymerization initiator.
It is preferable that the curable composition of this invention does not contain a photoinitiator. By not containing a photopolymerization initiator, there is a tendency that the modification of the curable composition due to the initiator decomposition product and the decrease in the mechanical strength of the cured product can be suppressed.

(Ingredient (F))
Component (F): The liquid medium is a component for dissolving the components (A) to (E), adjusting the viscosity when curing the curable composition, and obtaining a uniform cured product.

As the liquid medium, an organic solvent having a solubility parameter at 25 ° C. (hereinafter also referred to as “SP value”) of 8.0 to 11.5 is preferable. If SP value in 25 degreeC is more than the lower limit of the said range, the solubility of a component (C) is good. If SP value in 25 degreeC is below the upper limit of the said range, transparency of a curable composition is good. As organic solvents, toluene (9.1), xylene (9.1), ethyl acetate (8.7), butyl acetate (8.7), cyclohexanone (9.8), methyl ethyl ketone (9.0), methyl Examples thereof include isobutyl ketone (8.7), N-methylpyrrolidone (11.2), 1-methoxy-2-propanol (10.2) and the like. Numerical values in parentheses are SP values at 25 ° C.
The SP value is calculated by the method proposed by Fedors et al. Specifically, ROBERT F.R. FEDORS, “POLYMER ENGINEERING AND SCIENCE, FEBRUARY”, Vol. 14, No. 2, 1974, p. 147 to 154.

(Other ingredients)
Examples of other components include an active energy ray-reactive monomer, an active energy ray-curable oligomer (excluding component (C)), a photosensitizer, an epoxy compound, and other additives.

Examples of active energy ray reactive monomers include vinyl compounds, (meth) acrylamide compounds, (meth) acrylates, and the like.
Examples of the active energy ray-curable oligomer include epoxy (meth) acrylate, acrylic (meth) acrylate, polyester (meth) acrylate, polycarbonate (meth) acrylate, polybutadiene (meth) acrylate, and polyether (meth) acrylate.

As photosensitizers, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone Etc.

Other additives include fillers (glass fiber, glass beads, silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, mica, talc, kaolin, metal oxide, metal fiber, iron, lead, metal powder, Carbon fiber, carbon black, graphite, carbon nanotube, fullerene, etc.), antioxidant, heat stabilizer, UV absorber, hindered amine light stabilizer (HALS), anti-fingerprint agent, surface hydrophilizing agent, antistatic agent, slipperiness Giving agent, plasticizer, mold release agent, antifoaming agent, leveling agent, anti-settling agent, surfactant, thixotropy imparting agent, lubricant, flame retardant, flame retardant aid, polymerization inhibitor, filler, silane coupling agent , Pigments, dyes, hue adjusting agents, curing agents, catalysts, curing accelerators and the like.

(Ratio of each component)
Of the solid content of the curable composition of the present invention, the smaller number of moles of the number of moles of the conjugated diene structure possessed by component (A) and the number of moles of the dienophile structure possessed by component (B), and component (D) the sum of _{N 2} and the number of moles of is 0.05mmоl / g or more. The sum N ₂ in the curable composition of the present invention is preferably 0.1 mmol / g or more, and more preferably 0.3 mmol / g or more. Further, when importance is attached particularly the wound-healing properties, the sum _{N 2} is preferably not less than 0.3mmоl / g, more preferably at least 0.5mmоl / g. When the sum N ₂ is equal to or greater than the lower limit, the wound repairability and chemical resistance of the cured product are improved.
The upper limit value of the sum N ₂ is not particularly limited. The sum N ₂ may be appropriately adjusted according to the application of the curable composition. When the curable composition is used for the production of a workable film, the sum N ₂ is preferably 10 mmol / g or less, more preferably 5 mmol / g or less, and further preferably 3 mmol / g or less.
The sum N ₂ is equal to or less than the upper limit, there is a tendency that flexibility to the cured product obtained from the curable composition of the present invention is applied.
From the above, the sum N ₂ is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g, further preferably 0.3 to 3 mmol / g, and particularly preferably 0.5 to 3 mmol / g. preferable.

In the curable composition of the present invention, the number of moles of compound (1) in 1 g of curable composition (n ₁₂ mole) and the number of moles of compound (2) in 1 g of curable composition (n ₂₂ mole) The total number of moles (n ₁₂ mole) of the compound (1) in 1 g of the curable composition is 80 mol% with respect to 100 mole% in total with the number of moles (n ₃₂ mole) of the compound (3) in 1 g of the curable composition. The following is preferable, 60 mol% or less is more preferable, and 50 mol% or less is more preferable. When the number of moles (n ₁₂ mole) is equal to or less than the above upper limit value with respect to 100 mol% in total of the number of moles (n ₁₂ mole), the number of moles (n ₂₂ mole), and the number of moles (n ₃₂ mole), curing is achieved. It can be said that the composition is in a state before the reaction sufficiently proceeds, and the curable composition of the present invention has sufficient fluidity, and the effect of the curable composition of the present invention is easily obtained. Moreover, the solubility of a compound (1), a compound (2), and a compound (3) improves that it is below the said upper limit, and there exists a tendency for a curable composition to become uniform, Therefore The hardened | cured material obtained There is also a tendency to improve the uniformity.
The lower limit of the total number of moles (n ₁₂ moles), the number of moles (n ₁₂ moles), the number of moles (n ₂₂ moles), and the number of moles (n ₃₂ moles) is not particularly limited. For example, may be a number of moles _{(n 12 mоl)} the moles _{(n 22 mоl)} the moles _{(n 32 mоl)} 1mol% or more relative to the total 100 mol% of the may be 10 mol% or more, may be 20 mol% or more .

The molar ratio of the conjugated diene structure of component (A) to the dienophile structure of component (B) in the curable composition of the present invention (conjugated diene structure / dienophile structure) is preferably more than 1.0 and 10 or less, 1.1 More preferably, it is 2.5 or less. If the conjugated diene structure / dienophile structure is at least the lower limit of the above range, the unreacted dienophile structure (maleimide skeleton, etc.) in the component (B) decreases after the DA reaction between the component (A) and the component (B). . When the unreacted dienophile structure increases, another polymer network is formed by polymerization of the dienophile structure, and there is a possibility that the effect of the thermoreversible DA network cannot be exhibited sufficiently. If the conjugated diene structure / dienophile structure is less than or equal to the upper limit of the above range, useless conjugated diene structures that do not contribute to the DA reaction between the component (A) and the component (B) are reduced.

Ratio of total mass of component (A) and component (B) to total mass (100 mass%) of component (A), component (B) and component (C) in the curable composition of the present invention ((A + B) / (A + B + C)) may be appropriately set according to the use of the cured product of the curable composition. (A + B) / (A + B + C) is preferably 99% by mass or less. Further, (A + B) / (A + B + C) is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 4% by mass or more, further preferably 10% by mass or more, and particularly preferably 30% by mass or more. 40% by mass or more is most preferable. If (A + B) / (A + B + C) is not less than the lower limit of the above range, the reaction product of the component (A) and the component (B) tends to have excellent flaw repair properties due to the rDA reaction. If (A + B) / (A + B + C) is less than or equal to the upper limit of the above range, the dryness of the surface of the cured product is excellent and the three-dimensional formability tends to be good.

The amount of component (D) in the curable composition of the present invention is preferably 10 parts by mass or less with respect to 100 parts by mass in total of component (C), active energy ray-reactive monomer and active energy ray-curable oligomer. 5 parts by mass or less is more preferable. If the amount of component (D) is less than or equal to the lower limit of the above range, the mechanical strength of the cured product is unlikely to decrease due to the decomposition product of component (D).

The solid content concentration of the curable composition of the present invention is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, further preferably 15 to 70% by mass, and particularly preferably 15 to 60% by mass. Solid content is all the components except a component (E), and includes not only a solid state thing but a semi-solid thing, and a viscous liquid substance.

The compounding amount of other components in the curable composition of the present invention is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass in total of the components (A) to (C). If the blending amount of other components is not more than the upper limit of the above range, the effects of the present invention are unlikely to be impaired.

The curable composition of this invention can be prepared by mixing and stirring each component.
For example, among the solid content of the curable composition, the smaller number of moles of the number of moles of the conjugated diene structure possessed by the compound (2) and the number of moles of the dienophile structure possessed by the compound (3); such that the sum N ₂ of the moles is more than 0.05 mmol, like compound (2) with the compound (3) and a method in which mixing the urethane (meth) acrylate.
What is necessary is just to adjust the viscosity of the curable composition of this invention suitably according to the usage form etc. of a curable composition. The viscosity at 25 ° C. in the E-type viscometer (rotor 1 ° 34 ′ × R24) is preferably 10 to 50,000 mPa · s, and preferably 30 to 10000 mPas from the viewpoints of handleability, coatability, moldability, and three-dimensional modeling. S is more preferable, 30 to 5000 mPa · s is more preferable, and 30 to 2000 mPa · s is particularly preferable.

(Tensile modulus)
In the curable composition of the present invention, the tensile elastic modulus at 23 ° C. of the cured film I formed by the following method is preferably 1 MPa or more, more preferably 5 MPa or more, further preferably 10 MPa or more, further preferably 20 MPa or more, and 30 MPa. The above is particularly preferable, and 35 MPa or more is most preferable. The tensile elastic modulus at 23 ° C. of the cured film I is preferably 2000 MPa or less, more preferably 1500 MPa or less, further preferably 1000 MPa or less, and still more preferably 500 MPa or less. If the tensile modulus at 23 ° C. of the cured film I is equal to or greater than the lower limit of the above range, scratches due to elastic recovery force in addition to wound repair by dissociation of component (A) and component (B) by the rDA reaction of the DA network There is also a tendency to expect repairs. If the cured film I has a tensile modulus of elasticity at 23 ° C. that is less than or equal to the upper limit of the above range, the wound repair by the dissociation of the DA network into the component (A) and the component (B) by the rDA reaction and the wound repair by the elastic recovery force There is no hindrance and the cured product of the curable composition of the present invention tends to have excellent wound repairability.

The tensile elastic modulus at 23 ° C. of the cured film I can be adjusted by the mixing ratio of the component (C) and the DA network component (component (A) and component (B)). When the tensile modulus of the component (C) single film (the cured film III described above) is higher than that of the DA network single film, the proportion of the component (C) is decreased. The tensile modulus of the component (C) single film is DA. If it is lower than the network single membrane, the proportion of the component (C) may be increased.

Method for forming cured film I:
The curable composition was applied to a 1 mm thick polypropylene plate that had been peeled off with an applicator so that the thickness after curing was 50 μm. The coating film is irradiated with ultraviolet rays under conditions of 500 mJ / cm ² and cured at 23 ° C. for 1 day to form a cured film I.
In the case of active energy ray curing, the curable composition is coated on a glass or polypropylene plate having a thickness of 1 mm with a bar coater to form a coating film, and then dried at 70 ° C. for 30 minutes. (Curetron EBC-200-AA3, manufactured by NHV Corporation) was used to irradiate the dried coating film twice under the conditions of an acceleration voltage of 165 kV and an irradiation dose of 5 Mrad, and further cured at 23 ° C. for 1 day. After forming the cured film, the cured film is peeled off from the polypropylene plate to obtain a cured film having a thickness of about 50 μm.

In the curable composition of the present invention, the storage elastic modulus at 150 ° C. of the cured film II formed by the following method is preferably 5 × 10 ⁴ Pa or more, and more preferably 1 × 10 ⁵ Pa or more. The storage elastic modulus of the cured film II at 150 ° C. is preferably 5 × 10 ¹² Pa or less, and more preferably 1 × 10 ¹⁰ Pa or less. If the storage modulus at 150 ° C. of the cured film II is equal to or higher than the lower limit of the above range, scratches due to elastic recovery force in addition to wound repair by dissociation of component (A) and component (B) by the rDA reaction of the DA network There is a tendency to expect repairs. If the storage elastic modulus at 150 ° C. of the cured film II is not more than the upper limit of the above range, the wound repair by the dissociation into the component (A) and the component (B) by the rDA reaction of the DA network and the wound repair by the elastic recovery force There is no hindrance, and the wound repairability of the cured product of the curable composition of the present invention is excellent.

The storage elastic modulus at 150 ° C. of the cured film II can be adjusted by the ratio of the density of the urethane (meth) acrylate network and the DA network density. When the storage elastic modulus of the single film of component (C) (the cured film III described above) is higher than that of the DA network single film, the ratio of component (C) is lowered. The storage elastic modulus of the single film of component (C) is DA If it is lower than the network single membrane, the proportion of the component (C) may be increased.

Method for forming cured film II:
The curable composition was applied to the surface of the 100 μm-thick polyethylene terephthalate film that had been subjected to the release treatment with an applicator so that the thickness after curing was 50 μm, and the coating film was heated at 70 ° C. for 30 minutes. Then, the coating film is irradiated with ultraviolet rays using a high-pressure mercury lamp under the condition of an integrated light quantity of 500 mJ / cm ² and cured at 23 ° C. for 1 day to form a cured film II.

(Elongation at break)
In the curable composition of the present invention, the breaking elongation at 23 ° C. of the cured film I formed by the above method is preferably 50% or more, more preferably 80 to 500%, and further preferably 100 to 300%. When the breaking elongation of the cured film I at 23 ° C. is 50% or more, the three-dimensional workability tends to be excellent.
If the breaking elongation at 23 ° C. of the cured film I is equal to or greater than the lower limit of the above range, the cured product tends to have sufficient three-dimensional workability to be used for simultaneous molding decoration. If the breaking elongation at 23 ° C. of the cured film I is less than or equal to the upper limit of the above range, the dry touch of the cured product tends to be sufficient.

The breaking elongation at 23 ° C. of the cured film I can be adjusted by the mixing ratio of the component (C) and the sum of the component (A) and the component (B). In addition, the breaking elongation of the hardened | cured material of a component (C) is suitably adjusted with the hydrogen bond density of a urethane bond, and the covalent bond density of a (meth) acryloyl group. When the hydrogen bond density of the urethane bond is high, the elongation at break of the cured product of the component (C) is lowered, but the dryness to touch is improved. When the covalent bond density of the (meth) acryloyl group is high, the elongation at break of the cured product of component (C) is low, but the dryness to the touch is improved. If necessary, the elongation at break of the cured product of component (C) can be adjusted by adding other polyol to the chain aliphatic diol having 2 to 12 carbon atoms to the raw material of component (C). it can.

The curable composition of the present invention can be used as a cured product after being molded according to the application. It is not particularly limited, and can be used after being formed into a film or the like, or can be used by being laminated on another structure. Hereinafter, although the case where it uses as a hard-coat film | membrane is mentioned and demonstrated, this invention is not limited to this.

(Hard coat film)
The hard coat film can be formed, for example, as follows.
The curable composition of the present invention is applied to the surface of a substrate and heated to form a semi-cured film having a DA network. The semi-cured film is irradiated with active energy rays to form a hard coat film having a hybrid polymer network in which a DA network and a urethane (meth) acrylate network are combined.

Examples of the material of the base material include plastic, glass, metal and the like. Examples of the plastic include polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polyolefin (polypropylene, polyethylene, etc.), polyamide, polycarbonate, (meth) acrylic resin, and the like.
Examples of the shape of the substrate include a film, a sheet, a plate, and various three-dimensional shapes.

The coating method of the curable composition of the present invention includes a bar coating method, an applicator method, a curtain flow coating method, a roll coating method, a spray method, a gravure coating method, a comma coating method, a reverse roll coating method, a lip coating method, and a die coating. Method, slot die coating method, air knife coating method, dipping method and the like.

The heating temperature at the time of forming the semi-cured film is not less than the temperature at which the component (A) and the component (B) are DA-reacted and less than the temperature at which the component (A) and the component (B) are dissociated by the rDA reaction. When the conjugated diene structure in component (A) is a furan skeleton and the dienophile structure in component (B) is a maleimide skeleton, the heating temperature for forming the semi-cured film is preferably 40 to 95 ° C., and 70 to 90 ° C is more preferred.

As the active energy ray applied to the semi-cured film, an electron beam or an ultraviolet ray is preferable from the viewpoints of apparatus cost and productivity. Light sources include electron beam irradiation equipment, ultra high pressure mercury lamp, high pressure mercury lamp, medium pressure mercury lamp, low pressure mercury lamp, metal halide lamp, Ar laser, He-Cd laser, solid state laser, xenon lamp, high frequency induction mercury lamp, solar Light and the like.
The irradiation amount of the active energy ray is appropriately set according to the type of the active energy ray. The irradiation amount of the electron beam is preferably 1 to 15 Mrad. The irradiation amount of ultraviolet rays is preferably 50 to 1500 mJ / cm ² .

The thickness of the hard coat film is appropriately set according to the application. The thickness of the hard coat film is preferably 1 to 100 μm, more preferably 2 to 50 μm, and even more preferably 2 to 20 μm. If the thickness of the hard coat film is equal to or greater than the lower limit of the above range, the design and function will be good. If the thickness of the hard coat film is not more than the upper limit of the above range, the internal curability and the three-dimensional processability are good.

The heating temperature when the DA network is decomposed in the hard coat film is equal to or higher than the temperature at which the DA network dissociates into the component (A) and the component (B) by the rDA reaction. When the conjugated diene structure in component (A) is a furan skeleton and the dienophile structure in component (B) is a maleimide skeleton, the heating temperature for decomposing the DA network is preferably 100 to 160 ° C., and 110 to 150 ° C. Is more preferable.

Although one embodiment of the present invention has been described above, the present invention is not limited to the above-described embodiment. Hereinafter, the first aspect, the second aspect, and the third aspect of the present invention will be described.

<First aspect>
In the first aspect of the present invention, the component (C) may have a storage elastic modulus at 23 ° C. of a cured film III ′ formed by the following method of 5 × 10 ² Pa or more, and 5 × 10 ^3. The pressure may be Pa or higher, 5 × 10 ⁴ Pa or higher, or 1 × 10 ⁵ Pa or higher.
If the storage elastic modulus at 23 ° C. of the cured film III ′ is equal to or higher than the lower limit of the above range, in addition to the wound repair by dissociation of the DA network into the component (A) and the component (B) by the rDA reaction, Wound repair can also be expected. If the storage elastic modulus at 23 ° C. of the cured film III ′ is not more than the upper limit of the above range, the wound repair by the dissociation into the component (A) and the component (B) by the rDA reaction of the DA network and the wound repair by the elastic recovery force The cured product of the curable composition of the first aspect of the present invention tends to have excellent wound repairability.

Method for forming cured film III ′:
A mixture of component (C) dissolved in a solvent (methyl ethyl ketone, butyl acetate, cyclohexanone, etc.) has a thickness of 50 μm after curing on the surface of the peel-treated side of a 100 μm-thick polyethylene terephthalate film. The coated film is heated at 70 ° C. for 30 minutes, irradiated with ultraviolet light under a condition of an integrated light quantity of 500 mJ / cm ² using a high-pressure mercury lamp, and cured at 23 ° C. for 1 day to obtain a cured film III. 'Form.

In the curable composition of the first aspect of the present invention, the storage elastic modulus at 150 ° C. of the cured film II ′ formed by the following method may be 5 × 10 ² Pa or more, or 1 × 10 ⁴ Pa or more. It may be 1 × 10 ⁵ Pa or more. The storage elastic modulus at 150 ° C. of the cured film II ′ may be 5 × 10 ¹² Pa or less, or 1 × 10 ¹⁰ Pa or less. If the storage elastic modulus at 150 ° C. of the cured film II ′ is equal to or higher than the lower limit of the above range, in addition to wound repair by dissociation of the DA network into the component (A) and the component (B) by the rDA reaction, There is also a tendency to expect wound repair. If the storage elastic modulus at 150 ° C. of the cured film II ′ is not more than the upper limit of the above range, the wound repair by the dissociation of the DA network into the component (A) and the component (B) by the rDA reaction and the wound repair by the elastic recovery force The cured product of the curable composition of the first aspect of the present invention is excellent in wound repairability.

Method for forming cured film II ′:
The curable composition was applied to the surface of the 100 μm-thick polyethylene terephthalate film that had been subjected to the release treatment with an applicator so that the thickness after curing was 50 μm, and the coating film was heated at 70 ° C. for 30 minutes. Then, the coating film is irradiated with ultraviolet rays using a high-pressure mercury lamp under conditions of an integrated light quantity of 500 mJ / cm ² and cured at 23 ° C. for 1 day to form a cured film II ′.

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

<Measurement method>
[Content of conjugated diene structure]
The content of the furfuryl group in the component (A) was converted from the integral value by an internal standard method by ¹ H-NMR measurement.

[Molecular weight of component (C)]
Using a GPC apparatus (manufactured by Tosoh Corporation, HLC-8120GPC), the mass average molecular weight and number average molecular weight of each component (C) were determined under the following conditions.
Solvent: tetrahydrofuran,
Standard sample: polystyrene,
Column: TSKgel superH1000 + H2000 + H3000,
Liquid feeding speed: 0.5 mL / min,
Column oven temperature: 40 ° C.

<Raw material>
Abbreviations of raw materials and solvents used in Examples and Comparative Examples are as follows.
[Diisocyanate]
-IPDI: Isophorone diisocyanate (Evonik Degussa Japan Co., Ltd., trade name “VESTANAT IPDI”)

[Diol]
EG: ethylene glycol 1,4-BD: 1,4-butanediol ), Number average molecular weight = 1000, hydroxyl value: 115.2 mg-KOH / g
PCL210N: polycaprolactone diol “Placcel 210N” manufactured by Daicel Corporation, number average molecular weight = 1000, hydroxyl value: 113.9 mg-KOH / g
T-33: polyol represented by the following formula (T-33) (trade name “Dynesorb T-33” manufactured by Daiwa Kasei Co., Ltd.)
T-35: polyol represented by the following formula (T-35) (trade name “Dynesorb T-35” manufactured by Daiwa Kasei Co., Ltd.)

In the formula (T-35), n is an integer of about 0 to 20, and m is an integer of about 0 to 20.

[Hydroxyacrylate]
HEA: 2-hydroxyethyl acrylate V-300: mixture of 40-45% by mass of pentaerythritol triacrylate and 35-40% by mass of pentaerythritol tetraacrylate (catalog value) (trade name Biscoat 300, manufactured by Osaka Organic Chemical Co., Ltd.) (OH Value: OH group equivalent (molecular weight per hydroxyl group) 468 is calculated from 120 (analysis table item), and all components are defined as consisting of pentaerythritol triacrylate (PET3A) and pentaerythritol tetraacrylate (PET4A). PET3A / PET4A = 298 / (468-298) = 64/36% by mass was calculated)
R-167: 1,6-hexanediol diglycidyl ether diacrylate (“Kayarad (registered trademark) R-167” manufactured by Nippon Kayaku Co., Ltd.)

[Liquid medium]
-BA: Butyl acetate-MEK: Methyl ethyl ketone-PGM: 1-methoxy-2-propanol-CHN: Cyclohexanone

[Polymerization initiator]
Irg. 184: 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, Irgacure (registered trademark) 184)

[Surfactant]
・ S-651: Methyl ethyl ketone solution containing 10% Surflon S-651 (manufactured by AGC Seimi Chemical Co., Ltd.)

[Raw material for component (AA-1)]
GMA: glycidyl methacrylate (trade name “Blemmer (registered trademark) GH” manufactured by NOF Corporation)
MMA: Methyl methacrylate (trade name “Acryester (registered trademark) M” manufactured by Mitsubishi Rayon)
-EA: ethyl acrylate-AA: acrylic acid-MEK-ST: methyl ethyl ketone-dispersed colloid (silica sol average primary particle size: 15 nm (catalog value), silica solid content: 30% by mass) (trade name "MEK-" manufactured by Nissan Chemical Industries, Ltd.) ST ")

[Ratio of each compound]
N ₁ : Sum of the number of moles of the compound (1) contained in 1 g of the cured product and the number of moles of the compound having the smaller number of moles contained in 1 g of the cured product among the compounds (2) and (3) (Mmol)
N ₂ : Of the solid content of the composition, the smaller number of moles of the number of moles of the conjugated diene structure possessed by the compound (2) and the number of moles of the dienophile structure possessed by the compound (3); Sum with moles (mmol)

<Component (A)>
[Production of mixture 2-1]
61.4 g of polyisocyanate (manufactured by Asahi Kasei Corporation, Duranate TSA-100), 32.5 g of furfuryl alcohol, 2.5 g of tin (II) 2-ethylhexanoate, and 400 mL of tetrahydrofuran were mixed. The mixture was heated and stirred at 60 ° C. for 13 hours. Tetrahydrofuran was distilled off under reduced pressure to obtain a mixture 2-1 containing a component (A-1) represented by the following formula (A-1). The content of furfuryl group in the mixture 2-1 was 3.2 mmol / g.

[Production of Mixture 2-2]
34.6 g of polyisocyanate (Evonic, VESTANAT T1890 / 100), 14.4 g of furfuryl alcohol, 2.5 g of tin (II) 2-ethylhexanoate, and 200 mL of ethyl acetate were mixed. The mixture was heated and stirred at 60 ° C. for 13 hours. Ethyl acetate was distilled off under reduced pressure to obtain a mixture 2-2 containing a component (A-2) represented by the following formula (A-2). The content of furfuryl group in the mixture 2-2 was 2.7 mmol / g.

[Production of mixture 2-3]
62.7 g of polyisocyanate (manufactured by Asahi Kasei Corporation, Duranate 24A-100), 35.3 g of furfuryl alcohol, 6.0 g of tin (II) 2-ethylhexanoate, and 160 g of ethyl acetate were mixed. The mixture was heated and stirred at 60 ° C. for 4 hours. Ethyl acetate was distilled off under reduced pressure to obtain a mixture 2-3 containing a component (A-3) represented by the following formula (A-3). The content of furfuryl group in the mixture 2-3 was 3.2 mmol / g.

In the formula (A-3), R is C ₆ H ₁₂ .

[Production of Mixture 2-0]
10.42 g of polyisocyanate (manufactured by Tosoh Corp., Coronate HL), 2.51 g of furfuryl alcohol, 191 mg of tin (II) 2-ethylhexanoate, and 30 mL of tetrahydrofuran were mixed and mixed at 60 ° C. The mixture was stirred for several days to obtain a mixture 2-0 containing a component (A-0) represented by the following formula (A-0). The content of furfuryl group in the mixture 2-0 was 1.6 mmol / g.

[Production of component 2-5]
Macromolecules, 45, 2012, p. The following synthesis was carried out with reference to 7634.
To a 200 mL round bottom flask, 10.0 g of pentaerythritol tetraacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50 mL of methylene chloride (manufactured by Wako Pure Chemical Industries, Ltd.) were added and homogenized. To this, 8.88 g of 2-furfuryl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.188 g of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at room temperature for 4 hours or more using a stir bar. After removing the solvent and the like with an evaporator, 100 mL of tetrahydrofuran, 16.08 g of octyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.6 g of triethylamine were added, and the mixture was stirred in an oil bath at an oil temperature of 80 ° C. for 15 hours. . This was concentrated, and 3.0 g (yield 25%) of the target product was fractionated by silica gel column chromatography (hexane / ethyl acetate = 70/30 (mass ratio)). A component (A-5) represented by the following formula (A-5) (a trifunctional furan compound described in Non-Patent Document 1) was obtained. The furfuryl group content was 3.6 mmol / g. ¹ H-NMR (CDCl3-TMS): 7.37 (3H, m), 6.30 (3H, m), 6.20 (3H, m), 4.14 (8H, s), 3.74 ( 6H, s), 2.75 (8H, m), 2.61-2.50 (10H, m), 1.54 (2H, t), 1.30 (12H, m), 0.90 (3H) , T).

<Component (B)>
[Production of Component 3-1]
Non-Patent Document 2 p. In accordance with the method described in 3475, the component (B-2) represented by the following formula (B-2) (1,13-bismaleimide-4,7,10-trioxatridecane described in Non-Patent Document 1) )

[Production of component 3-2]
Component (B-3) represented by the following formula (B-3) (3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-5100 ) Was prepared.

[Production of Component 3-3]
A component (B-1) (4,4′-bismaleimide diphenylmethane) represented by the following formula (B-1) was prepared.

<Ingredient (C)>
[Production of Component 4-1]
A four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with IPDI: 110 g, 1,4-BD: 20 g, T4691: 222 g, MEK: 351 g, dioctyltin dilaurate: 0 0.04 g was added and reacted for 9 hours while heating to 80 ° C. in an oil bath, then T-33: 3.2 g and MEK: 9 g were added and the reaction was carried out for 5 hours. After completion of the reaction, the reaction mixture was cooled to 60 ° C., dioctyltin dilaurate: 0.08 g, methylhydroquinone: 0.20 g, MEK: 46 g were added, and R-167: 45 g was added dropwise to initiate the reaction. The reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath. After confirming the end point of the reaction by disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, MEK: 193 g was added, and component 4 -1 (urethane (meth) acrylate) was obtained.

[Production of Component 4-2]
A four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with IPDI: 123 g, 1,4-BD: 24 g, T4691: 222 g, MEK: 369 g, dioctyltin dilaurate: 0 0.04 g was added and reacted for 9 hours while heating to 80 ° C. in an oil bath, T-35: 19 g and MEK: 19 g were added, and the reaction was carried out for 5 hours. After completion of the reaction, the reaction mixture was cooled to 60 ° C., and then dioctyltin dilaurate: 0.08 g, methylhydroquinone: 0.20 g, MEK: 12 g were added, and HEA: 12 g was added dropwise to initiate the reaction. The reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath. After confirming the end point of the reaction by disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, MEK: 200 g was added, and component 4 -2 was obtained.

[Production of Component 4-3]
A four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with IPDI: 147 g, 1,4-BD: 41 g, PCL210N: 163 g, MEK: 350 g, dioctyltin dilaurate: 0 .04 g was added and reacted for 9 hours while heating to 80 ° C. in an oil bath. After completion of the reaction, the reaction mixture was cooled to 60 ° C., dioctyltin dilaurate: 0.08 g, methylhydroquinone: 0.20 g, MEK: 50 g were added, and R-167: 49 g was added dropwise to initiate the reaction. The reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath. After confirming the end point of the reaction by disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, MEK: 200 g was added, and component 4 -3 was obtained. The weight average molecular weight was 16000 and the number average molecular weight was 2900.

[Production of Component 4-4]
Into a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, IPDI: 218 g, EG: 54 g were added, and MEK: 272 g, bismuth tris (2-ethylhexanoate): 0. 02 g was added and reacted for 9 hours while heating to 80 ° C. in an oil bath. After completion of the reaction, the reaction mixture was cooled to 60 ° C., and then 0.32 g of bismuth tris (2-ethylhexanoate), 0.20 g of methylhydroquinone, and 128 g of MEK were added, and 128 g of V-300 (PET3A: 82 g / PET4A: 46g) The reaction was started dropwise. The reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath. After confirming the end point of the reaction by disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, MEK: 200 g was added, and component 4 -4 was obtained. The weight average molecular weight was 5600 and the number average molecular weight was 2900.

[Production of Component 4-5]
A four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with IPDI: 115 g, 1,4-BD: 23 g, T4691: 213 g, MEK: 350 g, dioctyltin dilaurate: 0 .04 g was added and reacted for 9 hours while heating to 80 ° C. in an oil bath. After completion of the reaction, the reaction mixture was cooled to 60 ° C., dioctyltin dilaurate: 0.08 g, methylhydroquinone: 0.20 g, MEK: 50 g were added, and R-167: 49 g was added dropwise to initiate the reaction. The reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath. After confirming the end point of the reaction by disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, MEK: 200 g was added, and component 4 -5 was obtained. The weight average molecular weight was 5000 and the number average molecular weight was 2500.

[Production of Component 4-6]
To a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, isophorone diisocyanate: 86.3 g, 1,4-butanediol: 40 g, MEK: 344 g, dioctyltin dilaurate: 0.03 g The mixture was allowed to react for 2 hours while heating to 80 ° C. in an oil bath. To this, 160 g of polycaprolactone diol (manufactured by Daicel, Plaxel 210N) was added dropwise and reacted for 5 hours. After cooling to 60 ° C., 0.08 g of dioctyltin dilaurate and 0.20 g of methylhydroquinone were added, and epichlorohydrin modified 1,6-hexanediol di (meth) acrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD R-167) 48.5 g 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 the end point of the urethanization reaction was confirmed by the disappearance of the peak derived from the isocyanate group in the infrared absorption spectrum. MEK: 585g was added to this and urethane acrylate was obtained. This was designated as Component 4-6. The weight average molecular weight was 29,000, the number average molecular weight was 3,500, the urethane bond amount was 3.31 × 10 ⁻³ eq / g, and the acryloyl group amount was 6.61 × 10 ⁻⁴ eq / g. .

[Production of component (AA-1)]
In a flask equipped with a thermometer, stirrer and reflux condenser, PGM: 150.0 g, GMA: 98.0 g, MMA: 1.0 g, EA: 1.0 g, mercaptopropyltrimethoxysilane: 1.9 g, and 2 , 2′-azobis (2,4-dimethylvaleronitrile): 1.0 g was added and reacted at 65 ° C. for 3 hours. Thereafter, 2,2′-azobis (2,4-dimethylvaleronitrile): 0.5 g was added and reacted for 3 hours, and then PGM: 199.3 g and p-methoxyphenol: 0.45 g were added. Heated to ° C. Next, AA: 49.7 g and tri (p-tris) phosphine: 1.83 g were added and reacted at 110 ° C. for 6 hours, whereby an acryloyl group and a methoxysilyl group, a glycidyl group and a carboxyl group, A (meth) acrylic acid ester-based polymer having a hydroxyl group generated by the above reaction and having a mass average molecular weight (Mw) of 12,000 and an unsaturated double bond concentration of 4.6 mmol / g and a hydroxyl group concentration of 4.6 mmol / g is obtained. Component (AA-1) (solid content: 30% by mass).

[Production of DA master batch]
Mixture 2-0: 0.8 g (furfuryl group: 2.1 mmol), component 3-2: 0.2 g (maleimide group: 1.1 mmol), MEK: 4.3 g, S-651: 0.50 g And completely dissolved to obtain DA master batch 2-0-2.0.
In the same manner as in DA master batch 2-0-2.0, each material shown in Table 1 was added to a sample bottle and completely dissolved to prepare the following DA master batches.
・ DA masterbatch 2-1-1.0
・ DA masterbatch 2-1-2.0
・ DA master batch 2-2-1.0
・ DA master batch 2-2.2.0
・ DA masterbatch 2-3-3-1.0
・ DA master batch 2-3-2.0
・ DA master batch 2-1-1.0-30
DA master batch 2-1.1.1-30
・ DA master batch 2-1 -1.5-30
・ DA master batch 2-1-2.0-30
・ DA master batch 2-2.1.1-30
・ DA master batch 2-2.2.0-30
・ DA masterbatch 2-3-3-2.0-30

[Production of UA masterbatch and AA masterbatch]
Component 4-1: 7.5 g, BA: 10.3 g, MEK: 5.2 g, S-651: 2.3 g, Irg. 184: 0.1 g was added to the sample bottle and dissolved completely to obtain a UA masterbatch 4-1-1.
In the same manner as in the UA master batch 4-1-1, according to the composition shown in Table 2, each material was added to the sample bottle and completely dissolved to prepare the following UA master batch and AA master batch.
・ UA Masterbatch 4-2-1
・ UA Masterbatch 4-2-2
・ UA Masterbatch 4-3-1
・ UA Masterbatch 4-4-1
・ UA Masterbatch 4-5-1
・ UA Masterbatch 4-5-2
・ UA Masterbatch 4-2-3
・ UA Masterbatch 4-6-3
-AA master batch (AA-1-1)

[Production of Curable Composition of Example 1]
103 mg (furfuryl group: 0.4 mmol) of component (A-2), 38 mg (maleimide group: 0.2 mmol) of component (B-2), 120 mg of component (C1-1), Irg. 184 mg of 184 and 755 mg of a mixed solvent of BA / MEK = 2/1 (mass ratio) were placed in a sample bottle and stirred for 1 hour with a mix rotor to obtain a curable composition.

[Production of curable compositions of Examples 1 to 87 and Comparative Examples 1 to 21]
Using each of the DA and UA master batches, the DA master batch and the UA master batch were mixed at the composition ratios shown in Tables 3 to 9 to produce curable compositions of the respective examples.
Here, in Comparative Examples 6 and 7, an acrylic masterbatch (AA-1-1) was used instead of the UA masterbatch.

[Manufacture of cured products]
A cured film was produced from each curable composition by the following method. The film-forming method A was used for the curable composition containing a polymerization initiator. The film-forming method B was used for the curable composition which does not contain a polymerization initiator.
(Film formation method A)
The curable composition is applied onto a blue plate glass or polypropylene plate using a bar coater or an applicator, the coating film is heated at 70 ° C. for 30 minutes, and an electrodeless ultraviolet irradiation device (D bulb) (manufactured by Heraeus) is used. The coated film was irradiated with ultraviolet rays having an integrated light amount of 500 mJ / cm ² and further cured at 23 ° C. for 1 day to form a cured film.
(Film formation method B)
A curable resin composition is coated on a blue plate glass or polypropylene plate with a bar coater to form a coating film, followed by drying at 70 ° C. for 30 minutes, and then an electron beam irradiation apparatus (Curetron EBC-200-AA3, NHV Corporation). The dried coating film was irradiated twice under the conditions of an acceleration voltage of 165 kV and an irradiation dose of 5 Mrad, and further cured at 23 ° C. for 1 day to form a cured film.

Evaluation of transparency, haze, tensile elastic modulus, glass transition point (Tg), storage elastic modulus, chemical resistance, and flaw repairability (flaw repairability (SW) or flaw repairability (CT)) of the obtained cured film Went. The results are shown in Tables 3-9. Here, the film thickness of the cured film in the flaw repairability, transparency, haze, and chemical resistance test was 10 μm. The film thickness of the cured film in the transparency test was 35 μm. The thickness of the cured film of the tensile test and storage elastic modulus (DMA) was 50 μm.

[Tensile modulus of cured film at 23 ° C.]
The cured film obtained by the above method is cut to a width of 10 mm, using a Tensilon tensile tester (Orientec Co., RTC-1210A), temperature 23 ° C., humidity 55% RH, tensile speed 50 mm / min, distance between chucks. A tensile test was performed under the condition of 50 mm, and the straight line connecting the stress at 0% elongation and the stress at 0.5% elongation of the obtained stress-strain curve was extended, and the stress converted at 100% elongation was tensile. Elastic modulus was used.

[Transparency of cured film]
The cured film obtained by the film forming method was visually confirmed, and the transparency was evaluated according to the following evaluation criteria.
○: The characters written below can be read through the cured film I.
X: The character written below through the cured film I cannot be read.

[Haze value]
The haze value of the cured film obtained by the film forming method was measured.
The haze value was measured according to JIS K7105 using a haze meter (“HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory Co., Ltd.). Here, it means that transparency is so high that a haze value is small.

[Wound repairability]
(Scratch repairability (SW): Repair of abrasion scratches with steel wool (SW))
The haze value measured before the steel wool abrasion test for the cured film obtained by the film forming method was H1. Under an atmosphere of 23 ° C. and 55% RH, a weight of 500 gf (per area 5.7 cm ² ) was placed on steel wool (# 0000) manufactured by Nippon Steel Wool Co., Ltd., and laminated on blue glass by the film forming method described above. About the cured film, the cured film surface laminated | stacked on the soda glass was made into 15 reciprocal scratches, and the haze value measured immediately after that was set to H2.
The cured film was heated at 150 ° C. for 10 minutes, and the haze value measured immediately after that was H3.
The difference between H2 and H1: ΔH21 (ΔH21 = H2−H1), the repair rate: (H2−H3) / H21 was determined, and the wound repairability (SW) was evaluated according to the following criteria.
X: Repair rate is less than 35%.
○: Repair rate is 35% or more and less than 50%.
A: The repair rate is 50% or more.
The haze value was measured according to JIS K7105 using a haze meter (“HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory Co., Ltd.).

(Wound repairability (CT): Repair of laceration with a cutter)
The cured film obtained by the above film forming method was wound with a 3 cm wound (corresponding to scratches caused by clothes fasteners) with a cutter. The cured film was heated at 110 ° C. for 15 minutes, at 150 ° C. for 10 minutes, and at 150 ° C. for 60 minutes.
○: No scratches are visible with the naked eye.
×: No change in the scratches.

[Chemical resistance test]
A sunscreen (manufactured by Johnson & Johnson, Neutrogena (registered trademark)) of 5 cm × 5 cm × thickness 50 μm (converted to 0.125 g) is applied to the surface of the cured film obtained by the above film formation method. Applied. After heating at 80 ° C. for 1 hour, the sunscreen was washed away with water. Water on the surface of the cured film was wiped off, and immediately after that, haze was measured and evaluated according to the following criteria. The haze value was measured according to JIS K7105 using a haze meter (“HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory Co., Ltd.).
A: Haze value is less than 10%.
○: Haze value is 10% or more and less than 40%.
X: Haze value is 40% or more.

[Storage modulus (DMS)]
The cured film obtained by the film forming method was peeled off from the glass plate or the polypropylene plate and cut into a width of 5 mm. About the cured film which cut | disconnected, the storage elastic modulus from the temperature 23 degreeC to 200 degreeC using a dynamic-viscoelasticity measuring apparatus (For example, SSI company make, DMS6100), temperature rising rate 3 degree-C / min, frequency 0.1Hz Measured under conditions.

In the column of storage elastic modulus in Table 4, “E” represents a power. For example, “1.10E + 08” represents “1.10 × 10 ⁸ ”.

(Example 88)
103 mg of component 2-5 (furfuryl group: 0.4 mmol), 38 mg of component 3-1 (maleimide group: 0.2 mmol), 120 mg of component 4-6, Irg. 184 mg of 184 and 755 mg of a mixed solvent of BA / MEK = 2/1 (mass ratio) were placed in a sample bottle and stirred for 1 hour with a mix rotor to obtain the curable composition of Example 88.
A cured film was formed by the above method, and scratch repairability and chemical resistance were evaluated. In Example 88, the result was excellent in the wound repairability (CT) of the laceration by the cutter and the chemical resistance. The results are shown in Table 9.

Example 89
200 mg (furfuryl group: 0.32 mmol) of mixture 2-0, 29 mg (maleimide group: 0.16 mmol) of component 3-3, 219 mg of component 4-6, Irg. The curable composition of Example 89 was obtained by putting 2.4 mg of 184 and 1225 mg of cyclohexanone into a sample bottle and stirring with a mix rotor for 1 hour.
A cured film was formed by the above method, and scratch repairability and chemical resistance were evaluated. Table 9 shows the evaluation results. In Example 89, the wound repairability (CT) of the laceration by the cutter was sufficient, and the result was excellent in chemical resistance. The results are shown in Table 9.

(Example 90)
150 mg (furfuryl group: 0.49 mmol) of the mixture 2-1, 54 mg (maleimide group: 0.24 mmol) of the component 3-2, 175 mg of the component 4-6, Irg. The curable composition of Example 90 was obtained by putting 2.2 mg of 184 and 1087 mg of a mixed solvent of BA / MEK = 2/1 (mass ratio) into a sample bottle and stirring for 1 hour with a mix rotor.
A cured film was formed by the above method, and scratch repairability and chemical resistance were evaluated. In Example 90, it was the result which was excellent in the crack repair property (CT) of the laceration by a cutter, and excellent in chemical resistance. The results are shown in Table 9.

(Example 91)
2.68 g of component 4-6 (5.36 g in a 50% MEK solution), 2.56 g of mixture 2-1 (furfuryl group: 7.9 mmol), 0.7 g of component 3-3 (maleimide group: 3.9 mmol) ), Irg. The curable composition of Example 91 was obtained by putting 0.3 g of 184 and 11.4 g of cyclohexanone into a sample bottle and stirring for 1 hour with a mix rotor. The results are shown in Table 9.

(Comparative Example 21)
1006 mg of component 4-6, Irg. 13 mg of 184 and 1505 mg of a mixed solvent of BA / MEK = 2/1 (mass ratio) were put in a sample bottle and stirred for 1 hour with a mix rotor to obtain a curable composition of Comparative Example 21.
A cured film was formed by the above method, and scratch repairability and chemical resistance were evaluated. In Comparative Example 21, the wound repairability (CT) of the laceration by the cutter was insufficient, and the chemical resistance was also insufficient. The results are shown in Table 9.

Claims (15)

1. Compound (1) represented by the following formula (1),
   A compound (2) represented by the following formula (2) and a precursor of the compound (1);
   A compound (3) represented by the following formula (3) and a precursor of the compound (1);
   Urethane (meth) acrylate,
   A cured product containing
   The number of moles of the compound (1) contained in 1 g of the cured product and the number of moles of the compound having the smaller number of moles contained in the cured product 1 g out of the compound (2) and the compound (3). sum _{N 1} is greater than or equal 0.05Mmol, cured product.
   

   

   [In the formula (1), R ¹ to R ⁴ , R ⁷ , R ⁸ are substituents, X ¹ is a divalent group,
   At least one of R ¹ to R ⁴ and X ¹ is a group having an electron donating group,
   X ² is a divalent group,
   At least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group.
   In the formula (2), R ¹ to R ⁴ are substituents, X ¹ is a divalent group,
   At least one of R ¹ to R ⁴ and X ¹ is a group having an electron donating group.
   In formula (3), R ⁷ and R ⁸ are substituents, X ² is a divalent group,
   At least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group. ]
2. The compound (1) is a compound (4) represented by the following formula (4),
   The compound (2) is a compound (5) represented by the following formula (5),
   The hardened | cured material of Claim 1 whose said compound (3) is a compound (6) represented by following formula (6).
   

   

   [In the formula (4), R ¹ to R ⁴ , R ⁷ and R ⁸ are substituents, R ¹¹ is an oxygen atom or —NR ¹² —, R ¹² is a substituent, and X ³ is an oxygen atom , A nitrogen atom or an alkylene group which may have a substituent, Y and Z are an oxygen atom or a sulfur atom,
   At least one of R ¹ to R ⁴ and X ³ is a group having an electron donating group,
   At least one of R ⁷ , R ⁸ and R ¹¹ is a group having an electron withdrawing group.
   In the formula (5), R ¹ to R ⁴ are substituents, X ³ is an oxygen atom, a nitrogen atom or an alkylene group which may have a substituent,
   At least one of R ¹ to R ⁴ and X ³ is a group having an electron donating group.
   In formula (6), R ⁷ and R ⁸ are substituents, R ¹¹ is an oxygen atom or —NR ¹² —, R ¹² is a substituent, and Y and Z are oxygen atoms or sulfur atoms,
   At least one of R ⁷ , R ⁸ and R ¹¹ is a group having an electron withdrawing group. ]
3. Hardened | cured material of Claim 1 or 2 whose glass transition point measured by dynamic viscosity measurement is 20 degreeC or more.
4. The cured product according to any one of claims 1 to 3, wherein a haze value measured in accordance with JIS K 7105 is 10% or less.
5. The urethane (meth) acrylate is a reaction product of polyisocyanate, a polyol containing a chain aliphatic diol having 2 to 12 carbon atoms, and a polyfunctional (meth) acrylate having a hydroxyl group. Hardened | cured material of any one.
6. The cured product according to any one of claims 1 to 5, which has scratch repair properties.
7. Compound (2) represented by the following formula (2),
   Compound (3) represented by the following formula (3),
   A compound (1) represented by the following formula (1), which is a reaction product of the compound (2) and the compound (3);
   Urethane (meth) acrylate,
   A composition comprising
   Of the solid content of the composition, the smaller number of moles of the number of moles of the conjugated diene structure possessed by the compound (2) and the number of moles of the dienophile structure possessed by the compound (3), and the number of moles of the compound (1) the sum of _{N 2} is at 0.05 mmol / g or more, the curable composition.
   

   

   [In the formula (1), R ¹ to R ⁴ , R ⁷ , R ⁸ are substituents, X ¹ is a divalent group,
   At least one of R ¹ to R ⁴ and X ¹ is a group having an electron donating group,
   X ² is a divalent group,
   At least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group.
   In the formula (2), R ¹ to R ⁴ are substituents, X ¹ is a divalent group,
   At least one of R ¹ to R ⁴ and X ¹ is a group having an electron donating group.
   In formula (3), R ⁷ and R ⁸ are substituents, X ² is a divalent group,
   At least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group. ]
8. The compound (1) is a compound (4) represented by the following formula (4),
   The compound (2) is a compound (5) represented by the following formula (5),
   The curable composition of Claim 7 whose said compound (3) is a compound (6) represented by following formula (6).
   

   

   [In the formula (4), R ¹ to R ⁴ , R ⁷ and R ⁸ are substituents, R ¹¹ is an oxygen atom or —NR ¹² —, R ¹² is a substituent, and X ³ is an oxygen atom , A nitrogen atom or an alkylene group which may have a substituent, Y and Z are an oxygen atom or a sulfur atom,
   At least one of R ¹ to R ⁴ and X ³ is a group having an electron donating group,
   At least one of R ⁷ , R ⁸ and R ¹¹ is a group having an electron withdrawing group.
   In the formula (5), R ¹ to R ⁴ are substituents, X ³ is an oxygen atom, a nitrogen atom or an alkylene group which may have a substituent, and R ¹ to R ⁴ and X ³ At least one is a group having an electron donating group.
   In formula (6), R ⁷ and R ⁸ are substituents, R ¹¹ is an oxygen atom or —NR ¹² —, R ¹² is a substituent, and Y and Z are oxygen atoms or sulfur atoms,
   At least one of R ⁷ , R ⁸ and R ¹¹ is a group having an electron withdrawing group. ]
9. The curable composition according to claim 7 or 8, wherein the compound (2), the compound (3) and the urethane (meth) acrylate do not have an acid group.
10. 10. The curable composition according to any one of claims 7 to 9, which does not contain a photopolymerization initiator.
11. The curable composition according to any one of claims 7 to 10, wherein the compound (3) comprises a compound having two or more dienophile structures.
12. The urethane (meth) acrylate is a reaction product of polyisocyanate, a polyol containing a chain aliphatic diol having 2 to 12 carbon atoms, and a polyfunctional (meth) acrylate having a hydroxyl group. The curable composition of any one of Claims.
13. Compound (2) represented by the following formula (2),
    Compound (3) represented by the following formula (3),
    Urethane (meth) acrylate,
    The composition containing is heated at a temperature above the temperature at which the compound (2) and the compound (3) undergo a Diels-Alder reaction and below the temperature at which the compound (2) and the compound (3) are dissociated by a retro Diels-Alder reaction. To obtain a semi-cured product,
    A method for producing a cured product, wherein the semi-cured product is irradiated with an active energy ray to obtain a cured product.
    

    

    [In Formula (2), R ¹ to R ⁴ are substituents, X ¹ is a divalent group, and at least one of R ¹ to R ⁴ and X ¹ is a group having an electron donating group. .
    In formula (3), R ⁷ and R ⁸ are substituents, X ² is a divalent group, and at least one of R ⁷ , R ⁸ and X ² is a group having an electron withdrawing group. ]
14. The compound (2) is a compound (5) represented by the following formula (5),
    The manufacturing method of the hardened | cured material of Claim 13 whose said compound (3) is a compound (6) represented by following formula (6).
    

    

    [In the formula (5), R ¹ to R ⁴ are substituents, X ³ is an oxygen atom, a nitrogen atom or an alkylene group which may have a substituent, and R ¹ to R ⁴ and X ³ At least one of them is a group having an electron donating group.
    In formula (6), R ⁷ and R ⁸ are substituents, R ¹¹ is an oxygen atom or —NR ¹² —, R ¹² is a substituent, and Y and Z are oxygen atoms or sulfur atoms,
    At least one of R ⁷ , R ⁸ and R ¹¹ is a group having an electron withdrawing group. ]
15. A method for repairing a wound generated in a cured product according to any one of claims 1 to 6, wherein the cured product in which a scratch has occurred is converted into a Diels Alder of the compound (2) and the compound (3). A method for repairing scratches on a cured product, wherein the Diels Alder network formed by the reaction is heated to a temperature at which it is dissociated into the Compound (2) and the Compound (3) by a Retro Diels Alder reaction and then cooled.