1,1-dicyanoethylene-containing composition, cured product, and laminate

Abstract

Disclosed is a 1,1-dicyanoethylene-containing composition which contains 1,1-dicyanoethylene and an o-substituted phenol compound (A-1) that is represented by a specific formula (I). Also disclosed is a 1,1-dicyanoethylene-containing composition which contains 1,1-dicyanoethylene, a phenol compound (A-2) that is represented by a specific formula (II), and a compound (C) that has a proton affinity (Epa) of 780 kJ / mol or less and a pKa of 5 or less when formed into an aqueous solution.

Description

1,1-dicyanoethylene-containing composition, cured product, and laminate

[0001] The present invention relates to a 1,1-dicyanoethylene-containing composition, a cured product, and a laminate.

[0002] 1,1-dicyanoethylene is sometimes used in curable adhesives due to its excellent reactivity.

[0003] However, due to its high reactivity, the use of 1,1-dicyanoethylene requires the use of an acid stabilizer to improve storage stability. Patent Documents 1 and 2 propose the use of benzenesulfonic acid, chlorobenzenesulfonic acid, p-toluenesulfonic acid, or the like as an acid stabilizer.

[0004] Methylenemalonic acid is a compound that has high reactivity similar to 1,1-dicyanoethylene. Patent Document 3 proposes that storage stability can be improved by adding an antioxidant and an acid to methylenemalonic acid. In Patent Document 3, acetic acid is specifically used as the acid in the examples.

[0005] US Patent No. 2,665,298 US Patent No. 2,535,861 Japanese Patent Application Laid-Open No. 2008-174494

[0006] However, as a result of research by the present inventors, it was found that the methods proposed in Patent Documents 1 and 2 are capable of inhibiting the anionic polymerization of 1,1-dicyanoethylene, but are not sufficient to inhibit radical polymerization.

[0007] Furthermore, since 1,1-dicyanoethylene has a higher reactivity with Lewis basic compounds than methylenemalonic acid, the teachings of Patent Document 3 do not immediately apply to 1,1-dicyanoethylene.

[0008] Therefore, there is still a need to improve the storage stability of 1,1-dicyanoethylene-containing compositions in order to prevent reaction and curing before use. Furthermore, if a 1,1-dicyanoethylene-containing composition with excellent storage stability could be provided, it would be expected that cured products and laminates that do not lose their desired physical properties could be provided.

[0009] On the other hand, phenolic compounds are commonly used as radical polymerization inhibitors. However, in a system in which 1,1-dicyanoethylene is present, 1,1-dicyanoethylene reacts with the hydroxy group of the phenolic compound, and the polymerization of 1,1-dicyanoethylene may not be sufficiently inhibited.

[0010] An object of the present invention is to provide a 1,1-dicyanoethylene-containing composition that has excellent storage stability, a cured product that uses the same components as the 1,1-dicyanoethylene-containing composition, and a laminate that includes the cured product.

[0011] As a result of intensive research, the present inventors have found that in a system in which 1,1-dicyanoethylene and a phenolic compound are present, a 1,1-dicyanoethylene-containing composition having excellent storage stability can be provided by stabilizing the hydroxy group of the phenolic compound. Specifically, the inventors have found that methods for stabilizing the hydroxy group of the phenolic compound include introducing a specific substituent into the phenolic compound and allowing the phenolic compound to coexist with a specific compound that stabilizes the hydroxy group of the phenolic compound.

[0012] That is, the present invention provides the following items [1] to

[40] : [1] A 1,1-dicyanoethylene-containing composition containing 1,1-dicyanoethylene and an o-substituted phenol compound (A-1) represented by the following formula (I): ...(I) (wherein, R １１ and R １５ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR １ａ (R １ａ is an alkyl group having 1 to 25 carbon atoms. １ｂ (R １ｂ is an alkyl group having 1 to 25 carbon atoms; １ｃ (R １ｃis an alkyl group having 1 to 25 carbon atoms; and R is an o-substituent selected from the group consisting of an acyloxy group represented by the formula (I), a halogen atom, and a haloalkyl group. １１ and R １５ Except when both of R are hydrogen atoms. １３ is a hydrogen atom or a p-substituent, and the p-substituent is the same as the o-substituent. １２ and R １４ are each independently a hydrogen atom or an m-substituent, and the m-substituent is the same as the p-substituent.) [2] R １１ and R １５ The 1,1-dicyanoethylene-containing composition according to [1], wherein one or both of the Taft steric parameter Es values ​​are less than 1.24. [3] R １１ and R １５ or both of the above are each independently one selected from the group consisting of a branched alkyl group, a cycloalkyl group, and an aryl group. [4] The 1,1-dicyanoethylene-containing composition according to any one of [1] to [3], wherein the o-substituted phenol compound (A-1) is at least one selected from 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-di-tert-butylphenol, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and 4,4'-butylidenebis(6-tert-butyl-m-cresol). [5] R １１ and R １５ The 1,1-dicyanoethylene-containing composition according to [1], wherein the Taft steric parameter Es values ​​of both of the above are less than 1.24. [6] R １１ and R １５are each independently one selected from the group consisting of a branched alkyl group, a cycloalkyl group, and an aryl group. [7] The 1,1-dicyanoethylene-containing composition according to any of [1] to [3], wherein the o-substituted phenol compound (A-1) comprises at least one selected from 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. [8] The 1,1-dicyanoethylene-containing composition according to any of [1] to [3], wherein R １１ and R １５ and (b) a 1,1-dicyanoethylene-containing composition according to any one of [1] to [7], excluding cases where both of the above are halogen atoms. [9] The 1,1-dicyanoethylene-containing composition according to any one of [1] to [8], further comprising a polymerizable monomer (B).

[10] The 1,1-dicyanoethylene-containing composition according to [9], wherein the polymerizable monomer (B) is at least one selected from the group consisting of ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, alkyl acrylate esters, alkyl methacrylate esters, acrylonitrile, vinyl chloride, vinylidene chloride, vinylidene fluoride, alkyl 2-cyanoacrylate esters, alkyl 2-cyanopentadienoate esters, and dialkyl methylidenemalonate esters.

[11] The 1,1-dicyanoethylene-containing composition according to

[10] , wherein the polymerizable monomer (B) contains a 2-cyanoacrylic acid alkyl ester.

[12] The 1,1-dicyanoethylene-containing composition according to

[11] , wherein the 2-cyanoacrylic acid alkyl ester is 2-cyanoacrylate ethyl.

[13] A cured product obtained by reacting 1,1-dicyanoethylene with a Lewis basic compound in the presence of an o-substituted phenol compound (A-1) represented by the following formula (I): ...(I) (wherein, R １１ and R １５ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR １ａ (R １ａ is an alkyl group having 1 to 25 carbon atoms. １ｂ (R １ｂ is an alkyl group having 1 to 25 carbon atoms; １ｃ (R １ｃ is an alkyl group having 1 to 25 carbon atoms; and R is an o-substituent selected from the group consisting of an acyloxy group represented by the formula (I), a halogen atom, and a haloalkyl group. １１ and R １５ Except when both of R are hydrogen atoms. １３ is a hydrogen atom or a p-substituent, and the p-substituent is the same as the o-substituent. １２ and R １４ are each independently a hydrogen atom or an m-substituent, and the m-substituent is the same as the p-substituent.)

[14] R １１ and R １５

[15] The cured product according to

[13] , wherein one or both of the Taft steric parameter Es values ​​are less than 1.24. １１ and R １５

[16] The cured product according to any one of

[13] to

[15] , wherein the o-substituted phenol compound (A-1) is at least one selected from the group consisting of 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-di-tert-butylphenol, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and 4,4'-butylidenebis(6-tert-butyl-m-cresol).

[17] R １１ and R １５ The cured product according to

[13] , wherein the Taft steric parameter Es values ​​of both of the above are less than 1.24.

[18] R １１ and R １５ are each independently one selected from the group consisting of a branched alkyl group, a cycloalkyl group, and an aryl group.

[19] The cured product according to any one of

[13] to

[15] , wherein the o-substituted phenol compound (A-1) comprises at least one selected from 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[20] R １１ and R １５and (b) are halogen atoms.

[21] The cured product according to any one of

[13] to

[19] , obtained by reacting 1,1-dicyanoethylene, a polymerizable monomer (B), and the Lewis base compound.

[22] The cured product according to

[21] , wherein the polymerizable monomer (B) is one or more selected from the group consisting of ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, alkyl acrylate esters, alkyl methacrylate esters, acrylonitrile, vinyl chloride, vinylidene chloride, vinylidene fluoride, alkyl 2-cyanoacrylate esters, alkyl 2-cyanopentadienoate esters, and dialkyl methylidenemalonate esters.

[23] The cured product according to

[22] , wherein the polymerizable monomer (B) contains a 2-cyanoacrylic acid alkyl ester.

[24] The cured product according to

[23] , wherein the 2-cyanoacrylic acid alkyl ester is 2-cyanoacrylate ethyl.

[25] A laminate comprising the cured product according to any one of

[13] to

[24] , and an adherend bonded to the cured product.

[26] A 1,1-dicyanoethylene-containing composition comprising 1,1-dicyanoethylene, a phenolic compound (A-2) represented by the following formula (II), and a compound (C) having a proton affinity (Epa) of 780 kJ / mol or less and a pKa of 5 or less when formed into an aqueous solution: ... (II) (wherein, R ２１ and R ２５ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR ２ａ (R ２ａ is an alkyl group having 1 to 25 carbon atoms. ２ｂ (R ２ｂ is a hydrogen atom or an alkyl group having 1 to 25 carbon atoms; ２ｃ (R ２ｃis an alkyl group having 1 to 25 carbon atoms. R is an o-substituent selected from the group consisting of an acyloxy group, a hydroxy group, an amino group, a halogen atom, and a haloalkyl group represented by the formula (I). ２３ is a hydrogen atom or a p-substituent, and the p-substituent is the same as the o-substituent. ２２ and R ２４ are each independently a hydrogen atom or an m-substituent, and the m-substituent is the same as the p-substituent.)

[27] R ２１ and R ２５ and (B) are hydrogen atoms.

[28] The 1,1-dicyanoethylene-containing composition according to

[26] or

[27] , wherein the compound (C) is at least one selected from the group consisting of methanesulfonic acid, sulfuric acid, and sulfur dioxide.

[29] The 1,1-dicyanoethylene-containing composition according to any one of

[26] to

[28] , further comprising a polymerizable monomer (B).

[30] The 1,1-dicyanoethylene-containing composition according to

[29] , wherein the polymerizable monomer (B) is at least one selected from the group consisting of ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, alkyl acrylate esters, alkyl methacrylate esters, acrylonitrile, vinyl chloride, vinylidene chloride, vinylidene fluoride, alkyl 2-cyanoacrylate esters, alkyl 2-cyanopentadienoate esters, and dialkyl methylidenemalonate esters.

[31] The 1,1-dicyanoethylene-containing composition according to

[30] , wherein the polymerizable monomer (B) comprises an alkyl 2-cyanoacrylate ester.

[32] The 1,1-dicyanoethylene-containing composition according to

[31] , wherein the 2-cyanoacrylic acid alkyl ester is 2-cyanoacrylic acid ethyl ester.

[33] A cured product obtained by reacting 1,1-dicyanoethylene with a Lewis basic compound in the presence of a phenolic compound (A-2) represented by the following formula (II) and a compound (C) having a proton affinity (Epa) of 780 kJ / mol or less and a pKa of 5 or less in aqueous solution: ... (II) (wherein, R ２１ and R ２５ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR ２ａ (R ２ａ is an alkyl group having 1 to 25 carbon atoms. ２ｂ (R ２ｂ is a hydrogen atom or an alkyl group having 1 to 25 carbon atoms; ２ｃ (R ２ｃ is an alkyl group having 1 to 25 carbon atoms. R is an o-substituent selected from the group consisting of an acyloxy group, a hydroxy group, an amino group, a halogen atom, and a haloalkyl group represented by the formula (I). ２３ are each independently a hydrogen atom or a p-substituent, and the p-substituent is the same as the o-substituent. ２２ and R ２４ are each independently a hydrogen atom or an m-substituent, and the m-substituent is the same as the p-substituent.)

[34] R ２１ and R ２５are hydrogen atoms.

[35] The cured product according to

[33] or

[34] , wherein compound (C) is at least one selected from the group consisting of methanesulfonic acid, sulfuric acid, and sulfur dioxide.

[36] The cured product according to any one of

[33] to

[35] , obtained by reacting 1,1-dicyanoethylene, polymerizable monomer (B), and the Lewis basic compound.

[37] The cured product according to

[36] , wherein the polymerizable monomer (B) is at least one selected from the group consisting of ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, alkyl acrylate esters, alkyl methacrylate esters, acrylonitrile, vinyl chloride, vinylidene chloride, vinylidene fluoride, alkyl 2-cyanoacrylate esters, alkyl 2-cyanopentadienoate esters, and dialkyl methylidenemalonate esters.

[38] The cured product according to

[37] , wherein the polymerizable monomer (B) comprises an alkyl 2-cyanoacrylate ester.

[39] The cured product according to

[38] , wherein the alkyl 2-cyanoacrylate ester is ethyl 2-cyanoacrylate.

[40] A laminate comprising the cured product according to any one of

[33] to

[39] and an adherend adhered to the cured product.

[0013] According to the present invention, it is possible to provide a 1,1-dicyanoethylene-containing composition having excellent storage stability. Furthermore, according to the present invention, it is possible to provide a cured product using the same components as the 1,1-dicyanoethylene-containing composition, and a laminate including the cured product.

[0014] The following describes an example of a mode for carrying out the present invention (hereinafter, sometimes referred to as "the present embodiment"). However, the embodiment described below is an example for embodying the technical idea of ​​the present invention, and the present invention is not limited to the following description. Furthermore, although preferred modes of the embodiment are shown in this specification, a combination of two or more of the individual preferred modes is also a preferred mode. For matters shown as numerical ranges, when there are several numerical ranges, the lower limit and upper limit can be selectively combined to form a preferred mode. In this specification, when a numerical range is described as "XX to YY," it means "XX or more and YY or less."

[0015] [First embodiment] [1,1-dicyanoethylene-containing composition according to the first embodiment] The 1,1-dicyanoethylene-containing composition according to the first embodiment of the present invention is a 1,1-dicyanoethylene-containing composition containing 1,1-dicyanoethylene and a specific o-substituted phenol compound (A-1). By including the specific o-substituted phenol compound (A-1) in the 1,1-dicyanoethylene-containing composition, it is possible to provide a 1,1-dicyanoethylene-containing composition having excellent storage stability. The specific o-substituted phenol compound (A-1) may be one type or multiple types.

[0016] (1,1-Dicyanoethylene) 1,1-dicyanoethylene may be produced according to the production method described in J. Am. Chem. Soc., 1989, 111, 9078-9081 or the production method described in U.S. Pat. No. 2,476,270. The purity of 1,1-dicyanoethylene to be used in the 1,1-dicyanoethylene-containing composition according to the embodiment of the present invention is preferably 95% or more, more preferably 97% or more, even more preferably 98% or more, and even more preferably 99% or more. The purity of 1,1-dicyanoethylene can be determined, for example, by gas chromatography. Furthermore, the produced 1,1-dicyanoethylene may be stored until immediately before use in the presence of, for example, aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane and heptane; naphthenic solvents such as cyclohexane; ester solvents such as ethyl acetate; and ether solvents such as tetrahydrofuran and diethyl ether.

[0017] (Specific o-substituted phenol compound (A-1)) The specific o-substituted phenol compound (A-1) is represented by the following formula (I). ...(I)

[0018] In the formula (I), R １１ and R １５ is a hydrogen atom or an o-substituent. The o-substituent refers to a substituent that is located at the o-position relative to the hydroxy group (the —OH group in the formula (I)) of the phenol compound. However, in the first embodiment, R １１ and R １５ The case where both of R are hydrogen atoms (i.e., both of the o-positions) is excluded. １１ and R １５where neither of the hydroxyl groups (i.e., neither of the two o-positions) is a hydrogen atom, the o-substituent can stabilize the hydroxy group of the phenolic compound. The reason for the stabilization of the hydroxy group is not limited to this, but it is thought that the o-substituent in the vicinity of the hydroxy group acts as a steric hindrance, suppressing the reactivity of the hydroxy group. Furthermore, it is thought that the stabilization of the hydroxy group of the phenolic compound can suppress the reaction with coexisting 1,1-dicyanoethylene. The reaction between 1,1-dicyanoethylene and the phenolic compound can be confirmed by thickening or solidification (precipitation) of the composition, as exemplified in the Examples section.

[0019] In the formula (I), R １１ and R １５ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR １ａ (R １ａ is an alkyl group having 1 to 25 carbon atoms. １ｂ (R １ｂ is an alkyl group having 1 to 25 carbon atoms; １ｃ (R １ｃ is an alkyl group having 1 to 25 carbon atoms.) is an o-substituent which is one selected from the group consisting of an acyloxy group represented by the formula (I), a halogen atom, and a haloalkyl group. １１ and R １５ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR １ａ (R １ａ is an alkyl group having 1 to 25 carbon atoms. １ｂ (R １ｂ is an alkyl group having 1 to 25 carbon atoms; １ｃ (R １ｃ is an alkyl group having 1 to 25 carbon atoms.

[0020] R１１ and R １５ The alkyl group that may be taken by is preferably an alkyl group having 1 to 25 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group.

[0021] R １１ and R １５ The cycloalkyl group which may be taken by is preferably a cycloalkyl group having 3 to 12 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0022] R １１ and R １５ The aryl group which may be taken by is preferably an aryl group having 6 to 25 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0023] R １１ and R １５ The alkoxy group which may be taken by is preferably an alkoxy group having 1 to 25 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

[0024] R １１ and R １５ The ester group (-COOR) １ａ ), acyl group (—COR １ｂ ) and acyloxy groups (—OCOR １ｃ ) in which R １ａ , R １ｂ and R １ｃ Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group.

[0025] R １１and R １５ Examples of the acid anhydride group that can be taken include acid anhydride groups derived from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0026] R １１ and R １５ Examples of halogen atoms that R can have include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. １１ and R １５ The haloalkyl group that can be taken is preferably a haloalkyl group having 1 to 12 carbon atoms, and more preferably a haloalkyl group having 1 to 6 carbon atoms. Examples of halogen atoms constituting the haloalkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0027] R １１ and R １５ Specific examples of the o-substituent that may be taken by include a linear alkyl group having 1 to 25, preferably 1 to 12, and more preferably 1 to 6 carbon atoms; a branched alkyl group having 3 to 25, preferably 3 to 12, and more preferably 3 to 6 carbon atoms; a cycloalkyl group having 5 to 25, preferably 5 to 12, and more preferably 5 to 6 carbon atoms; an alkoxy group having 1 to 25, preferably 1 to 12, and more preferably 1 to 6 carbon atoms; and an aryl group having 6 to 25, preferably 6 to 12, and more preferably 6 carbon atoms. Among these, the o-substituent is preferably a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an aryl group having 5 to 12 carbon atoms, more preferably a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, cyclohexyl group, or phenyl group, even more preferably a t-butyl group, cyclohexyl group, or phenyl group, and still more preferably a t-butyl group.

[0028] In one preferred embodiment, R１１ and R １５ The Taft steric parameter Es value (hereinafter referred to as "Taft value") of one or both of the above is less than 1.24. As the Taft value, the value described in Non-Patent Document 1 (John A. M., ANNICK P. and JACQUES-EMILE D. Tetrahedron, 1978, 34, 3553-3562) can usually be adopted.

[0029] The Taft value is preferably less than 0.08, more preferably 0.01 or less, even more preferably -0.06 or less, still more preferably less than -0.16, still more preferably -0.78 or less, and still more preferably -1.00 or less. Examples of substituents having a Taft value of -1.00 or less include an s-butyl group and a t-butyl group.

[0030] Preferably, R １１ and R １５ The steric parameter Es values ​​(Taft values) of both Tafts are less than 1.24. A more preferable range of the Taft value is as described above.

[0031] In another preferred embodiment, R １１ and R １５ One or both of R are independently one selected from the group consisting of branched alkyl groups, cycloalkyl groups, and aryl groups. １１ and R １５ or both of which are independently one selected from the group consisting of a branched alkyl group, a cycloalkyl group, and an aryl group. Examples of the branched alkyl group, the cycloalkyl group, and the aryl group include those described above.

[0032] In one embodiment, R １１ and R １５ In this case, the case where both of the above are halogen atoms is excluded. This makes it possible to more reliably achieve the desired effect.

[0033] In the formula (I), R １３is a hydrogen atom or a p-substituent, and the p-substituent is the same as the o-substituent. The p-substituent being the same as the o-substituent means that examples of the p-substituent are the same as examples of the o-substituent. Therefore, the p-substituent and the o-substituent may be different from each other or may be the same. The p-substituent refers to a substituent that is located at the p-position relative to the hydroxy group (the —OH group in the formula (I)) of the phenol compound. That is, in the formula (I), R １３ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, -COOR １ａ (R １ａ is an alkyl group having 1 to 25 carbon atoms. １ｂ (R １ｂ is an alkyl group having 1 to 25 carbon atoms; １ｃ (R １ｃ is an alkyl group having 1 to 25 carbon atoms.

[0034] R １３ Examples of the p-substituent that may be taken by the group include a linear alkyl group having 1 to 25, preferably 1 to 12, and more preferably 1 to 6 carbon atoms, a branched alkyl group having 3 to 25, preferably 3 to 12, and more preferably 3 to 6 carbon atoms, a cycloalkyl group having 5 to 25, preferably 5 to 12, and more preferably 5 to 6 carbon atoms, an alkoxy group having 1 to 25, preferably 1 to 12, and more preferably 1 to 6 carbon atoms, an aryl group having 6 to 25, preferably 6 to 12, and more preferably 6 carbon atoms, an alkyl group having 1 to 25, preferably 1 to 12, and more preferably 1 to 6 carbon atoms, and -COOR １ａ (R １ａ is an alkyl group having 1 to 25 carbon atoms; and a combination of an alkyl group having 1 to 25 carbon atoms, preferably 1 to 12, more preferably 1 to 6 carbon atoms, —COOR １ａ (R １ａ is an alkyl group having 1 to 25 carbon atoms; an alkyl group having 1 to 25 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms; —OCOR １ｃ (R １ｃis an alkyl group having 1 to 25 carbon atoms; and a combination of an alkyl group having 1 to 25 carbon atoms, preferably 1 to 12, more preferably 1 to 6 carbon atoms, and an aryl group having 6 to 25 carbon atoms, preferably 6 to 12, more preferably 6 carbon atoms (this aryl group may have an optional substituent, for example, a hydroxy group or a t-butyl group).

[0035] In the formula (I), R １２ and R １４ are each independently a hydrogen atom or an m-substituent, and the m-substituent is the same as the p-substituent. The m-substituent being the same as the p-substituent means that the examples of the m-substituent are the same as the examples of the p-substituent. Therefore, the m-substituent and the p-substituent may be different from each other or may be the same. The m-substituent refers to a substituent that is located in the m-position relative to the hydroxy group (the —OH group in the formula (I)) that the phenol compound has. That is, in the formula (I), R １２ and R １４ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR １ａ (R １ａ is an alkyl group having 1 to 25 carbon atoms. １ｂ (R １ｂ is an alkyl group having 1 to 25 carbon atoms; １ｃ (R １ｃ is an alkyl group having 1 to 25 carbon atoms. R is an acyloxy group represented by the following formula (I), a halogen atom, or a haloalkyl group. １２ and R １４ are each independently preferably one selected from the group consisting of a hydrogen atom, a linear alkyl group having 1 to 25, preferably 1 to 12, more preferably 1 to 6 carbon atoms, and a branched alkyl group having 3 to 25, preferably 3 to 12, more preferably 3 to 6 carbon atoms, and more preferably a hydrogen atom.

[0036] Specific examples of the specific o-substituted phenol compound (A-1) include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-di-tert-butylphenol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), phenol), 2,2'-methylenebis-(4-ethyl-6-t-butylphenol) (Yoshinox 425), 4,4'-butylidenebis-(6-t-butyl-3-methylphenol) (Yoshinox BB), 2,2'-methylenebis[6-tert-butyl-4-methylphenol] (Sumilizer MDP-S), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (Adekastab AO-30), 4,4'-butylidenebis(6-tert-butyl-m -cresol) (ADEKA STAB AO-40), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (ADEKA STAB AO-50), 2,2'-dimethyl-2,2'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1'-diyl bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate] (ADEKA STAB AO-80), 1,3,5-trimethyl-2,4,6- Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (ADEKA STAB AO-330), 4,4'-thiobis[3-methyl-6-(tert-butyl)phenol] (SUMIRAIZER WX-R), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene, 1'-hydroxy[2,2'-ethylidenebis[4,6-bis(1,Examples of suitable o-disubstituted phenols include 2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl acrylate (Sumilizer GM), and 2-tert-butyl-6-methyl-4-{3-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl}phenol (Sumilizer GP). Among these, compounds belonging to the o-disubstituted phenols are preferred. In a preferred embodiment, the specific o-substituted phenol compound (A-1) is at least one selected from 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-di-tert-butylphenol, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and 4,4′-butylidenebis(6-tert-butyl-m-cresol). In a more preferred embodiment, the specific o-substituted phenol compound (A-1) is at least one selected from 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 2,4-di-tert-butylphenol. In a more preferred embodiment, the specific o-substituted phenol compound (A-1) is at least one selected from 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. In an even more preferred embodiment, the specific o-substituted phenol compound (A-1) is 2,The compound contains at least one selected from 6-di-tert-butylphenol and 2,6-di-tert-butyl-4-methylphenol. When a compound belonging to the o-monosubstituted phenol group is used, it is preferable to use it in combination with an acidic compound other than a phenolic compound, and it is more preferable to use it in combination with compound (C) described later in the second embodiment.

[0037] From the viewpoint of suppressing coloration of the 1,1-dicyanoethylene-containing composition, the specific o-substituted phenol compound (A-1) preferably has, as a p-substituent, a substituent other than a hydrogen atom, and more preferably has a substituent other than a hydrogen atom or a halogen atom.

[0038] (Component (B): Polymerizable Monomer) The 1,1-dicyanoethylene-containing composition according to the first embodiment may further contain a polymerizable monomer (B). 1,1-dicyanoethylene is excluded from the polymerizable monomer (B). The polymerizable monomer (B) is preferably reactive with 1,1-dicyanoethylene. The polymerizable monomer (B) may be one type or multiple types. The polymerizable monomer (B) may be a radical polymerizable monomer or an anion polymerizable monomer.

[0039] Examples of the polymerizable monomer (B) include ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, alkyl acrylates such as butyl acrylate, alkyl methacrylates such as methyl methacrylate and dodecyl methacrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinylidene fluoride, alkyl 2-cyanoacrylates, alkyl 2-cyanopentadienoates, and dialkyl methylidenemalonates. Among these, from the viewpoint of excellent reactivity with 1,1-dicyanoethylene, the polymerizable monomer (B) is preferably at least one selected from the group consisting of ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, alkyl acrylate esters, alkyl methacrylate esters, acrylonitrile, vinyl chloride, vinylidene chloride, vinylidene fluoride, alkyl 2-cyanoacrylate esters, alkyl 2-cyanopentadienoate esters, and dialkyl methylidenemalonate esters, more preferably alkyl 2-cyanoacrylate esters, and even more preferably, the alkyl 2-cyanoacrylate ester is ethyl 2-cyanoacrylate.

[0040] The method for producing the polymerizable monomer (B) is not particularly limited, and known methods can be used alone or in combination to produce the polymerizable monomer (B). The polymerizable monomer (B) may be a commercially available product.

[0041] (Other Components) The 1,1-dicyanoethylene-containing composition according to the first embodiment may contain one or more other components. Examples of such other components include Bronsted acidic compounds other than phenolic compounds, acid anhydrides, Lewis acidic compounds, thickeners, dehydrating agents, radical polymerization inhibitors (excluding the phenolic compounds described above), plasticizers, pigments, organic solvents, rubber, organic fillers, and inorganic fillers. The other components can be used in a content range that does not impair the intended effects of the present invention. The acid anhydride may function as a dehydrating agent. The rubber may function as an organic filler. The inorganic filler may function as a thickener.

[0042] Examples of acidic compounds other than phenolic compounds include methanesulfonic acid, sulfuric acid, sulfur dioxide, hydrochloric acid, nitric acid, sulfurous acid, p-toluenesulfonic acid, and phosphoric acid. Among these, it is preferable to use a compound belonging to the group of compounds (C) described later in the second embodiment.

[0043] When an acidic compound other than a phenolic compound is used as another component, the amount of such an acidic compound is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, even more preferably 2.0 parts by mass or less, and still more preferably 1.0 part by mass or less, relative to 100 parts by mass of the total amount of the monomers (1,1-dicyanoethylene and the polymerizable monomer (B) used as needed). From the viewpoint of further improving the storage stability of the 1,1-dicyanoethylene-containing composition, the amount of the acidic compound is preferably 0.0005 parts by mass or more, more preferably 0.001 parts by mass or more, and even more preferably 0.005 parts by mass or more, relative to 100 parts by mass of the total amount of the monomers.

[0044] Furthermore, from the viewpoint of further enhancing the storage stability of the 1,1-dicyanoethylene-containing composition, the content of the acidic compound is preferably 0.0005% by mass or more, more preferably 0.0009% by mass or more, even more preferably 0.004% by mass or more, and is preferably 10% by mass or less, more preferably 5.0% by mass or less, even more preferably 2.0% by mass or less, and still more preferably 1.0% by mass or less, when the entire 1,1-dicyanoethylene-containing composition is taken as 100% by mass.

[0045] (Content of Each Component) When the entire 1,1-dicyanoethylene-containing composition according to the first embodiment is taken as 100% by mass, the total amount of the monomers (1,1-dicyanoethylene and the polymerizable monomer (B) used as needed) is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, from the viewpoint of achieving desired physical properties. When the polymerizable monomer (B) is used, the mass ratio of 1,1-dicyanoethylene to the polymerizable monomer (B) is not particularly limited, but may be 99:1 to 1:99, 80:20 to 20:80, or 70:30 to 30:70.

[0046] The specific o-substituted phenol compound (A-1) is used in an amount of preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, even more preferably 2.0 parts by mass or less, and still more preferably 1.5 parts by mass or less, based on 100 parts by mass of the total amount of the monomers (1,1-dicyanoethylene and the polymerizable monomer (B) used as needed). From the viewpoint of improving the storage stability of the 1,1-dicyanoethylene-containing composition, the specific o-substituted phenol compound (A-1) is used in an amount of preferably 0.0005 parts by mass or more, more preferably 0.001 parts by mass or more, and even more preferably 0.005 parts by mass or more, based on 100 parts by mass of the total amount of the monomers.

[0047] Furthermore, from the viewpoint of enhancing the storage stability of the 1,1-dicyanoethylene-containing composition, the content of the specific o-substituted phenol compound (A-1) is preferably 0.00003% by mass or more, more preferably 0.00006% by mass or more, even more preferably 0.00009% by mass or more, and is preferably 10% by mass or less, more preferably 5.0% by mass or less, even more preferably 2.0% by mass or less, and still more preferably 1.5% by mass or less, when the entire 1,1-dicyanoethylene-containing composition is taken as 100% by mass.

[0048] (Applications) The 1,1-dicyanoethylene-containing composition according to this embodiment can be used as an (instant) adhesive. Applications of such adhesives include general household adhesives, medical applications, hemostatic adhesives, lamination, bookbinding, shoe assembly, automotive parts, air conditioning systems, components for electrical or electronic devices or other durable consumer goods, assembly of components used in the building industry (e.g., insulating, thermal, and / or acoustic applications), packaging, die-bonding applications, wound closure, surgical suturing, medical device applications, and all types of labeling, eyelash extension adhesives, and cosmetic adhesives. While instant adhesives containing 2-cyanoethyl acrylate as a primary ingredient are widely known, 2-cyanoethyl acrylate has the drawback of being poor in heat resistance and moisture resistance, and as a result, these instant adhesives suffer from poor heat resistance and moisture resistance. On the other hand, 1,1-dicyanoethylene has excellent heat resistance and moisture resistance, and the adhesive using the 1,1-dicyanoethylene-containing composition according to the present invention has excellent heat resistance and moisture resistance.

[0049] The 1,1-dicyanoethylene-containing composition according to this embodiment can also be used as a coating material. Applications of such coating materials include film capacitors, insulating layers for EL devices, electrostatic induction conversion elements, sensors (e.g., touch sensors, vibration sensors, biosensors, tire sensors (particularly sensors installed on the inner surface of tires)), actuators, touch panels, haptic devices, vibration power generation devices (e.g., vibration power generation floors, vibration power generation tires), speakers, microphones, vibration-damping sheets, hollow fiber membranes for water purification, and resist films. An example of a haptic device is a device that has the function of providing tactile feedback to a user.

[0050] [Cured Product According to First Embodiment] The cured product according to the first embodiment of the present invention is a cured product obtained by reacting 1,1-dicyanoethylene with a Lewis basic compound in the presence of an o-substituted phenol compound (A-1) represented by the following formula (I):

[0051] ...(I) (wherein, R １１ and R １５are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR １ａ (R １ａ is an alkyl group having 1 to 25 carbon atoms. １ｂ (R １ｂ is an alkyl group having 1 to 25 carbon atoms; １ｃ (R １ｃ is an alkyl group having 1 to 25 carbon atoms; and R is an o-substituent selected from the group consisting of an acyloxy group represented by the formula (I), a halogen atom, and a haloalkyl group. １１ and R １５ In other words, in the formula (I), R １１ and R １５ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR １ａ (R １ａ is an alkyl group having 1 to 25 carbon atoms. １ｂ (R １ｂ is an alkyl group having 1 to 25 carbon atoms; １ｃ (R １ｃ is an alkyl group having 1 to 25 carbon atoms. R is an acyloxy group represented by the following formula (I), a halogen atom, or a haloalkyl group. １３ is a hydrogen atom or a p-substituent, and a p-substituent is the same as an o-substituent. １３ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, -COOR １ａ (R １ａ is an alkyl group having 1 to 25 carbon atoms. １ｂ (R １ｂ is an alkyl group having 1 to 25 carbon atoms; １ｃ (R １ｃ is an alkyl group having 1 to 25 carbon atoms. R is an acyloxy group represented by the following formula (I), a halogen atom, or a haloalkyl group. １２ and R１４ are each independently a hydrogen atom or an m-substituent, and the m-substituent is the same as the p-substituent. That is, R １２ and R １４ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR １ａ (R １ａ is an alkyl group having 1 to 25 carbon atoms. １ｂ (R １ｂ is an alkyl group having 1 to 25 carbon atoms; １ｃ (R １ｃ is an alkyl group having 1 to 25 carbon atoms. ) is an acyloxy group represented by the following formula (I), a halogen atom, or a haloalkyl group. The cured product according to the first embodiment of the present invention may be a cured product obtained by reacting the above-mentioned 1,1-dicyanoethylene-containing composition.

[0052] (Monomer Mixture) 1,1-dicyanoethylene may or may not constitute a monomer mixture together with the polymerizable monomer (B). In the case of a monomer mixture, the 1,1-dicyanoethylene and the o-substituted phenol compound (A-1) represented by the above formula (I) are the same as the 1,1-dicyanoethylene and the o-substituted phenol compound (A-1) represented by the above formula (I), respectively, contained in the 1,1-dicyanoethylene-containing composition according to the first embodiment. The polymerizable monomer (B) that may be contained in the monomer mixture is the same as the polymerizable monomer (B) that may be contained in the 1,1-dicyanoethylene-containing composition according to the first embodiment. The monomer mixture may contain one or more other components. Such other components are the same as the other components that may be contained in the 1,1-dicyanoethylene-containing composition according to the first embodiment. In one embodiment, the cured product is obtained by reacting 1,1-dicyanoethylene, a polymerizable monomer (B), and a Lewis basic compound in the presence of an o-substituted phenol compound (A-1) represented by formula (I).

[0053] (Lewis Basic Compound) The Lewis basic compound usually functions as a polymerization catalyst for 1,1-dicyanoethylene or the above-mentioned monomer mixture. Examples of the Lewis basic compound include water, alcohols, and alkylamines.

[0054] Examples of alcohols include methanol, ethanol, and propanol.

[0055] Examples of alkylamines include tertiary amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, and N,N-dimethylisopropylamine.

[0056] In one embodiment, water is used as the Lewis basic compound.

[0057] (Other Additives) The cured product according to this embodiment may contain at least one additive selected from the group consisting of thickeners (e.g., organic thickeners, inorganic thickeners such as silica), dehydrating agents (e.g., carboxylic acid anhydrides such as acetic anhydride, cyclic sulfonic acid esters such as propane sultone, and phosphoric acid anhydrides such as diphosphorus pentaoxide), radical polymerization inhibitors (e.g., stable radical compounds, metal salts), plasticizers (e.g., ester compounds such as phthalates and adipates), rubbers (e.g., natural rubber, styrene-butadiene rubber, hydrogenated styrene-butadiene rubber, acrylic rubber, nitrile rubber, hydrogenated nitrile rubber, etc.), pigments, and fillers (e.g., inorganic fillers, organic fillers), in an amount that does not excessively impair the intended effects of the present invention. Specific examples of organic thickeners include polymer compounds such as ethylene-vinyl acetate copolymers, (meth)methyl acrylate resins, polystyrene resins, (modified) cellulose resins, and acrylonitrile resins. A specific example of a stable radical compound is TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl). The inorganic thickener may function as an inorganic filler. The radical polymerization inhibitors mentioned above exclude the phenolic compounds. The rubber may function as an organic filler. Furthermore, for the purpose of improving the adhesion speed, a curing accelerator such as a polyethylene glycol derivative, crown ether, or calixarene may be added. Furthermore, fillers, elastomers, thixotropy-imparting agents, adhesion-imparting agents, crosslinking agents, fragrances, etc. may be added depending on the purpose.

[0058] (Method for Producing Cured Product) The method for producing the cured product is not particularly limited. For example, the cured product can be obtained by mixing the above-mentioned monomer mixture and a Lewis basic compound at room temperature (23°C).

[0059] The amount of the Lewis basic compound is not particularly limited, but is preferably 0.001 to 1.0 part by mass, and more preferably 0.01 to 0.5 part by mass, relative to 100 parts by mass of the monomer mixture. When the content of the Lewis basic compound is within this range, the monomer mixture reacts quickly.

[0060] (Uses) The cured product according to this embodiment may be a cured product of an (instant) adhesive. Uses of the adhesive are as described above.

[0061] The cured product according to this embodiment may be a coating material, the uses of which are as described above.

[0062] [Laminate according to the first embodiment] The laminate according to the first embodiment of the present invention is a laminate including the cured product according to the first embodiment and an adherend adhered to the cured product. The laminate according to the first embodiment of the present invention may be a laminate including a cured product obtained by reacting the 1,1-dicyanoethylene-containing composition described above and an adherend adhered to the cured product. There are no particular restrictions on the laminate configuration, but the cured product may be formed on one adherend, or the cured product may be located between two adherends. By having the cured product between the two adherends, the adherends can be firmly bonded to each other.

[0063] The adherend used in the laminate of the present invention is not particularly limited, and examples thereof include natural polymers, synthetic polymers, metals, ceramics, and fabrics. Examples of natural polymers include cellulose, natural rubber, starch, and modified resins thereof. Examples of synthetic polymers include polyolefin resins such as polyethylene, polypropylene, copolymers of ethylene with one or more α-olefins having 3 to 20 carbon atoms (e.g., propylene, 1-butene, 1-pentene, 1-hexene, etc.), ethylene-propylene-diene copolymers (EPDM), ethylene-vinyl acetate copolymers, and ethylene-acrylic acid copolymers; polyurethane resins, polyamide resins, polyester resins, polycarbonate resins, vinyl chloride resins, acrylonitrile butadiene styrene rubber, natural rubber, butadiene rubber, styrene butadiene rubber, and acrylonitrile butadiene rubber. Examples of metals include steel sheets such as stainless steel sheets, cold-rolled steel sheets, and galvanized steel sheets, as well as copper, aluminum, and magnesium alloys.

[0064] There is no particular limitation on the thickness of the adherends constituting the laminate. On the other hand, from the viewpoint of firmly bonding the adherends together, the thickness of the layer containing the cured product is preferably 0.01 to 2.0 mm, more preferably 0.015 to 1.5 mm, and even more preferably 0.02 to 1.2 mm.

[0065] Although there are no particular limitations on the method for producing the laminate, it is preferable to produce the laminate by the laminate production method of the present invention, which includes a bonding step of bonding a first adherend and a second adherend via the cured product. There are no particular limitations on the method for bonding the first adherend and the second adherend with the 1,1-dicyanoethylene-containing composition, but for example, the first adherend and the second adherend can be bonded by applying the 1,1-dicyanoethylene-containing composition to one adherend, placing the other adherend on top of it, and curing the composition.

[0066] The method for applying the 1,1-dicyanoethylene-containing composition to an adherend is not particularly limited, and examples thereof include spin coating, spray coating, bar coating, knife coating, roll coating, roll knife coating, blade coating, die coating, and gravure coating.

[0067] The amount of the 1,1-dicyanoethylene-containing composition to be applied to the adherend is not particularly limited, but is preferably 0.01 to 3.0 μL / mm ２ It is preferable that the concentration is 0.05 to 2.5 μL / mm ２ More preferably, it is 0.1 to 2.0 μL / mm ２ When the coating amount is equal to or greater than the lower limit, the adherends can be firmly bonded to each other, whereas when the coating amount is equal to or less than the upper limit, the two can be bonded with an appropriate amount.

[0068] [Second Embodiment] [1,1-Dicyanoethylene-Containing Composition According to a Second Embodiment] A 1,1-dicyanoethylene-containing composition according to a second embodiment of the present invention is a 1,1-dicyanoethylene-containing composition containing 1,1-dicyanoethylene, a phenolic compound (A-2), and a specific compound (C). As will be described in detail below, the specific compound (C) is a compound having a specified proton affinity (Epa) value and a specified pKa value when formed into an aqueous solution. By including the specific phenolic compound (A-2) and the specific compound (C) in the 1,1-dicyanoethylene-containing composition, it is possible to provide a 1,1-dicyanoethylene-containing composition having excellent storage stability. The phenolic compound (A-2) may be one type or multiple types. The specific compound (C) may be one type or multiple types.

[0069] (1,1-dicyanoethylene) The 1,1-dicyanoethylene contained in the 1,1-dicyanoethylene-containing composition according to the second embodiment is the same as the 1,1-dicyanoethylene contained in the 1,1-dicyanoethylene-containing composition according to the first embodiment.

[0070] (Phenol Compound (A-2)) The phenol compound (A-2) is represented by the following formula (II). ... (II)

[0071] In the formula (II), R ２１ and R ２５ is a hydrogen atom or an o-substituent. The o-substituent refers to a substituent that is o-positioned relative to the hydroxy group (the —OH group in the formula (II)) of the phenol compound. Here, in the second embodiment, unlike the first embodiment, R ２１ and R ２５where both of the hydroxyl groups are hydrogen atoms (i.e., both of the o-positions are hydrogen atoms). This is because the 1,1-dicyanoethylene-containing composition according to the second embodiment contains the specific compound (C), which stabilizes the hydroxyl groups of the phenolic compound. It is believed that the stabilization of the hydroxyl groups of the phenolic compound makes it possible to inhibit the reaction with coexisting 1,1-dicyanoethylene. The reaction between 1,1-dicyanoethylene and the phenolic compound can be confirmed by thickening or solidification (precipitation) of the composition, as exemplified in the Examples section.

[0072] In the formula (II), R ２１ and R ２５ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR ２ａ (R ２ａ is an alkyl group having 1 to 25 carbon atoms. ２ｂ (R ２ｂ is a hydrogen atom or an alkyl group having 1 to 25 carbon atoms; ２ｃ (R ２ｃ is an alkyl group having 1 to 25 carbon atoms.) is an o-substituent selected from the group consisting of an acyloxy group, a hydroxy group, an amino group, a halogen atom, and a haloalkyl group. That is, in the formula (II), R ２１ and R ２５ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR ２ａ (R ２ａ is an alkyl group having 1 to 25 carbon atoms. ２ｂ (R ２ｂ is an alkyl group having 1 to 25 carbon atoms; ２ｃ (R ２ｃ is an alkyl group having 1 to 25 carbon atoms. In a preferred embodiment, R ２１ and R ２５are hydrogen atoms. ２１ and R ２５ Even when both of are hydrogen atoms, the second embodiment can provide a 1,1-dicyanoethylene-containing composition having excellent storage stability.

[0073] R ２１ and R ２５ The alkyl group that may be taken by is preferably an alkyl group having 1 to 25 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group.

[0074] R ２１ and R ２５ The cycloalkyl group which may be taken by is preferably a cycloalkyl group having 3 to 12 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0075] R ２１ and R ２５ The aryl group which may be taken by is preferably an aryl group having 6 to 25 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0076] R ２１ and R ２５ The alkoxy group which may be taken by is preferably an alkoxy group having 1 to 25 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

[0077] R ２１ and R ２５ The ester group (-COOR) ２ａ ), acyl group (—COR ２ｂ ) and acyloxy groups (—OCOR ２ｃ ) in which R ２ａ , R ２ｂ and R ２ｃExamples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group.

[0078] R ２１ and R ２５ Examples of the acid anhydride group that can be taken include acid anhydride groups derived from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0079] R ２１ and R ２５ Examples of halogen atoms that R can have include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ２１ and R ２５ The haloalkyl group that can be taken is preferably a haloalkyl group having 1 to 12 carbon atoms, and more preferably a haloalkyl group having 1 to 6 carbon atoms. Examples of halogen atoms constituting the haloalkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0080] R ２１ and R ２５Specific examples of the o-substituent that may be taken by include a linear alkyl group having 1 to 25, preferably 1 to 12, and more preferably 1 to 6 carbon atoms; a branched alkyl group having 3 to 25, preferably 3 to 12, and more preferably 3 to 6 carbon atoms; a cycloalkyl group having 5 to 25, preferably 5 to 12, and more preferably 5 to 6 carbon atoms; an alkoxy group having 1 to 25, preferably 1 to 12, and more preferably 1 to 6 carbon atoms; and an aryl group having 6 to 25, preferably 6 to 12, and more preferably 6 carbon atoms. Among these, the o-substituent is preferably a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an aryl group having 5 to 12 carbon atoms, more preferably a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, cyclohexyl group, or phenyl group, even more preferably a t-butyl group, cyclohexyl group, or phenyl group, and still more preferably a t-butyl group.

[0081] In another preferred embodiment, R ２１ and R ２５ One or both of R are independently one selected from the group consisting of branched alkyl groups, cycloalkyl groups, and aryl groups. ２１ and R ２５ or both of which are independently one selected from the group consisting of a branched alkyl group, a cycloalkyl group, and an aryl group. Examples of the branched alkyl group, the cycloalkyl group, and the aryl group include those described above.

[0082] In the formula (II), R ２３ is a hydrogen atom or a p-substituent, and the p-substituent is the same as the o-substituent. The p-substituent being the same as the o-substituent means that examples of the p-substituent are the same as the examples of the o-substituent. Therefore, the p-substituent and the o-substituent may be different from each other or may be the same. The p-substituent refers to a substituent that is located at the p-position relative to the hydroxy group (the —OH group in the formula (II)) of the phenol compound. That is, in the formula (II), R ２３represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, -COOR ２ａ (R ２ａ is an alkyl group having 1 to 25 carbon atoms. ２ｂ (R ２ｂ is an alkyl group having 1 to 25 carbon atoms; ２ｃ (R ２ｃ is an alkyl group having 1 to 25 carbon atoms.

[0083] R ２３ Examples of p-substituents that R may have include a linear alkyl group having 1 to 25, preferably 1 to 12, more preferably 1 to 6 carbon atoms; a branched alkyl group having 3 to 25, preferably 3 to 12, more preferably 3 to 6 carbon atoms; a cycloalkyl group having 5 to 25, preferably 5 to 12, more preferably 5 to 6 carbon atoms; an alkoxy group having 1 to 25, preferably 1 to 12, more preferably 1 to 6 carbon atoms; a hydroxy group; and an aryl group having 6 to 25, preferably 6 to 12, more preferably 6 carbon atoms. ２３ is one p-substituent selected from a hydroxy group, a methyl group, and a methoxy group.

[0084] R ２３ The p-substituent that may be taken by may be an aldehyde group. That is, an acyl group (—COR ２ｂ ) R ２ｂ may be a hydrogen atom. ２３ The p-substituents that can be taken by are an amino group and -COR ２ｂ In this case, the p-substituent contains an amide bond. ２３ The p-substituents that can be taken by ２ｂ and a combination of an amino group and an alkyl group, in which case the p-substituent contains an amide bond.

[0085] In the formula (II), R ２２ and R ２４are each independently a hydrogen atom or an m-substituent, and the m-substituent is the same as the p-substituent. The m-substituent being the same as the p-substituent means that examples of the m-substituent are the same as the examples of the p-substituent. Therefore, the m-substituent and the p-substituent may be different from each other or may be the same. The m-substituent refers to a substituent that is located in the m-position relative to the hydroxy group (the —OH group in the formula (II)) that the phenol compound has. That is, in the formula (II), R ２２ and R ２４ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR ２ａ (R ２ａ is an alkyl group having 1 to 25 carbon atoms. ２ｂ (R ２ｂ is an alkyl group having 1 to 25 carbon atoms; ２ｃ (R ２ｃ is an alkyl group having 1 to 25 carbon atoms. R is an acyloxy group represented by the following formula (I), a halogen atom, or a haloalkyl group. ２２ and R ２４ are each independently preferably one selected from the group consisting of a hydrogen atom, a linear alkyl group having 1 to 25, preferably 1 to 12, more preferably 1 to 6 carbon atoms, and a branched alkyl group having 3 to 25, preferably 3 to 12, more preferably 3 to 6 carbon atoms, and more preferably a hydrogen atom.

[0086] Specific examples of the phenol compound (A-2) include hydroquinone, p-methylphenol, p-methoxyphenol, t-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-di-tert-butylphenol, 2,4-di-tert-butylphenol, , 2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis-(4-ethyl-6-t-butylphenol) (Yoshinox 425), 4,4'-butylidenebis-(6-t-butyl-3-methylphenol) (Yoshinox BB), 2,2'-methylenebis[6-tert-butyl-4-methylphenol] (Sumilizer MDP-S), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (Adekastab AO-30), 4,4'-butyl methyl-2,2'-dimethyl-2,2'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1'-diyl bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate] (ADK STAB AO-80), 1,3,5-trimethyl-2,2'-dimethyl-4-hydroxy-5-methylphenylpropanoate (ADK STAB AO-40), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (ADK STAB AO-50), 2,2'-dimethyl-2,2'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1'-diyl bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate] (ADK STAB AO-80), 1,3,5-trimethyl-2,2'-dimethyl-4-hydroxy-5-methylphenylpropanoate ... ethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (ADEKA STAB AO-330), 4,4'-thiobis[3-methyl-6-(tert-butyl)phenol] (SUMIRAIZER WX-R), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene, 1'-hydroxy[2,2'-ethylidenebis[4,6-bis(1,Examples of suitable acrylates include 2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl acrylate (Sumilizer GM), and 2-tert-butyl-6-methyl-4-{3-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl}phenol (Sumilizer GP). In a preferred embodiment, the ester is at least one selected from 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 2,4-di-tert-butylphenol. In a more preferred embodiment, the ester is at least one selected from 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0087] From the viewpoint of suppressing coloration of the 1,1-dicyanoethylene-containing composition, the phenol compound (A-2) preferably has a p-substituent other than a hydrogen atom, and more preferably has a substituent other than a hydrogen atom or a halogen atom.

[0088] (Specific Compound (C)) As described above, the 1,1-dicyanoethylene-containing composition according to the second embodiment contains the specific compound (C). This specific compound (C) is a compound having a proton affinity (Epa) of 780 kJ / mol or less and a pKa of 5 or less when in aqueous solution.

[0089] (Proton Affinity (Epa) and pKa in Aqueous Solution) Literature values ​​can be used as the proton affinity (Epa) value. Examples of literature include Non-Patent Document 2 (Edward P. H., Dharon G. L., Journal of Physical and Chemical Reference Data 1998, 27, 413-656). The Epa of the specific compound (C) is preferably 775 kJ / mol or less, more preferably 770 kJ / mol or less, and even more preferably 765 kJ / mol or less. The lower limit of the Epa is preferably a value higher than the Epa of water (691 kJ / mol), and may be, for example, more than 691 kJ / mol or 695 kJ / mol or more.

[0090] For the pKa value when the compound is in aqueous solution, see Non-Patent Document 3 (pKa table by D. H. Ripin and D. A. Evans; available at https: / / depts.washington.edu / eooptic / linkfiles / evans_pKa_table.pdf). The pKa of the specific compound (C) when in aqueous solution is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less. The lower limit of the pKa is not particularly limited, but may be, for example, -5 or more or -4 or more.

[0091] Examples of compounds having an EPA of 780 kJ / mol or less and a pKa of 5 or less in aqueous solution include methanesulfonic acid (EPA: 761.3 kJ / mol, pKa: -2.6), sulfuric acid (EPA: 699.4 kJ / mol, pKa: -3.0), sulfur dioxide (EPA: 672.3 kJ / mol, pKa as sulfurous acid: 1.9), and nitric acid (EPA: 751.4 kJ / mol, pKa: -1.3). In one embodiment, methanesulfonic acid is used as the specific compound (C). In another embodiment, at least one compound selected from the group consisting of methanesulfonic acid, sulfuric acid, and sulfur dioxide is used as the specific compound (C).

[0092] (Component (B): Polymerizable Monomer) The 1,1-dicyanoethylene-containing composition according to the second embodiment may further contain a polymerizable monomer (B). 1,1-dicyanoethylene is excluded from the polymerizable monomer (B). The polymerizable monomer (B) is preferably reactive with 1,1-dicyanoethylene. The polymerizable monomer (B) may be one type or multiple types. The polymerizable monomer (B) may be a radical polymerizable monomer or an anionic polymerizable monomer. Examples of the polymerizable monomer (B) and the method for producing the polymerizable monomer (B) are as described in the first embodiment.

[0093] (Other Components) The 1,1-dicyanoethylene-containing composition according to the second embodiment may contain one or more other components. Examples of such other components include acid anhydrides, Lewis acid compounds, thickeners, dehydrating agents, radical polymerization inhibitors (excluding the phenolic compounds described above), plasticizers, pigments, organic solvents, rubber, organic fillers, and inorganic fillers. The other components can be used in a content range that does not impair the intended effects of the present invention. The acid anhydride may function as a dehydrating agent. The acid anhydride may function as a dehydrating agent. The rubber may function as an organic filler. The inorganic filler may function as a thickener.

[0094] (Content of Each Component) When the entire 1,1-dicyanoethylene-containing composition according to the second embodiment is taken as 100% by mass, the total amount of the monomers (1,1-dicyanoethylene and the polymerizable monomer (B) used as needed) is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, from the viewpoint of achieving desired physical properties. When the polymerizable monomer (B) is used, the mass ratio of 1,1-dicyanoethylene to the polymerizable monomer (B) is not particularly limited, but may be 99:1 to 1:99, 80:20 to 20:80, or 70:30 to 30:70.

[0095] The phenol compound (A-2) is used in an amount of preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, even more preferably 2.0 parts by mass or less, and still more preferably 1.5 parts by mass or less, based on 100 parts by mass of the total amount of the monomers (1,1-dicyanoethylene and the polymerizable monomer (B) used as needed). From the viewpoint of improving the storage stability of the 1,1-dicyanoethylene-containing composition, the phenol compound (A-2) is used in an amount of preferably 0.0005 parts by mass or more, more preferably 0.001 parts by mass or more, and even more preferably 0.005 parts by mass or more, based on 100 parts by mass of the total amount of the monomers.

[0096] Furthermore, from the viewpoint of enhancing the storage stability of the 1,1-dicyanoethylene-containing composition, the content of the phenol compound (A-2) is preferably 0.00003% by mass or more, more preferably 0.00006% by mass or more, even more preferably 0.00009% by mass or more, and is preferably 10% by mass or less, more preferably 5.0% by mass or less, even more preferably 2.0% by mass or less, and still more preferably 1.5% by mass or less, when the entire 1,1-dicyanoethylene-containing composition is taken as 100% by mass.

[0097] The specific compound (C) is used in an amount of preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, even more preferably 2.0 parts by mass or less, and still more preferably 1.0 part by mass or less, relative to 100 parts by mass of the total amount of the monomers (1,1-dicyanoethylene and the polymerizable monomer (B) used as needed). From the viewpoint of improving the storage stability of the 1,1-dicyanoethylene-containing composition, the specific compound (C) is used in an amount of preferably 0.0005 parts by mass or more, more preferably 0.001 parts by mass or more, and even more preferably 0.005 parts by mass or more, relative to 100 parts by mass of the total amount of the monomers.

[0098] Furthermore, from the viewpoint of enhancing the storage stability of the 1,1-dicyanoethylene-containing composition, the content of the specific compound (C) is preferably 0.0005% by mass or more, more preferably 0.0009% by mass or more, even more preferably 0.004% by mass or more, and is preferably 10% by mass or less, more preferably 5.0% by mass or less, even more preferably 2.0% by mass or less, and still more preferably 1.0% by mass or less, when the entire 1,1-dicyanoethylene-containing composition is taken as 100% by mass.

[0099] The mass ratio of the specific compound (C) to the phenol compound (A-2) is not limited as long as the desired effects of the present invention are achieved, but can be, for example, within a range of 1:10,000 to 10,000: 1, preferably within a range of 1:1,000 to 1,000: 1, more preferably within a range of 1:500 to 500: 1, and even more preferably within a range of 1:250 to 250: 1. In a preferred embodiment, the content (parts by mass) of the specific compound (C) is the same as or less than the content (parts by mass) of the phenol compound (A-2).

[0100] (Uses) The 1,1-dicyanoethylene-containing composition according to this embodiment can be used as an (instant) adhesive. The uses of such an adhesive are as described in the first embodiment. Although instant adhesives containing 2-ethyl cyanoacrylate as a main ingredient are widely known, 2-ethyl cyanoacrylate has poor moisture resistance, and therefore such instant adhesives also have poor moisture resistance. On the other hand, 1,1-dicyanoethylene has excellent moisture resistance, and adhesives using the 1,1-dicyanoethylene-containing composition according to this embodiment have excellent moisture resistance.

[0101] The 1,1-dicyanoethylene-containing composition according to this embodiment can also be used as a coating material. The uses of such a coating material are as described in the first embodiment.

[0102] [Cured Product According to Second Embodiment] A cured product according to a second embodiment of the present invention is a cured product obtained by reacting 1,1-dicyanoethylene with a Lewis basic compound in the presence of a phenolic compound (A-2) represented by the following formula (II) and a compound (C) having a proton affinity (Epa) of 780 kJ / mol or less and a pKa of 5 or less in aqueous solution.

[0103] ... (II) (wherein, R ２１ and R ２５ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR ２ａ (R ２ａ is an alkyl group having 1 to 25 carbon atoms. ２ｂ (R ２ｂ is a hydrogen atom or an alkyl group having 1 to 25 carbon atoms; ２ｃ (R ２ｃ is an alkyl group having 1 to 25 carbon atoms.) is an o-substituent selected from the group consisting of an acyloxy group, a hydroxy group, an amino group, a halogen atom, and a haloalkyl group. That is, in the formula (II), R ２１ and R ２５ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR ２ａ (R ２ａ is an alkyl group having 1 to 25 carbon atoms. ２ｂ (R ２ｂ is an alkyl group having 1 to 25 carbon atoms; ２ｃ (R ２ｃ is an alkyl group having 1 to 25 carbon atoms. R is an acyloxy group represented by the following formula (I), a halogen atom, or a haloalkyl group. ２３ are each independently a hydrogen atom or a p-substituent, and the p-substituent is the same as the o-substituent. That is, R ２３represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, -COOR ２ａ (R ２ａ is an alkyl group having 1 to 25 carbon atoms. ２ｂ (R ２ｂ is an alkyl group having 1 to 25 carbon atoms; ２ｃ (R ２ｃ is an alkyl group having 1 to 25 carbon atoms. R is an acyloxy group represented by the following formula (I), a halogen atom, or a haloalkyl group. ２２ and R ２４ are each independently a hydrogen atom or an m-substituent, and the m-substituent is the same as the p-substituent. ２２ and R ２４ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or —COOR ２ａ (R ２ａ is an alkyl group having 1 to 25 carbon atoms. ２ｂ (R ２ｂ is an alkyl group having 1 to 25 carbon atoms; ２ｃ (R ２ｃ is an alkyl group having 1 to 25 carbon atoms. ) is an acyloxy group, a halogen atom, or a haloalkyl group. The cured product according to the second embodiment of the present invention may be a cured product obtained by reacting the above-mentioned 1,1-dicyanoethylene-containing composition.

[0104] (Monomer Mixture) 1,1-dicyanoethylene may or may not constitute a monomer mixture together with the polymerizable monomer (B). In the case of a monomer mixture, the 1,1-dicyanoethylene, the phenol compound (A-2) represented by the above formula (II), and the specific compound (C) are the same as the 1,1-dicyanoethylene, the phenol compound (A-2) represented by the above formula (II), and the specific compound (C) contained in the 1,1-dicyanoethylene-containing composition according to the second embodiment, respectively. The polymerizable monomer (B) that may be contained in the monomer mixture is the same as the polymerizable monomer (B) that may be contained in the 1,1-dicyanoethylene-containing composition according to the second embodiment. The monomer mixture may contain one or more other components. Such other components are the same as the other components that may be contained in the 1,1-dicyanoethylene-containing composition according to the second embodiment. In one embodiment, the cured product is obtained by reacting 1,1-dicyanoethylene, a polymerizable monomer (B), and a Lewis basic compound in the presence of a phenol compound (A-2) represented by formula (II).

[0105] (Lewis Basic Compound) The Lewis basic compound usually functions as a polymerization catalyst for 1,1-dicyanoethylene or the monomer mixture. Examples of the Lewis basic compound include water, alcohols, and alkylamines. Examples of the alcohols and alkylamines are the same as those described in the first embodiment. Of these, in one aspect, water is used as the Lewis basic compound.

[0106] (Other Additives) The cured product according to this embodiment may contain at least one additive selected from the group consisting of thickeners (e.g., organic thickeners, inorganic thickeners such as silica), dehydrating agents (e.g., carboxylic acid anhydrides such as acetic anhydride, cyclic sulfonic acid esters such as propane sultone, and phosphoric acid anhydrides such as diphosphorus pentaoxide), radical polymerization inhibitors (e.g., stable radical compounds, metal salts), plasticizers (e.g., ester compounds such as phthalates and adipates), rubbers (e.g., natural rubber, styrene-butadiene rubber, hydrogenated styrene-butadiene rubber, acrylic rubber, nitrile rubber, hydrogenated nitrile rubber, etc.), pigments, and fillers (e.g., inorganic fillers, organic fillers), in an amount that does not excessively impair the intended effects of the present invention. Specific examples of organic thickeners include polymer compounds such as ethylene-vinyl acetate copolymers, (meth)methyl acrylate resins, polystyrene resins, (modified) cellulose resins, and acrylonitrile resins. A specific example of a stable radical compound is TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl). The inorganic thickener may function as an inorganic filler. The radical polymerization inhibitors mentioned above exclude the phenolic compounds. The rubber may function as an organic filler. Furthermore, for the purpose of improving the adhesion speed, a curing accelerator such as a polyethylene glycol derivative, crown ether, or calixarene may be added. Furthermore, fillers, elastomers, thixotropy-imparting agents, adhesion-imparting agents, crosslinking agents, fragrances, etc. may be added depending on the purpose.

[0107] (Method for Producing Cured Product) The method for producing the cured product is not particularly limited. For example, the cured product can be obtained by mixing the above-mentioned monomer mixture and a Lewis basic compound at room temperature (23°C).

[0108] The amount of the Lewis basic compound is not particularly limited, but is preferably 0.001 to 1.0 part by mass, and more preferably 0.01 to 0.5 part by mass, relative to 100 parts by mass of the monomer mixture. When the content of the Lewis basic compound is within this range, the monomer mixture reacts quickly.

[0109] (Uses) The cured product according to this embodiment may be a cured product of an (instant) adhesive. Uses of the adhesive are as described above.

[0110] The cured product according to this embodiment may be a coating material, the uses of which are as described above.

[0111] [Laminate according to a second embodiment] A laminate according to a second embodiment of the present invention is a laminate including a cured product according to the second embodiment and an adherend adhered to the cured product. The laminate according to the second embodiment of the present invention may be a laminate including a cured product obtained by reacting the above-described 1,1-dicyanoethylene-containing composition and an adherend adhered to the cured product. The layer structure, the adherend, and the method for producing the laminate are the same as those described in the first embodiment.

[0112] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. [First Example] [Components] The components used in the examples and comparative examples are as follows.

[0113] <1,1-dicyanoethylene> 1,1-Dicyanoethylene: 1,1,3,3-tetracyanopropane was synthesized from malononitrile in a 73% yield by the production method described in J. Am. Chem. Soc., 1989, 111, 9078-9081. The resulting crystalline 1,1,3,3-tetracyanopropane was mixed with diphosphorus pentoxide and subjected to thermal decomposition at 180°C to obtain a crude 1,1-dicyanoethylene product (yield 60%). The crude product was purified by reduced pressure distillation (480 Pa) to obtain 1,1-dicyanoethylene with a purity of 99%.

[0114] <Component (B): Polymerizable Monomer> (B1): 2-Ethyl cyanoacrylate (manufactured by Aldrich)

[0115] <Component (A-1): o-Substituted Phenol Compound> (A11): 2,6-di-tert-butyl-4-methylphenol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (Taft value of t-butyl group at o-position: −1.54) (A12): 2,6-di-tert-butylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (Taft value of t-butyl group: −1.54) (A13): “Irganox (registered trademark) 1010” (pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) (Taft value of t-butyl group: −1.54) (A14): “Irganox (registered trademark) 1010” (pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) (Taft value of t-butyl group: −1.54) (A15): “Irganox (registered trademark) 1010” (pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) (Taft value of t-butyl group: −1.54) 1076" (octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (Taft value of t-butyl group: -1.54) (A15): 2,4-di-tert-butylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (Taft value of t-butyl group: -1.54, Taft value of hydrogen atom: 1.24) The Taft values ​​used above were those based on literature values ​​for the substituent at the o-position relative to the hydroxy group of the phenol (literature: Non-Patent Document 1).

[0116] <(A-1) Comparative Components> (A'11): N-nitroso-N-phenylhydroxylamine aluminum ("Q-1301" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A'12): p-benzoquinone (manufactured by Nacalai Tesque, Inc.) (A'13): hydroquinone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A'14): p-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (A'15): p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0117] <Other ingredients> Methanesulfonic acid: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0118] [Evaluation Method] The liquid 1,1-dicyanoethylene-containing compositions obtained in the Examples and Comparative Examples were used as samples and evaluated as follows.

[0119] <Storage Stability> (Storage Test) Five 1 mL samples were placed in 10 mL HDPE containers, sealed, and marked on the side of the container at a position corresponding to the sample liquid level. The state of the sample in each container was visually observed immediately before the start of the storage test. The five containers were then left to stand in a 50% humidity environment for 24 hours at 25°C, 48 hours at 25°C, 1 hour at 50°C, 1 hour at 80°C, and 3 hours at 80°C, respectively. The storage test was conducted in this manner.

[0120] (Observation) Then, each container was inverted, and the state of the sample in the container was visually observed 5 seconds after the inversion was completed. The observation results were divided into the following three stages. "Liquid": 90% or more by volume of the sample in the container exceeded the mark when viewed from the side. "Thickened": 10% or more by volume of the sample in the container exceeded the mark when viewed from the side, but 90% or more by volume did not exceed the mark when viewed from the side. This meant that the fluidity of the sample had decreased compared to immediately before the start of the storage test (0 minutes). "Solidified": Less than 10% by volume of the sample in the container exceeded the mark when viewed from the side.

[0121] (Evaluation) Subsequently, based on the five types of observation results of the samples in the five containers after the storage test, evaluation was performed according to the following criteria. "A": The total number of "thickening" and "solidification" was 0. "B": The total number of "thickening" and "solidification" was 1. "C": The total number of "thickening" and "solidification" was 2 or 3. Of these, "C1" had 1 "solidification", "C2" had 2 "solidification", and "C3" had 3 "solidification". "D": The total number of "thickening" and "solidification" was 4. "E": The total number of "thickening" and "solidification" was 5.

[0122] <Coloring> (Observation) At the same time as the visual observation in the <Storage test>, the color of the sample in the container was visually observed. The observed sample colors were classified into three levels: "colorless," "light yellow," and "yellow." Note that "yellow" means that the color was darker than "light yellow."

[0123] (Evaluation) Next, based on the six types of observation results (including the observation result at 0 minutes) of the samples in the five containers after the storage test, evaluation was performed according to the following criteria. "A": The total number of "light yellow" and "yellow" particles was 0. "B": The number of "light yellow" particles was 1 to 3, and the number of "yellow" particles was 0. "C": The number of "light yellow" particles was 4 or 5, and the number of "yellow" particles was 0. "D": The number of "yellow" particles was 1 to 4. "E": The number of "yellow" particles was 5 or more.

[0124] Example 1-1: Under nitrogen, 100 parts by mass of 1,1-dicyanoethylene and 0.0001 parts by mass of 2,6-di-tert-butyl-4-methylphenol, the component (A11), were mixed to prepare a 1,1-dicyanoethylene-containing composition 1-1. The prepared 1,1-dicyanoethylene-containing composition 1-1 was used to evaluate the storage stability and colorability described above. The results are shown in Table 1.

[0125] Examples 1-2 to 1-22 and Comparative Examples 1-1 to 1-12 1,1-dicyanoethylene-containing compositions 1-2 to 1-22 and 1'-1 to 1'-12 were prepared according to the formulations shown in Tables 1, 2, and 3. Multiple components were mixed simultaneously. Using the prepared 1,1-dicyanoethylene-containing compositions, storage stability and colorability were evaluated in the same manner as in Example 1-1. The results are shown in Tables 1 to 3.

[0126]

[0127]

[0128]

[0129] Tables 1 to 3 show that the 1,1-dicyanoethylene-containing compositions of Examples 1-1 to 1-22 had superior storage stability compared to the 1,1-dicyanoethylene-containing compositions of Comparative Examples 1-1 to 1-12. Furthermore, Comparative Examples 1-2 and 1-3 show that N-nitroso-N-phenylhydroxylamine aluminum and p-benzoquinone, known as radical polymerization inhibitors, contribute very little to the storage stability of the 1,1-dicyanoethylene-containing compositions. Furthermore, Example 1 provides a 1,1-dicyanoethylene-containing composition with excellent storage stability. Therefore, it is expected that the cured product and laminate thereof can also suppress deterioration in physical properties due to loss of storage stability of the 1,1-dicyanoethylene-containing composition.

[0130] [Second Example] [Components] The components used in the examples and comparative examples are as follows.

[0131] <1,1-dicyanoethylene> 1,1-dicyanoethylene: 1,1-dicyanoethylene prepared in the first example

[0132] <Component (B): Polymerizable Monomer> (B1): 2-cyanoethyl acrylate (manufactured by Aldrich Chemical Company) (B2): methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd. (purity > 99.8%)) (B3): styrene (manufactured by Tokyo Chemical Industry Co., Ltd. (purity > 99.0%)) (B4): vinyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd. (purity > 99.0%))

[0133] <Component (A-2): Phenolic Compound> (A21): Hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) (A22): p-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (A23): p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (A24): 2,6-di-tert-butyl-4-methylphenol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A25): 2,6-di-tert-butylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (A26): "Irganox (registered trademark) 1010" manufactured by BASF (A27): "Irganox (registered trademark) 1076" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (A28): 2,4-di-tert-butylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) The components (A21), (A22), and (A23) were the same as the components (A'13), (A'14), and (A'15) in the first example, respectively, and the components (A24), (A25), (A26), (A27), and (A28) were the same as the components (A11), (A12), (A13), (A14), and (A15) in the first example, respectively.

[0134] <Component (C): Compound with specific EPA and pKa> (C1): Methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) According to literature, the EPA of this methanesulfonic acid was 761.3 kJ / mol (Reference: Non-Patent Document 2), and the pKa of the resulting aqueous solution was -2.6 (Reference: Non-Patent Document 3). Note that the methanesulfonic acid used as the other component in Example 1 was the same as the methanesulfonic acid used as the other component in Example 1. (C2): Sulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) According to literature, the EPA of this sulfuric acid was 699.4 kJ / mol (Reference: Non-Patent Document 2), and the pKa of the resulting aqueous solution was -3.0 (Reference: Non-Patent Document 3).

[0135] <Component (C')> (C'1): Acetic acid (manufactured by Kanto Chemical Co., Inc.) According to literature, the EPA of this acetic acid was 783.7 kJ / mol (Reference: Non-Patent Document 2), and the pKa of the aqueous solution was 4.8 (Reference: Non-Patent Document 3).

[0136] [Evaluation Method] The liquid 1,1-dicyanoethylene-containing compositions obtained in the Examples and Comparative Examples were used as samples to evaluate storage stability and coloration in the same manner as in the first Example.

[0137] Example 2-1 A 1,1-dicyanoethylene-containing composition was prepared by mixing 100 parts by mass of 1,1-dicyanoethylene, 1 part by mass of hydroquinone (component (A22)), and 0.01 parts by mass of methanesulfonic acid (component (C)) under nitrogen. The prepared 1,1-dicyanoethylene-containing composition was used to evaluate the storage stability and colorability described above. The results are shown in Table 4.

[0138] Examples 2-2 to 2-6 and 21 to 27 1,1-dicyanoethylene-containing compositions were prepared according to the formulations shown in Table 4. Multiple components were mixed simultaneously. Using the prepared 1,1-dicyanoethylene-containing compositions, evaluations of storage stability and colorability were carried out in the same manner as in Example 2-1. The results are shown in Tables 4 and 6.

[0139] <Examples 2-7 to 2-20> Examples 2-7 to 2-20 are the same as Examples 1-5 to 1-14, Example 1-16, Example 1-18, Example 1-20, and Example 1-22 shown in the first example, respectively, and are shown in Tables 5 and 6 together with their evaluation results.

[0140] Comparative Examples 2-1 to 2-7 and 2-12 to 2-14 Comparative Examples 2-1 to 2-7 and 2-12 to 2-14 are the same as Comparative Example 1-1 and Comparative Examples 1-4 to 1-12 shown in the first example, respectively, and are shown in Tables 7 and 8 together with their evaluation results.

[0141] Comparative Examples 2-8 to 2-11 1,1-dicyanoethylene-containing compositions were prepared according to the formulations shown in Table 8. Multiple components were mixed simultaneously. Using the prepared 1,1-dicyanoethylene-containing compositions, evaluations of storage stability and colorability were performed in the same manner as in Example 2-1. The results are shown in Table 8.

[0142]

[0143]

[0144]

[0145]

[0146]

[0147] It is clear from Tables 4 to 8 that the 1,1-dicyanoethylene-containing compositions of Examples 2-1 to 2-27 had superior storage stability compared to the 1,1-dicyanoethylene-containing compositions of Comparative Examples 2-1 to 2-14. It is also clear that the storage stability of the 1,1-dicyanoethylene-containing composition can be improved by using component (C) in combination with some of the embodiments that corresponded to the Comparative Examples in the first example. It is also clear that the storage stability and / or colorability of the 1,1-dicyanoethylene-containing composition can be further improved by using component (C) in combination with some of the embodiments that corresponded to the Examples in the first example.

[0148] Furthermore, according to the second example, a 1,1-dicyanoethylene-containing composition having excellent storage stability can be provided, and it has been found that it is expected that the deterioration of physical properties resulting from the loss of storage stability of the 1,1-dicyanoethylene-containing composition can also be suppressed in a cured product and a laminate thereof.

[0149] [Example of Laminate] [Substrate] Steel plate (manufactured by Standard Test Piece Co., Ltd., length 25 mm, width 100 mm, thickness 1.6 mm) Aluminum plate (manufactured by Standard Test Piece Co., Ltd., length 25 mm, width 100 mm, thickness 1.6 mm) Hard polyvinyl chloride (PVC) plate (manufactured by Nippon Test Panel Co., Ltd., length 25 mm, width 100 mm, thickness 2.0 mm)

[0150] [Measurement Method] Using the laminates obtained in the Examples and Comparative Examples as samples, the tensile shear adhesive strength was measured as follows.

[0151] <Lap-shear adhesive strength> The lap-shear adhesive strength of the laminate was measured at a room temperature of 25°C and a humidity of 25% using a universal material testing machine Model 5969 (manufactured by Instron) at a pulling rate of 20 mm / min.

[0152] Examples 3-1 to 3-10, Comparative Examples 3-1 to 3-3 100 μL of the 1,1-dicyanoethylene-containing composition shown in Table 9 was applied to an area of ​​12.5 mm x 25 mm of the adherend (1) shown in Table 9, and the adherend (2) shown in Table 9 was then placed on the applied surface. The 1,1-dicyanoethylene-containing composition was then allowed to stand for one day at room temperature of 23°C and a humidity of 50% to cure, thereby bonding the adherends (1) and (2) together to obtain a laminate. The tensile shear bond strength was measured using the resulting laminate. The results are shown in Table 9. In Example 3-3, the adherend broke, making it impossible to measure the tensile shear bond strength.

[0153]

[0154] It can be seen from Table 9 that the laminates of Examples 3-1, 3-2, and 3-4 to 3-10 have higher tensile shear adhesive strength than the laminates of Comparative Examples 3-1 to 3-3. In other words, it was found that the deterioration of physical properties due to the loss of storage stability of the 1,1-dicyanoethylene-containing composition can be suppressed.

Claims

1. A 1,1-dicyanoethylene-containing composition comprising 1,1-dicyanoethylene and an o-substituted phenol compound (A-1) represented by the following formula (I): (In the above formula (I), R １１ and R １５ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or -COOR １ａ (R １ａ is an alkyl group having 1 to 25 carbon atoms. １ｂ (R １ｂ is an alkyl group having 1 to 25 carbon atoms; １ｃ (R １ｃ is an alkyl group having 1 to 25 carbon atoms; an o-substituent selected from the group consisting of an acyloxy group represented by the formula (I), a halogen atom, and a haloalkyl group (wherein R １１ and R １５ Except when both are hydrogen atoms. １３ is a hydrogen atom or a p-substituent, and the p-substituent is the same as the o-substituent. １２ and R １４ are each independently a hydrogen atom or an m-substituent, and the m-substituent is the same as the p-substituent.

2. R １１ and R １５ The 1,1-dicyanoethylene-containing composition according to claim 1, wherein one or both of the above has a Taft steric parameter Es value of less than 1.

24.

3. R １１ and R １５ 2. The 1,1-dicyanoethylene-containing composition according to claim 1, wherein one or both of the above are independently one selected from the group consisting of a branched alkyl group, a cycloalkyl group, and an aryl group.

4. The 1,1-dicyanoethylene-containing composition according to claim 1, wherein the o-substituted phenol compound (A-1) is at least one selected from the group consisting of 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-di-tert-butylphenol, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and 4,4'-butylidenebis(6-tert-butyl-m-cresol).

5. R １１ and R １５ The 1,1-dicyanoethylene-containing composition according to claim 1, wherein both of the Taft steric parameter Es values ​​are less than 1.

24.

6. R １１ and R １５ and each independently represent one selected from the group consisting of a branched alkyl group, a cycloalkyl group, and an aryl group.

7. The 1,1-dicyanoethylene-containing composition according to claim 1, wherein the o-substituted phenol compound (A-1) comprises at least one selected from the group consisting of 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

8. R １１ and R １５ The 1,1-dicyanoethylene-containing composition according to claim 1, except when both of are halogen atoms.

9. The 1,1-dicyanoethylene-containing composition according to any one of claims 1 to 8, further comprising a polymerizable monomer (B).

10. The 1,1-dicyanoethylene-containing composition according to claim 9, wherein the polymerizable monomer (B) is at least one selected from the group consisting of ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, alkyl acrylates, alkyl methacrylates, acrylonitrile, vinyl chloride, vinylidene chloride, vinylidene fluoride, alkyl 2-cyanoacrylates, alkyl 2-cyanopentadienoates, and dialkyl methylidenemalonates.

11. The 1,1-dicyanoethylene-containing composition of claim 10, wherein the polymerizable monomer (B) comprises a 2-cyanoacrylic acid alkyl ester.

12. The 1,1-dicyanoethylene-containing composition of claim 11, wherein the 2-cyanoacrylic acid alkyl ester is ethyl 2-cyanoacrylate.

13. A cured product obtained by reacting 1,1-dicyanoethylene with a Lewis base compound in the presence of an o-substituted phenol compound (A-1) represented by the following formula (I): (In the above formula (I), R １１ and R １５ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or -COOR １ａ (R １ａ is an alkyl group having 1 to 25 carbon atoms. １ｂ (R １ｂ is an alkyl group having 1 to 25 carbon atoms; １ｃ (R １ｃ is an alkyl group having 1 to 25 carbon atoms; an o-substituent selected from the group consisting of an acyloxy group represented by the formula (I), a halogen atom, and a haloalkyl group (wherein R １１ and R １５ Except when both are hydrogen atoms. １３ is a hydrogen atom or a p-substituent, and the p-substituent is the same as the o-substituent. １２ and R １４ are each independently a hydrogen atom or an m-substituent, and the m-substituent is the same as the p-substituent.

14. R １１ and R １５ The cured product according to claim 13, wherein one or both of the Taft steric parameter Es values ​​are less than 1.

24.

15. R １１ and R １５ The cured product according to claim 13, wherein one or both of the above are each independently one type selected from the group consisting of a branched alkyl group, a cycloalkyl group, and an aryl group.

16. The cured product according to claim 13, wherein the o-substituted phenol compound (A-1) is one selected from the group consisting of 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-di-tert-butylphenol, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and 4,4'-butylidenebis(6-tert-butyl-m-cresol).

17. R １１ and R １５ The cured product according to claim 13, wherein both of the Taft steric parameter Es values ​​are less than 1.

24.

18. R １１ and R １５ and each independently represent one selected from the group consisting of a branched alkyl group, a cycloalkyl group, and an aryl group.

19. The cured product according to claim 13, wherein the o-substituted phenol compound (A-1) comprises at least one selected from the group consisting of 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

20. R １１ and R １５ The cured product according to claim 13 , except when both of the above are halogen atoms.

21. The cured product according to claim 13, obtained by reacting 1,1-dicyanoethylene, the polymerizable monomer (B), and the Lewis base compound.

22. The cured product according to claim 21, wherein the polymerizable monomer (B) is one or more selected from the group consisting of ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, alkyl acrylates, alkyl methacrylates, acrylonitrile, vinyl chloride, vinylidene chloride, vinylidene fluoride, alkyl 2-cyanoacrylates, alkyl 2-cyanopentadienoates, and dialkyl methylidenemalonates.

23. The cured product according to claim 22, wherein the polymerizable monomer (B) comprises a 2-cyanoacrylic acid alkyl ester.

24. The cured product of claim 23, wherein the 2-cyanoacrylic acid alkyl ester is 2-cyanoacrylate ethyl.

25. A laminate comprising the cured product according to any one of claims 13 to 24 and an adherend to which the cured product is adhered.

26. A 1,1-dicyanoethylene-containing composition comprising 1,1-dicyanoethylene, a phenol compound (A-2) represented by the following formula (II), and a compound (C) having a proton affinity (Epa) of 780 kJ / mol or less and a pKa of 5 or less when in an aqueous solution: (II) (wherein, R ２１ and R ２５ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or -COOR ２ａ (R ２ａ is an alkyl group having 1 to 25 carbon atoms. ２ｂ (R ２ｂ is a hydrogen atom or an alkyl group having 1 to 25 carbon atoms; ２ｃ (R ２ｃ is an alkyl group having 1 to 25 carbon atoms. R is an o-substituent selected from the group consisting of an acyloxy group, a hydroxy group, an amino group, a halogen atom, and a haloalkyl group represented by the formula (I). ２３ is a hydrogen atom or a p-substituent, and the p-substituent is the same as the o-substituent. ２２ and R ２４ are each independently a hydrogen atom or an m-substituent, and the m-substituent is the same as the p-substituent.

27. R ２１ and R ２５ The 1,1-dicyanoethylene-containing composition of claim 26, wherein both of are hydrogen atoms.

28. The 1,1-dicyanoethylene-containing composition according to claim 26, wherein compound (C) is at least one selected from the group consisting of methanesulfonic acid, sulfuric acid, and sulfur dioxide.

29. The 1,1-dicyanoethylene-containing composition according to any one of claims 26 to 28, further comprising a polymerizable monomer (B).

30. The 1,1-dicyanoethylene-containing composition according to claim 29, wherein the polymerizable monomer (B) is at least one member selected from the group consisting of ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, styrene, methyl methacrylate, dodecyl methacrylate, 2-cyanoacrylic acid alkyl esters, 2-cyanopentadienoic acid alkyl esters, and methylidenemalonic acid dialkyl esters.

31. The 1,1-dicyanoethylene-containing composition of claim 30, wherein the polymerizable monomer (B) comprises a 2-cyanoacrylic acid alkyl ester.

32. The 1,1-dicyanoethylene-containing composition of claim 31, wherein the 2-cyanoacrylic acid alkyl ester is ethyl 2-cyanoacrylate.

33. A cured material obtained by reacting 1,1-dicyanoethylene with a Lewis base compound in the presence of a phenol compound (A-2) represented by the following formula (II) and a compound (C) having a proton affinity (Epa) of 780 kJ / mol or less and a pKa of 5 or less when in an aqueous solution. (II) (wherein, R ２１ and R ２５ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, or -COOR ２ａ (R ２ａ is an alkyl group having 1 to 25 carbon atoms. ２ｂ (R ２ｂ is a hydrogen atom or an alkyl group having 1 to 25 carbon atoms; ２ｃ (R ２ｃ is an alkyl group having 1 to 25 carbon atoms. R is an o-substituent selected from the group consisting of an acyloxy group, a hydroxy group, an amino group, a halogen atom, and a haloalkyl group represented by the formula (I). ２３ are each independently a hydrogen atom or a p-substituent, and the p-substituent is the same as the o-substituent. ２２ and R ２４ are each independently a hydrogen atom or an m-substituent, and the m-substituent is the same as the p-substituent.

34. R ２１ and R ２５ The cured product according to claim 33, wherein both of are hydrogen atoms.

35. The cured product according to claim 33, wherein compound (C) is at least one selected from the group consisting of methanesulfonic acid, sulfuric acid, and sulfur dioxide.

36. The cured product according to claim 33, obtained by reacting 1,1-dicyanoethylene, the polymerizable monomer (B), and the Lewis base compound.

37. The cured product according to claim 36, wherein the polymerizable monomer (B) is one or more selected from the group consisting of ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, alkyl acrylates, alkyl methacrylates, acrylonitrile, vinyl chloride, vinylidene chloride, vinylidene fluoride, alkyl 2-cyanoacrylates, alkyl 2-cyanopentadienoates, and dialkyl methylidenemalonates.

38. The cured product according to claim 37, wherein the polymerizable monomer (B) comprises a 2-cyanoacrylic acid alkyl ester.

39. The cured product of claim 38, wherein the 2-cyanoacrylic acid alkyl ester is 2-cyanoacrylate ethyl.

40. A laminate comprising the cured product according to any one of claims 33 to 39 and an adherend to which the cured product is adhered.

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