KR20240001162A - Compounds, curable compositions and cured products - Google Patents

Abstract

(식 (1) 중, R¹, R², R³ 및 R⁴ 는, 각각 독립적으로, 수소 원자, 탄소 원자수 1 ∼ 50 의 중합성 관능기 또는 탄소 원자수 1 ∼ 50 의 알킬기를 나타낸다. 그 알킬기는, 헤테로 원자를 갖고 있어도 된다. 그 알킬기 중의 메틸렌기의 일부가, 에테르 결합, 티오에테르 결합, 에스테르 결합, 아미드 결합, 이미드 결합 또는 카르보닐기로 치환되어 있어도 된다. 그 알킬기 중의 수소 원자의 일부가, 할로겐 원자로 치환되어 있어도 된다. n1 은, 1 ∼ 10 의 정수를 나타낸다. R¹, R², R³ 및 R⁴ 중 적어도 1 개는 탄소 원자수 1 ∼ 50 의 중합성 관능기를 나타낸다. 단, R¹, R², R³ 및 R⁴ 중 어느 2 개가 연결되어, 고리 구조로 되는 화합물을 제외한다.)A compound represented by the following formula (1) is provided.
[Formula 1]

(In formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a polymerizable functional group with 1 to 50 carbon atoms, or an alkyl group with 1 to 50 carbon atoms. The alkyl group may have a hetero atom. A part of the methylene group in the alkyl group may be substituted with an ether bond, thioether bond, ester bond, amide bond, imide bond or carbonyl group. A part of the hydrogen atom in the alkyl group may be substituted with a halogen atom. n1 represents an integer from 1 to 10. At least one of R ¹ , R ² , R ³ and R ⁴ represents a polymerizable functional group having 1 to 50 carbon atoms. However, , R ¹ , R ² , R ³ and R ⁴ are connected to form a ring structure.)

Description

Compounds, curable compositions and cured products

The present invention relates to a compound having a specific structure, a curable composition containing the compound, and a cured product obtained by curing the curable composition. The curable composition can be used for self-repairing materials, surface coating agents, paints, adhesives, or battery materials.

While polymer materials exhibit high mechanical strength and high durability based on strong covalent bonds, they lack reprocessability and reusability, making it difficult to repair scratches or breaks, especially self-repair. Materials that have excellent durability and reprocessability, are easy to repair, and can self-repair include approaches based on intermolecular interactions such as host-guest interactions (e.g., see Patent Documents 1 and 2) and polymers. Self-repairing materials utilizing dangling chains bonded to a cross-linked structure (for example, see Patent Document 3), microcapsules encapsulating polymerizable monomers or catalysts in a matrix such as a resin material, etc. are blended, and microcapsules, etc. In the case of damage to the matrix accompanied by destruction, a new monomer component is supplemented and polymerized to restore the function of the matrix (for example, see Patent Documents 4 and 5). However, in the methods of Patent Documents 1 to 3, there were problems such as that a complicated process was required to manufacture the material, and in the methods of Patent Documents 4 and 5, there was a limitation in the number of times of self-repair depending on the amount of microcapsules mixed, etc. . Additionally, recently, in order to solve this problem, self-repairing materials using reversible bond dissociation and recombination by applying an external stimulus to materials using dynamic covalent bonds have been known (for example, see Patent Document 6 and Non-Patent Document 1) ).

International Publication No. 2013/162019 International Publication No. 2016/006413 International Publication No. 2007/069765 International Publication No. 2014/201290 Japanese Patent Publication No. 2017-218519 Japanese Patent Publication No. 2017-202980

A. Takahashi, R. Goseki, K. Ito, and H. Otsuka, ACS Macro Letters, 6, 1280 (2017).

However, the self-repairing materials described in Patent Documents 1 to 6 and Non-Patent Document 1 did not have sufficient self-repairing power.

Therefore, the present invention was made in consideration of the above problems and situations, and its purpose is to provide a material with excellent self-repairing ability.

In order to solve the above problem, the present inventors have carefully studied the causes of the above problem, etc., and have found that a compound having a specific structure can solve the above problem, leading to the present invention.

That is, the present invention is represented by [1] to [9] below.

[1] A compound represented by the following formula (1).

[Formula 1]

In formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a polymerizable functional group with 1 to 50 carbon atoms, or an alkyl group with 1 to 50 carbon atoms. The alkyl group may have a hetero atom. A part of the methylene group in the alkyl group may be substituted with an ether bond, thioether bond, ester bond, amide bond, imide bond, or carbonyl group. Some of the hydrogen atoms in the alkyl group may be substituted with halogen atoms. n1 represents an integer from 1 to 10. At least one of R ¹ , R ² , R ³ and R ⁴ represents a polymerizable functional group having 1 to 50 carbon atoms. However, compounds in which any two of R ¹ , R ² , R ³ and R ⁴ are connected to form a ring structure are excluded.

[2] Polymerizable functional groups having 1 to 50 carbon atoms, vinyl group, allyl group, acrylic group, methacryl group, hydroxy group, isocyanate group, amino group, amide group, epoxy group, oxetanyl group, episulfide group , a carboxyl group, a heteroaryl group, a thiol group, a group containing a carboxylic acid anhydride structure, and a group containing a cyclic imide structure, and a functional group selected from the group combined with a hydrocarbon group, and a portion of the methylene group in the hydrocarbon group The compound according to [1] may be substituted with an ether bond, thioether bond, ester bond, amide bond, imide bond, or carbonyl group, and some of the hydrogen atoms in the polymerizable functional group may be substituted with a halogen atom.

[3] The compound described in [1], wherein the polymerizable functional group having 1 to 50 carbon atoms is a group represented by the following formula (L-1).

[Formula 2]

In formula (L-1), L ¹ and L ² each independently represent an alkanediyl group having 1 to 5 carbon atoms. n represents an integer from 0 to 5. When n is an integer of 2 or more, a plurality of L ¹ may have the same contribution or different contributions. * represents the bonding position with the nitrogen atom in formula (1).

[4] A curable composition containing the compound according to any one of [1] to [3].

[5] The curable composition according to [4], which further contains at least one member selected from the group consisting of a curing agent and a polymerization initiator.

[6] The curable composition according to [5], wherein the curing agent is at least one selected from the group consisting of amine compounds, amide compounds, acid anhydride compounds, thiol compounds, phenol compounds, imidazole compounds, and latent curing agents.

[7] The curable composition according to [5], wherein the polymerization initiator is a cationic polymerization initiator or a radical polymerization initiator.

[8] The curable composition according to [4], which is a self-repairing material, surface coating agent, paint, adhesive, or battery material.

[9] A cured product obtained by curing the curable composition according to [4].

According to the present invention, a material having excellent self-repairing ability can be provided.

Hereinafter, embodiments of the present invention will be described in detail.

First, the compounds of the present invention will be described. In addition, in this specification, a compound having an oxirane ring in its structure may be described as an epoxy compound.

＜Compound＞

The compound of the present invention is represented by the following formula (1).

[Formula 3]

R ¹ , R ² , R ³ and R ⁴ in formula (1) each independently represent a hydrogen atom, a polymerizable functional group with 1 to 50 carbon atoms, or an alkyl group with 1 to 50 carbon atoms. The alkyl group may have a hetero atom. Part of the methylene group (-CH ₂ -) in the alkyl group may be substituted with an ether bond, thioether bond, ester bond, amide bond, imide bond, or carbonyl group. Some of the hydrogen atoms in the alkyl group may be substituted with halogen atoms. n1 represents an integer from 1 to 10. At least one of R ¹ , R ² , R ³ and R ⁴ represents a polymerizable functional group having 1 to 50 carbon atoms. However, compounds in which any two of R ¹ , R ² , R ³ and R ⁴ are connected to form a ring structure are excluded.

In this specification, heteroatoms include nitrogen atom, oxygen atom, silicon atom, fluorine atom, sulfur atom, phosphorus atom, aluminum atom, and selenium atom.

From the viewpoint of easy purification of the compound, n1 is preferably an integer of 1 to 4, and is more preferably 1.

Examples of alkyl groups having 1 to 50 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ in formula (1) include methyl, ethyl, propyl, isopropyl, butyl, and sec-butyl. group, isobutyl group, tert-butyl group, pentyl group, 2-pentyl group, 3-pentyl group, isopentyl group, hexyl group, 2-hexyl group, 3-hexyl group, cyclopentyl group, cyclohexyl group, hep Tyl group, isoheptyl group, tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, dodecyl (lauryl) group, tridecyl group Syl group, tetradecyl (myristyl) group, pentadecyl group, hexadecyl (palmityl) group, peptadecyl group, octadecyl (stearyl) group, eicosyl group, heneicosyl group, docosyl group, tricosyl group, tetracosyl group , pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, or triacontyl (myricyl, melicyl) group, etc.

The polymerizable functional groups having 1 to 50 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ in formula (1) include vinyl group, allyl group, acrylic group, methacryl group, hydroxy group and isocyanate group. , an amino group, an amide group, an epoxy group, an oxetanyl group, an episulfide group, a carboxyl group, a heteroaryl group, a thiol group, a group containing a carboxylic acid anhydride structure, and a group containing a cyclic imide structure. It is a group in which a functional group and a hydrocarbon group are connected. A portion of the methylene group (-CH ₂ -) in the hydrocarbon group may be substituted with an ether bond, thioether bond, ester bond, amide bond, imide bond, or carbonyl group, and may be a polymerizable functional group having 1 to 50 carbon atoms. Some of the hydrogen atoms may be replaced with halogen atoms.

The isocyanate group as a functional group is expressed as -N=C=O.

The amino group as a functional group is represented by -NR ⁹ R ¹⁰ , and R ⁹ and R ¹⁰ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group includes those exemplified as alkyl groups represented by R ¹ , R ² , R ³ and R ⁴ and having 1 to 6 carbon atoms. From the viewpoint of developing better self-repairing ability, R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom, a methyl group, or an ethyl group.

The amide group as a functional group is represented by -(C=O)-NR ¹¹ R ¹² , and R ¹¹ and R ¹² represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group includes those exemplified as alkyl groups represented by R ¹ , R ² , R ³ and R ⁴ and having 1 to 6 carbon atoms. From the viewpoint of developing better self-repairing ability, R ¹¹ and R ¹² are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom, a methyl group, or an ethyl group.

A carboxyl group as a functional group also serves to contain a compound having a carboxyl group in the structure. Compounds having a carboxyl group include, for example, dicarboxylic acid compounds such as maleic acid, succinic acid, phthalic acid, fumaric acid, glutaric acid, adipic acid, and itaconic acid, and tricarboxylic acid compounds such as citric acid or aconitic acid. etc. can be mentioned.

Heteroaryl groups as functional groups include, for example, thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, 1,2,3-oxadiazolyl group, 1 ,2,4-oxadiazolyl group, 1,2,5-oxadiazolyl group, 1,3,4-oxadiazolyl group, 1,2,3-thiadiazolyl group, 1,2,4-thia Diazolyl group, 1,2,5-thiadiazolyl group, 1,3,4-thiadiazolyl group, isothiazol-3-yl group, isothiazol-4-yl group, isothiazol-5-yl group, Oxazol-2-yl group, oxazol-4-yl group, oxazol-5-yl group, isoxazol-3-yl group, isoxazol-4-yl group, isoxazol-5-yl group, 1,2,4 -Triazol-3-yl group, 1,2,4-triazol-5-yl group, 1,2,3-triazol-4-yl group, 1,2,3-triazol-5-yl group, tetrazolyl group , 2-pyrazine-2-yl group, pyrazine-4-yl group, pyrazine-5-yl group, 2-pyrimidin-2-yl group, 4-pyrimidin-2-yl group, 5-pyrimidin-2-yl group, etc. You can.

Groups containing a carboxylic acid anhydride structure as a functional group include, for example, carboxylic acid anhydrides such as maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, or itaconic anhydride. Containing groups may be mentioned.

Examples of groups containing a cyclic imide structure as a functional group include groups containing cyclic imide compounds such as maleimide, succinimide, or phthalic imide in the structure.

In the compound of the present invention, some of the hydrogen atoms in the functional group may be substituted with a halogen atom, an alkyl group, an alkenyl group, or a combination thereof.

The hydrocarbon group connected to the functional group plays the role of connecting the functional group to the nitrogen atom of the compound represented by formula (1). Examples of the hydrocarbon group include a straight-chain alkyl group, a branched alkyl group, or an alkyl group containing an alicyclic compound. Part of the methylene group in the hydrocarbon group may be substituted with an ether bond, thioether bond, ester bond, amide bond, imide bond, or carbonyl group. Some of the hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms.

Alicyclic compounds in the hydrocarbon group include monocyclic alkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cycloundecane, or cyclododecane, bicycloundecane, and deca bicyclic alkanes such as hydronaphthalene, decalin or norbornane, tricyclic alkanes such as tricyclooundecane or tricyclotridecane, tetracyclooctacosane or tetracyclotridecane, etc. there is.

In the polymerizable functional group having 1 to 50 carbon atoms, the connection between the functional group and the hydrocarbon group involves substituting some of the hydrogen atoms in the hydrocarbon group with the functional group, saturated alicyclic groups such as epoxy groups, oxetanyl groups, and episulfide groups. A functional group with a structure and an alicyclic compound in a hydrocarbon group share part of the ring to form a condensed ring, or a functional group with a saturated alicyclic structure and an alicyclic compound in a hydrocarbon group combine through some carbon atoms to form a spiro. This is done by forming a structure. In one polymerizable functional group having 1 to 50 carbon atoms, it may have a plurality of points where the functional group and the hydrocarbon group are connected. When a polymerizable functional group having 1 to 50 carbon atoms has a plurality of points where the functional group and the hydrocarbon group are connected, each connection structure may be the same or different.

From the viewpoint of making the effect of the present invention remarkable, the compound of the present invention is a polymerizable compound having 1 to 50 carbon atoms whose functional group is an acrylic group, methacryl group, epoxy group, oxetanyl group, episulfide group or hydroxy group. It is preferable to have a functional group, and it is more preferable to have a polymerizable functional group having 1 to 50 carbon atoms, where the functional group is an acrylic group, methacryl group, epoxy group, or hydroxy group.

Specific examples of preferred polymerizable functional groups having 1 to 50 carbon atoms include hydroxyethyl group, acryloyloxyethyl group, methacryloyloxyethyl group, allyl group, 2-(7-oxabicyclo[4.1.0] Heptan-3-yl) acetate ethyl group, 2-(4-methyl-7-oxabicyclo[4.1.0]heptan-3-yl)acetate ethyl group, 2-(3-oxatricyclo[3.2.1.02.4] Octan-6-yl) acetate ethyl group, 1H-imidazole-1-carboxylate ethyl group, glycinate ethyl group, methyl glycinate ethyl group, dimethyl glycinate ethyl group, piperidine-4-carboxylate ethyl group, mer Captoacetate ethyl group, isocyanate methoxyethyl group, 2,5-dioxatetrahydrofuran-3-carboxylate ethyl group, 1,3-dioxa-1,3-dihydroisobenzofuran-5-carboxylate-ethyl group , 2-(tyran-2-ylmethoxy)ethyl group, methacryloyloxyethylaminocarbonyloxyethyl group, group represented by the following formula (L-1), etc. Among these, from the viewpoint that the effect of the present invention becomes remarkable, the group represented by the following formula (L-1) is more preferable as the polymerizable functional group having 1 to 50 carbon atoms.

[Formula 4]

In formula (L-1), L ¹ and L ² each independently represent an alkanediyl group having 1 to 5 carbon atoms. L ¹ and L ² may have the same contribution or different contributions. n represents an integer from 0 to 5. When n is an integer of 2 or more, a plurality of L ¹ may have the same contribution or different contributions. * represents the bonding position with the nitrogen atom in formula (1).

Alkanediyl groups having 1 to 5 carbon atoms represented by L ¹ and L ² include methanediyl group, 1,2-ethanediyl group, 1,2-propanediyl group, 1,3-propanediyl group, 1, 4-butanediyl group, 1,5-pentanediyl group, etc. are mentioned. From the viewpoint of enhancing the effect of the present invention, L ¹ and L ² are each independently a methanediyl group, 1,2-ethanediyl group, 1,2-propanediyl group, or 1,3-propanediyl group. A compound having a polymerizable functional group is preferable, and a compound having a polymerizable functional group in which L ¹ and L ² are each independently a 1,2-ethanediyl group or a 1,2-propanediyl group is more preferable.

From the viewpoint of making the effect of the present invention remarkable, n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and most preferably 0 or 1.

Specific examples of the group represented by formula (L-1) include glycidyloxymethyl group, glycidyloxyethoxyethyl group, glycidyloxyethoxyethoxyethyl group, or glycidyloxyisopropyloxyisopropyl group, etc. can be mentioned. Among these, glycidyloxyethyl group or glycidyloxyethoxyethoxyethyl group is preferable from the viewpoint of making the effect of the present invention more noticeable.

From the viewpoint of obtaining a compound with superior self-repairing ability, the number of carbon atoms of the polymerizable functional group is preferably in the range of 1 to 30, more preferably in the range of 1 to 20, and even more preferably in the range of 1 to 10. do.

From the viewpoint of obtaining a compound with superior self-repairing ability, it is preferable that at least two of R ¹ , R ² , R ³ and R ⁴ are polymerizable functional groups having 1 to 50 carbon atoms, and R ¹ , R ² It is more preferable that two of R ³ and R ⁴ are polymerizable functional groups having 1 to 50 carbon atoms. When at least two of R ¹ , R ² , R ³ and R ⁴ are polymerizable functional groups having 1 to 50 carbon atoms, each polymerizable functional group may be the same or different. When at least two of R ¹ , R ² , R ³ and R ⁴ are polymerizable functional groups having 1 to 50 carbon atoms, at least one of R ¹ and R ² is selected from the viewpoint of obtaining a compound with superior self-healing ability. It is preferable that at least one of R ³ and R ⁴ is a polymerizable functional group having 1 to 50 carbon atoms.

Additionally, the combination of R ¹ and R ² and the combination of R ³ and R ⁴ may be different, but are preferably the same from the viewpoint of obtaining a compound with superior self-repair ability.

In addition, compounds in which the combination of R ¹ and R ² and the combination of R ³ and R ⁴ are the same include, for example, compounds No. 1 to No. 3, No. 5 to No. 10, and No. 12 to No. 1 to be described later. No.19, No.21 to No.23, No.25 and No.26 are mentioned. In addition, examples of compounds in which the combination of R ¹ and R ² and the combination of R ³ and R ⁴ are different include compounds No. 4, No. 11, No. 20 and No. 24 described later. .

Specific examples of the compound represented by the above formula (1) include No. 1 to No. 26 below, but the present invention is not limited by these compounds. Additionally, “tBu” represents a tert-butyl group.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

The compound represented by formula (1) is prepared, for example, by adding sodium acetate and dimethylformamide to an amino compound having a polymerizable functional group having 1 to 50 carbon atoms, adding disulfur dichloride dropwise under a nitrogen atmosphere, The resulting precipitate is recovered by filtration, washed with water, and concentrated to prepare the desired compound, or a diaminodisulfide compound having a hydroxy group is mixed with a compound having a corresponding polymerizable reactive group having 1 to 50 carbon atoms. It can be produced by a reaction method.

More specifically, when preparing the above compound No. 1, 2-(tert-butylamino)ethyl methacrylate, sodium acetate, and dimethylformamide are added to a reaction vessel, and then sulfur dichloride is added dropwise for reaction, It can be obtained by distilling off the solvent, extracting with butyl acetate and water, then washing with water and drying.

The compound of the present invention has a polysulfide skeleton, and can exhibit excellent self-repairing ability by easily breaking and recombining chemical bonds between sulfur atoms of the polysulfide skeleton by heating or light irradiation. Additionally, the compounds of the present invention can be produced by a simple method.

Excellent self-repair ability means, for example, the ability to self-repair even if the damage is large, the number of times it can self-repair, and the ability to recover sufficient mechanical strength when self-repairing from a damaged state. says In particular, the compound of the present invention has an excellent self-repairing ability that can restore the strength of the material before damage. Additionally, materials with self-healing properties can be expected to have the effect of relieving stress generated during hardening.

＜Epoxy resin＞

Epoxy resins can be prepared using the compounds of the present invention. For example, an epoxy resin can be produced by a production method including a step of reacting a compound represented by the following formula (2) with epihalohydrins. In the present invention, the epoxy resin is not only the product and by-product generated when the compound represented by formula (2) is reacted with epihalohydrins, but also the compound represented by formula (2) or epihalohydrin as a raw material. Drin may be included in the ingredients. In the present invention, the effect of the present invention becomes remarkable when the product produced by reacting the compound represented by formula (2) with epihalohydrins is a compound represented by the above formula (1) containing an epoxy group. Therefore, it is more desirable.

[Formula 31]

(In formula (2), R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 50 carbon atoms which may have a hydrogen atom or a hydroxy group. The alkyl group is a hetero atom. May have. Part of the methylene group in the alkyl group may be substituted with an ether bond, thioether bond, ester bond, amide bond, imide bond, or carbonyl group. Part of the hydrogen atom in the alkyl group may be substituted with a halogen atom. n2 represents an integer from 1 to 10. At least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ represents an alkyl group having 1 to 50 carbon atoms and having a hydroxy group. However, R ⁵ Compounds in which any two of R ⁶ , R ⁷ and R ⁸ are connected to form a ring structure are excluded.)

The alkyl group having 1 to 50 carbon atoms represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ in formula (2) is an alkyl group having 1 to 50 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ The same things as those exemplified can be mentioned. The alkyl group having 1 to 50 carbon atoms and having a hydroxy group represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ represents a group in which some of the hydrogen atoms in the alkyl group described above are replaced with hydroxy groups. The alkyl group may have a hetero atom, part of the methylene group in the alkyl group may be substituted with an ether bond, thioether bond, ester bond, amide bond, imide bond, or carbonyl group, and part of the hydrogen atom in the alkyl group It may be substituted with a halogen atom. From the viewpoint of excellent properties of the cured product, it is preferable that at least one of R ⁵ and R ⁶ and at least one of R ⁷ and R ⁸ are an alkyl group having 1 to 50 carbon atoms and having a hydroxy group.

From the viewpoint of easy purification of the compound, n2 is preferably an integer of 1 to 4, and is more preferably 1.

Examples of the epihalohydrins include epichlorohydrin, β-methylepichlorohydrin, epibromohydrin, and β-methylepibromohydrin. Among these, epichlorohydrin is preferable from the viewpoint of availability and economic efficiency.

A specific example of the method for producing an epoxy resin is, for example, reacting the compound represented by formula (2) with epichlorohydrin in the presence of an alkali, Lewis acid, or correlation transfer catalyst, as shown in Scheme 1 below. There are ways to do it. From the viewpoint of increasing the yield of the epoxy resin, the above reaction is preferably performed under conditions of 20°C to 100°C, and more preferably performed under conditions of 30°C to 80°C. In addition, in Scheme 1 below, the definitions of R ⁶ , R ⁸ and n2 are the same as those in the above formula (2), and m1 and m2 each independently represent an integer of 1 to 50.

[Formula 32]

Examples of the alkali used in the above reaction include the alkali described in Japanese Patent No. 5698072. Examples of the Lewis acid and correlation transfer catalyst used in the above reaction include the Lewis acid and correlation transfer catalyst described in Japanese Patent No. 5698072.

Additionally, conventionally known solvents can be used for the above reaction. Examples of solvents that can be used in the reaction include the solvents described in Japanese Patent No. 5698072.

The amount of epihalohydrins used in the method for producing an epoxy resin of the present invention is 1 per mole of hydroxyl group contained in the compound represented by formula (2) from the viewpoint of obtaining a high-purity epoxy resin. It is preferable that the amount is more than a mole, and it is more preferable that the amount is 1 mole to 20 mole. From the viewpoint of obtaining a high-purity epoxy resin, the amount of the alkali used is preferably 0.1 mole to 2.0 mole, and 0.3 mole to 1.5 mole per 1 mole of hydroxyl group contained in the compound represented by formula (2). It is more preferable that the amount is sufficient. From the viewpoint of obtaining a high-purity epoxy resin, the amount of the Lewis acid or correlation transfer catalyst used is preferably 0.01 mol% to 10 mol% relative to the amount of hydroxyl group contained in the compound represented by formula (2). It is more preferable that the amount is 0.2 mol% to 5 mol%.

An alkali-developable resin can be obtained by adding an unsaturated monobasic acid to the epoxy resin of the present invention.

Unsaturated monobasic acids used herein include, for example, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate/malate, hydroxyethyl acrylate/maleate, and hydrochloric acid. Roxypropyl methacrylate/malate, hydroxypropyl acrylate/malate, dicyclopentadiene/maleate or polyfunctional (meth)acrylate having one carboxyl group and two or more (meth)acryloyl groups, etc. I can hear it. In this specification, (meth)acrylate represents acrylate or methacrylate, and (meth)acryloyl group represents an acryloyl group or a methacryloyl group.

Examples of the polyfunctional (meth)acrylate having one carboxyl group and two or more (meth)acryloyl groups include the following compounds.

[Formula 33]

From the viewpoint of increasing the sensitivity of the obtained alkali-developable resin, it is preferable to add the carboxyl group contained in the unsaturated monobasic acid in a ratio of 0.1 to 1 with respect to one epoxy group contained in the epoxy resin of the present invention, It is more preferable to add it at a ratio of 0.3 to 1.0 pieces.

<Curable composition>

Next, the curable composition of the present invention is explained.

The curable composition of the present invention contains a compound represented by formula (1) (hereinafter also referred to as “compound of the present invention”). The curable composition of the present invention may further contain a component capable of forming a cured product by reacting with the compound of the present invention, preferably at least one member selected from the group consisting of a curing agent and a polymerization initiator. Additionally, the curable composition of the present invention may contain monomers other than the compounds of the present invention (hereinafter also referred to as “other monomers”) as curable monomers.

When the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group of 1 to 50 carbon atoms in which the functional group in formula (1) is an epoxy group, an episulfide group, or an oxetanyl group, an epoxy group, It may further contain a known curing agent capable of reacting with an episulfide group or oxetanyl group. As the curing agent, it is preferable to use an amine compound, amide compound, acid anhydride compound, thiol compound, phenol compound, imidazole compound or latent curing agent because the curing reaction of the curable composition of the present invention is promoted. The hardening agent may be used alone or in combination of two or more types.

Examples of the amine compound as the curing agent include the amine compounds described in International Publication No. 2020/175321.

Examples of the amide compound as the curing agent include the amide compound described in International Publication No. 2020/175321.

Examples of the acid anhydride compound as the curing agent include the acid anhydride compound described in International Publication No. 2020/175321.

Examples of the thiol compound as the curing agent include aliphatic thiol compounds, aromatic thiol compounds, aliphatic polythiol compounds, mercaptocarboxylic acid ester compounds, mercaptocarboxylic acid, and mercaptoether. Among these, bifunctional thiol compounds are preferable from the viewpoint that the cured product exhibits excellent self-repairing ability. Examples of the bifunctional thiol compound include compounds described in International Publication No. 2020/175321. Moreover, the thiol compound represented by the following formula (3) is preferable from the viewpoint of heat resistance.

[Formula 34]

In formula (3), A represents an alkylene group having 1 to 10 carbon atoms, ^m3 represents an integer of 1 to 6, and Represents a saturated hydrocarbon group.

Saturated hydrocarbon groups having 1 to 20 carbon atoms and having the same valence as ^m3 represented by , alkanes with 1 to 20 carbon atoms such as decane, undecane, dodecane, tridecane, tetradecane, pentacane or icosane, alicyclic compounds with 3 to 20 carbon atoms, or combinations thereof, the same number as m3. It indicates that the hydrogen atom has been removed. The alicyclic compound refers to the alicyclic compound satisfying the predetermined number of carbon atoms.

Examples of the phenol compound as the curing agent include the phenol compounds described in International Publication No. 2020/175321.

Examples of the imidazole compound as the curing agent include 2-ethyl-4-methylimidazole, 2-methyl-1-phenylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine, 2 -Phenylimidazoline, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, and imidazole compounds described in Japanese Patent Application Laid-Open No. 2015-017059.

Examples of the latent curing agent as the curing agent include, for example, a modified amine latent curing agent having at least one amino group having an active hydrogen in the molecule formed by reacting a polyamine compound and an epoxy compound, a latent curing agent containing a phenolic resin, Dicyandiamide, modified polyamine, hydrazide, 4,4'-diaminodiphenyl sulfone, boron trifluoride amine complex salt, urea, melamine, International Publication No. 2012/020572 and Japanese Patent Publication No. 2014-177525. The compounds described, etc. can be mentioned.

In addition, when the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group of 1 to 50 carbon atoms in which the functional group in formula (1) is an epoxy group, oxetanyl group, or episulfide group, other As a monomer, it may additionally contain an epoxy compound.

Examples of the epoxy compound include alicyclic epoxy compounds, aromatic epoxy compounds, and aliphatic epoxy compounds.

Examples of the alicyclic epoxy compound include compounds described in International Publication No. 2019/138953. Commercially available products of alicyclic epoxy compounds include, for example, UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200 (manufactured by Union Carbide), Celoxide 2021, Celoxide 2021P, and Celox. Side 2081, Celoxide 2083, Celoxide 2085, Celoxide 2000, Celoxide 3000, Cyclomer A200, Cyclomer M100, Cyclomer M101, Epolyde GT-301, Epolyde GT-302, Epolyde 401, Epolid 403, ETHB, Epolid HD300 or EHPE-3150 (manufactured by Daicel Co., Ltd.) can be mentioned. Among alicyclic epoxy compounds, epoxy compounds having a cyclohexene oxide structure are preferable because they cure quickly.

Examples of the aromatic epoxy compound include compounds described in International Publication No. 2019/138953. Commercially available products of the aromatic epoxy compound include, for example, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Denacol Coat EX-1020, Oncoat EX-1030, Oncote EX-1040, Oncote EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (Nagase Chemtex Co., Ltd. ) manufactured by ) ; Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC Corporation); ESN-475V (manufactured by Nittetsu Chemical & Materials Co., Ltd.); Epicoat YX8800 (manufactured by Mitsubishi Chemical Corporation); Muff Loop G-0105SA, Muff Loop G-0130SP (manufactured by Nichiyu Co., Ltd.); Epiclon N-665, Epiclon HP-7200 (manufactured by DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (manufactured by ADEKA Co., Ltd.); Or TECHMORE VG-3101L (manufactured by Printech Co., Ltd.).

Examples of the aliphatic epoxy compound include compounds described in International Publication No. 2019/138953. Commercially available products of the aliphatic epoxy compound include, for example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX -614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832 , Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase Chemtex Co., Ltd.); EPOLITE M-1230, EPOLITE 40E, EPOLITE 100E, EPOLITE 200E, EPOLITE 400E, EPOLITE 70P, EPOLITE 200P, EPOLITE 400P, EPOLITE 1500NP, EPOLITE 1600, EPOLITE 80MF, EPOLITE 100MF ( (manufactured by Kyoeisha Chemical Co., Ltd.), Adecaglycirol ED-503, Adecaglycirol ED-503G, Adecaglycirol ED-506, Adecaglycirol ED-523T, Adeka Resin EP-4088S, or Adeka Resin EP-4080E (manufactured by ADEKA Co., Ltd.).

Additionally, as the epoxy compound, a urethane-modified epoxy compound to which a urethane skeleton is provided may be used. A urethane-modified epoxy compound has an epoxy group and a urethane bond in the molecule, and can be obtained, for example, by reacting a compound having an isocyanate group with an epoxy compound having a hydroxy group in the molecule.

In addition, when the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group of 1 to 50 carbon atoms in which the functional group in formula (1) is an epoxy group, oxetanyl group, or episulfide group, other As the monomer, monomers such as compounds having an unsaturated hydrocarbon group may be additionally contained within a range that does not adversely affect the effect of the present invention.

The compound having the unsaturated hydrocarbon group can be used without particular limitation as long as it is a commonly used compound known as a compound capable of copolymerizing with a vinyl group, an acrylic group, or a methacryl group. For example, compounds having a vinyl group, compounds having an allyl group, acrylate compounds, or methacrylate compounds can be mentioned.

Examples of the compound having a vinyl group and a compound having an allyl group include compounds described in International Publication No. 2020/175321.

Examples of the acrylate compound include monofunctional acrylate compounds, bifunctional acrylate compounds, and trifunctional or more multifunctional acrylate compounds.

Examples of the monofunctional acrylate compound, the bifunctional acrylate compound, and the polyfunctional acrylate compound include compounds described in International Publication No. 2020/175321.

Examples of the methacrylate compound include monofunctional methacrylate compounds, bifunctional methacrylate compounds, and trifunctional or more polyfunctional methacrylate compounds.

Examples of the monofunctional methacrylate compound, bifunctional methacrylate compound, or trifunctional or more polyfunctional methacrylate compound include the compounds described in International Publication No. 2020/175321.

When the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group of 1 to 50 carbon atoms in which the functional group in formula (1) is an epoxy group, oxetanyl group, or episulfide group, in the cured product From the viewpoint of suppressing the amount of remaining unreacted curable monomer and curing agent used, the compounding amount of the curing agent is preferably 0.01 to 2.0 mole per mole of curable monomer.

When the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group of 1 to 50 carbon atoms in which the functional group in formula (1) is a hydroxy group, a known curing agent capable of reacting with the hydroxy group is used. It may additionally contain. As the curing agent, it is preferable to use the epoxy compound, the latent curing agent, or the isocyanate compound because the curing reaction of the curable composition of the present invention is accelerated. The hardening agent may be used alone or in combination of two or more types.

Isocyanate compounds as the curing agent include, for example, monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; Hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate , a terminal isocyanate group obtained by the reaction of polyfunctional isocyanate compounds such as paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate, or a polyfunctional isocyanate compound with an active hydrogen compound such as trimethylolpropane. Containing compounds, etc. can be mentioned. From the viewpoint of improving the curing reaction of the curable composition of the present invention, the isocyanate compound blended in the curable composition of the present invention is preferably a compound having a plurality of isocyanate groups, and is hexamethylene diisocyanate, isophorone diisocyanate, or xylene diisocyanate. It is more preferable to be

When the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group having 1 to 50 carbon atoms whose functional group in formula (1) is a hydroxy group, it further contains a polyol compound as another monomer. can do.

The polyol compound refers to a compound having two or more hydroxy groups in the molecule, and the hydroxy groups may be alcoholic or phenolic. Specifically, the compounds described in International Publication No. 2020/175321, etc. can be mentioned.

In addition, when the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group of 1 to 50 carbon atoms whose functional group in formula (1) is a hydroxy group, the unsaturated hydrocarbon group is used as another monomer. Curable monomers such as compounds may be additionally contained within a range that does not adversely affect the effect of the present invention.

When the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group having 1 to 50 carbon atoms whose functional group in formula (1) is a hydroxy group, unreacted curable monomer remaining in the cured product And from the viewpoint of suppressing the amount of curing agent used, the compounding amount of the curing agent is preferably 0.5 to 2.0 mole, and more preferably an equivalent amount, per 1 mole of hydroxyl group contained in the curable monomer.

When the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group of 1 to 50 carbon atoms whose functional group in formula (1) is an isocyanate group, a known curing agent capable of reacting with an isocyanate group is added. It can be contained as. As a curing agent, it is preferable to use the phenol compound or the epoxy compound because the curing reaction of the curable composition of the present invention is promoted. The hardening agent may be used alone or in combination of two or more types.

When the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group of 1 to 50 carbon atoms whose functional group in formula (1) is an isocyanate group, the other monomer may include a compound having the above-mentioned unsaturated hydrocarbon group, etc. The curable monomer may be additionally contained within a range that does not adversely affect the effect of the present invention.

When the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group of 1 to 50 carbon atoms whose functional group in formula (1) is an isocyanate group, the unreacted curable monomer remaining in the cured product and From the viewpoint of suppressing the amount of curing agent used, the compounding amount of the curing agent is preferably 0.5 to 1.5 moles per mole of the functional group that the curing monomer can react with the curing agent, and more preferably an equivalent amount.

When the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group having 1 to 50 carbon atoms whose functional group in formula (1) is a vinyl group, an acrylic group, or a methacryl group, the compound of the present invention As a component that can react with and form a cured product, a known polymerization initiator may be additionally contained. Examples of the polymerization initiator include a radical polymerization initiator and a cationic polymerization initiator. The polymerization initiator may be used alone or in combination of two or more types.

When the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group having 1 to 50 carbon atoms in which the functional group in formula (1) is a vinyl group, an acrylic group, or a methacryl group, polymerization of the curable composition From the viewpoint of performing the reaction satisfactorily and improving the physical properties of the cured product after the reaction, the amount of the polymerization initiator mixed is preferably 0.001% by mass to 20% by mass, and more preferably 0.1% by mass to 10% by mass, relative to the curable composition. desirable.

Examples of the radical polymerization initiator include an optical radical polymerization initiator or a thermal radical polymerization initiator.

Examples of the radical photopolymerization initiator include acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds, bisimidazole-based compounds, acridine-based compounds, acylphosphine-based compounds, and oxime ester compounds. You can.

Examples of the acetophenone-based compound include compounds described in International Publication No. 2016/098471.

Examples of the benzyl-based compound include compounds described in International Publication No. 2016/098471.

Examples of the benzophenone-based compound include compounds described in International Publication No. 2016/098471.

Examples of the thioxanthone-based compound include compounds described in International Publication No. 2016/098471.

Examples of the bisimidazole-based compound include compounds described in International Publication No. 2019/138953 or International Publication No. 00/52529.

Examples of the acridine-based compound include compounds described in International Publication No. 2019/138953.

Examples of the acylphosphine-based compound include compounds described in International Publication No. 2019/138953.

Examples of the oxime ester compound include compounds described in International Publication No. 2019/138953.

Examples of the thermal radical polymerization initiator include the compounds described in International Publication No. 2019/138953.

The cationic polymerization initiator may be any compound as long as it can release a substance that initiates cationic polymerization by irradiation of energy rays or heating, but preferably an onium salt that releases a Lewis acid by irradiation of energy rays. It is phosphorus polychloride, or its derivative.

Examples of onium salts include salts of a cation and an anion represented by [M] ^{r +} [G] ^{r -} .

Here, the cation [M] ^r+ is preferably onium, and its structure can be represented by the formula [(R ⁹ )fQ] ^r+ , for example.

R ⁹ is an organic group that has 1 to 60 carbon atoms and may contain several atoms other than carbon atoms. f is an integer from 1 to 5. f ^R9 's may be the same or different. Moreover, it is preferable that at least one of f R ¹³ is an organic group having an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F and N=N. Additionally, when the valence of Q in the cation [M] ^r+ is set to q, the relationship r=fq must be established (however, N=N is treated as valence 0).

Moreover, specific examples of the anion [G] ^r- include monovalent ones, such as halide ions such as chloride ion, bromide ion, iodide ion, and fluoride ion; Inorganic anions such as perchlorate ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion, hexafluoroantimonate ion, and tetrafluoroborate ion; Borates such as tetrakis(pentafluorophenyl)borate, tetra(3,5-difluoro-4-methoxyphenyl)borate, tetrafluoroborate, tetraarylborate, tetrakis(pentafluorophenyl)borate, etc. anion; Methanesulfonic acid ion, dodecylsulfonic acid ion, benzenesulfonic acid ion, toluenesulfonic acid ion, trifluoromethanesulfonic acid ion, naphthalenesulfonic acid ion, diphenylamine-4-sulfonic acid ion, 2-amino-4-methyl-5-chlorobenzenesulfonic acid ion, 2-amino-5-nitrobenzenesulfonic acid ion, phthalocyaninesulfonic acid ion, fluorosulfonic acid ion, trinitrobenzenesulfonic acid anion, camphorsulfonic acid ion, nonafluorobutanesulfonic acid ion, hexadecafluorooctanesulfonic acid ion, polymerizable substituent. Sulfonic acid ion having, Japanese Patent Laid-open No. 10-235999, Japanese Patent Laid-Open No. 10-337959, Japanese Patent Laid-Open No. 11-102088, Japanese Patent Laid-Open No. 2000-108510, Japanese Patent Laid-Open No. 2000-168223. No. 2001-209969, Japanese Patent Application Publication No. 2001-322354, Japanese Patent Application Publication No. 2006-248180, Japanese Patent Application Publication No. 2006-297907, Japanese Patent Application Publication No. 8-253705, published in Japan organic sulfonic acid-based anions such as sulfonic acid ions described in Patent Publication No. 2004-503379, Japanese Patent Application Publication No. 2005-336150, and International Publication No. 2006/28006; Organic phosphates such as octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, and 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphonate ion. Anion, bistrifluoromethylsulfonylimide ion, bisperfluorobutanesulfonylimide ion, perfluoro-4-ethylcyclohexanesulfonate ion, tetrakis(pentafluorophenyl)borate ion or tris(fluorophenyl) Roalkyl sulfonyl) carbo anion, etc. are mentioned, and as divalent ones, for example, benzene disulfonate ion, naphthalene disulfonate ion, etc. are mentioned.

Among such onium salts, it is preferable to use aromatic sulfonium salts such as aryldiazonium salt, diaryliodonium salt, or triaryl sulfonium salt because the polymerization reaction of the curable composition of the present invention becomes good.

Aromatic sulfonium salts can be commercially available, for example, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638 (manufactured by Wako Pure Chemical Industries, Ltd.), CPISO-100P, CPISO-101A. , CPISO-200K, CPISO-210S (manufactured by San-Apro Co., Ltd.), Adeka Accrue SP-056, Adeka Accrue SP-066, Adeka Accrue SP-130, Adeka Accrue SP-140, Adeka Acruz Cruz SP-082, Adeka Accrue SP-103, Adeka Accrue SP-601, Adeka Accrue SP-606, Adeka Accrue SP-701, Adeka Accrue SP-150, Adeka Accrue SP -170 (manufactured by ADEKA Co., Ltd.), etc.

When the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group of 1 to 50 carbon atoms in which the functional group in formula (1) is a vinyl group, an acrylic group, or a methacryl group, as another monomer, Curable monomers such as the above-mentioned epoxy compound, the above-mentioned polyol compound, and the above-mentioned compound having an unsaturated hydrocarbon group may be additionally contained within the range that does not adversely affect the effect of the present invention.

When the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group having 1 to 50 carbon atoms where the functional group in formula (1) is a vinyl group, an epoxy group, or an oxetanyl group, the compound of the present invention As a component that can react with and form a cured product, the cationic polymerization initiator may be additionally contained.

When the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group of 1 to 50 carbon atoms whose functional group in formula (1) is a vinyl group, an epoxy group, or an oxetanyl group, as another monomer, Curable monomers such as the epoxy compound and the compound having an unsaturated hydrocarbon group may be additionally contained within a range that does not adversely affect the effect of the present invention.

When the curable composition of the present invention contains as a curable monomer a compound having a polymerizable functional group of 1 to 50 carbon atoms in which the functional group in formula (1) is a vinyl group, an epoxy group, or an oxetanyl group, polymerization of the curable composition From the viewpoint of performing the reaction satisfactorily and improving the physical properties of the cured product after the reaction, the amount of the cationic polymerization initiator mixed is preferably 0.001% by mass to 20% by mass, and 0.1% by mass to 10% by mass, based on the curable composition. It is more preferable to be

In the curable composition of the present invention, the compounding amount of the compound of the present invention as a curable monomer and other monomers is not particularly limited and can be adjusted appropriately based on the properties required for the cured product, etc. From the viewpoint that the cured product is likely to maintain excellent self-healing ability, the total amount of the compound of the present invention as a curable monomer and other monomers is preferably 0.01% by mass to 99.999% by mass, 0.05% by mass, relative to the curable composition of the present invention. It is more preferable that it is mass % - 99.9 mass %, and it is still more preferable that it is 0.1 mass % - 97 mass %.

Additionally, the curable composition of the present invention may contain the compound of the present invention as a curing agent. The compounds of the present invention as a curing agent include vinyl group, acrylic group, methacryl group, hydroxy group, isocyanate group, amino group, amide group, epoxy group, oxetanyl group, episulfide group, carboxyl group, heteroaryl group, thiol group, Examples include compounds represented by formula (1) having a functional group selected from the group consisting of a group containing a carboxylic acid anhydride structure and a group containing a cyclic imide structure.

In addition, when using the compound of the present invention as a curing agent, the compounding amount of the curing agent in the curable composition of the present invention described above is the total amount of the compound of the present invention and the known curing agent.

The curable composition of the present invention may further contain a polymer compound, epoxy cured product, urethane cured product, or rubber component.

As a polymer compound that can be used in the curable composition of the present invention, conventionally known polymer compounds may be used, and examples include the polymer compounds described in International Publication No. 2020/175321.

Epoxy cured materials that can be used in the curable composition of the present invention include those obtained by curing conventionally known epoxy resins.

Examples of the urethane cured material that can be used in the curable composition of the present invention include those obtained by curing conventionally known urethane resins.

As a rubber component that can be used in the curable composition of the present invention, conventionally known rubber components may be used, and examples include the rubber component described in International Publication No. 2020/175321.

The curable composition of the present invention may contain an organic solvent as a diluent in order to uniformly mix the materials, or to ensure good moldability and good film forming properties of the curable composition of the present invention. The organic solvent does not correspond to the compound of the present invention, other monomers, curing agents, or polymerization initiators, but refers to a liquid state at 25°C and atmospheric pressure.

Organic solvents that can be used in the curable composition of the present invention include, for example, alcohol-based solvents, ketone-based solvents, amide-based solvents, ether-based solvents, ester-based solvents, aliphatic hydrocarbon-based solvents, aromatic solvents, or halogen-containing solvents. etc. can be mentioned.

Examples of the alcohol-based solvent include the alcohol-based solvent described in International Publication No. 2020/175321. These alcohol-based solvents may be used alone or in combination of two or more types.

Examples of the ketone-based solvent include the ketone-based solvent described in International Publication No. 2020/175321. These ketone-based solvents may be used alone or in combination of two or more types.

Examples of the amide-based solvent include the amide-based solvent described in International Publication No. 2020/175321. These amide-based solvents may be used alone or in combination of two or more types.

Examples of the ether solvent system include the ether solvent described in International Publication No. 2020/175321. These ether-based solvents may be used alone or in combination of two or more types.

Examples of the ester-based solvent include the ester-based solvent described in International Publication No. 2020/175321. These ester-based solvents may be used alone or in combination of two or more types.

Examples of the aliphatic hydrocarbon-based solvent include the aliphatic hydrocarbon-based solvent described in International Publication No. 2020/175321. These aliphatic hydrocarbon-based solvents may be used alone or in combination of two or more types.

Examples of the aromatic hydrocarbon-based solvent include the aromatic hydrocarbon-based solvent described in International Publication No. 2020/175321. These aromatic hydrocarbon-based solvents may be used alone or in combination of two or more types.

Examples of the halogen-containing solvent include the halogen-containing solvent described in International Publication No. 2020/175321. These halogen-containing solvents may be used alone or in combination of two or more types.

In the curable composition of the present invention, only one type of the organic solvent may be used, or two or more types may be used in combination. The type and mixing amount of these organic solvents can be appropriately selected depending on the viscosity of the curable composition, the shape to be molded, etc. From the viewpoint of ease of handling of the curable composition of the present invention, the compounding amount of the organic solvent is preferably 0.1% by mass to 90% by mass, more preferably 0.5% by mass to 80% by mass, relative to the curable composition of the present invention. , it is more preferable that it is 10 mass% to 70 mass%.

In addition, as long as it does not impair the effect of the present invention, an ultraviolet absorber, a light stabilizer, an adhesion aid, a polymerization inhibitor, a sensitizer, an antioxidant, a smoothness imparting agent, an orientation control agent, an infrared absorber, a thixotropic agent, and an antistatic agent may be added as necessary. , known additives such as antifoaming agents, colorants, emulsifiers, surfactants, conductivity imparting agents, hydrolysis inhibitors, cellulose nanofibers, polymerization catalysts, or fillers such as fillers, in known amounts, using known methods of curing the present invention. It may be mixed in the composition.

The use of the curable composition of the present invention is not particularly limited, but it can be preferably used as a self-repairing material. A self-repairing material is a material that can self-repair the scratches or damage without external stimulation or by specific manipulation, processing, or external stimulation when a scratch or damage occurs due to an abrasion or blow under the material's use environment. It refers to materials that can be used. Stimuli from the outside include contact, light irradiation, heating or pressure, and these may be applied individually, or two or more types of external stimuli may be applied sequentially or simultaneously.

The curable composition of the present invention can also be used as a surface coating agent, paint, adhesive, or battery material. Surface coating agents are used for the purpose of protecting the surface of a substrate, providing design or optical properties to the substrate, controlling the physical properties of the surface, or providing anti-contamination, chemical resistance, weather resistance, etc. to the substrate. The method of applying the curable composition of the present invention to the surface of the substrate may be carried out by any known method, for example, die coater method, comma coater method, curtain coater method, spray coater method, gravure coater method, flexo method. Examples include the coater method, knife coater method, doctor blade method, reverse roll method, brush application method, dip method, inkjet method, or wire bar coater method. When using the curable composition of the present invention as a surface coating agent, the composition before curing can be applied to the surface of the substrate, and then cured by the method described later. When using the curable composition of the present invention as a surface coating agent, paint, adhesive, or battery material, known additives used in surface coating agents, paints, adhesives, or battery materials may be added.

＜Hardened product＞

Next, the cured product of the present invention will be described.

The cured product of the present invention is obtained by curing the curable composition described above. The cured product of the present invention is not limited by hardness, physical properties, etc.

As a method of curing the above-described curable composition, for example, the cured product of the present invention can be obtained by applying the above-mentioned curable composition to a substrate, or after molding the above-described curable composition, by irradiating the above-described curable composition with energy rays or heating. . Energy ray irradiation and heating may be performed either one way, each may be performed alternately, may be performed simultaneously, or may be performed while changing over time.

When the curable composition of the present invention is cured by irradiation with energy rays, examples of the energy rays include ultraviolet rays, electron beams, Examples of ultraviolet light sources include mercury lamps, xenon lamps, carbon arc lamps, metal halide lamps, sunlight, laser light sources, and LED light sources. The light source may be appropriately selected depending on the optical radical initiator optionally added to the curable composition of the present invention, but from the viewpoint of operability, UV-LED (wavelength: 350 to 450 nm) is preferable. The integrated irradiation amount may be appropriately changed depending on the thickness of the object. However, if the integrated irradiation amount is insufficient, the curing reaction does not proceed sufficiently, and if the integrated irradiation amount is too large, the object may be colored. From the viewpoint of facilitating control of the curing reaction, the cumulative irradiation amount is preferably in the range of 1 mJ/cm2 to 100,000 mJ/cm2.

When curing the curable composition of the present invention by heating, the heating is preferably 200°C or lower, and more preferably 140°C or lower, from the viewpoint of facilitating control of the curing reaction. Moreover, from the viewpoint of carrying out the curing reaction satisfactorily, heating is preferably performed at 40°C or higher, and more preferably at 50°C or higher. The heating time may be appropriately selected depending on the heating temperature, etc., but is preferably 1 second to 20 hours, and more preferably 10 seconds to 10 hours.

The pressure at the time of producing the cured product can usually be carried out at atmospheric pressure, but it can also be carried out by applying pressure under conditions of 1,000 atmospheres or less. The atmosphere for producing the cured product may be an appropriate environment selected depending on the composition of the curable composition, etc., and may be an atmospheric atmosphere or an inert gas atmosphere such as nitrogen gas or argon gas.

The cured product of the present invention may be manufactured by molding and curing the curable composition without using an organic solvent, or may be manufactured by molding and curing the curable composition after adjusting the viscosity, etc., using an organic solvent. Additionally, the prepared cured product may be dissolved or swelled in a solvent and then molded or formed into a film. Additionally, the cured product may be produced in an emulsified or dispersed state in water by emulsion polymerization or suspension polymerization in an aqueous system.

Uses of the cured product of the present invention include, for example, sealing materials, heat insulating materials, soundproofing materials, coatings, sanitary materials, hose clips, pipes for fluid transportation, flexible hoses, hot melt adhesives, additives for adhesives, optical materials, electrical equipment, It can be preferably used in applications that require fracture resistance or fatigue resistance, such as battery materials, vehicles, ships, aircraft, buildings, housing and construction materials, civil engineering materials, medical, curtains, sheets, containers, glasses, bag cases, or sporting goods. .

More specific uses include optical films, optical sheets, optical filters, high-brightness prism sheets, optical light condensers, anti-reflective materials such as anti-glare films, lighting equipment, transparent lighting materials, protective films, surface materials for pen input devices, electric cables, and sheaths. , wire covering materials, electrical insulation members, electronic device casings, mechanical parts, vibration-resistant fatigue members, capacitors, separators for secondary batteries, binders for secondary batteries, solid electrolytes, fiber-reinforced materials, rust inhibitors, corrosion inhibitors, spray pigments, barrier materials. Paints such as (organic substances, gases, humidity), building materials for pets, building materials such as floors, walls, doors, etc., waterproof sheets, waterproof sheets, actuators, cleaning pads, bath tubs, basins, tubs, bathing accessories, automobile materials, artificial Leather, synthetic leather, artificial skin, stents for endovascular treatment, dental composite restorative materials, sleeve materials, laminated glass, transfer foil, flame retardant film, shaft for writing instruments, cushioning material, buffering agent, agricultural film, decorative film, cosmetic sheet, vinyl Examples include house sheets, insect-proof nets, furniture, clothing, bags, shoes, goggles, ski plates, snowboards, rackets, tents, containers, cutting boards, cutting boards, antibacterial films, antibacterial molded bodies, barrier films or packing.

Applying the curable composition of the present invention to a surface coating agent has the effect of improving processing defects caused by coating, and, for example, by using it as a hard coat material for in-mold molding, processability during molding processing can be improved. there is.

When the curable composition of the present invention is applied to a paint, the effect of self-repairing scratches in the coating film is obtained. For example, when used as a paint for automobiles, scratches in the paint can be repaired simply by heating, making repainting unnecessary.

When the curable composition of the present invention is applied to an adhesive, an effect is obtained in which the cured product after adhesion is spontaneously bonded after cutting, and peeling due to adhesion failure or deterioration can be suppressed. In addition, hardening after stress relaxation can be provided, making it possible to improve adhesive strength.

When the curable composition of the present invention is applied to a battery material, the effect of self-repairing after fracture is obtained. For example, when a secondary battery is repeatedly charged and discharged, the electrode may expand and the binder may break. However, even if broken, the binder self-repairs and prevents decomposition of the electrode, preventing deterioration of battery performance. You can.

＜Other＞

In this disclosure, the following aspects can be mentioned.

[1] A compound represented by the following formula (1).

[Formula 35]

In formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a polymerizable functional group with 1 to 50 carbon atoms, or an alkyl group with 1 to 50 carbon atoms. The alkyl group may have a hetero atom. A part of the methylene group in the alkyl group may be substituted with an ether bond, thioether bond, ester bond, amide bond, imide bond, or carbonyl group. Some of the hydrogen atoms in the alkyl group may be substituted with halogen atoms. n1 represents an integer from 1 to 10. At least one of R ¹ , R ² , R ³ and R ⁴ represents a polymerizable functional group having 1 to 50 carbon atoms. However, compounds in which any two of R ¹ , R ² , R ³ and R ⁴ are connected to form a ring structure are excluded.

[2] Polymerizable functional groups having 1 to 50 carbon atoms, vinyl group, allyl group, acrylic group, methacryl group, hydroxy group, isocyanate group, amino group, amide group, epoxy group, oxetanyl group, episulfide group , a carboxyl group, a heteroaryl group, a thiol group, a group containing a carboxylic acid anhydride structure, and a group containing a cyclic imide structure, and a functional group selected from the group combined with a hydrocarbon group, and a portion of the methylene group in the hydrocarbon group The compound according to [1] may be substituted with an ether bond, thioether bond, ester bond, amide bond, imide bond, or carbonyl group, and some of the hydrogen atoms in the polymerizable functional group may be substituted with a halogen atom.

[3] The compound according to [1] or [2], wherein the polymerizable functional group having 1 to 50 carbon atoms is a group represented by the following formula (L-1).

[Formula 36]

In formula (L-1), L ¹ and L ² each independently represent an alkanediyl group having 1 to 5 carbon atoms. n represents an integer from 0 to 5. When n is an integer of 2 or more, a plurality of L ¹ may have the same contribution or different contributions. * represents the bonding position with the nitrogen atom in formula (1).

[4] A curable composition containing the compound according to any one of [1] to [3].

[5] The curable composition according to [4], which further contains at least one member selected from the group consisting of a curing agent and a polymerization initiator.

[6] The curable composition according to [5], wherein the curing agent is at least one selected from the group consisting of amine compounds, amide compounds, acid anhydride compounds, thiol compounds, phenol compounds, imidazole compounds, and latent curing agents.

[7] The curable composition according to [5] or [6], wherein the polymerization initiator is a cationic polymerization initiator or a radical polymerization initiator.

[8] The curable composition according to any one of [4] to [7], which is a self-repairing material, surface coating agent, paint, adhesive, or battery material.

[9] A cured product obtained by curing the curable composition according to any one of [4] to [8].

[Example]

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these.

[Example 1] Preparation of compound No.2

In a 500 mL round bottom flask, 200 g of dimethylformamide, 50.0 g of 2-(tert-butylamino)ethylacrylate, and 27.0 g of sodium acetate were added and stirred to mix, then 19.7 g of disulfur dichloride was added to 59.2 g of dimethylformamide. g was dissolved dropwise at room temperature and stirred for 2 hours to react. After completion of the reaction, butyl acetate and water were added to separate oil and water. After washing with water, the solvent was distilled off under reduced pressure, the mixture was allowed to stand at -37°C for 48 hours, and the precipitated solid was separated by filtration to obtain 43.7 g of colorless crystals. As a result of analysis by ¹ H-NMR and elemental analysis, the obtained colorless crystal was confirmed to be compound No. 2, the target compound. The yield of the obtained compound was 77%. The analysis results are shown below.

(2) Elemental analysis

C: 54.5 mass% (theoretical value: 55.5 mass%), H: 8.2 mass% (theoretical value: 8.4 mass%), N: 6.6 mass% (theoretical value: 6.5 mass%), S: 14.5 mass% (theoretical value: 14.8 mass%) )

[Example 2] Preparation of compound No. 12

In a 300 mL round-bottom flask, 15.0 g of Compound No. 2 prepared in Example 1, 21.3 g of water, 61.5 g of ethanol, and 14.5 g of 35% potassium hydroxide aqueous solution were added, stirred for 1 hour to mix, and then added to 400 mL of toluene. All of the mixed solutions in the flask were added, an additional 200 mL of water was added, and water washing was repeated until the aqueous layer became neutral. After confirming that the aqueous layer had become neutral, the solvent was distilled off under reduced pressure and left to stand at room temperature. After 24 hours, the precipitated crystals were separated by filtration and dried under vacuum to obtain 6.88 g of white powdery crystals. As a result of analysis by ¹ H-NMR and elemental analysis, the obtained white powder was confirmed to be compound No. 12, the target compound. The yield of the obtained compound was 67%. The analysis results are shown below.

(2) Elemental analysis

C: 48.5 mass% (theoretical value: 48.6 mass%), H: 9.6 mass% (theoretical value: 9.5 mass%), N: 9.2 mass% (theoretical value: 9.5 mass%), S: 21.2 mass% (theoretical value: 21.6 mass%) )

[Example 3] Preparation of compound No. 6 (epoxy resin)

In a 100 mL round bottom flask, 5.00 g of compound No. 12 prepared in Example 2, 49.88 g of epichlorohydrin, and 0.185 g of tetramethylammonium chloride were added, the temperature was raised to 70° C., and stirred to dissolve compound No. 12. Then, 3.51 g of 48% sodium hydroxide aqueous solution was slowly added and stirred for 3 hours. After stirring, the solvent was distilled off under reduced pressure, 100 mL of toluene was added, 100 mL of water was further added, oil and water were separated, and water washing was repeated until the aqueous layer became neutral. After confirming that the aqueous layer had become neutral, toluene was distilled off under reduced pressure and separated by filtration to obtain 6.54 g of a viscous liquid. The epoxy equivalent weight of the obtained liquid was calculated by the following method to be 235, and it was confirmed that it was an epoxy resin containing compound No. 6 as the main component. The yield of the obtained epoxy resin was 94.9%. The analysis results are shown below.

(1) Epoxy equivalent

In accordance with JIS K7237, the amine equivalent is calculated by differential titration with perchloric acid. In accordance with JIS K7236, the total amount of epoxy equivalent and amine equivalent is calculated by differential titration with perchloric acid. The epoxy equivalent is the total and amine equivalent. It was calculated as the difference between .

(2) Element analysis The values in parentheses are the theoretical values of compound No.6 (epoxy resin)

C: 52.5 mass% (52.9 mass%), H: 8.9 mass% (8.9 mass%), N: 6.9 mass% (6.9 mass%), S: 15.5 mass% (15.7 mass%)

[Example 4]

As the compound of the present invention, 10 parts by mass of compound No. 2 prepared in Example 1, 90 parts by mass of hexyl methacrylate as another monomer, 5.0 parts by mass of 2,2-dimethoxyacetophenone as a polymerization initiator, and 2,2' -Azobis(2,4-dimethylvaleronitrile) 1.0 parts by mass was mixed to prepare the curable composition of Example 4. This curable composition was applied onto a glass plate, covered with a cover film, irradiated with a high-pressure mercury lamp at an output of 3 mW/cm2 for 660 seconds, left to stand in a 50°C oven for 12 hours, and completely cured to obtain a coating film sample. The obtained coating film sample was scratched with a 4B pencil, left to stand in an oven at 120°C, and the scratches were observed under a microscope over time. As a result, disappearance of the scratches was confirmed in 2 hours.

[Comparative Example 1]

Except that ethoxylated bisphenol A methacrylate (NK Ester BPE-200, manufactured by Shinnakamura Chemical Industries, Ltd.) was used instead of compound No. 2, the curable composition of Comparative Example 1 was prepared in the same manner as in Example 4, and a coating film sample was prepared. got it The obtained coating sample was scratched with a 4B pencil, left to stand in an oven at 120°C, and the scratches were observed under a microscope over time. As a result, it was confirmed that the scratches remained even after 3 hours. became

[Example 5, Example 6, Comparative Example 2 and Comparative Example 3]

A curable composition was prepared by mixing an epoxy resin containing compound No. 6 obtained in Example 3 as a main component, the following compounds a and b as other monomers, and the following compound c as a curing agent in the formulation shown in Table 1 below. did. After apply|coating the obtained curable composition on a glass plate, a cover film was covered, it left still in a 120 degreeC oven for 42 hours, and it hardened and obtained the coating film sample. The obtained coating film sample was scratched with a 2H pencil, left to stand in an oven at 60°C, and the scratches after 16 hours, 24 hours, and 40 hours were observed under a microscope with a magnification of 10x. Cases where the scratches disappeared during observation using a microscope were evaluated as 「○」, and cases where the scratches disappeared with the naked eye, but scratches could be confirmed during observation using a microscope were evaluated as 「△」, and when the scratches were visible with the naked eye, the Cases where scratches could be identified were evaluated as “×”. The evaluation results are shown in Table 1.

Compound a (other monomer): dicyclopentadienedimethanol diglycidyl ether

Compound b (other monomer): 2,2-dimethyl-1,3-propanediol diglycidyl ether

Compound c (prepared by curing): 2-ethyl-4-methylimidazole

From the above results, according to the present invention, a material having excellent self-healing ability can be obtained by using an epoxy resin obtained by reacting the compound represented by formula (1) or the compound represented by formula (2) with epihalohydrins. You can.

Claims (9)

A compound represented by the following formula (1).

(In formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a polymerizable functional group with 1 to 50 carbon atoms, or an alkyl group with 1 to 50 carbon atoms. The alkyl group may have a hetero atom. A part of the methylene group in the alkyl group may be substituted with an ether bond, thioether bond, ester bond, amide bond, imide bond or carbonyl group. A part of the hydrogen atom in the alkyl group may be substituted with a halogen atom. n1 represents an integer from 1 to 10. At least one of R ¹ , R ² , R ³ and R ⁴ represents a polymerizable functional group having 1 to 50 carbon atoms. However, , R ¹ , R ² , R ³ and R ⁴ are connected to form a ring structure.) According to claim 1,
The polymerizable functional group having 1 to 50 carbon atoms is vinyl group, allyl group, acrylic group, methacryl group, hydroxy group, isocyanate group, amino group, amide group, epoxy group, oxetanyl group, episulfide group, and carboxyl group. , a group in which a hydrocarbon group is connected to a functional group selected from the group consisting of a heteroaryl group, a thiol group, a group containing a carboxylic acid anhydride structure, and a group containing a cyclic imide structure, and a portion of the methylene group in the hydrocarbon group is, A compound that may be substituted with an ether bond, thioether bond, ester bond, amide bond, imide bond, or carbonyl group, and part of the hydrogen atoms in the polymerizable functional group may be substituted with a halogen atom. According to claim 1,
A compound in which the polymerizable functional group having 1 to 50 carbon atoms is a group represented by the following formula (L-1).

(In formula (L-1), L ¹ and L ² each independently represent an alkanediyl group having 1 to 5 carbon atoms. n represents an integer from 0 to 5. When n is an integer of 2 or more. , a plurality of L ¹ may have the same contribution or different contributions. * indicates the bonding position with the nitrogen atom in formula (1).) A curable composition containing the compound according to any one of claims 1 to 3. According to claim 4,
A curable composition further containing at least one member selected from the group consisting of a curing agent and a polymerization initiator. According to claim 5,
A curable composition wherein the curing agent is at least one selected from the group consisting of amine compounds, amide compounds, acid anhydride compounds, thiol compounds, phenol compounds, imidazole compounds, and latent curing agents. According to claim 5,
A curable composition wherein the polymerization initiator is a cationic polymerization initiator or a radical polymerization initiator. According to claim 4,
A curable composition that is a self-repairing material, surface coating agent, paint, adhesive, or battery material. A cured product obtained by curing the curable composition according to claim 4.