TW202311205A - Compound, curable composition, and cured product - Google Patents

Abstract

The present invention provides a compound which is represented by formula (1). (In formula (1), each of R1, R2, R3 and R4 independently represents a hydrogen atom, a polymerizable functional group having 1 to 50 carbon atoms or an alkyl group having 1 to 50 carbon atoms; the alkyl group may have a heteroatom; some methylene groups in the alkyl group may be substituted by an ether bond, a thioether bond, an ester bond, an amide bond, an imide bond or a carbonyl group; some hydrogen atoms in the alkyl group may be substituted by a halogen atom; n1 represents an integer of 1 to 10; and at least one of the R1, R2, R3 and R4 moieties represents a polymerizable functional group having 1 to 50 carbon atoms; provided that the cases where any two of the R1, R2, R3 and R4 moieties combine with each other to form a ring structure are excluded.).

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-healing materials, surface coating agents, paints, adhesives, or materials for batteries.

Although polymer materials exhibit high mechanical strength or high durability based on strong covalent bonds, they lack reworkability or reusability, so it is difficult to repair scratches or fractures, especially difficult to self-repair. As a self-healing material that is excellent in durability or reworkability and is easy to repair, there are known methods based on intermolecular interactions such as host-guest interactions (see, for example, Patent Documents 1 and 2), or by using bonds in Self-healing materials with catenary chains on the cross-linked polymer structure (see, for example, Patent Document 3), microcapsules in which polymerizable monomers or catalysts are mixed into a matrix of resin materials, etc., are accompanied by damage to the microcapsules, etc. When the matrix is damaged, it will be replaced by new monomer components and polymerized, thereby restoring the function of the matrix (see, for example, Patent Documents 4 and 5). However, the methods of Patent Documents 1 to 3 require complicated steps in the production of materials, and the methods of Patent Documents 4 and 5 have the problem that the number of times of self-repair is limited due to the amount of microcapsules blended. Also, in order to solve these problems in recent years, a self-healing material using reversible bond dissociation-rebonding is known by applying an external stimulus to a material using a dynamic covalent bond (see, for example, Patent Document 6 and Non-Patent Document 6). Literature 1). [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2013/162019 [Patent Document 2] International Publication No. 2016/006413 [Patent Document 3] International Publication No. 2007/069765 [Patent Document 4] International Publication No. 2014/201290 [Patent Document 5] Japanese Patent Laid-Open No. 2017-218519 [Patent Document 6] Japanese Patent Laid-Open No. 2017-202980 [Non-patent literature]

[Non-Patent Document 1] A. Takahashi, R. Goseki, K. Ito, H. Otsuka, ACS Macro Letters, 6, 1280(2017).

[Problem to be Solved by the Invention]

However, the self-healing power of the self-healing materials described in Patent Documents 1 to 6 and Non-Patent Document 1 is not sufficient. Therefore, the present invention was made in view of the above-mentioned problems and situations, and an object of the present invention is to provide a material having excellent self-healing ability. [Means to solve the problem]

In order to solve the above-mentioned problems, the inventors of the present invention intensively studied the causes of the above-mentioned problems and found that a compound having a specific structure can solve the above-mentioned problems, and thus arrived at the present invention. That is, the present invention is as shown in the following [1] to [9].

[1] 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 also have heteroatoms. Part of the methylene group in the alkyl group may be substituted by an ether bond, thioether bond, ester bond, amide bond, imide bond or carbonyl. Part of the hydrogen atoms in the alkyl group may be substituted by 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, any two of R ¹ , R ² , R ³ and R ⁴ are removed to form a compound having a ring structure.

[2] The compound as described in [1], wherein the polymerizable functional group having 1 to 50 carbon atoms is selected from the group consisting of vinyl, allyl, acryl, methacryl, hydroxyl, isocyanate, amine, Amide group, epoxy group, epoxypropylene group, episulfide group, carboxyl group, heteroaryl group, mercapto group, groups containing carboxylic acid anhydride structures and groups containing cyclic imide structures and hydrocarbon groups A group formed by bonding, a part of the methylene group in the hydrocarbon group can also be substituted by an ether bond, a thioether bond, an ester bond, an amide bond, an imide bond or a carbonyl group, and the hydrogen in the polymerizable functional group Part of the atoms may also be replaced by halogen atoms.

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

In the 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, L ¹ of the plural number may be the same base or different bases. * represents the bonding position with the nitrogen atom in the formula (1).

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

[5] The curable composition according to [4], further comprising 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 of [4], which is a self-healing material, surface coating agent, paint, adhesive, or battery material. [9] A cured product obtained by hardening the curable composition described in [4]. [Invention effect]

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

Embodiments of the present invention will be described in detail below. First, the compound of the present invention will be described. Furthermore, in this specification, a compound having an oxirane (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).

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 also have heteroatoms. Part of the methylene group (-CH ₂ -) in the alkyl group may also be substituted by an ether bond, thioether bond, ester bond, amide bond, imide bond or carbonyl. Part of the hydrogen atoms in the alkyl group may be substituted by 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, any two of R ¹ , R ² , R ³ and R ⁴ are removed to form a compound having a ring structure.

In the present specification, examples of heteroatoms include nitrogen atoms, oxygen atoms, silicon atoms, fluorine atoms, sulfur atoms, phosphorus atoms, aluminum atoms, and selenium atoms.

In view of the ease of purification of the compound, n1 is preferably an integer of 1 to 4, more preferably 1.

As an alkyl group having 1 to 50 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ in formula (1), for example, methyl, ethyl, propyl, isopropyl, butyl base, sec-butyl, isobutyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, isopentyl, hexyl, 2-hexyl, 3-hexyl, cyclopentyl, cyclohexyl, Heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl (lauryl), Tridecyl, tetradecyl (myristyl), pentadecyl, hexadecyl (palmityl), heptadecyl, octadecyl (stearyl), eicosyl, hexadecyl, di Dodecyl, 23 bases, 24 bases, 25 bases, 26 bases, 27 bases, 28 bases, 29 bases or 30 bases (myricyl, Wax acid group (mericyl)) and so on.

Examples of polymerizable functional groups having 1 to 50 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ in formula (1) include, for example, those selected from vinyl, allyl, and acryl groups. , methacryl group, hydroxyl group, isocyanate group, amine group, amido group, epoxy group, epoxypropylene group, episulfide group, carboxyl group, heteroaryl group, mercapto group, group containing carboxylic acid anhydride structure and containing ring The base formed by linking the functional group formed by the base of the imide structure and the hydrocarbon group. Part of the methylene group (-CH ₂ -) in the hydrocarbon group can also be substituted by an ether bond, thioether bond, ester bond, amide bond, imide bond or carbonyl group, polymerizable with 1 to 50 carbon atoms Part of the hydrogen atoms in the functional group may be substituted by a halogen atom.

The isocyanate group as the active group is represented by -N=C=O.

The amine group as the active 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. Examples of the alkyl group include those having 1 to 6 carbon atoms among the alkyl groups exemplified as R ¹ , R ² , R ³ and R ⁴ . From the standpoint of exhibiting more excellent self-healing ability, R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, preferably a hydrogen atom, methyl or ethyl.

The amido group as an active 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. Examples of the alkyl group include those having 1 to 6 carbon atoms among the alkyl groups exemplified as R ¹ , R ² , R ³ and R ⁴ . From the viewpoint of exhibiting more excellent self-healing ability, R ¹¹ and R ¹² are each independently preferably a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, preferably a hydrogen atom, a methyl group or an ethyl group.

The carboxyl group as an active group may be a group including a compound having a carboxyl group in its structure. Examples of compounds having a carboxyl group include dicarboxylic acid compounds such as maleic acid, succinic acid, phthalic acid, fumaric acid, glutaric acid, adipic acid, and itaconic acid, or dicarboxylic acid compounds such as citric acid or aconitic acid. Tricarboxylic acid compounds, etc.

As the heteroaryl group as the active group, for example, thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1 ,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiazolyl Oxadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, oxazole- 2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 1,2,4-triazole -3-yl, 1,2,4-triazol-5-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5-yl, tetrazolyl, 2- Pyrazin-2-yl, pyrazin-4-yl, pyrazin-5-yl, 2-pyrimidin-2-yl, 4-pyrimidin-2-yl, 5-pyrimidin-2-yl, etc.

As the active group containing a carboxylic anhydride structure, for example, anhydrous maleic acid, anhydrous succinic acid, anhydrous phthalic acid, anhydrous glutaric acid, anhydrous adipic acid or anhydrous itaconic acid in the structure Contains carboxylic acid anhydride groups.

As the group containing a cyclic imide structure as the active group, for example, compounds containing a cyclic imide in the structure, such as maleimide, succinimide, or phthalimide, can be mentioned. foundation.

Part of the hydrogen atoms in the active groups of the compounds of the present invention may also be substituted by halogen atoms, alkyl groups, alkenyl groups or combinations thereof.

The hydrocarbon group linked to the active group serves to link the active group to the nitrogen atom of the compound represented by formula (1). Examples of the hydrocarbon group include linear alkyl groups, branched alkyl groups, and alkyl groups containing alicyclic compounds. Part of the methylene group in the hydrocarbon group may be substituted by an ether bond, thioether bond, ester bond, amide bond, imide bond or carbonyl. Part of the hydrogen atoms in the hydrocarbon group may be substituted by halogen atoms.

Examples of the alicyclic compound in the hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cycloundecane or cyclododecane Monocyclic alkanes such as bicycloundecane, decahydronaphthalene, decahydronaphthalene or norbornane, etc. Tetracycloalkanes such as octacosane or tetracyclotridecane, etc.

Among the polymerizable functional groups with 1 to 50 carbon atoms, the connection between the active group and the hydrocarbon group is through: replacing a part of the hydrogen atoms in the hydrocarbon group with the above-mentioned active group; epoxy group, epoxypropylene group, episulfide ( The functional group having a saturated alicyclic structure such as an episulfide) group and the alicyclic compound in the hydrocarbon group share a part of the ring to form a condensed ring; or, the functional group having a saturated alicyclic structure is separated from the alicyclic compound in the hydrocarbon group It is carried out by combining some carbon atoms to form a spiro structure. In one polymerizable functional group with 1 to 50 carbon atoms, there may be a plurality of sites for linking the functional group and the hydrocarbon group. In the case where one polymerizable functional group having 1 to 50 carbon atoms has a plurality of sites for linking the functional group and the hydrocarbon group, the individual linking structures may be the same or different.

From the viewpoint that the effect of the present invention becomes remarkable, in the compound of the present invention, the functional group is a carbon atom having an acryl group, a methacryl group, an epoxy group, a propylene oxide group, an episulfide group or a hydroxyl group. A polymerizable functional group with a number of 1-50 is preferable, and a polymerizable functional group with an acryl group, a methacryl group, an epoxy group or a hydroxyl group with a carbon number of 1-50 is more preferable.

Specific examples of polymerizable functional groups with preferably 1 to 50 carbon atoms include, for example, hydroxyethyl, acryloxyethyl, methacryloxyethyl, allyl, 2-( 7-oxabicyclo[4.1.0]hept-3-yl)acetate ethyl, 2-(4-methyl-7-oxabicyclo[4.1.0]hept-3-yl)acetate ethyl Base, 2-(3-oxatricyclo[3.2.1.0 ^2.4 ]oct-6-yl)ethyl acetate, 1H-imidazole-1-carboxylate ethyl, glycinate ethyl, methyl Ethyl glycinate, ethyl dimethylglycinate, ethyl piperidine-4-carboxylate, ethyl thioglycolate, methoxyethyl isocyanate, 2,5-dioxatetrahydrofuran -3-Carboxylate ethyl, 1,3-dioxa-1,3-dihydroisobenzofuran-5-carboxylate-ethyl, 2-(thiapropane-2-ylmethoxy ) ethyl group, methacryloxyethylaminocarbonyloxyethyl group, a group represented by the following formula (L-1), etc. Among these, from the viewpoint that the effect of the present invention becomes remarkable, a group represented by the following formula (L-1) is preferable as the polymerizable functional group having 1 to 50 carbon atoms.

In the 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 be the same group or different groups. n represents an integer from 0 to 5. When n is an integer of 2 or more, the plural L ¹ may be the same group or different groups. * represents the bonding position with the nitrogen atom in the formula (1).

Examples of the alkanediyl groups having 1 to 5 carbon atoms represented by ^L1 and ^L2 include methanediyl, 1,2-ethanediyl, 1,2-propanediyl, 1,3- Propanediyl, 1,4-butanediyl, 1,5-pentanediyl, etc. From the point of view that the effect of the present invention becomes remarkable, the ^L1 and ^L2 systems each independently have methanediyl, 1,2-ethanediyl, 1,2-propanediyl or 1,3-propanediyl A compound having a polymerizable functional group is preferred, and a compound in which L ¹ and L ² are each independently a polymerizable functional group having a 1,2-ethanediyl group or a 1,2-propanediyl group is preferred.

From the standpoint that the effect of the present invention becomes remarkable, n is preferably an integer of 0-3, more preferably an integer of 0-2, most preferably 0 or 1.

Specific examples of the group represented by formula (L-1) include, for example, glycidoxymethyl, glycidoxyethoxyethyl, glycidoxyethoxyethoxy Ethyl or glycidoxy isopropoxy isopropyl, etc. Among them, a glycidoxyethyl group or a glycidoxyethoxyethoxyethyl group is preferable from the viewpoint that the effect of the present invention becomes remarkable.

From the viewpoint of obtaining compounds with more excellent self-healing ability, the number of carbon atoms in the polymerizable functional group is preferably in the range of 1-30, more preferably in the range of 1-20, and more preferably in the range of 1-10 .

From the viewpoint of obtaining a compound with more excellent self-healing ability, at least two of R ¹ , R ² , R ³ and R ⁴ are preferably polymerizable functional groups with 1 to 50 carbon atoms, and R ¹ , R ^2. Two of R ³ and R ⁴ are preferably polymerizable functional groups with 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, the individual polymerizable functional groups may be the same or different. When at least two of R ¹ , R ² , R ³ and R ⁴ are polymerizable functional groups with 1 to 50 carbon atoms, from the viewpoint of obtaining a compound with more excellent self-healing ability, R ¹ and R ² At least one of ^R3 and ^R4 is preferably a polymerizable functional group having 1 to 50 carbon atoms.

Also, the combination of ^R1 and ^R2 may be different from the combination of ^R3 and ^R4 , but they are preferably the same from the viewpoint of obtaining a compound with a more excellent self-healing ability.

Furthermore, the combination of ^R1 and ^R2 is the same compound as the combination of ^R3 and ^R4 , for example, compounds No.1 to No.3, No.5 to No.10, and No. 12~No.19, No.21~No.23, No.25 and No.26. Also, the combination of R ¹ and R ² is different from the combination of R ³ and R ⁴ , for example, compounds No. 4, No. 11, No. 20 and No. 24 described below.

Specific examples of the compound represented by the above formula (1) include the following No.1 to No.26, but the present invention is not limited to these compounds. Also, "tBu" means tert-butyl.

The compound represented by formula (1) can be obtained by, for example, adding sodium acetate and dimethylformamide to an amino compound having a polymerizable functional group with carbon atoms of 1 to 50, and dropping dichloride dichloride under a nitrogen environment. Sulfur, the method of filtering and separating the produced precipitate and recovering it, washing with water and concentrating to produce the desired compound, or making the diaminodisulfide compound having a hydroxyl group and the corresponding one having 1 to 50 carbon atoms It is produced by reacting the compound of the polymerizable reactive group.

More specifically, in the case of producing the above compound No.1, after adding 2-(tert-butylamino)ethyl methacrylate, sodium acetate and dimethylformamide to the reaction vessel, It is obtained by dropping sulfur dichloride to react, distilling off the solvent, extracting with butyl acetate and water, washing with water, and drying.

The compound of the present invention has a polythioether skeleton, and since the chemical bond between the sulfur atoms of the polythioether skeleton is easily broken and rebonded by heating or light irradiation, it can exhibit excellent self-healing ability. In addition, the compound of the present invention can be produced by a simple method. Excellent self-healing ability means, for example, that it can self-repair even if the damage is large; the number of self-repairs can be large; after self-repairing from the damaged state, it can still restore sufficient mechanical strength; etc. performance. In particular, the compounds of the present invention have excellent self-healing power capable of restoring back to the strength of the material before damage. In addition, a material having self-healing power can be expected to have the effect of alleviating the stress generated during hardening.

＜Epoxy resin＞ The compounds of the present invention can be used to make epoxy resins. For example, an epoxy resin can be manufactured by the manufacturing method which has the process of making the compound represented by following formula (2) react with epihalohydrins (epihalohydrins). In the present invention, the epoxy resin includes not only the products and by-products produced when the compound represented by the formula (2) is reacted with epihalohydrins, but also the compound represented by the formula (2) or the epihalohydrin as a raw material. Alcohols as ingredients. In the present invention, the product obtained by reacting the compound represented by the formula (2) with epihalohydrins is represented by the above formula (1) containing an epoxy group, since the effect of the present invention will become remarkable. compounds are preferred.

(In formula (2), R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group with 1 to 50 carbon atoms that may have a hydroxyl group. The alkyl group may also have a heteroatom. The alkane A part of the methylene group in the group can also be substituted by an ether bond, a thioether bond, an ester bond, an amide bond, an imide bond or a carbonyl group. A part of the hydrogen atom in the alkyl group can also be substituted by a halogen atom .n2 represents an integer of 1 to 10. At least one of ^{R 5} , R ⁶ , R ⁷ and R ⁸ represents an alkyl group with 1 to 50 carbon atoms having a hydroxyl group. However, removing R ⁵ , R ⁶ , R ⁷ and R Any two of ⁸ are connected to form a compound with a ring structure.)

The alkyl groups having 1 to 50 carbon atoms represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ in the formula (2) include, for example, those represented by R ¹ , R ² , R ³ and R ⁴ The examples of the alkyl group having 1 to 50 carbon atoms are the same. The C1-50 alkyl groups having hydroxyl groups represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ represent groups in which a part of the hydrogen atoms in the above-mentioned alkyl groups are substituted by hydroxyl groups. The alkyl group may also have a heteroatom, and a part of the methylene group in the alkyl group may also be substituted by an ether bond, a thioether bond, an ester bond, an amide bond, an imide bond or a carbonyl group, and the hydrogen in the alkyl group Part of the atoms may also be substituted by halogen atoms. From the standpoint of excellent properties of the cured product, at least one of ^R5 and ^R6 , and at least one of ^R7 and ^R8 is preferably an alkyl group with 1 to 50 carbon atoms having a hydroxyl group.

In view of the ease of purification of the compound, n2 is preferably an integer of 1 to 4, more preferably 1.

Examples of the epihalohydrins include epichlorohydrin, β-methylepichlorohydrin, epibromohydrin, and β-methylepibromohydrin. Among them, epichlorohydrin is preferable from the viewpoint of easy acquisition and economical efficiency.

As a specific example of the production method of epoxy resin, for example, in the presence of a base, a Lewis acid or a phase transfer catalyst, as shown in the following reaction formula 1, the compound represented by the formula (2) is combined with the Chlorohydrin reaction method. From the standpoint of increasing the yield of epoxy resin, it is better to carry out the above reaction under the condition of 20°C~100°C, more preferably under the condition of 30°C~80°C. Furthermore, in the following reaction formula 1, 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 1-50.

As a base used for the said reaction, the base etc. which are described in Japanese Patent No. 5698072 are mentioned, for example. Examples of the Lewis acid and phase transfer catalyst used in the above reaction include those described in Japanese Patent No. 5698072 and the like.

In addition, conventionally known solvents can be used in the above reaction. As a solvent which can be used for the said reaction, the solvent etc. which are described in Japanese Patent No. 5698072 are mentioned, for example.

The usage amount of the epihalohydrin in the manufacture method of epoxy resin of the present invention is from the viewpoint that can obtain high-purity epoxy resin, relative to the contained hydroxyl group 1 mole of the compound shown in formula (2), It is preferably in an amount of 1 mole or more, more preferably in an amount of 1 mole to 20 moles. The use amount of the above-mentioned base is from the viewpoint of obtaining high-purity epoxy resin, relative to 1 mole of hydroxyl contained in the compound represented by formula (2), it is better to become the amount of 0.1 mole to 2.0 mole , preferably in an amount of 0.3 mol to 1.5 mol. The use amount of the above-mentioned Lewis acid or phase transfer catalyst is from the viewpoint of obtaining high-purity epoxy resin, relative to the amount of hydroxyl groups contained in the compound represented by formula (2), to become 0.01 mol % ~ 10 mol The amount of mol% is preferable, and the amount of 0.2 mol% to 5 mol% is more preferable.

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

Examples of the unsaturated monobasic acid used here include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate maleate, hydroxyethyl acrylate Maleate, hydroxypropyl methacrylate・maleate, hydroxypropylacrylate・maleate, dicyclopentadiene・maleate, or one carboxyl group and two or more ( Multifunctional (meth)acrylate of meth)acryl group, etc. In this specification, (meth)acrylate means acrylate or methacrylate, and (meth)acryl means acryl or methacryl.

As a polyfunctional (meth)acrylate which has the said 1 carboxyl group and 2 or more (meth)acryl groups, the following compound etc. are mentioned, for example.

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

＜Hardening composition＞ Next, the curable composition of the present invention will be described. The curable composition of the present invention contains the compound represented by formula (1) (hereinafter also referred to as "the compound of the present invention"). The curable composition of the present invention may further contain a component capable of reacting with the compound of the present invention to form a cured product, preferably at least one selected from the group consisting of a curing agent and a polymerization initiator. In addition, the curable composition of the present invention may contain monomers other than the compound of the present invention (hereinafter also referred to as "other monomers") as curable monomers.

The curable composition of the present invention contains a compound having a polymerizable functional group with 1 to 50 carbon atoms whose functional group in formula (1) is an epoxy group, an episulfide group or a propylene oxide group as a curable unit. In the case of a solid body, a known hardener capable of reacting with an epoxy group, an episulfide group or a propylene oxide group may be included. As a curing agent, it is preferable to use an amine compound, an amide compound, an acid anhydride compound, a mercaptan compound, a phenol compound, an imidazole compound or a latent curing agent because the curing reaction of the curable composition of the present invention is accelerated. The curing agent may be used alone or in combination of two or more.

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

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

As an acid anhydride compound which is the said hardening|curing agent, the acid anhydride compound described in international publication 2020/175321 is mentioned, for example.

Examples of the thiol compound of the curing agent include aliphatic thiol compounds, aromatic thiol compounds, aliphatic polythiol compounds, mercaptocarboxylate compounds, mercaptocarboxylic acids, and mercaptoethers. Among them, difunctional thiol compounds are preferable from the viewpoint that the cured product exhibits excellent self-healing power. Examples of the bifunctional thiol compound include compounds described in International Publication No. 2020/175321. Also, from the viewpoint of heat resistance, a thiol compound represented by the following formula (3) is preferable.

In formula (3), A represents an alkylene group having 1 to 10 carbon atoms, m3 represents an integer of 1 to 6, and ^X1 represents a saturated hydrocarbon group having 1 to 20 carbon atoms having the same valence as m3.

The saturated hydrocarbon group with 1 to 20 carbon atoms having the same valence as m3 represented by ^X1 represents, for example, methane, ethane, propane, isopropane, butane, isobutane, pentane, hexane, C1-20 alkanes such as heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane or eicosane, and carbon number 3 ~20 alicyclic compounds or their combination, removing the same number of hydrogen atoms as m3. The alicyclic compound means the aforementioned alicyclic compound satisfying the specified number of carbon atoms.

Examples of the phenolic compound as the curing agent include phenolic 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-tri oxazine, 2-phenylimidazoline, 2,3-dihydro-1H-pyrrole[1,2-a]benzimidazole, imidazole compounds described in JP-A-2015-017059, etc.

As the latent curing agent as the above-mentioned curing agent, for example, a denatured amine latent curing agent having at least one amine group having an active hydrogen in the molecule obtained by reacting a polyamine compound and an epoxy compound, Latent hardeners containing phenolic resins, dicyandiamide, denatured polyamines, hydrazines, 4,4'-diaminodiphenylsulfone, boron trifluoride ammonium zirconium salts, ureas, melamine, Compounds described in International Publication No. 2012/020572 and Japanese Patent Laid-Open No. 2014-177525, etc.

In addition, the curable composition of the present invention contains a compound having a polymerizable functional group with 1 to 50 carbon atoms whose active group in formula (1) is an epoxy group, a propylene oxide group, or an episulfide group as a curable compound. In the case of a permanent monomer, an epoxy compound may be further included as another monomer.

As said epoxy compound, an alicyclic epoxy compound, an aromatic epoxy compound, an aliphatic epoxy compound etc. are mentioned, for example.

As said alicyclic epoxy compound, the compound etc. which were described in international publication 2019/138953 are mentioned, for example. Examples of commercially available alicyclic epoxy compounds include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200 (the above are manufactured by Union Carbide), Ceroxide 2021, and Ceroxide 2021P. , Ceroxide 2081, Ceroxide 2083, Ceroxide 2085, Ceroxide 2000, Ceroxide 3000, Cyclomer A200, Cyclomer M100, Cyclomer M101, Epolead GT-301, Epolead GT-302, Epolead 401, EpoleadHPE403, ETHB, 30E1 , (shares) made by Daicel), etc. Among alicyclic epoxy compounds, epoxy compounds having a cyclohexene oxide structure are preferred because they harden quickly.

As said aromatic epoxy compound, the compound etc. which were described in international publication 2019/138953 are mentioned, for example. Examples of commercially available aromatic epoxy compounds include Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncoat EX- 1020, Oncoat EX-1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (manufactured by Nagase Chemical Co., Ltd.); OGSOLPG-100, OGSOLEG -200, OGSOLEG-210, OGSOLEG-250 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC Co., Ltd.); ESN-475V (manufactured by Nippon Steel Chemical & Materials Co., Ltd.) ; Epikote YX8800 (manufactured by Mitsubishi Chemical Corporation); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation); EpiclonN-665, EpiclonHP-7200 (manufactured by DIC Corporation); EOCN- 1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (Nippon Kayaku Co., Ltd.); Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (manufactured by ADEKA Corporation); or TECHMORE VG-3101L (manufactured by Printec Corporation).

As said aliphatic epoxy compound, the compound etc. which were described in international publication 2019/138953 are mentioned, for example. Examples of commercially available aliphatic epoxy compounds include Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, 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 Chemical Co., Ltd.); Epolight M-1230, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP , Epolight 1600, Epolight 80MF, Epolight 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Glycyllol ED-503, Adeka Glycyllol ED-503G, Adeka Glycyllol ED-506, Adeka Glycyllol ED-523T, Adeka Resin EP-4088S , or Adeka Resin EP-4080E (manufactured by ADEKA Corporation), etc.

In addition, as the epoxy compound, a urethane-modified epoxy compound provided with a urethane skeleton can also be used. The urethane-modified epoxy compound has an epoxy group and a urethane bond in the molecule, for example, by reacting an epoxy compound having a hydroxyl group in the molecule with a compound having an isocyanate group. obtain.

In addition, the curable composition of the present invention contains a compound having a polymerizable functional group with 1 to 50 carbon atoms whose active group in formula (1) is an epoxy group, a propylene oxide group, or an episulfide group as a curable compound. In the case of non-reactive monomers, monomers such as compounds having unsaturated hydrocarbon groups may be further contained as other monomers within the range that does not adversely affect the effects of the present invention.

The above-mentioned compound having an unsaturated hydrocarbon group can be used without particular limitation as long as it is a known and generally used compound capable of copolymerizing with a vinyl group, an acryl group or a methacryl group. For example, a compound which has a vinyl group, a compound which has an allyl group, an acrylate compound, or a methacrylate compound etc. are mentioned.

As a compound which has the said vinyl group and an allyl group, the compound etc. which are described in international publication 2020/175321 are mentioned, for example.

As said acrylate compound, a monofunctional acrylate compound, a difunctional acrylate compound, or a trifunctional or more polyfunctional acrylate compound is mentioned, for example.

As said monofunctional acrylate compound, said bifunctional acrylate compound, and said polyfunctional acrylate compound, the compound etc. which were described in international publication 2020/175321 are mentioned, for example.

As said methacrylate compound, a monofunctional methacrylate compound, a difunctional methacrylate compound, or a trifunctional or more polyfunctional methacrylate compound is mentioned, for example.

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

The curable composition of the present invention contains a compound having a polymerizable functional group with 1 to 50 carbon atoms whose functional group in formula (1) is an epoxy group, a propylene oxide group or an episulfide group as a curable unit. In the case of solids, from the viewpoint of suppressing the amount of unreacted hardening monomer and hardening agent in the remaining hardened product, the blending amount of the above hardening agent is 0.01~2.0 moles relative to 1 mole of hardening monomer The amount of ear is better.

When the curable composition of the present invention contains a compound having a polymerizable functional group having 1 to 50 carbon atoms whose functional group is a hydroxyl group in formula (1) as a curable monomer, it may further contain a compound capable of reacting with a hydroxyl group. Known hardeners. As the curing agent, it is preferable to use the above-mentioned epoxy compound, the above-mentioned latent curing agent, or an isocyanate compound because the curing reaction of the curable composition of the present invention will be accelerated. The curing agent may be used alone or in combination of two or more.

The isocyanate compounds of the above-mentioned curing agent include, for example, monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; hexamethylene diisocyanate, 2,4-toluene diisocyanate, Isocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylene diisocyanate, p-phenylene diisocyanate, 1, Polyfunctional isocyanate compounds such as 3,6-hexamethylene triisocyanate and dicycloheptane triisocyanate, or terminal isocyanate groups obtained by reacting polyfunctional isocyanate compounds with active hydrogen compounds such as trimethylolpropane compounds etc. From the viewpoint that the curing reaction of the curable composition of the present invention becomes favorable, the isocyanate compound blended in the curable composition of the present invention is preferably a compound having multiple isocyanate groups, such as hexamethylene diisocyanate, isocyanate Phorne diisocyanate or xylene diisocyanate is preferred.

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

The above-mentioned polyalcohol compound refers to a compound having two or more hydroxyl groups in the molecule, and the hydroxyl groups may be alcoholic or phenolic. Specifically, the compound described in International Publication No. 2020/175321, etc. are mentioned.

In addition, 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 is a hydroxyl group in formula (1), it does not affect the effect of the present invention. In the range where adverse effects are produced, curable monomers such as the above-mentioned compounds having unsaturated hydrocarbon groups may be further contained as other monomers.

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 is a hydroxyl group in formula (1), it is possible to suppress the remaining in the cured product. From the viewpoint of the usage amount of the unreacted hardening monomer and the hardening agent, the blending amount of the above hardening agent is preferably 0.5~2.0 moles relative to 1 mole of the hydroxyl group contained in the hardening monomer. The equivalent amount is preferable.

When the curable composition of the present invention contains a compound having a polymerizable functional group having 1 to 50 carbon atoms whose functional group is an isocyanate group in formula (1) as a curable monomer, it may further contain Reactive known hardener. As the curing agent, it is preferable to use the above-mentioned phenolic compound or the above-mentioned epoxy compound because the curing reaction of the curable composition of the present invention is accelerated. The curing agent may be used alone or in combination of two or more.

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 is an isocyanate group in formula (1), it does not adversely affect the effect of the present invention. The range of influence may further contain curable monomers such as the above-mentioned compounds having unsaturated hydrocarbon groups as other monomers.

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 is an isocyanate group in the formula (1), it is suppressed from remaining in the cured product. From the viewpoint of the usage amount of the unreacted hardening monomer and the hardener, the blending amount of the above-mentioned hardening agent is 0.5~1.5 mol relative to 1 mol of the functional group of the hardening monomer that can react with the hardening agent. The amount is preferred, and the equivalent amount is preferred.

The curable composition of the present invention contains, as a curable monomer, a compound having a polymerizable functional group with 1 to 50 carbon atoms in which the active group in formula (1) is vinyl, acryl or methacryl. In some cases, a known polymerization initiator may be further included as a component capable of reacting with the compound of the present invention to form a cured product. As a polymerization initiator, a radical polymerization initiator, a cationic polymerization initiator, etc. are mentioned, for example. The polymerization initiator may be used alone or in combination of two or more.

The curable composition of the present invention contains, as a curable monomer, a compound having a polymerizable functional group with 1 to 50 carbon atoms in which the active group in formula (1) is vinyl, acryl or methacryl. In this case, from the viewpoint of making the polymerization reaction of the curable composition progress well and improving the physical properties of the cured product after the reaction, the blending amount of the polymerization initiator is 0.001% by mass to 20% by mass relative to the curable composition. % by mass is preferable, more preferably 0.1% by mass to 10% by mass.

As said radical polymerization initiator, a photo radical polymerization initiator or a thermal radical polymerization initiator is mentioned, for example.

Examples of the photoradical polymerization initiator include acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds, bisimidazole-based compounds, acridine-based compounds, acyl phosphine compounds or oxime ester compounds, etc.

As said acetophenone compound, the compound etc. which are described in international publication 2016/098471 are mentioned, for example.

As said benzyl type compound, the compound etc. which are described in international publication 2016/098471 are mentioned, for example.

As said benzophenone compound, the compound etc. which are described in international publication 2016/098471 are mentioned, for example.

As said thioxanthone compound, the compound etc. which are described in international publication 2016/098471 are mentioned, for example.

Examples of the biimidazole-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 above-mentioned acylphosphine compounds include compounds described in International Publication No. 2019/138953, and the like.

As said oxime ester compound, the compound etc. which were described in international publication 2019/138953 are mentioned, for example.

As said thermal radical polymerization initiator, the compound etc. which were described in international publication 2019/138953 are mentioned, for example.

As the above-mentioned cationic polymerization initiator, any compound may be used as long as it is a compound that releases a substance that initiates cationic polymerization by irradiation with energy rays or heating. Double salts of onium salts that release Lewis acids by irradiation with energy rays, or its derivatives are preferred.

Examples of the onium salt include salts of cations and anions represented by [M] ^r+ [G] ^r- . Here, the cation [M] ^r+ is preferably an onium cation, and its structure can be represented by, for example, the formula [(R ⁹ )fQ] ^r+ .

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

Also, as a specific example of the anion [G] ^r- , as a monovalent one, halide ions such as chloride ion, bromide ion, iodide ion, fluoride ion, etc.; perchlorate ion, chlorine Inorganic anions such as acid ion, thiocyanate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tetrafluoroborate ion, etc.; tetrakis (pentafluorophenyl) borate, tetrakis (3,5-difluoro-4- Methoxyphenyl) borate, tetrafluoroborate, tetraaryl borate, tetrakis (pentafluorophenyl) borate and other borate anions; methanesulfonate ion, dodecylsulfonate ion, benzenesulfonic acid Ion, toluenesulfonate ion, trifluoromethanesulfonate ion, naphthalenesulfonate ion, diphenylamine-4-sulfonate ion, 2-amino-4-methyl-5-chlorobenzenesulfonate ion, 2- Amino-5-nitrobenzenesulfonate ion, phthalocyaninesulfonate ion, fluorosulfonate ion, trinitrobenzenesulfonate anion, camphorsulfonate ion, nonafluorobutanesulfonate ion, hexadecafluorooctane Sulfonate ion, sulfonate ion having a polymerizable substituent, JP-A-10-235999, JP-10-337959, JP-11-102088, JP-2000-108510, JP 2000-168223, JP 2001-209969, JP 2001-322354, JP 2006-248180, JP 2006-297907, JP 8- 253705 Gazette, JP 2004-503379 Gazette, JP 2005-336150 Gazette, International Publication No. 2006/28006 and other organic sulfonic acid anions such as sulfonic acid ions; octyl phosphate ion, dodeca Phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2'-methylene bis(4,6-di-tert-butylphenyl) phosphonic acid ion, etc. Organic phosphoric acid series anion, bistrifluoromethylsulfonyl imide ion, bis perfluorobutanesulfonyl imide ion, perfluoro-4-ethylcyclohexanesulfonate ion, tetrakis (pentafluorophenyl ) borate ion or ginseng(fluoroalkylsulfonyl)carbanion, etc., as divalent ones, for example, benzene disulfonate ion, naphthalene disulfonate ion, etc.

Among such onium salts, it is preferable to use aromatic permeic salts such as aryl diazonium salts, diaryl permeic acid salts, or triaryl permeic acid salts, because the polymerization reaction of the hardening composition of the present invention will become good. .

Aromatic permeicium 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 Arkls SP-056, Adeka Arkls SP-066, Adeka Arkls SP-130, Adeka Arkls SP-140, Adeka Arkls SP-082 , Adeka Arkls SP-103, Adeka Arkls SP-601, Adeka Arkls SP-606, Adeka Arkls SP-701, Adeka Arkls SP-150, Adeka Arkls SP-170 (manufactured by ADEKA Co., Ltd.), etc.

The curable composition of the present invention contains, as a curable monomer, a compound having a polymerizable functional group with 1 to 50 carbon atoms in which the active group in formula (1) is vinyl, acryl or methacryl. In some cases, curable monomers such as the above-mentioned epoxy compound, the above-mentioned polyalcohol compound, and the above-mentioned compound having an unsaturated hydrocarbon group may be further contained as other monomers within the range that does not adversely affect the effect of the present invention.

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 is vinyl, epoxy or propylene oxide in formula (1). In some cases, the above-mentioned cationic polymerization initiator may be further included as a component capable of reacting with the compound of the present invention to form a cured product.

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 is vinyl, epoxy or propylene oxide in formula (1). In some cases, curable monomers such as the above-mentioned epoxy compound and the above-mentioned compound having an unsaturated hydrocarbon group may be further contained as other monomers within the range that does not adversely affect the effect of the present invention.

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 is vinyl, epoxy or propylene oxide in formula (1). In some cases, from the standpoint of making the polymerization reaction of the curable composition proceed well and improving the physical properties of the cured product after the reaction, the blending amount of the above-mentioned cationic polymerization initiator is 0.001% by mass to the curable composition. 20% by mass is preferable, more preferably 0.1% by mass to 10% by mass.

The compounding quantity of the compound of this invention which is a curable monomer, and other monomers in the curable composition of this invention is not specifically limited, It can adjust suitably based on the characteristic etc. required for a cured product. From the viewpoint of easy maintenance of the excellent self-healing ability of the cured product, the total amount of the compound of the present invention as a curable monomer and other monomers is 0.01% by mass to 99.999% by mass relative to the curable composition of the present invention. Better, more preferably 0.05% by mass to 99.9% by mass, more preferably 0.1% by mass to 97% by mass.

Also, the curable composition of the present invention may contain the compound of the present invention as a curing agent. The compound of the present invention as a curing agent can include, for example, a compound having a compound selected from vinyl, acryl, methacryl, hydroxyl, isocyanate, amine, amide, epoxy, epoxypropylene, A compound represented by the formula (1) of an episulfide group, a carboxyl group, a heteroaryl group, a mercapto group, a group including a group having a carboxylic anhydride structure, and a group including a cyclic imide structure.

Furthermore, when the compound of the present invention is used as a curing agent, the amount of the curing agent blended in the above-mentioned curable composition of the present invention is the total amount of the compound of the present invention and known curing agents.

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

As the polymer compound that can be used in the curable composition of the present invention, conventionally known polymer compounds can be used, for example, polymer compounds described in International Publication No. 2020/175321 and the like.

Examples of cured epoxy resins that can be used in the curable composition of the present invention include cured epoxy resins that have been conventionally known.

Examples of cured urethane resins that can be used in the curable composition of the present invention include cured conventionally known urethane resins.

As the rubber component that can be used in the curable composition of the present invention, conventionally known rubber components can be used, for example, rubber components described in International Publication No. 2020/175321 and the like.

The curable composition of the present invention may also contain an organic solvent as a diluent in order to uniformly mix materials, or to ensure good formability and film forming properties of the curable composition of the present invention. The organic solvent is not the compound, other monomers, hardeners or polymerization initiators of the present invention, and is liquid at 25°C and atmospheric pressure.

Examples of organic solvents that can be used in the curable composition of the present invention include 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.

As an alcoholic solvent, the alcoholic solvent etc. which were described in international publication 2020/175321 are mentioned, for example. These alcohol-based solvents may be used alone or in combination of two or more.

As a ketone-type solvent, the ketone-type solvent etc. which are described in international publication 2020/175321 are mentioned, for example. These ketone-based solvents may be used alone or in combination of two or more.

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

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

As an ester type solvent, the ester type solvent etc. which were described in international publication 2020/175321 are mentioned, for example. These ester-based solvents may be used alone or in combination of two or more.

As an aliphatic hydrocarbon solvent, the aliphatic hydrocarbon solvent etc. which are described in international publication 2020/175321 are mentioned, for example. These aliphatic hydrocarbon-based solvents may be used alone or in combination of two or more.

As an aromatic hydrocarbon solvent, the aromatic hydrocarbon solvent etc. which are described in international publication 2020/175321 are mentioned, for example. These aromatic hydrocarbon solvents may be used alone or in combination of two or more.

As a halogen-containing solvent, the halogen-containing solvent of International Publication No. 2020/175321, etc. are mentioned, for example. These halogen-containing solvents may be used alone or in combination of two or more.

In the curable composition of the present invention, the above-mentioned organic solvents may be used alone or in combination of two or more. The type or blending amount of these organic solvents can be appropriately selected according to the viscosity of the curable composition, the shape to be molded, and the like. From the viewpoint of the ease of handling of the curable composition of the present invention, relative to the curable composition of the present invention, the blending amount of the organic solvent is preferably 0.1% by mass to 90% by mass, and preferably 0.5% by mass to 80% by mass. % is better, more preferably 10% by mass to 70% by mass.

In addition, as long as the effects of the present invention are not impaired, ultraviolet absorbers, light stabilizers, adhesive additives, polymerization inhibitors, sensitizers, antioxidants, smoothness imparting agents, alignment control agents, infrared absorbers, etc. agent, thixotropic agent, antistatic agent, defoamer, colorant, emulsifier, surfactant, conductivity imparting agent, hydrolysis inhibitor, cellulose nanofiber, polymerization catalyst or filler, etc. Known additives are blended into the curable composition of the present invention at known contents and using methods.

The use of the curable composition of the present invention is not particularly limited, and it can be suitably used as a self-healing material. Self-healing materials refer to materials that can self-repair scratches or damages without external stimuli, or through specific operations or treatments or external stimuli, when they are scratched or damaged by scratches or blows in the environment in which they are used. s material. External stimuli refer to contact, light irradiation, heat or pressure, etc., and these may be given alone, or two or more kinds of external stimuli may be given sequentially or simultaneously.

The curable composition system 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, imparting design or optical properties to a substrate, controlling surface physical properties, and imparting anti-pollution, chemical resistance, or weather resistance to a substrate. As a method for coating the curable composition of the present invention on the substrate surface, it may be carried out by known methods, for example, die coating (die coating) method, comma coating (comma coating) method , curtain coating method, spray coating method, gravure coating method, flexo coating method, knife coating (knife coating) method, doctor blade coating (doctor blade coating) method, reverse roll method, brush coating method, Dipping method, inkjet method or wire bar coating method, etc. When using the curable composition of the present invention as a surface coating agent, it is sufficient to apply the composition before hardening to the surface of the substrate, and then harden it by the method described later. When the curable composition of the present invention is used as a surface coating agent, paint, adhesive, or battery material, known additives used in surface coating agents, paints, adhesives, or battery materials can also be blended. .

＜hardened material＞ Next, the cured product of the present invention will be described. The cured product of the present invention is obtained by curing the above curable composition. The hardened product of the present invention is not limited by hardness, physical properties, and the like.

As a method of curing the above-mentioned curable composition, for example, after applying the above-mentioned curable composition to a substrate, or after molding the above-mentioned curable composition, the curing of the present invention can be obtained by irradiating energy rays or heating. thing. Irradiation of energy rays and heating may be performed either, may be performed individually and alternately, may be performed simultaneously, or may be performed while changing over time.

When the curable composition of the present invention is cured by irradiating energy rays, examples of energy rays include ultraviolet rays, electron rays, X-rays, radiation rays, high frequency, etc., and ultraviolet rays are preferable from an economic point of view. . As a light source of ultraviolet light, a mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, sunlight, a laser light source, or an LED light source etc. are mentioned, for example. The light source can be properly selected according to the photo-radical initiator optionally added to the curable composition of the present invention. In terms of operability, UV-LED (wavelength: 350~450nm) is preferred. The cumulative exposure dose can be appropriately changed according to the thickness of the object. If the cumulative exposure dose is insufficient, the curing reaction will not proceed sufficiently. If the cumulative exposure dose is too large, the object may be colored. From the viewpoint of making it easier to control the curing reaction, the cumulative exposure dose is preferably in the range of 1 mJ/cm ² to 100,000 mJ/cm ² .

When the curable composition of the present invention is cured by heating, the heating is preferably 200°C or lower, more preferably 140°C or lower, from the viewpoint of easy control of the curing reaction. In addition, from the viewpoint that the curing reaction can proceed favorably, the heating system is preferably at least 40°C, more preferably at least 50°C. The heating can be appropriately selected according to the heating temperature, etc., preferably 1 second to 20 hours, and more preferably 10 seconds to 10 hours.

The pressure in the production of hardened products can usually be carried out at atmospheric pressure, and it can also be carried out by applying pressure under the condition of 1,000 atmospheric pressure. The environment for manufacturing the cured product can be selected according to the composition of the curable composition, etc., and can be in the atmosphere or in an inert gas environment such as nitrogen or argon.

The cured product of the present invention may be produced by molding and curing a curable composition without using an organic solvent, or may be produced by molding and curing the curable composition after adjusting the viscosity of the curable composition using an organic solvent. In addition, a solvent may be used to dissolve or swell the produced cured product to perform molding and film formation. Moreover, it is also possible to produce a cured product in a state of being emulsified or dispersed in water by aqueous emulsion polymerization or suspension polymerization.

As the use of the hardened product of the present invention, it can be suitably used, for example, in sealing materials, heat insulating materials, soundproofing materials, coating agents, sanitary materials, hose clamps, fluid conveying pipes, hoses, hot-melt adhesives, adhesives, etc. Additives for pharmaceuticals, optical materials, electronic equipment, battery materials, vehicles, ships, aircraft, buildings, housing and construction materials, civil engineering materials, clothing materials, curtains, sheets, containers, glasses, casings or sporting goods, etc. For applications with fracture resistance or fatigue resistance.

More specific applications include anti-reflection materials such as optical films, optical sheets, optical filters, high-brightness flakes, optical concentrators, anti-glare films, lighting fixtures, transparent lighting materials, and protective films. , Surface materials for pen input devices, cables, sheaths, wire covering materials, electrical insulation members, electronic equipment housings, mechanical parts, vibration fatigue-resistant members, capacitors, separators for secondary batteries, adhesives for secondary batteries , solid electrolyte, fiber reinforced material, anti-rust agent, anti-food material, spray paint, coating for barrier materials (organic matter, gas, humidity), etc., building materials for pets, building materials for floors, walls, doors, etc., water-shielding sheets, waterproofing Sheets, actuators, cleaning pads, bathtubs, basins, buckets, bathing aids, automotive materials, artificial leather, synthetic leather, artificial skin, stents for endovascular therapy, composite restoration materials for dentistry, sleeve materials, laminated glass , transfer foil, flame retardant film, stationery shaft, cushioning material, cushioning agent, agricultural film, decorative film, cosmetic sheet, greenhouse sheet, insect net, furniture, clothes, bags, shoes, goggles , ski board, snowboard, racket, tent, container, chopping board, cutting board, antibacterial film, antibacterial molded body, barrier film or liner, etc.

When the curable composition of the present invention is applied to a surface coating agent, it has the effect of improving the poor processing caused by coating. For example, the processing during molding can be improved by using it as a hard coating material for in-mold molding. sex.

When the curable composition of the present invention is applied to paint, it can achieve the effect of self-healing the damage of the paint film. For example, when it is used as a paint for automobiles, since the damage of the paint can be repaired only by heating, it becomes unnecessary to repaint.

When the curable composition of the present invention is used as an adhesive, the cured product after bonding can be spontaneously bonded after cutting, and peeling due to poor bonding or deterioration can be suppressed. In addition, hardening after stress relaxation can be imparted, and adhesive strength can be improved.

When the curable composition of the present invention is used as a battery material, the effect of self-healing after fracture can be obtained. For example, when the secondary battery is repeatedly used for charging and discharging, the electrode may expand and the binder may break, but even if the binder is broken, the binder will still repair itself to prevent the electrode from decomposing, thereby preventing battery performance from deteriorating.

＜Other＞ In this disclosure, the following aspects can be mentioned. [1] 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 also have heteroatoms. Part of the methylene group in the alkyl group may be substituted by an ether bond, thioether bond, ester bond, amide bond, imide bond or carbonyl. Part of the hydrogen atoms in the alkyl group may be substituted by 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, any two of R ¹ , R ² , R ³ and R ⁴ are removed to form a compound having a ring structure.

[2] The compound as described in [1], wherein the polymerizable functional group having 1 to 50 carbon atoms is selected from the group consisting of vinyl, allyl, acryl, methacryl, hydroxyl, isocyanate, and amino , amide group, epoxy group, epoxypropylene group, episulfide group, carboxyl group, heteroaryl group, mercapto group, group containing carboxylic acid anhydride structure and group containing cyclic imide structure. A group in which a hydrocarbon group is bonded, a part of the methylene group in the hydrocarbon group may be substituted by an ether bond, a thioether bond, an ester bond, an amide bond, an imide bond or a carbonyl group, and the hydrogen atom in the polymerizable functional group A part may also be substituted by a halogen atom.

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

In the 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 represents an integer of 2 or more, L ¹ of the plural number may be the same base or different bases. * represents the bonding position with the nitrogen atom in the formula (1).

[4] A curable composition comprising the compound described in any one of [1] to [3].

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

[6] The curable composition as described in [5], wherein the curing agent is at least 1 selected from the group consisting of amine compounds, amide compounds, acid anhydride compounds, thiol compounds, phenol compounds, imidazole compounds and latent curing agents. kind.

[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 described in any one of [4] to [7], which is a self-healing material, surface coating agent, paint, adhesive, or battery material.

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

Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these.

[Example 1] Production of Compound No. 2 Add 200 g of dimethylformamide, 50.0 g of 2-(tert-butylamino) ethyl acrylate, and 27.0 g of sodium acetate to a 500 mL round-bottomed flask. After stirring and mixing, 19.7 g of disulfur dichloride was dissolved in 59.2 g of dimethylformamide dropwise at room temperature, and stirred for 2 hours to react. After completion of the reaction, butyl acetate and water were added to perform oil-water separation. After washing with water, the solvent was distilled off under reduced pressure, and it was left to stand at -37°C for 48 hours, and the precipitated solid was separated by filtration to obtain 43.7 g of colorless crystals. The obtained colorless crystals were confirmed to be Compound No. 2 of the target compound from the analysis results obtained by ¹ H-NMR and elemental analysis. The yield of the obtained compound was 77%. The analysis results are shown below.

(1) ¹ H-NMR(400MHz,CDCl3) δ=1.24(s, 18H), 1.96(s, 6H), 3.12-3.28(br, 4H), 4.36 (t, 4H), 5.55-5.60(m, 2H), 6.11-6.15(m, 2H)

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

[Example 2] Production of Compound No. 12 Add 15.0 g of Compound No. 2 produced in Example 1, 21.3 g of water, 61.5 g of ethanol and 14.5 g of 35% aqueous potassium hydroxide solution to a 300 mL round bottom flask, and stir After mixing for 1 hour, all the mixed solution in the round bottom flask was added to 400 mL of toluene, and then 200 mL of water was added, and water washing was repeated until the water layer became neutral. After confirming that the aqueous layer had become neutral, the solvent was distilled off under reduced pressure, and the mixture was left standing at room temperature as it was. After 24 hours, the precipitated crystals were separated by filtration and vacuum-dried to obtain 6.88 g of white powder crystals. The obtained white powder was confirmed to be Compound No. 12 of the target compound by ¹ H-NMR and elemental analysis. The yield of the obtained compound was 67%. The analysis results are shown below.

(1) ¹ H-NMR (400MHz, CDCl3) δ=1.26(s, 18H), 2.82-2.90(m, 2H), 3.02-3.14 (m, 4H), 3.81-3.94(m, 4H)

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

[Example 3] Production of Compound No.6 (epoxy resin) Add 5.00 g of compound No.12 produced in Example 2, 49.88 g of epichlorohydrin, and 0.185 g of tetramethylammonium chloride to a 100 mL round-bottomed flask, heat up to 70°C and stir to dissolve compound No.12 , 3.51 g of 48% aqueous sodium hydroxide solution was gradually added and stirred for 3 hours. After stirring, the solvent was distilled off under reduced pressure, 100 mL of toluene was added, and 100 mL of water was added for oil-water separation, and water washing was repeated until the water layer became neutral. After confirming that the water layer became neutral, toluene was distilled off under reduced pressure, and 6.54 g of viscous liquid was obtained by filtering and separating. The obtained liquid had an epoxy equivalent of 235 calculated by the following method, and it was confirmed that it was an epoxy resin mainly composed of Compound No. 6. The yield of the obtained epoxy resin was 94.9%. The analysis results are shown below.

(1) epoxy equivalent According to JIS K7237, the amine equivalent is calculated by using the differential titration of perchloric acid. According to JIS K7236, the total amount of epoxy equivalent and amine equivalent is calculated by using the differential titration of perchloric acid. The epoxy equivalent is calculated as The difference between the total amount and the amine equivalent.

(2) Elemental analysis The value in brackets is the theoretical value of compound No.6 (epoxy resin) C: 52.5% by mass (52.9% by mass), H: 8.9% by mass (8.9% by mass), N: 6.9% by mass (6.9% by mass), S: 15.5% by mass (15.7% by mass)

[Example 4] Mix 10 parts by mass of Compound No. 2 produced in Example 1 as the compound of the present invention, 90 parts by mass of hexyl methacrylate as another monomer, and 2,2-dimethyl as a polymerization initiator 5.0 parts by mass of oxyacetophenone and 1.0 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) were used to prepare the curable composition of Example 4. After coating this curable composition on a glass plate, put a cover film on it, irradiate a high-pressure mercury lamp with an output of 3mW/ ^cm2 for 660 seconds, and then let it stand in an oven at 50°C for 12 hours to completely harden it. Obtain a coating sample. The obtained coating film sample was given scratch marks with a 4B pencil, left to stand in an oven at 120°C, and the scratch marks were observed with a microscope over time, and it was confirmed that the scratch marks disappeared after 2 hours.

[Comparative example 1] Except for replacing compound No.2 with ethoxylated bisphenol A methacrylate (NK Ester BPE-200 manufactured by Shin Nakamura Chemical Industry Co., Ltd.), the other operations were the same as in Example 4 to prepare a comparative example. 1 curable composition to obtain coating samples. The obtained coating film samples were scratched with a 4B pencil, left to stand in an oven at 120° C., and scratches were observed with a microscope over time. Even after 3 hours, scratches remained.

[Example 5, Example 6, Comparative Example 2 and Comparative Example 3] Using the epoxy resin whose main component is Compound No. 6 obtained in Example 3, the following compound a and compound b as other monomers, and the following compound c as a hardening agent, the mixture shown in the following Table 1 was used. Mix together to prepare a curable composition. After coating the obtained curable composition on a glass plate, put a cover film on it, and let it stand in an oven at 120° C. for 42 hours to harden to obtain a coating film sample. For the obtained coating film sample, use a 2H pencil to give scratch marks, then let it stand in an oven at 60°C, and observe the scratch marks after 16 hours, 24 hours, and 40 hours with a microscope with a magnification of 10 times . Under observation using a microscope, the case where scratches disappeared was evaluated as "○", and the case where scratches disappeared visually, but scratches were confirmed under microscope observation was evaluated as "△", and those that could be observed visually The case where scratch marks were confirmed was evaluated as "x". The evaluation results are shown in Table 1.

Compound a (other monomers): Dicyclopentadiene Dimethanol Diglycidyl Ether Compound b (other monomers): 2,2-dimethyl-1,3-propanediol diglycidyl ether Compound c (hardener): 2-ethyl-4-methylimidazole

From the above results, it can be known that according to the present invention, the epoxy resin having the Materials with excellent self-healing ability.

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, and the alkyl group is also It may have a heteroatom, and a part of the methylene group in the alkyl group may also be substituted by an ether bond, a thioether bond, an ester bond, an amide bond, an imide bond or a carbonyl group, and a part of the hydrogen atom in the alkyl group It can also be substituted by halogen atoms, n1 represents an integer from 1 to 10, and at least one of R ¹ , R ² , R ³ and R ⁴ represents a polymerizable functional group with 1 to 50 carbon atoms; however, R ¹ and R ² A compound in which any two of R ³ and R ⁴ are linked to form a ring structure. The compound of claim 1, wherein the above-mentioned polymerizable functional group with 1 to 50 carbon atoms is selected from the group consisting of vinyl, allyl, acryl, methacryl, hydroxyl, isocyanate, amine, and amide group, epoxy group, propylene oxide group, episulfide group, carboxyl group, heteroaryl group, mercapto group, group containing carboxylic acid anhydride structure and group containing cyclic imide structure are linked with hydrocarbon group A part of the methylene group in the aforementioned hydrocarbon group may also be substituted by an ether bond, a thioether bond, an ester bond, an amide bond, an imide bond or a carbonyl group, and a part of the hydrogen atom in the aforementioned polymerizable functional group It can also be substituted by a halogen atom. The compound of claim 1, wherein the polymerizable functional group with 1 to 50 carbon atoms is a group represented by the following formula (L-1);

In the formula (L-1), ^L1 and ^L2 each independently represent an alkanediyl group with 1 to 5 carbon atoms, n represents an integer of 0 to 5, and when n is an integer of 2 or more, the plural ^L1 may be The same group may also be a different group, and * represents the bonding position with the nitrogen atom in formula (1). A curable composition comprising the compound according to any one of claims 1-3. The curable composition according to claim 4, further comprising at least one selected from the group consisting of curing agents and polymerization initiators. The curable composition according to claim 5, wherein the hardener is at least one selected from the group consisting of amine compounds, amide compounds, acid anhydride compounds, thiol compounds, phenolic compounds, imidazole compounds, and latent hardeners. The curable composition according to claim 5, wherein the aforementioned polymerization initiator is a cationic polymerization initiator or a radical polymerization initiator. The curable composition of claim 4 is a self-healing material, a surface coating agent, a paint, an adhesive, or a battery material. A hardened product, which is obtained by hardening the curable composition according to claim 4.