JP7577482B2 - Compound, composition containing said compound, and cured product - Google Patents

Description

The present invention relates to a compound having a specific structure, a composition containing the compound, and a cured product obtained by curing the composition. The composition can be used as a surface coating agent, paint, adhesive, battery material, and self-repairing material.

Polymer materials exhibit high mechanical strength and durability based on strong covalent bonds, but they are poor in reworkability and reusability, making it difficult to repair scratches and breaks, especially self-repair. As self-repairable materials that are excellent in durability and reworkability and easy to repair, approaches based on intermolecular interactions such as host-guest interactions (see, for example, Patent Documents 1 and 2), self-repairing materials that utilize dangling chains bonded to a polymer cross-linked structure (see, for example, Patent Document 3), and a technology in which microcapsules containing polymerizable monomers or catalysts are blended into a matrix of a resin material, etc., and when the matrix is damaged with the destruction of the microcapsules, etc., new monomer components are filled in and polymerized, thereby restoring the function of the matrix (see, for example, Patent Documents 4 and 5). However, there are problems such as the fact that the methods of Patent Documents 1 to 3 require complicated processes for manufacturing the material, and the fact that the methods of Patent Documents 4 and 5 have limitations on the number of times self-repair can be performed due to the amount of microcapsules blended, etc. In recent years, in order to solve these problems, self-repairing materials have been developed that use dynamic covalent bonds and undergo reversible bond dissociation and recombination when an external stimulus is applied to the material (see, for example, 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 JP 2017-218519 A JP 2017-202980 A

A. Takahashi, R. Goseki, K. Ito, 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 do not have sufficient self-repairing power.
Therefore, the present invention has been made in consideration of the above problems and circumstances, and has an object to provide a material having excellent self-repairing ability.

Means for Solving the Problems The present inventors conducted extensive research into the causes of the above problems in order to solve the above problems, and as a result, found that a compound having a specific structure can solve the above problems, thereby completing the present invention.
That is, the present invention is shown in the following [1] to [16].

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

In the formula, ^X1 and ^X2 each independently represent a polymerizable reactive group having 1 to 50 carbon atoms, ^R1 to ^R8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 10, except for compounds in which both ^X1 and ^X2 are an acrylic group and/or a methacrylic group.

[2] The compound according to [1], wherein the polymerizable reactive groups represented by ^X1 and ^X2 in general formula (1) are selected from the group consisting of a group having an ethylenically unsaturated bond, a hydroxy group, an amino group, an amide group, a group containing an oxirane ring, a group containing a thiirane ring, a heteroaryl group, a thiol group, and a group containing an acid anhydride, a saturated aliphatic hydrocarbon group containing the functional group, a group in which the functional group is bound to a divalent linking group, or a group consisting of a combination of the functional group, a saturated aliphatic hydrocarbon group, and a divalent linking group.

[3] The compound according to [1] or [2], wherein R ¹ to R ⁸ in the general formula (1) are methyl groups.

[4] A compound according to any one of [1] to [3], in which n in general formula (1) is 1.

[5] The compound according to any one of [1] to [4], wherein the polymerizable reactive groups represented by X ¹ and X ² in the general formula (1) contain a heteroaryl group as a functional group.

[6] A composition comprising a compound according to any one of [1] to [5].

[7] The composition according to [6], further comprising at least one selected from the group consisting of a curing agent and a polymerization initiator.

[8] The composition according to [7], 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, and latent curing agents.

[9] The composition according to [7], wherein the polymerization initiator is an imidazole compound, a cationic polymerization initiator, or a radical polymerization initiator.

[10] The composition according to any one of [6] to [9], further comprising a compound having an oxirane ring.

[11] A cured product obtained by curing the composition described in any one of [6] to [10].

[12] A self-repairing material comprising the composition according to any one of [6] to [10].

[13] A surface coating agent comprising the composition according to any one of [6] to [10].

[14] A paint containing the composition described in any one of [6] to [10].

[15] An adhesive comprising the composition according to any one of [6] to [10].

[16] A battery material comprising the composition according to any one of [6] to [10].

The present invention provides a material with excellent self-repairing properties.

Hereinafter, an embodiment of the present invention will be described in detail.
First, the compound of the present invention will be described. In this specification, a compound having an oxirane ring in its structure may be referred to as an epoxy compound.

<Compound>
The compound of the present invention is represented by the following general formula (1).

In general formula (1), ^X1 and ^X2 each independently represent a polymerizable reactive group having 1 to 50 carbon atoms, ^R1 to ^R8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 10, except for compounds in which both ^X1 and ^X2 are an acrylic group and/or a methacrylic group.

The compound represented by the general formula (1) is characterized by having a polysulfide skeleton. Since the chemical bonds between sulfur atoms in the polysulfide skeleton are easily broken and rebonded by heating or light irradiation, for example, as shown in Patent Document 6 and Non-Patent Document 1, their use as skeletons of self-repairing materials has been considered. However, since the molecular structures of the compounds described in Patent Document 6 and Non-Patent Document 1 are complex, there are problems such as low productivity and insufficient self-repairing ability. On the other hand, the compound of the present invention can easily synthesize a compound having excellent self-repairing ability.
The term "excellent self-repairing ability" refers to, for example, the ability to repair even if the damage is large, the number of times that the material can be repaired, and the ability to recover sufficient mechanical strength even if the material is repaired from a damaged state. In particular, the compound of the present invention has an excellent self-repairing ability that can repair the material to the strength before the damage. In addition, the material with self-repairing ability can also be expected to have the effect of alleviating the stress generated during hardening.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ to R ⁸ in general formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a 2-pentyl group, a 3-pentyl group, an isopentyl group, a hexyl group, a 2-hexyl group, a 3-hexyl group, a cyclopentyl group, and a cyclohexyl group.

From the viewpoint of exhibiting a superior self-repairing ability, R ¹ to R ⁸ in the general formula (1) are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group, or a phenyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

In order to achieve a superior self-repairing ability, n in general formula (1) is preferably an integer from 1 to 8, more preferably an integer from 1 to 5, and even more preferably 1.

The polymerizable reactive groups represented by ^X1 and ^X2 include a functional group capable of participating in a polymerization reaction, a saturated aliphatic hydrocarbon group containing the functional group, a group in which the functional group is bound to a divalent linking group, or a group in which the functional group, a saturated aliphatic hydrocarbon group, and a divalent linking group are combined.

The functional group may be, for example, a group having an ethylenically unsaturated bond, a hydroxy group, an isocyanate group, an amino group, an amide group, a group containing an oxirane ring, a group containing a thiirane ring, a heteroaryl group, a thiol group, and a group containing an acid anhydride. The hydrogen atom in the functional group may be substituted with a halogen atom.

Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, acrylic groups, methacrylic groups, acryloyl groups, and methacryloyl groups.

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

The amino group is represented by -NR ⁹ R ¹⁰ , where R ⁹ and R ¹⁰ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. From the viewpoint of exhibiting a more excellent self-repairing ability, R ⁹ and R ¹⁰ are preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom.

The amide group is represented by -(C=O)-NR ¹¹ R ¹² , where R ¹¹ and R ¹² represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. From the viewpoint of exhibiting a more excellent self-repairing ability, R ¹¹ and R ¹² are preferably a hydrogen atom, a methyl group, or an ethyl group, and it is more preferable that either R ¹¹ or R ¹² is a hydrogen atom.

The oxirane ring is a three-membered ether ring, also known as ethylene oxide. In the present invention, the hydrogen atoms in the oxirane ring may be substituted with alkyl groups or halogen atoms.

A thiirane ring is a three-membered thioether ring, also known as ethylene sulfide. In the present invention, the hydrogen atoms in the thiirane ring may be substituted with alkyl groups or halogen atoms.

Examples of heteroaryl groups include 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-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, and oxazol-2-yl. , 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-pyrazin-2-yl group, pyrazin-4-yl group, pyrazin-5-yl group, 2-pyrimidin-2-yl group, 4-pyrimidin-2-yl group, or 5-pyrimidin-2-yl group.

Examples of thiol groups as functional groups include mercaptocarboxylic acids, aliphatic mercaptocarboxylic acids, and esters of aliphatic mercaptocarboxylic acids and polyhydric alcohols.

The aliphatic mercaptocarboxylic acid is a mercaptocarboxylic acid having 1 to 10 carbon atoms, such as thioglycolic acid and mercaptopropionic acid.

The above polyhydric alcohols include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, and sorbitol, and divalent or trivalent hydroxyalkyl isocyanurates such as tris(2-hydroxyethyl)isocyanurate.

The acid anhydride may be a group containing phthalic anhydride or succinic anhydride as the skeleton, and the hydrogen atom of the phthalic anhydride or succinic anhydride may be substituted with a halogen atom, an alkyl group, an alkenyl group, a carbonyl group, or a combination thereof.

The saturated aliphatic hydrocarbon group represents a linear or branched alkyl group, and the hydrogen atoms of the alkyl group may be substituted with halogen atoms.

The divalent linking group represents an ether bond, a thioether bond, a carbonyl group, an ester group, or a combination thereof.

In the compound of the present invention, the polymerizable reactive groups represented by ^X1 and ^X2 may have a plurality of functional groups, saturated aliphatic hydrocarbon groups, or divalent bonding groups, and the plurality of functional groups, the plurality of saturated aliphatic hydrocarbon groups, or the plurality of divalent bonding groups may be the same or different.

Specific examples of compounds represented by the above general formula (1) include the following compounds No. 1 to No. 12, but the present invention is not limited to these compounds.

In the compound of the present invention, in terms of exhibiting an excellent repair function, it is preferable that the polymerizable reactive groups represented by ^X1 and ^X2 have a heteroaryl group as a functional group, and among them, it is preferable that both ^X1 and ^X2 are polymerizable reactive groups having a heteroaryl group as a functional group. Furthermore, it is preferable that the polymerizable reactive groups having a heteroaryl group as a functional group represented by ^X1 and ^X2 are groups in which a heteroaryl group is bonded to a divalent bond selected from an ether bond, a thioether bond, a carbonyl group, and an ester bond, and it is more preferable that the polymerizable reactive groups having a heteroaryl group as a functional group are groups in which a heteroaryl group is bonded to a divalent bond selected from an ether bond, a thioether bond, a carbonyl group, and an ester bond, and it is more preferable that the polymerizable reactive groups having a heteroaryl group and a carbonyl group are bonded to a divalent bond selected from an ether bond, a thioether bond, a carbonyl group, and an ester bond.

In the compound of the present invention, when the polymerizable reactive group represented by ^X1 and ^X2 is a polymerizable reactive group having a heteroaryl group as a functional group, the heteroaryl group is preferably a nitrogen-containing heteroaryl group containing a nitrogen atom in the heteroaryl ring, more preferably a triazole group, a pyrazole group or an imidazole group, and even more preferably an imidazole group, in terms of exhibiting a better repair function. In the compound of the present invention, the polymerizable reactive group represented by ^X1 and ^X2 is preferably an imidazolylcarbonyl group in terms of exhibiting a better repair function.

The compound represented by general formula (1) can be produced, for example, by reacting 2,2,6,6-tetramethylpiperidinol with a compound having a corresponding polymerizable reactive group, adding sodium acetate and dehydrated dimethylformamide, maintaining the temperature at 0°C under a nitrogen atmosphere, dropping disulfur dichloride, stirring while maintaining the temperature at 0°C, filtering and recovering the resulting precipitate, washing with water, and concentrating to produce the desired compound, or by reacting bis(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)disulfide with a compound having a corresponding polymerizable reactive group.

More specifically, when producing compound No. 1, bis(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl) disulfide, carbonyldiimidazole, and tetrahydrofuran are added to a reaction vessel, stirred at 25°C for 1 hour, the solvent is removed by distillation, and the product is extracted with ethyl acetate and water, washed with water, and dried.

In addition, when manufacturing compound No. 8, a compound obtained by reacting 2,2,6,6-tetramethylpiperidinol with 2-(chloromethyl)oxirane, ADKEA Corporation product name "ADK STAB LA-87" (2,2,6,6-tetramethyl-4-piperidyl methacrylate), sodium acetate and dehydrated dimethylformamide are added to a reaction vessel, maintained at 0°C under a nitrogen atmosphere, disulfur dichloride is added dropwise, the mixture is stirred for 2 hours to react, water is added, the resulting precipitate is collected by filtration, washed with water and dried.

<Composition>
Next, the composition of the present invention will be described.
The composition of the present invention may be any composition containing a compound represented by general formula (1) (hereinafter referred to as the "compound of the present invention"). In the composition of the present invention, the compound of the present invention may be used as a curable monomer that is cured by a curing agent or a polymerization initiator, or may be used as a curing agent for curing the curable monomer.

In addition, when the compound of the present invention is a compound having a polymerizable reactive group with a hydroxyl group as the functional group, it is preferable to include a compound having an isocyanate group capable of polymerizing with the hydroxyl group in the composition of the present invention, since this facilitates curing.

When the compound of the present invention is a compound having a polymerizable reactive group with an isocyanate group as the functional group, it is preferable that the composition of the present invention contains a compound having a hydroxy group capable of undergoing a polymerization reaction with the isocyanate group, since this facilitates curing.

When the compound of the present invention is used as a curable monomer in the composition of the present invention, the curable monomer in the composition of the present invention may be only the compound of the present invention, or the compound of the present invention may be used in combination with a compound that is activated by heat or energy ray irradiation to cause a polymerization or crosslinking reaction. The amount of the compound of the present invention to be blended is not particularly limited, and can be appropriately selected based on known compositions.

When the compound of the present invention is used as a curable monomer, it is preferable to contain a curing agent and/or a polymerization initiator to cure the curable monomer in the composition of the present invention, since this facilitates curing.

In the composition of the present invention, a curing agent or polymerization initiator can be used without particular limitation as long as it is publicly known and generally used, but for example, when a compound having a polymerizable reactive group with an oxirane ring as the functional group in ^X1 or ^X2 in the general formula (1) is used as a curable monomer, it is preferable to use a curing agent selected from the group consisting of amine compounds, amide compounds, acid anhydride compounds, thiol compounds, phenol compounds and latent curing agents, since the curing reaction is accelerated. The curing agent may be used alone or in combination of two or more.

Examples of the amine compounds include aliphatic amine compounds such as ethylenediamine, diethylenetriamine, and hexamethylenediamine; arylaliphatic amine compounds such as N-methylaniline, m-xylylenediamine, p-xylylenediamine, diphenylamine, and hydroxyphenylglycine; and cyclic aliphatic amine compounds such as 1,3-bisaminomethylcyclohexane, N-methylpiperazine, morpholine, piperidine, isophoronediamine, and 4,4-methylenebiscyclohexaneamine.

An example of the amide compound is dicyandiamide.

Examples of the acid anhydride compounds include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenetetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, ethylene glycol bisanhydrotrimellitate, glycerin bis(anhydrotrimellitate) monoacetate, dodecenyl succinic anhydride, aliphatic dibasic acid polyanhydrides, chlorendic anhydride, methylbutenyltetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, methylhimic anhydride, succinic anhydride substituted with an alkenyl group, glutaric anhydride, and the like.

Examples of thiol compounds used as the curing agent include aliphatic thiol compounds, aromatic thiol compounds, aliphatic polythiol compounds, mercaptocarboxylic acid ester compounds, mercaptocarboxylic acids, mercaptoethers, etc.

Among these thiol compounds, bifunctional thiol compounds are preferred from the viewpoint that the cured product exhibits excellent self-repairing ability. Specific examples of bifunctional thiol compounds include 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,3-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 3, 6-dichloro-1,2-benzenedithiol, toluene-3,4-dithiol, 1,5-naphthalenedithiol, ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bisthioglycolate, tetraethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(thioglycolate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)-ethyl]isocyanurate, pentaerythritol tetrakis(thioglycolate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, dimercaptodiethyl sulfide, 1,8-dimercapto-3,6-dithiaoctane, 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, tetrakis(7-mercapto-2,5-dithiaheptane (ethyl)methane, trithiocyanuric acid, 1,2-benzenedimethane, thiol, 4,4'-thiobisbenzenethiol, 2-di-n-butylamino-4,6-dimercapto-s-triazine, 2-di-n-butylamino-4,6-dimercapto-s-triazine, 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto-3,6-dioxaoctane, 1,5-dimercapto-3-thiapentane, trimercaptopropionic acid tris( 2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, bis(4-(2-mercaptopropoxy)phenyl)methane, 1,1-bis(4-(2-mercaptopropoxy)phenyl)ethane, 2,2-bis(4-(2-mercaptopropoxy)phenyl)propane, 2,2-bis(4-(2-mercaptopropoxy)phenyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, bis(4-(2-mercaptopropoxy)phenyl)methane, 1,1-bis(4-(2-mercaptopropoxy)phenyl)ethane, 2,2-bis(4-(2-mercaptopropoxy)phenyl)propane, 2,2-bis(4-(2-mercaptopropoxy)phenyl)butane, 1,1-bis(4-(2-mercaptopropoxy)phenyl)isobutane, 2,2-bis(4-(2-mercaptopropoxy)-3-methylphenyl)propane, 2,2-bis(4-(2-mercaptopropoxy)-5-methylphenyl)propane, bis(2-(2-mercaptopropoxy)-5-methylphenyl)methane, 2,2-bis(4-(2-mercaptopropoxy)-3-tert-butylphenyl)propane Examples of the thiol compounds include alkyl vinyl ether adducts of propane, tris(4-(2-mercaptopropoxy)phenyl)methane, 1,1,1-tris(4-(2-mercaptopropoxy)phenyl)ethane, bis(4-(2-mercaptobutoxy)phenyl)methane, 2,2-bis(4-(2-mercaptobutoxy)phenyl)propane, tris(4-(2-mercaptobutoxy)phenyl)methane, and 1,3,5-triazine-2,4,6-trithiol. However, the thiol compounds are not limited to these. In addition, the thiol compounds represented by the following general formula (2) are preferred from the viewpoint of heat resistance.

(In the formula, A represents an alkylene group having 1 to 10 carbon atoms, m represents an integer of 1 to 6, and ^X3 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and having the same valence as m.)

Examples of the phenolic compounds include phenol novolac and cresol novolac.

The above-mentioned latent curing agents include, for example, modified amine latent curing agents having at least one amino group with active hydrogen in the molecule, which are obtained by reacting a polyamine compound with an epoxy compound, latent curing agents containing phenolic resins, dicyandiamide, modified polyamines, hydrazides, 4,4'-diaminodiphenyl sulfone, boron trifluoride amine complex salts, ureas, melamine, and those described in WO 2012/020572 and JP 2014-177525 A.

When the compound of the present invention has a polymerizable reactive group in which ^X1 or ^X2 in the general formula (1) is a group having an ethylenically unsaturated bond as a functional group, it is preferable to use a radical polymerization initiator as the polymerization initiator since the curing is promoted. The polymerization initiator may be used alone or in combination of two or more kinds.

Radical polymerization initiators that can be used in the composition of the present invention include photoradical polymerization initiators and thermal radical polymerization initiators.

The above-mentioned photoradical polymerization initiators include acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds, bisimidazole-based compounds, acridine-based compounds, acylphosphine-based compounds, oxime ester compounds, etc.

Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxyacetophenone, Examples include cyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, etc.

The benzyl compounds include benzyl, etc.

Examples of the benzophenone compounds include benzophenone, o-benzoylmethylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.

The above thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, etc.

As the bisimidazole compound, hexaarylbisimidazole (HABI, a dimer of triaryl-imidazole) can be used. Specifically, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl -1,2'-biimidazole, 2,4,5,2',4',5'-hexaphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenylbisimidazole, 2,2'-bis(2-bromophenyl)-4,5,4',5'-tetraphenylbisimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,5,4',5'-tetraphenylbisimidazole phenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetrakis(3-methoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetrakis(3,4,5-trimethoxyphenyl)-bisimidazole, 2,5,2',5'-tetrakis(2-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)bisimidazole, 2,2'-bis(2,6-dichlorophenyl)-4,5,4',5'-tetraphenylbisimidazole, 2,2'-bis(2-nitrophenyl)-4,5,4',5'-tetraphenylbisimidazole, 2,2'-di-o-tolyl-4,5,4',5'-tetraphenylbisimidazole, 2,2'-bis(2-ethoxyphenyl)-4,5 , 4',5'-tetraphenylbisimidazole and 2,2'-bis(2,6-difluorophenyl)-4,5,4',5'-tetraphenylbisimidazole, 5'-tetra(p-iodophenyl)biimidazole, 2,2'-bis(o-chlorophenyl-4,4',5,5'-tetra(m-methoxyphenyl)biimidazole, 2,2'-bis(p-methylthiophenyl) -4,5,4',5'-diphenyl-1,1'-biimidazole, bis(2,4,5-triphenyl)-1,1'-biimidazole, 5,5'-tetra(p-chloronaphthyl)biimidazole, etc., tautomers covalently bonded at 1,2'-, 1,4'-, and 2,4'- as disclosed in JP-B-45-37377, and compounds described in WO 00/52529, etc. are included.

The above acridine compounds include acridine, 9-phenylacridine, 9-(p-methylphenyl)acridine, 9-(p-ethylphenyl)acridine, 9-(p-isopropylphenyl)acridine, 9-(p-n-butylphenyl)acridine, 9-(p-tert-butylphenyl)acridine, 9-(p-methoxyphenyl)acridine, 9-(p-ethoxyphenyl)acridine, 9-(p-acetylphenyl)acridine, 9-(p-dimethylaminophenyl)acridine, 9-(p-cyanophenylphenyl)acridine, phenyl)acridine, 9-(p-chlorophenyl)acridine, 9-(p-bromophenyl)acridine, 9-(m-methylphenyl)acridine, 9-(m-n-propylphenyl)acridine, 9-(m-isopropylphenyl)acridine, 9-(m-n-butylphenyl)acridine, 9-(m-tert-butylphenyl)acridine, 9-(m-methoxyphenyl)acridine, 9-(m-ethoxyphenyl)acridine, 9-(m-acetylphenyl)acridine, 9-(m-dimethylaminophenyl)acridine , 9-(m-diethylaminophenyl)acridine, 9-(cyanophenyl)acridine, 9-(m-chlorophenyl)acridine, 9-(m-bromophenyl)acridine, 9-methylacridine, 9-ethylacridine, 9-n-propylacridine, 9-iso-propylacridine, 9-cyanoethylacridine, 9-hydroxyethylacridine, 9-chloroethylacridine, 9-bromoacridine, 9-hydroxyacridine, 9-nitroacridine, 9-aminoacridine, 9-methoxyacridine, 9-ethoxy Acridine, 9-n-propoxyacridine, 9-iso-propoxyacridine, 9-chloroethoxyacridine, 4,6-bis(dimethylamino)acridine, 10-acetate acridine, 10-methylacetate acridine, 3,6-dimethylacridine, 7,13-dimethylacridine, 7,13-bis(dimethylamino)acridine, 3,6-dimethyl-10-acetate acridine, 3,5-dimethyl-10-methylacetate acridine, 7,13-dimethyl-10-acetate acridine, 7,13-dimethyl-10-methylacetate 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinyl)pentane, 1,3-bis(9-acridinyl)propane, 2,7-dibenzoyl-9-phenylacridine, 2,7-bis(α-hydroxybenzyl)-9-phenylacridine, 2,7-bis(α-acetoxybenzyl)-9-phenylacridine, 2,7-dimethyl-9-(4-methylphenyl)acridine, 2,7-dimethyl-9-phenylacridine, 2,7-bis(3,4-dimethyl-benzoyl)-9-(3,4-dimethyl 2,7-bis(α-acetoxy-4-tert-butylbenzyl)-9-(4-tert-butylphenyl)acridine, 2,7-dimethyl-9-(3,4-dichlorophenyl)acridine, 2,7-dimethyl-9-(4-benzoylphenyl)acridine, 2,7-bis(2-chlorobenzoyl)-9-(2-chlorophenyl)acridine, 2-(α-hydroxy-3-bromobenzyl)-6-methyl-9-(3-bromophenyl)acridine, 2,5-bis(4-tert-butylbenzoyl)-9 -(4-tert-butylphenyl)acridine, 1,4-bis(2,7-dimethyl-9-acridinyl)benzene, 2,7-bis(α-phenylaminocarbonyloxy-3,4-dimethylbenzyl)-9-(3,4-dimethylphenyl)acridine and 2,7-bis(3,5-dimethyl-4-hydroxy-4'-fluorodiphenylmethyl)-9-(4-fluorophenyl)acridine, 9,10-dihydroacridine, 1-methylacridine, 4-methylacridine, 2,3-dimethylacridine, 1-phenylacridine, 4-phenylacridine, 1-benzyl acridine, 4-benzyl acridine, 1-chloroacridine, 2,3-dichloroacridine, 10-butyl-2-chloroacridin-9(10H)-one, 10-propyl-2-chloroacridin-9(10H)-one, 10-butyl-2-chloroacridin-9(10H)-one 1,2-bis(9-acridinyl)ethane, 1,3-bis(9-acridinyl)propane, 1,4-bis(9-acridinyl)butane, 1,6-bis(9-acridinyl)hexane, 1,7 ...4-bis(9-acridinyl)butane, 1,6-bis(9-acridinyl)hexane, 1,7-bis(9-acridinyl)ethane, 1,4-bis(9-acridinyl)butane, 1,6-bis(9-acridinyl)hexane, 1,7-bis(9-acridinyl)ethane, 1,3-bis(9-acridinyl)propane, 1,4-bis(9-acridinyl)butane, 1,6-bis(9-acridinyl)hexane, 1,7-bis(9-acridinyl)ethane, 1,4-bis(9-acridinyl)butane, 1,6 bis(9-acridinyl)heptane, 1,8-bis(9-acridinyl)octane, 1,9-bis(9-acridinyl)nonane, 1,10-bis(9-acridinyl)decane, 1,11-bis(9-acridinyl)undecane, 1,12-bis(9-acridinyl)dodecane, 1,14-bis(9-acridinyl)tetradecane, 1,16-bis(9-acridinyl)hexadecane, 1,18-bis(9-acridinyl)octadecane, 1,20-bis(9-acridinyl)eicosane, 1,3-bis(9-acridinyl)-2-thiapropane, 1, 5-bis(9-acridinyl)-3-thiapentane 7-methyl-benzo[c]acridine, 7-ethyl-benzo[c]acridine, 7-propyl-benzo[c]acridine, 7-butyl-benzo[c]acridine, 7-pentyl-benzo[c]acridine, 7-hexyl-benzo[c]acridine, 7-heptyl-benzo[c]acridine, 7-octyl-benzo[c]acridine, 7-nonyl-benzo[c]acridine, 7-decyl-benzo[c]acridine, 7-undecyl-benzo[c]acridine, 7-dodecyl-benzo[c]acridine c]acridine, 7-tridecyl-benzo[c]acridine, 7-tetradecyl-benzo[c]acridine, 7-pentadecyl-benzo[c]acridine, 7-hexadecyl-benzo[c]acridine, 7-heptadecyl-benzo[c]acridine, 7-octadecyl-benzo[c]acridine, 7-nonadecyl-benzo[c]acridine, 1,1-bis(7-benzo[c]acridinyl)methane, 1,2-bis(7-benzo[c]acridinyl)ethane, 1,3-bis(7-benzo[c]acridinyl)propane, 1,4-bis( 1,7-bis(7-benzo[c]acridinyl)butane, 1,5-bis(7-benzo[c]acridinyl)pentane, 1,6-bis(7-benzo[c]acridinyl)hexane, 1,7-bis(7-benzo[c]acridinyl)heptane, 1,8-bis(7-benzo[c]acridinyl)octane, 1,9-bis(7-benzo[c]acridinyl)nonane, 1,10-bis(7-benzo[c]acridinyl)decane, 1,11-bis(7-benzo[c]acridinyl)undecane, 1,12-bis(7-benzo[c]acridinyl)dodecane, 1, 13-bis(7-benzo[c]acridinyl)tridecane, 1,14-bis(7-benzo[c]acridinyl)tetradecane, 1,15-bis(7-benzo[c]acridinyl)pentadecane, 1,16-bis(7-benzo[c]acridinyl)hexadecane, 1,17-bis(7-benzo[c]acridinyl)heptadecane, 1,18-bis(7-benzo[c]acridinyl)octadecane, 1,19-bis(7-benzo[c]acridinyl)nonadecane, 1,20-bis(7-benzo[c]acridinyl)eicosane, 7-phenanthroline, 1,3-bis(7-benzo[c]acridinyl)benzene, 1,4-bis(7-benzo[c]acridinyl)benzene, 7-[1-propen-3-yl(benzo[c]acridinyl)], 7-[1-ethylpentyl-(benzo[c]acridinyl)], 7-[8-heptadecenyl-(benzo[c]acridinyl)], 7,8-diphenyl-benzo[c]acridinyl, 7-(2-chlorophenyl)-benzo[c]acridinyl, 7-(4-methylphenyl)-benzo[c]acridinyl, 7-(4-nitrophenyl)-benzo[c]acridinyl, 1,14-bis(7-benzo[c]acridinyl)tetradecane, 1,2-bis(7-benzo[c]acridinyl)ethylene, 1-methyl-1,2-bis(7-benzo[c]acridinyl)ethylene, 7-styryl-benzo[c]acridine, 7-(1-propenyl)-benzo[c]acridine, 7-(1-pentenyl)-benzo[c]acridine, 9-(2-pyridyl)acridine, 9-(3-pyridyl)acridine, 9-(4-pyridyl)acridine, 9-(4-pyrimidinyl)acridine, 9-(2-pyrazinyl)acridine Examples include lysine, 9(5-methyl-2-pyrazinyl)acridine, 9-(2-quinolinyl)acridine, 9-(2-pyridyl)-2-methyl-acridine, 9-(2-pyridyl)-2-ethylacridine, 9-(3-pyridyl)-2-methyl-acridine, 9-(3-pyridyl)-2,4-diethyl-acridine, 3,6-diamino-acridine sulfonate, 3,6-bis-(dimethylamino)-acridine sulfonate, 3,6-diamino-10-methyl-acridinium chloride, and 9-acridine carboxylic acid.

The acylphosphine compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO; manufactured by BASF), isobutyryl-methylphosphinic acid methyl ester, isobutyryl-phenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid methyl ester, 2-ethylhexanoyl-phenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid isopropyl ester, p-toluyl-phenylphosphinic acid methyl ester, o-toluyl-phenylphosphinic acid methyl ester, 2,4-dimethylbenzoyl-phenylphosphinic acid methyl ester, p-tert-butylbenzoyl-phenylphosphinic acid isopropyl ester, propyl ester, acryloyl-phenylphosphine acid methyl ester, isobutyryl-diphenylphosphine oxide, 2-ethylhexanoyl-diphenylphosphine oxide, o-toluyl-diphenylphosphine oxide, p-tert-butylbenzoyl-diphenylphosphine oxide, 3-pyridylcarbonyl-diphenylphosphine oxide, acryloyl-diphenylphosphine oxide, benzoyl-diphenylphosphine oxide, pivaloyl-phenylphosphinic acid vinyl ester, adipoyl-bis-diphenylphosphine Sphing oxides, pivaloyl-diphenylphosphine oxide, p-toluyl-diphenylphosphine oxide, 4-(tert-butyl)-benzoyl-diphenylphosphine oxide, 2-methylbenzoyl-diphenylphosphine oxide, 2-methyl-2-ethylhexanoyl-diphenylphosphine oxide, 1-methyl-cyclohexanoyl-diphenylphosphine oxide, pivaloyl-phenylphosphinic acid methyl ester and pivaloyl-phenylphosphinic acid isopropyl ester, 4-octylphenylphosphine oxide, terephthaloyl-bis-diphenylphosphine oxide, 1-methyl-cyclohexylcarbonyldiphenylphosphine oxide, versatoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-diisobutoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Irgacure 819; manufactured by BASF), bis(2,4,6-trimethylbenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichloro-3,4 ,5-trimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichloro-3,4,5-trimethoxybenzoyl)-4-ethoxyphenylphosphine oxide, bis(2-methyl-1-naphthoyl)-2,5-dimethylphenylphosphine oxide, bis(2-methyl-1-naphthyl)-4-ethoxyphenylphosphine oxide, bis(2-methyl-1-naphthyl)-2-naphthylphosphine oxide, bis(2-methyl-1-naphthyl)-4-propylphenylphosphine oxide, bis(2- methyl-1-naphthoyl)-2,5-dimethylphenylphosphine oxide, bis(2-methoxy-1-naphthoyl)-4-ethoxyphenylphosphine oxide, bis(2-chloro-1-naphthoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dioctyloxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-diisopropoxyphenylphosphine oxide phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dihexyloxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2-propoxy-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-diisopentyloxyphenylphosphine oxide, bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-phenylphosphine oxide Examples include sphingoside oxide, bis(2,6-dichlorobenzoyl)-4-biphenylylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2-naphthylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide (CGI403), and 6-trimethylbenzoyl-ethyl-phenyl-phosphinate (SPEEDCURE TPO-L; manufactured by Lambson).

Examples of the oxime ester compounds include ethanone-1-[9-ethyl-6-(2-methylbenzoyl-9H-carbazol-3-yl]-1-(o-acetyl oxime), 1-[9-ethyl-6-benzoyl-9H-carbazol-3-yl]-octan-1-one oxime-o-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-o-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-o-benzoate, ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(o-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime), etc.

The above-mentioned thermal radical polymerization initiators include azo-based initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl isobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'-azobis(1-acetoxy-1-phenylethane); peroxide-based initiators such as benzoyl peroxide, di-tert-butylbenzoyl peroxide, tert-butyl peroxypivalate, and di(4-tert-butylcyclohexyl)peroxydicarbonate; and persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. These can be used alone or in combination of two or more.

The above radical polymerization initiators may be used alone or in combination of two or more. From the viewpoint of easy control of the polymerization reaction, the amount of the polymerization initiator in the composition of the present invention is preferably 0.001% by mass to 20% by mass, and more preferably 0.1% by mass to 10% by mass.

Next, a composition in which the compound of the present invention is used as a curing agent will be described.
When the compound of the present invention is used as a curing agent in the composition of the present invention, it is preferred to contain a compound having an oxirane ring, since this improves the curing reaction.

Examples of compounds having an oxirane ring include alicyclic epoxy compounds, aromatic epoxy compounds, and aliphatic epoxy compounds.

The above-mentioned alicyclic epoxy compound refers to an epoxy compound having an alicyclic ring, and examples thereof include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, and cyclohexene oxide- or cyclopentene oxide-containing compounds obtained by epoxidizing cyclohexene- or cyclopentene ring-containing compounds with an oxidizing agent. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexane carboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane carboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexa Examples of such compounds include dimethylaminoethyl ether, ...

In the composition of the present invention, the above alicyclic epoxy compound may be a commercially available product. For example, UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200 (all manufactured by Union Carbide Corporation), Celloxide 2021, Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, Celloxide 2000, Celloxide 3000, Cyclomer A200, Cyclomer B200, Cyclomer C200, Cyclomer D200, Cyclomer E200, Cyclomer F200, Cyclomer H200, Cyclomer I ... Examples of the epoxy resins include Epolead M100, Cyclomer M101, Epolead GT-301, Epolead GT-302, Epolead 401, Epolead 403, ETHB, Epolead HD300, EHPE-3150 (all manufactured by Daicel Corporation), Adeka Arcles KRM-2110, Adeka Arcles KRM-2199 (all manufactured by ADEKA Corporation). Among the above alicyclic epoxy compounds, epoxy resins having a cyclohexene oxide structure are preferred because they cure quickly.

The aromatic epoxy compound refers to an epoxy compound containing an aromatic ring. Examples of aromatic epoxy compounds include mono/polyglycidyl ethers of polyhydric phenols having at least one aromatic ring, such as phenol, cresol, and butylphenol, or their alkylene oxide adducts, such as glycidyl ethers of bisphenol A, bisphenol F, or compounds obtained by further adding alkylene oxides to these, and epoxy novolac resins; mono/polyglycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups, such as resorcinol, hydroquinone, and catechol; glycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, such as phenyl dimethanol, phenyl diethanol, and phenyl dibutanol; glycidyl esters of polybasic aromatic compounds having two or more carboxylic acids, such as phthalic acid, terephthalic acid, and trimellitic acid, glycidyl esters of benzoic acid, epoxidized products of styrene oxide, or divinylbenzene, and the like.

The above aromatic epoxy compounds can be commercially available products. For example, 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 ChemteX Corporation); Oxol PG-100, Oxol EG-200, Oxol EG-210, Oxol EG-250 (manufactured by Osaka Gas Chemicals Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC Corporation); ESN-475 V (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); Epicoat YX8800 (manufactured by Mitsubishi Chemical Co., Ltd.); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corp.); Epicron N-665, Epicron HP-7200 (manufactured by DIC Corp.); EOCN-1020, EOCN-102S, EOCN-103S, EOCN- 104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kayaku Co., Ltd.); ADEKA RESIN EP-4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4100, ADEKA RESIN EP-4901 (manufactured by ADEKA Corporation); TECHMORE VG-3101L (manufactured by Printec Co., Ltd.), etc.

Specific examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, and copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate with other vinyl monomers. Representative compounds include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin, and diglycidyl esters of aliphatic long-chain dibasic acids. Further examples include monoglycidyl ethers of aliphatic higher alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy octyl stearate, epoxy butyl stearate, and epoxidized polybutadiene.
In the composition of the present invention, the aliphatic epoxy compound is preferably one having a saturated condensed ring and one having multiple functions, because they have excellent curing properties.

In the composition of the present invention, commercially available aliphatic epoxy compounds can be used. For example, 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 E X-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 Corporation); Epolight M-1230, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP, Epolight Examples include ADEKA 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), ADEKA GLYCILOR ED-503, ADEKA GLYCILOR ED-503G, ADEKA GLYCILOR ED-506, ADEKA GLYCILOR ED-523T, ADEKA RESIN EP-4088S, ADEKA RESIN EP-4080E (manufactured by ADEKA Corporation).

In addition, in the composition of the present invention, a urethane-modified epoxy resin in which a urethane skeleton is added to a compound having an oxirane ring may be used. The urethane-modified epoxy resin has an epoxy group and a urethane bond in the molecule, and can be obtained, for example, by reacting an epoxy compound having a hydroxyl group in the molecule with a compound having an isocyanate group.

In the composition of the present invention, the compound of the present invention that can be used as a curing agent for curing the compound having an oxirane ring is preferably one in which ^X1 or ^X2 in the above general formula (1) has a polymerizable reactive group having an amino group, an amide group, a heteroaryl group, a thiol group or an acid anhydride group as a functional group, since the curing reaction is favorable.

Among these, in terms of showing an excellent repair function, it is preferable that the polymerizable reactive groups represented by ^X1 and ^X2 in the above general formula (1) have a heteroaryl group as a functional group, and among them, it is preferable that both ^X1 and ^X2 are polymerizable reactive groups having a heteroaryl group as a functional group. Furthermore, it is preferable that the polymerizable reactive groups having a heteroaryl group as a functional group represented by ^X1 and ^X2 are groups in which a heteroaryl group is bonded to a divalent bond group selected from an ether bond, a thioether bond, a carbonyl group, and an ester bond, and it is more preferable that the heteroaryl group is a group in which a carbonyl group is bonded to a heteroaryl group. In addition, it is preferable that the heteroaryl group is a nitrogen-containing heteroaryl group containing a nitrogen atom in the heteroaryl ring, more preferably a triazole group, a pyrazole group, or an imidazole group, and more preferably an imidazole group, in terms of showing a more excellent repair function.

More preferably, a compound in which the polymerizable reactive groups represented by ^X1 and ^X2 in the above general formula (1) are imidazolylcarbonyl groups is used as a curing agent, since this shows a particularly excellent repair function.

In the composition of the present invention, the curable monomer to be cured using the compound in which at least one of ^X1 and ^X2 in the above general formula (1) is a heteroaryl group as a curing agent includes a compound having an oxirane ring, and an epoxy compound having an alicyclic ring is preferable because it has a good curing reaction with the compound of the present invention, and dicyclopentadiene dimethanol glycidyl ether is more preferable because the cured product obtained by the curing reaction with the compound of the present invention shows excellent repair function. Also, a compound in which at least one of ^X1 and ^X2 in the above general formula (1) has a polymerizable reactive group containing an oxirane ring can be used as a curable monomer.

When the compound of the present invention is used as a curing agent in the composition of the present invention, the molar ratio of the compound to the curable monomer in the composition of the present invention is preferably in the range of 0.01 to 2.0, and an equivalent amount is more preferable since this can reduce the amount of unreacted monomer remaining in the cured product or the amount of the compound of the present invention used as a curing agent.

Next, we will explain the composition containing the compound of the present invention having a polymerizable reactive group with an isocyanate group or a hydroxyl group as the functional group.

When the compound of the present invention is a compound in which ^X1 or ^X2 in the general formula (1) has a polymerizable reactive group with an isocyanate group as a functional group, the composition of the present invention preferably contains a compound having a hydroxy group capable of polymerizing the isocyanate group. As the compound having a hydroxy group, a polyol compound having a good curing reaction is preferable.

The above polyol compound refers to a compound having two or more hydroxyl groups in the molecule, and the hydroxyl groups may be alcoholic hydroxyl groups or phenolic hydroxyl groups. Specifically, ethylene glycol, diethylene glycol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,6-hexanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol, 1,2-dimethylolcyclohexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 1,12-dodecanediol, polybutene, Examples include tetramethylene glycol, neopentyl glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, mannitol, sorbitol, pentaerythritol, polyester polyols obtained by condensation polymerization of polyols and polycarboxylic acids or hydroxycarboxylic acids, polyether polyols obtained by adding ethylene oxide or propylene oxide to alcohols or phenols, polyester polyols obtained by ring-opening polymerization of lactones, polycarbonate polyols having a carbonate skeleton in the molecule, phenoxy resins, polybutadienes having hydroxyl groups, and acrylic polyols.

When the compound of the present invention is a compound having a polymerizable reactive group with a hydroxy group as the functional group, the composition of the present invention contains a compound having an isocyanate group capable of undergoing a polymerization reaction with the hydroxy group.

Examples of the compound having an isocyanate group include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and compounds containing terminal isocyanate groups obtained by reacting a polyfunctional isocyanate compound with an active hydrogen compound such as trimethylolpropane.

The amount of the compound having a hydroxyl group or the compound having an isocyanate group blended in the composition is preferably such that the molar ratio to the compound of the present invention is in the range of 0.5 to 2.0, and it is more preferable that the amount is an equivalent amount, since this can reduce the amount of unreacted monomer remaining in the cured product or the amount of the compound of the present invention used as a curing agent.

In the composition of the present invention, in addition to the compound of the present invention and the above-mentioned compounds, other monomer compounds can be included. Examples of other monomer compounds include compounds having an unsaturated hydrocarbon group and polyol compounds.

Examples of compounds having an unsaturated hydrocarbon group include compounds having a vinyl group, compounds having an allyl group, acrylate compounds, and methacrylate compounds.

Examples of compounds having a vinyl group and compounds having an allyl group include alkene compounds such as ethylene, propene, 1-butene, 2-butene, iso-butene, 1-pentene, 1-hexene, and 1-octene; cyano group-containing unsaturated hydrocarbon compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and α-cyanoethylacrylonitrile; vinyl ethyl ether, vinyl butyl ether, vinyl phenyl ether, vinyl 2-chloroethyl ether, 3,4-dihydro-2H-pyran, 2,3-dihydrofuran, Vinyl ether compounds such as 1,4-dioxene, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, and isopropenyl methyl ether; vinyl ester compounds such as vinyl acetate, vinyl butyrate, isopropenyl acetate, vinyl caprate, and vinyl benzoate; unsaturated alcohols such as allyl alcohol and cinnamic alcohol; 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, 2,5-dimethylaminopropane, and the like. conjugated diene compounds such as ethyl-2,4-hexadiene and chloroprene; styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4,6-trimethylstyrene, 4-butylstyrene, 4-phenylstyrene, 4-fluorostyrene, 2,3,4,5,6-pentafluorostyrene, 4-chlorostyrene, 4-bromostyrene, 4-iodostyrene, 4-hydroxystyrene, 4-aminostyrene, 4-carboxystyrene, 4-acetoxystyrene, 4-cyanomethylstyrene, 4-chloromethylstyrene, 4 -Methoxystyrene, 4-nitrostyrene, sodium 4-styrenesulfonate, 4-styrenesulfonic acid chloride, 4-vinylphenylborane acid, α-methylstyrene, trans-β-methylstyrene, 2-methyl-1-phenylpropene, 1-phenyl-1-cyclohexene, β-bromostyrene, sodium β-styrenesulfonate, 2-vinylpyridine, 4-vinylpyridine, 2-iso-propenylnaphthalene, 1-vinylimidazole and other aromatic vinyl compounds; allylbenzene, triallyl cyanurate, etc.

Examples of acrylate compounds that can be used in the composition of the present invention include monofunctional acrylate compounds, difunctional acrylate compounds, and trifunctional or higher polyfunctional acrylate compounds.

Examples of the monofunctional acrylate compounds include alkyl acrylates such as acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, tert-pentyl acrylate, neopentyl acrylate, hexyl acrylate, octyl acrylate, dodecyl acrylate, and stearyl acrylate, benzyl acrylate, alkylphenols (butylphenol, octylphenol, nonylphenol, dodecylphenol, and the like), acrylates of ethylene oxide adducts, isobornyl acrylate, cyclohexyl acrylate, tricyclodecane monomethylol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate. Acrylate, 4-hydroxybutyl acrylate, hydroxypentyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, diethylene glycol monoacrylate, triethylene glycol monoacrylate, polyethylene glycol monoacrylate, dipropylene glycol monoacrylate, polypropylene glycol monoacrylate, glycerin monoacrylate, acryloyloxyethyl phthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-acryloyloxypropyl phthalate, β-carboxyethyl acrylate, acrylic acid dimer, ω-carboxy-polycaprolactone monoacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, N-vinylpyrrolidone, N-vinylformamide, acryloylmorpholine, etc.

Examples of the bifunctional acrylate compounds include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, butylene glycol diacrylate, pentyl glycol diacrylate, neopentyl glycol diacrylate, hydroxypivalyl hydroxypivalate diacrylate, hydroxypivalyl hydroxypivalate dicaprolactonate diacrylate, 1,6-hexanediol diacrylate, 1,2-hexanediol diacrylate, 1,5-hexanediol diacrylate, 2,5-hexanediol diacrylate, 1,7-heptanediol diacrylate, 1,8-octanediol diacrylate, 1,2-octanediol diacrylate, 1,9-nonanediol diacrylate, 1,2-decanediol diacrylate, 1,10-decanediol diacrylate, 1 ,2-decanediol diacrylate, 1,12-dodecanediol diacrylate, 1,2-dodecanediol diacrylate, 1,14-tetradecanediol diacrylate, 1,2-tetradecanediol diacrylate, 1,16-hexadecanediol diacrylate, 1,2-hexadecanediol diacrylate, 2-methyl-2,4-pentanediol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 2-methyl-2-propyl-1,3-propanediol diacrylate, 2,4-dimethyl- 2,4-pentanediol diacrylate, 2,2-diethyl-1,3-propanediol diacrylate, 2,2,4-trimethyl-1,3-pentanediol diacrylate, dimethylol octane diacrylate, 2-ethyl-1,3-hexanediol diacrylate, 2,5-dimethyl-2,5-hexanediol diacrylate, 2-methyl-1,8-octanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 2,4-diethyl-1,5-pentanediol diacrylate, 1, 2-Hexanediol diacrylate, 1,5-Hexanediol diacrylate, 2,5-Hexanediol diacrylate, 1,7-Heptanediol diacrylate, 1,8-Octanediol diacrylate, 1,2-Octanediol diacrylate, 1,9-Nonanediol diacrylate, 1,2-Decanediol diacrylate, 1,10-Decanediol diacrylate, 1,2-Decanediol diacrylate, 1,12-Dodecanediol diacrylate, 1,2-Dodecanediol diacrylate, 1,14-Tet Ladecanediol diacrylate, 1,2-tetradecanediol diacrylate, 1,16-hexadecanediol diacrylate, 1,2-hexadecanediol diacrylate, 2-methyl-2,4-pentane diacrylate, 3-methyl-1,5-pentanediol diacrylate, 2-methyl-2-propyl-1,3-propanediol diacrylate, 2,4-dimethyl-2,4-pentanediol diacrylate, 2,2-diethyl-1,3-propanediol diacrylate, 2,2,4-trimethyl-1,3-pentanediol diacrylate ol diacrylate, dimethylol octane diacrylate, 2-ethyl-1,3-hexanediol diacrylate, 2,5-dimethyl-2,5-hexanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 2,4-diethyl-1,5-pentanediol diacrylate, tricyclodecane dimethylol diacrylate, tricyclodecane dimethylol dicaprolactonate diacrylate, bisphenol A tetraethylene oxide adduct diacrylate, bisphenol F tetraethylene Examples of such compounds include bisphenol A diacrylate, bisphenol S tetraethylene oxide adduct diacrylate, water-added bisphenol A tetraethylene oxide adduct diacrylate, water-added bisphenol F tetraethylene oxide adduct diacrylate, water-added bisphenol A diacrylate, water-added bisphenol F diacrylate, bisphenol A tetraethylene oxide adduct dicaprolactonate diacrylate, and bisphenol F tetraethylene oxide adduct dicaprolactonate diacrylate.

Examples of the polyfunctional acrylate compound include glycerin triacrylate, trimethylolpropane triacrylate, trimethylolpropane tricaprolactonate triacrylate, trimethylolethane triacrylate, trimethylolhexane triacrylate, trimethyloloctane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetracaprolactonate tetraacrylate, diglycerin tetraacrylate, ditrimethylolpropane tetraacrylate, ditrimethylol Examples of the acrylate include propane tetracaprolactonate tetraacrylate, ditrimethylolethane tetraacrylate, ditrimethylolbutane tetraacrylate, ditrimethylolhexane tetraacrylate, ditrimethyloloctane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, and tripentaerythritol polyalkylene oxide heptaacrylate.
Other examples include polyfunctional acrylates such as urethane acrylate and polyester acrylate.

Methacrylate compounds that can be used in the composition of the present invention include, for example, monofunctional methacrylate compounds, bifunctional methacrylate compounds, and trifunctional or higher polyfunctional methacrylate compounds.

Examples of the monofunctional methacrylate compounds include alkyl methacrylates such as methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, tert-pentyl methacrylate, neopentyl methacrylate, hexyl methacrylate, octyl methacrylate, dodecyl methacrylate, and stearyl methacrylate, benzyl methacrylate, alkylphenols (butylphenol, octylphenol, nonylphenol, dodecylphenol, and the like), methacrylates of ethylene oxide adducts, isobornyl methacrylate, cyclohexyl methacrylate, tricyclodecane monomethylol methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2 ... Examples of the methacrylate include hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, hydroxypentyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-methoxypropyl methacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, polyethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, polypropylene glycol monomethacrylate, glycerin monomethacrylate, acryloyloxyethyl phthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-acryloyloxypropyl phthalate, β-carboxyethyl methacrylate, acrylic acid dimer, ω-carboxy-polycaprolactone monomethacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N-vinylpyrrolidone, N-vinylformamide, and acryloylmorpholine.

The bifunctional methacrylate compounds include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, pentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, hydroxypivalyl hydroxypivalyl, and the like. dimethacrylate, hydroxypivalyl hydroxypivalate dicaprolactonate dimethacrylate, 1,6-hexanediol dimethacrylate, 1,2-hexanediol dimethacrylate, 1,5-hexanediol dimethacrylate, 2,5-hexanediol dimethacrylate, 1,7-heptanediol dimethacrylate, 1,8-octanediol dimethacrylate, 1,2-octanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,2-decanediol dimethacrylate, 1,10-decanediol dimethacrylate 1,2-decanediol dimethacrylate, 1,12-dodecanediol dimethacrylate, 1,2-dodecanediol dimethacrylate, 1,14-tetradecanediol dimethacrylate, 1,2-tetradecanediol dimethacrylate, 1,16-hexadecanediol dimethacrylate, 1,2-hexadecanediol dimethacrylate, 2-methyl-2,4-pentanediol dimethacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 2-methyl-2-propyl-1,3-propanediol dimethacrylate, 2,4-dimethyl- ethyl-2,4-pentanediol dimethacrylate, 2,2-diethyl-1,3-propanediol dimethacrylate, 2,2,4-trimethyl-1,3-pentanediol dimethacrylate, dimethylol octane dimethacrylate, 2-ethyl-1,3-hexanediol dimethacrylate, 2,5-dimethyl-2,5-hexanediol dimethacrylate, 2-methyl-1,8-octanediol dimethacrylate, 2-butyl-2-ethyl-1,3-propanediol dimethacrylate, 2,4-diethyl-1,5-pentanediol dimethacrylate, 1,2-Hexanediol dimethacrylate, 1,5-Hexanediol dimethacrylate, 2,5-Hexanediol dimethacrylate, 1,7-Heptanediol dimethacrylate, 1,8-Octanediol dimethacrylate, 1,2-Octanediol dimethacrylate, 1,9-Nonanediol dimethacrylate, 1,2-Decanediol dimethacrylate, 1,10-Decanediol dimethacrylate, 1,2-Decanediol dimethacrylate, 1,12-Dodecanediol dimethacrylate, 1,2-Dodecanediol dimethacrylate, 1,1 4-Tetradecanediol dimethacrylate, 1,2-Tetradecanediol dimethacrylate, 1,16-Hexadecanediol dimethacrylate, 1,2-Hexadecanediol dimethacrylate, 2-Methyl-2,4-pentanediol dimethacrylate, 3-Methyl-1,5-pentanediol dimethacrylate, 2-Methyl-2-propyl-1,3-propanediol dimethacrylate, 2,4-Dimethyl-2,4-pentanediol dimethacrylate, 2,2-Diethyl-1,3-propanediol dimethacrylate, 2,2,4-Trimethyl-1,3-pentanediol dimethacrylate Tandiol dimethacrylate, dimethylol octane dimethacrylate, 2-ethyl-1,3-hexanediol dimethacrylate, 2,5-dimethyl-2,5-hexanediol dimethacrylate, 2-butyl-2-ethyl-1,3-propanediol dimethacrylate, 2,4-diethyl-1,5-pentanediol dimethacrylate, tricyclodecane dimethylol dimethacrylate, tricyclodecane dimethylol dicaprolactonate dimethacrylate, bisphenol A tetraethylene oxide adduct dimethacrylate, bisphenol F tetraethylene oxide adduct dimethacrylate, Examples of such compounds include ethylene oxide adduct dimethacrylate, bisphenol S tetraethylene oxide adduct dimethacrylate, water-added bisphenol A tetraethylene oxide adduct dimethacrylate, water-added bisphenol F tetraethylene oxide adduct dimethacrylate, water-added bisphenol A dimethacrylate, water-added bisphenol F dimethacrylate, bisphenol A tetraethylene oxide adduct dicaprolactonate dimethacrylate, and bisphenol F tetraethylene oxide adduct dicaprolactonate dimethacrylate.

The above-mentioned polyfunctional methacrylate compounds include glycerin trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tricaprolactonate trimethacrylate, trimethylolethane trimethacrylate, trimethylolhexane trimethacrylate, trimethyloloctane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetracaprolactonate tetramethacrylate, diglycerin tetramethacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylol Examples of the methacrylate include propane tetracaprolactonate tetramethacrylate, ditrimethylolethane tetramethacrylate, ditrimethylolbutane tetramethacrylate, ditrimethylolhexane tetramethacrylate, ditrimethyloloctane tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, tripentaerythritol hexamethacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, and tripentaerythritol polyalkylene oxide heptamethacrylate. Other methacrylates such as urethane methacrylate and polyester methacrylate can also be used.

The proportion of the monomer compound in the composition of the present invention is not particularly limited, and can be appropriately blended based on known compositions. Specifically, the total of the compound of the present invention and the monomer compound in the composition is preferably 0.01% by mass to 99.999% by mass, more preferably 0.05% by mass to 99.9% by mass, and even more preferably 0.1% by mass to 97% by mass in terms of exhibiting excellent repair function.

The composition of the present invention may further contain a polymer compound.

Examples of polymeric compounds that can be used in the composition of the present invention include polyesters, polyamides, polylactones, polystyrenes, polyalkylene oxides, polysiloxanes, polydimethylsiloxanes, polycarbonates, polylactides, polyolefins, polyisobutylenes, polyamideimides, polyimides, polyphenols, polyureas, polyurethane ureas, polyglucosides, polybutadienes, epoxy resins, polyacetylenes, polyvinyls, nylons, polyethylene terephthalate, polybutylene terephthalate, polyvinylidene chloride, polyacrylonitrile, polyacrylates, polymethacrylates, polyvinyl alcohols, and copolymerized compounds thereof, derivative compounds thereof, epoxy cured products, urethane cured products, silicone resins, and rubber components.

Examples of epoxy cured products include those obtained by reacting the epoxy compounds exemplified above with a polymerization initiator or curing agent for curing the compound represented by general formula (1).

Examples of urethane cured products include those obtained by reacting the polyol compounds exemplified above with the isocyanate compounds exemplified above.

Examples of rubber components include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiokol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, Examples of such rubbers include styrene-ethylene-butylene random copolymers, ethylene-propylene copolymers (EPR), ethylene-(1-butene) copolymers, ethylene-(1-hexene) copolymers, ethylene-(1-octene) copolymers, ethylene-propylene-diene copolymers (EPDM), and core-shell types such as butadiene-acrylonitrile-styrene-core-shell rubber (ABS), methyl methacrylate-butadiene-styrene-core-shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core-shell rubber (MAS), octyl acrylate-butadiene-styrene-core-shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubber (AABS), butadiene-styrene-core-shell rubber (SBR), and siloxane-containing core-shell rubbers such as methyl methacrylate-butyl acrylate siloxane.

The composition of the present invention may contain an organic solvent to mix the materials uniformly or to ensure good moldability and film-forming properties of the composition.

Organic solvents that can be used in the 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, halogen-containing solvents, etc.

Examples of alcohol-based solvents include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, and n-nonyl alcohol. monoalcohol solvents such as 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, and diacetone alcohol; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,4, Examples of the polyhydric alcohol solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and the like. These alcohol solvents may be used alone or in combination of two or more.

Examples of ketone solvents include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl iso-butyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone. These ketone solvents may be used alone or in combination of two or more.

Examples of amide solvents include N,N-dimethylimidazolidinone, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone. These amide solvents may be used alone or in combination of two or more.

Examples of ether solvents include ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, and diethylene glycol dimethyl. Examples of the ether solvent include ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxy triglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diphenyl ether, and anisole. These ether solvents may be used alone or in combination of two or more.

Examples of ester solvents include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol acetate. Examples of the ester solvent include monoethyl ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate. These ester solvents may be used alone or in combination of two or more.

Examples of aliphatic hydrocarbon solvents include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, cyclohexane, and methylcyclohexane. These aliphatic hydrocarbon solvents may be used alone or in combination of two or more.

Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, di-isopropylbenzene, n-amylnaphthalene, trimethylbenzene, tetralin, anisole, etc. These aromatic hydrocarbon solvents may be used alone or in combination of two or more.

Examples of halogen-containing solvents include dichloromethane, chloroform, fluorocarbons, chlorobenzene, dichlorobenzene, etc. These halogen-containing solvents may be used alone or in combination of two or more.

The organic solvents described above may be used alone or in combination of two or more. The type and amount of these organic solvents can be appropriately selected depending on the viscosity of the solution, the shape to be molded, etc. From the viewpoint of ease of handling of the composition of the present invention, the 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, and even more preferably 10% by mass to 70% by mass, based on the composition.

In addition, the composition of the present invention may contain known additives such as ultraviolet absorbers, light stabilizers, adhesion aids, polymerization inhibitors, sensitizers, antioxidants, smoothness imparting agents, orientation control agents, infrared absorbers, thixotropic agents, antistatic agents, defoamers, colorants, emulsifiers, surfactants, conductivity imparting agents, hydrolysis inhibitors, cellulose nanofibers, fillers, etc., in known amounts and in known usage methods, as necessary, as long as the effects of the present invention are not impaired.

The use of the composition of the present invention is not particularly limited, but it can be suitably used as a self-repairing material. A self-repairing material is a material that can repair itself without external stimuli or by a specific operation, treatment, or external stimuli when it is scratched or damaged due to rubbing, impact, or the like in the environment in which it is used. The external stimuli include contact, light irradiation, heating, pressure, etc., and these may be applied alone, or two or more types of external stimuli may be applied sequentially or simultaneously.

The composition of the present invention can also be used as a surface coating agent, paint, adhesive, or battery material. The surface coating agent is used for the purpose of protecting the surface of the substrate, imparting design and optical properties to the substrate, controlling the physical properties of the surface, and imparting antifouling, chemical resistance, weather resistance, and the like to the substrate. The composition of the present invention can be applied to the surface of the substrate by a known method, such as a die coater method, a comma coater method, a curtain coater method, a spray coater method, a gravure coater method, a flexo coater method, a knife coater method, a doctor blade method, a reverse roll method, a brush coating method, a dip method, an inkjet method, a wire bar coater method, and the like. When the composition of the present invention is used as a surface coating agent, the composition before curing is applied to the surface of the substrate, and then cured by the method described below. When the 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, battery materials, and the like may be blended.

<Cured Product>
Next, the cured product of the present invention will be described.
The cured product of the present invention can be obtained by polymerization reaction using the compound of the present invention and a curing agent or a polymerization initiator. The form of the polymerization reaction may be homopolymerization or copolymerization. The cured product of the present invention is not limited by hardness, strength, etc.

For example, after applying the composition of the present invention to a substrate or molding the composition of the present invention, the composition of the present invention can be cured by light irradiation or heating. The light irradiation and heating may be performed either alone, alternately, simultaneously, or while changing over time.

When the composition of the present invention is cured by energy rays, examples of the energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequency waves, but ultraviolet rays are preferred from an economical viewpoint. Examples of light sources for ultraviolet rays 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 photoradical initiator optionally added to the composition of the present invention, but UV-LED (wavelength: 350 to 450 nm) is preferred from the viewpoint of operability. The cumulative dose may be appropriately changed depending on the thickness of the object, but if the cumulative dose is insufficient, the curing reaction may not proceed sufficiently, and if the cumulative dose is too large, the object may be colored. In general, the cumulative dose is preferably in the range of 1 mJ/cm ² to 100,000 mJ/cm ² .

When the composition of the present invention is cured by heating, the heating temperature is preferably 200°C or less, and more preferably 140°C or less, since this makes it easier to control the curing reaction. Heating is also preferably 40°C or more, and more preferably 50°C or more. 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 for producing the cured product is usually 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 can be selected appropriately depending on the composition of the composition, etc., and may be air or an inert gas atmosphere such as nitrogen gas or argon gas.

The cured product of the present invention may be produced by molding and curing the composition without using an organic solvent, or may be produced by adjusting the viscosity of the composition using an organic solvent and then molding and curing. The produced cured product may be dissolved or swollen in a solvent, molded, and formed into a film. The cured product may also be produced in a state of being emulsified or dispersed in water by emulsion polymerization or suspension polymerization in a water-based system.

The compositions and cured products containing the compounds of the present invention can be used in applications requiring resistance to breakage and fatigue, such as sealing materials, heat insulating materials, soundproofing materials, coating agents, sanitary materials, hose clips, pipes for transporting fluids, flexible hoses, hot melt adhesives, additives for adhesives, optical materials, electrical equipment, battery materials, vehicles, ships, aircraft, buildings, housing and construction materials, civil engineering materials, clothing, curtains, sheets, containers, glasses, suitcases, sporting goods, etc.

More specific applications include optical films, optical sheets, optical filters, high-brightness prism sheets, optical light collectors, anti-glare films and other anti-reflection materials, lighting fixtures, transparent light-gathering materials, protective films, surface materials for pen input devices, electric cables, sheaths, electric wire coating materials, electrical insulation materials, electronic device housings, machine parts, vibration fatigue resistant materials, capacitors, separators for secondary batteries, binders for secondary batteries, solid electrolytes, fiber reinforcement materials, rust inhibitors, corrosion inhibitors, spray pigments, barrier materials (organic substances, gases, humidity) and other paints, building materials for pets, building materials for floors, walls, doors, etc., waterproof sheets, waterproof shields, etc. These include: seats, actuators, cleaning pads, bathtubs, basins, buckets, bathing aids, automotive materials, artificial leather, synthetic leather, artificial skin, stents for intravascular treatment, composite dental restorative materials, sleeve materials, laminated glass, transfer foils, flame-retardant films, writing instrument barrels, cushioning materials, buffer materials, agricultural films, decorative films, decorative sheets, sheets for vinyl greenhouses, insect nets, furniture, clothing, bags, shoes, goggles, skis, snowboards, rackets, tents, containers, cutting boards, antibacterial films, antibacterial molded bodies, barrier films, and packing.

When the composition of the present invention is applied to a surface coating agent, it has the effect of improving processing defects caused by coating. For example, when it is used as a hard coat material for in-mold molding, it can improve the processability during molding processing.

When the composition of the present invention is applied to paint, scratches in the paint film can be repaired by itself. For example, when used as an automobile paint, scratches in the paint can be repaired simply by heating, eliminating the need to repaint the paint.

When the composition of the present invention is applied to an adhesive, the cured product after adhesion will spontaneously bond after cutting, preventing peeling due to adhesion failure or deterioration. It is also possible to impart curing after stress relaxation, which makes it possible to improve adhesive strength.

When the composition of the present invention is applied to battery materials, the effect of self-repair after breakage is obtained. For example, when a secondary battery is repeatedly charged and discharged, the electrode may expand and the binder may break, but even if the battery breaks, the binder will self-repair and prevent the electrode from decomposing, preventing deterioration of battery performance.

The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these.

[Example 1] Preparation of Compound No. 1 1.88 g of bis(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl) disulfide, 1.70 g of carbonyldiimidazole, and 8.2 g of tetrahydrofuran were added to a 1 L glass four-neck flask, mixed by stirring, and then reacted at 25°C for 1 hour by stirring. After the reaction was completed, the solvent was distilled off under reduced pressure, and ethyl acetate and water were added to separate the oil and water. The mixture was washed with water and dried by adding anhydrous sodium sulfate. The solvent was further distilled off under reduced pressure, and the obtained solid was washed with a mixture of hexane and ethyl acetate and dried in vacuum at 50°C to obtain a white solid. The obtained white solid was analyzed by ¹ H-NMR and confirmed to be the target compound, Compound No. 1. The yield of the obtained compound was 95%, and the HPLC purity was 99%. The analysis results are shown below.

^1H -NMR (400MHz, _CDCl3 )
δ/ppm: 8.12 (s, 2H), 7.41 (dd, 1.4MHz, 1.4Hz, 2H), 7.07 (dd, 0.76Hz, 1.5Hz, 2H), 5.34 -5.26 (m, 2 H), 2.15 (dd, 3.98Hz, 12.22Hz, 4H), 1.71 (dd, 11.88Hz, 11.88Hz, 4H), 1.51 (s, 12H), 1.30 ( s, 12H)

Example 2
A composition was prepared by mixing 10 parts by mass of Compound No. 1 obtained in Example 1 and 100 parts by mass of ADEKA RESIN EP-4088S (manufactured by ADEKA CORPORATION). This composition was applied onto a glass plate, covered with a cover film, and heated in an oven at 90°C for 3 days to completely cure, thereby obtaining a coating film sample of Example 2. The obtained coating film sample was scratched with a 9H pencil and then heated in an oven at 120°C for 3 hours, and it was confirmed that the scratch had been repaired.

Comparative Example 1
A coating sample of Comparative Example 1 was obtained in the same manner as in Example 2, except that Compound No. 1 was changed to 2-ethyl-4-methylimidazole. The obtained coating sample was scratched with a 9H pencil and then heated in an oven at 120° C. for 3 hours, whereupon it was confirmed that the scratch remained.

From the above results, according to the present invention, by using a compound represented by general formula (1), it is possible to obtain a material with excellent self-repairing ability.

Claims (15)

A compound represented by the following general formula (1):

(In the formula, ^X1 and ^X2 each independently represent a polymerizable reactive group having 1 to 50 carbon atoms, the polymerizable reactive group containing a heteroaryl group as a functional group, ^R1 to ^R8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 10. ) The compound according to claim 1, wherein the polymerizable reactive groups represented by ^X1 and ^X2 in the general formula (1) contain a saturated aliphatic hydrocarbon group containing a heteroaryl group, a group in which a heteroaryl group and a divalent linking group are linked, or a group consisting of a combination of a heteroaryl group, a saturated aliphatic hydrocarbon group, and a divalent linking group. 3. The compound according to claim 1, wherein R ¹ to R ⁸ in the general formula (1) are methyl groups. The compound according to any one of claims 1 to 3, wherein n in the general formula (1) is 1. A composition comprising a compound according to any one of claims 1 to 4 . The composition according to claim 5 , further comprising at least one member selected from the group consisting of a curing agent and a polymerization initiator. The composition according to claim 6 , wherein the curing agent is at least one selected from the group consisting of an amine compound, an amide compound, an acid anhydride compound, a thiol compound, a phenol compound, and a latent curing agent. The composition according to claim 6 , wherein the polymerization initiator is an imidazole compound, a cationic polymerization initiator or a radical polymerization initiator. The composition according to any one of claims 5 to 8, further comprising a compound having an oxirane ring. A cured product obtained by curing the composition according to any one of claims 5 to 9 . A self-repairing material comprising the composition according to any one of claims 5 to 9 . A surface coating agent comprising the composition according to any one of claims 5 to 9 . A paint comprising the composition according to any one of claims 5 to 9 . An adhesive comprising the composition according to any one of claims 5 to 9 . A battery material comprising the composition according to any one of claims 5 to 9 .