Adhesive composition, cured product, and method for producing cured product

Abstract

An adhesive composition comprising: a compound (1) represented by general formula (1); and at least one selected from an azo compound (2) represented by general formula (2), an azo compound (3) represented by general formula (3), and an azo compound (4) represented by general formula (4). (1): A(R1)n1. (2): B1(R2)2. (3): C1(R3)3. (4): D(R4)4

Description

Adhesive composition, cured product, and method for producing the cured product 【0001】 The present invention relates to an adhesive composition, a cured product, and a method for producing a cured product. This application claims priority under Japanese Patent Application No. 2024-217563, filed in Japan on December 12, 2024, the contents of which are incorporated herein by reference. 【0002】 Conventional high-strength, high-durability adhesives often leave adhesive residue when the bonded substrate (substrate, battery pack, building interior and exterior materials, etc.) is peeled off, making it difficult to reuse the substrate. In recent years, the development of easily dismantled adhesives aimed at reusing the bonded substrate has attracted attention as one of the technologies that contribute to a resource-recycling society. To realize easily dismantled adhesives, they need to possess two seemingly contradictory properties: the ability to maintain sufficient adhesive performance during use, and the ability to be easily dismantled by applying external energy at the desired timing. 【0003】 Conventional technologies include heat-melt type hot-melt adhesives (all-over method) (see Non-Patent Document 1), UV-curing adhesive tapes (dicing tapes) (see Non-Patent Document 2), and adhesives containing thermally expandable microcapsules (see Non-Patent Document 3). In recent years, there has been active research on easily dismantled adhesives using microwaves, which have excellent remoteness and penetration properties and are an unusual stimulus. Examples of easily dismantled adhesives include adhesives with added ionic liquids (see Patent Document 1), adhesives made of fluorine-based polymers (see Patent Document 2), and adhesives with added inorganic metal ions or inorganic particles (see Patent Document 3 and Non-Patent Document 4). 【0004】 Japanese Patent Publication No. 6974823, Japanese Unexamined Patent Publication No. 2023-176758, Japanese Patent Publication No. 7181571 【0005】Hideo Tomita, A new building material construction method using electromagnetic induction heating, "All-over construction method", Polymer 54, 413-413 (2005). K. Ebe, H. Seno, K. Horigome, UV curable pressure-sensitive adhesives for fabricating semiconductors. I. Development of easily peelable dicing tapes. J. Appl. Polym. Sci. 90, 436-441 (2003). H. Ishikawa, K. Seto, S. Shimotuma, N. Kishi, C. Sato, Bond strength and disbonding behavior of elastomer and emulsion-type dismantable adhesives used for building materials. Int. J. Adhes. Adhes. 25, 193-199 (2005). Y. Li, P. Sun, J. -F. Xu, X. Zhang, A Microwave-Responsive Supramolecular Adhesive for Strong Adhesion of Thermolabile Substrates. ACS Materials Lett. 5, 2528-2533 (2023). 【0006】 Conventional microwave-based easy-to-disassemble bonding technologies show only a small change in shear peel strength (around 20%) before and after microwave irradiation (see Patent Document 2). This results in adhesive residue remaining on the surface of the adherend after peeling, making reuse of the adherend difficult (see Patent Document 3 and Non-Patent Document 4). Furthermore, when a large amount (10% by mass or more) of microwave-responsive components is added to existing adhesives, there are concerns that the sample may become non-uniform if the adhesive viscosity is low, and that workability may deteriorate if the adhesive viscosity is high (see Patent Documents 1 and 3). 【0007】The present invention has been made in view of the above circumstances, and aims to provide an adhesive composition, a cured product, and a method for producing a cured product, in which the shear peel strength is significantly reduced by having a molecular structure that releases nitrogen gas upon microwave irradiation, and in which the adherend can be reused because the adhesive after peeling can be easily cleaned. 【0008】 The present invention has the following embodiments: [1] An adhesive composition comprising a compound (1) represented by the following general formula (1), and at least one selected from an azo compound (2) represented by the following general formula (2), an azo compound (3) represented by the following general formula (3), and an azo compound (4) represented by the following general formula (4). 【0009】 (However, n1 is the valence of A. A is carbon, nitrogen, silicon, boron, phosphoryl group, amino group, phenyl group, cyclohexyl group, difluoromethylene group, or dialkylsiloxy group. R １ R is an organic group having one or more carbon atoms, and includes a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. １ They may be the same or different from each other. 【0010】 (However, B １ R is an organic group having one or more carbon atoms, and the organic group has an azo group. ２ R is an organic group having one or more carbon atoms, and includes a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. ２ They may be the same or different from each other. 【0011】 (However, C １ R is CH, nitrogen, or silicon. ３ R is an organic group having one or more carbon atoms, and the organic group has an azo group and includes a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. ３ They may be the same or different from each other. 【0012】 (However, D is carbon, a nitrogen cation having a counter anion, or silicon. R ４ is an organic group having 1 or more carbon atoms, the organic group has an azo group, and contains a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. R ４ may be the same as or different from each other.) 【0013】 A cured product of the adhesive composition according to [2][1], which is a cured product represented by the following general formula (5). 【0014】 (However, E is carbon, nitrogen, silicon, boron, a phosphoryl group, an amino group, a phenyl group, a cyclohexyl group, a difluoromethylene group, or a dialkylsiloxy group. n2 is the valence of E. R ５ is -a-(b-c) ｎ３ -d (n3 is an integer of 2 or more). a is an alkylene group having 1 or more carbon atoms which may have a functional group. b is at least one selected from a urethane bond, a thiourethane bond, a urea bond, and a thiourea bond. c is an organic group having 1 or more carbon atoms, and at least a part of the plurality of organic groups has an azo group. d is a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. R ５ may be the same as or different from each other.) 【0015】 [3] A method for producing a cured product, which includes a step of reacting a compound (1) represented by the following general formula (1) with at least one selected from an azo compound (2) represented by the following general formula (2), an azo compound (3) represented by the following general formula (3), and an azo compound (4) represented by the following general formula (4). 【0016】 (However, n1 is the valence of A. A is carbon, nitrogen, silicon, boron, a phosphoryl group, an amino group, a phenyl group, a cyclohexyl group, a difluoromethylene group, or a dialkylsiloxy group. R １ is an organic group having 1 or more carbon atoms, and contains a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. R １They may be the same or different from each other. 【0017】 (However, B １ R is an organic group having one or more carbon atoms, and the organic group has an azo group. ２ R is an organic group having one or more carbon atoms, and includes a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. ２ They may be the same or different from each other. 【0018】 (However, C １ R is CH, nitrogen, or silicon. ３ R is an organic group having one or more carbon atoms, and the organic group has an azo group and includes a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. ３ They may be the same or different from each other. 【0019】 (However, D is carbon, a nitrogen cation with a counter-anion, or silicon. R ４ R is an organic group having one or more carbon atoms, and the organic group has an azo group and includes a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. ４ (These may be the same or different from each other.) [4] A two-component curing adhesive comprising a first agent containing a compound (A) represented by the following formula (A1) or (A2), and a second agent containing an azo compound (B) represented by the following formula (B1) or (B2). In formula (A1), X １ is N, CR ｘ１ , B, P=O, or SiR ｘ２ And R ｘ１ and R ｘ２ Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and multiple Z １ Each of these is independently a hydroxyl group, an amino group, an isocyanate group, or an isothiocyanate group, and n1 is a number from 1 to 6. In formula (A2), X ２ is N ＋ , C, or Si, and multiple Z ２Each of these is independently a hydroxyl group, an amino group, an isocyanate group, or an isothiocyanate group, and n2 is a number from 1 to 6. In formula (B1), multiple Z ３ Each of these is independently a hydroxyl group, an amino group, an isocyanate group, or an isothiocyanate group, L ５ and L ６ Each of these is an alkylene group having 2 to 6 carbon atoms, X ３ and X ４ Each is independently -O- or -NH-, and R １ ~R ４ Each of these is an alkyl group having 1 to 3 carbon atoms. In formula (B2), multiple Z ４ Each of these is independently a hydroxyl group, an amino group, an isocyanate group, or an isothiocyanate group, L １１ and L １２ Each is independently - (CH ２ ) ｓ -NR Ｌ１ - (CH ２ ) ｔ It is a group represented by -, where s and t are independently numbers from 2 to 6, R Ｌ１ Y is an alkyl group having 1 to 3 carbon atoms. ７ and Y ８ Each of these is independently a urethane bond, a thiourethane bond, a urea bond, or a thiourea bond, L ９ and L １０ Each of these is an alkylene group having 2 to 6 carbon atoms, X ５ and X ６ Each is independently -O- or -NH-, and R ５ ~R ８b2 is a number from 2 to 10, where each is an alkyl group having 1 to 3 carbon atoms independently. [5] The two-component curing adhesive according to [4], wherein one of the compound (A) and the azo compound (B) has a hydroxyl group or an amino group, and the other has an isocyanate group or an isothiocyanate group. [6] The two-component curing adhesive according to [4] or [5], wherein at least one of the first agent or the second agent further comprises an ultraviolet absorber. [7] A cured product of the two-component curing adhesive according to [4], obtained by mixing the first agent and the second agent and curing it. [8] The cured product according to [7], having a urethane bond, a thiourethane bond, a urea bond, or a thiourea bond. [9] A method for using the two-component curing adhesive according to any one of [4] to [6], comprising irradiating the cured product of the two-component curing adhesive according to any one of [4] to [6] with microwaves to generate nitrogen gas and reduce the molecular weight of the cured product.

[10] A method for using the two-component curing adhesive according to [9], comprising washing and removing the low-molecular-weight cured product. 【0020】 According to the present invention, an adhesive composition, a cured product, and a method for producing a cured product can be provided, in which the shear peel strength is significantly reduced by using a molecular structure that releases nitrogen gas upon microwave irradiation, and the adherend can be reused because the adhesive can be easily cleaned after peeling. 【0021】 This figure shows the FT-IR spectra of diisothiocyanates and oligomers. １ H-NMR spectrum and １３This figure shows the 13C-NMR spectrum. This figure shows the results of thermogravimetric-mass spectrometry (TG-MS) of the cured product made from the compound obtained in Example 1. This figure shows the results of measuring the adhesive strength of the cured product made from the compound obtained in Example 2. This figure shows the results of measuring the adhesive strength of the cured product made from the compound obtained in Example 2. This figure shows the results of measuring the adhesive strength of the cured product made from the compound obtained in Example 2. This figure shows the results of evaluating the peelability of the cured product made from the compound obtained in Example 2. This figure shows the evaluation of the adhesive strength of the adhesive of Example 2 using various test materials. This figure shows the adhesive strength of the adherend before microwave irradiation using the adhesive of Example 2. This figure shows the state of the sample in Figure 9 after microwave irradiation. This figure shows the result of re-adhesion by irradiating the adhesive surface with microwaves using the adhesive of Example 2. This figure shows the change in nitrogen gas generation due to microwave irradiation time using the adhesive of Example 2. This figure shows the evaluation results of the rheological properties using the adhesive of Example 2. This figure shows the change in adhesive strength with microwave irradiation time using the adhesive of Example 2. This figure shows the evaluation of the sensitivity of the adhesive of Example 2 under high temperature conditions, low temperature conditions, hard conditions, and ultraviolet irradiation conditions. 【0022】 [Adhesive Composition] An adhesive composition according to one embodiment of the present invention comprises a compound (1) represented by the following general formula (1), and at least one selected from an azo compound (2) represented by the following general formula (2), an azo compound (3) represented by the following general formula (3), and an azo compound (4) represented by the following general formula (4). 【0023】 【0024】 (However, n1 is the valence of A. A is carbon, nitrogen, silicon, boron, phosphoryl group, amino group, phenyl group, cyclohexyl group, difluoromethylene group, or dialkylsiloxy group. R １ R is an organic group having one or more carbon atoms, and includes a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. １ They may be the same or different from each other. 【0025】 【0026】 (However, B １ R is an organic group having one or more carbon atoms, and the organic group has an azo group. ２ R is an organic group having one or more carbon atoms, and includes a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. ２ They may be the same or different from each other. 【0027】 【0028】 (However, C １ R is CH, nitrogen, or silicon. ３ R is an organic group having one or more carbon atoms, and the organic group has an azo group and includes a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. ３ They may be the same or different from each other. 【0029】 【0030】 (However, D is carbon, a nitrogen cation with a counter-anion, or silicon. R ４ R is an organic group having one or more carbon atoms, and the organic group has an azo group and includes a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. ４ They may be the same or different from each other. 【0031】 In the above general formula (1), R １ The group is an organic group having one or more carbon atoms, and preferably contains an alkylene group. The alkylene group may have substituents. Specifically, the alkylene group may be -CH ２ -CH ２ -ien-CH ２ -C(CH ３ ) H-, -CH ２ -C(CH ３ ) ２ -ien-CH ２ -CH ２ Examples include -O-, etc. R １ It is preferable that the compound has a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group at its terminal end. 【0032】In the general formula (1) above, n1 is the valence of A, and it is preferable that it is a natural number between 1 and 4. 【0033】 Examples of compounds represented by the general formula (1) above include the compounds represented by the following chemical formulas (6) to (34). Note that the "X" in chemical formulas (21), (28) to (31) － The symbol " represents the counter anion. Monovalent counter anions include fluoride ions, chloride ions, bromide ions, iodide ions, bicarbonate ions, nitrate ions, hydroxide ions, acetate ions, trifluoroacetate ions, tetrafluoroborate ions, hexafluorophosphate ions, trifluoromethanesulfonate ions, bis(fluorosulfonyl)imide ions, and bis(trifluoromethanesulfonyl)imide ions. Divalent counter anions include carbonate ions and sulfate ions. Trivalent counter anions include phosphate ions, etc. 【0034】 【0035】 【0036】 【0037】 【0038】 【0039】 【0040】 【0041】 【0042】 【0043】 【0044】 【0045】 【0046】 【0047】 【0048】 【0049】 【0050】 【0051】 【0052】 【0053】 【0054】 【0055】 【0056】 【0057】 【0058】 【0059】 【0060】 【0061】 【0062】 【0063】 In the above general formula (2), B １ is, for example, -CH ２ -CH ２ -N=N-CH ２ -CH ２ -, -CH ２ -CH ２ -C(CH ３ ) ２ -N=N-C(CH ３ ) ２ -CH ２ -CH ２ - and the like. In the above general formula (2), R ２ is, for example, -CH ２ -CH ２ -, -CH ２ -CH ２ -O-CH ２ -CH ２ - and the like, and contains an organic group. R２ It is preferable that the compound has a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group at its terminal end. 【0064】 Examples of compounds represented by the general formula (2) above include the compound represented by the following chemical formula (35). 【0065】 【0066】 In the above general formula (3), R ３ For example, -CH ２ -CH ２ -N = N - CH ２ -CH ２ -ien-CH ２ -CH ２ -C(CH ３ ) ２ -N = N - C(CH ３ ) ２ -CH ２ -CH ２ Contains organic groups such as -. R ３ It is preferable that the compound has a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group at its terminal end. 【0067】 Examples of compounds represented by the general formula (3) above include the compounds represented by the following chemical formulas (36) to (38). 【0068】 【0069】 【0070】 【0071】 In the general formula (4) above, R ４ For example, -CH ２ -CH ２ -N = N - CH ２ -CH ２ -ien-CH ２ -CH ２ -C(CH ３ ) ２ -N = N - C(CH ３ ) ２ -CH ２ -CH ２ Contains organic groups such as -. R４ It is preferable that the compound has a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group at its terminal end. 【0072】 Examples of compounds represented by the general formula (4) above include the compounds represented by the following chemical formulas (39) to (41). Note that in chemical formula (41), "X － The symbol " represents the counter anion. Monovalent counter anions include fluoride ions, chloride ions, bromide ions, iodide ions, bicarbonate ions, nitrate ions, hydroxide ions, acetate ions, trifluoroacetate ions, tetrafluoroborate ions, hexafluorophosphate ions, trifluoromethanesulfonate ions, bis(fluorosulfonyl)imide ions, and bis(trifluoromethanesulfonyl)imide ions. Divalent counter anions include carbonate ions and sulfate ions. Trivalent counter anions include phosphate ions, etc. 【0073】 【0074】 【0075】 【0076】 One of the azo compounds selected from azo compound (2), azo compound (3), and azo compound (4) may be used alone, or two or more selected from azo compound (2), azo compound (3), and azo compound (4) may be used in combination. When two or more selected from azo compound (2), azo compound (3), and azo compound (4) are used in combination, the mixing ratio of each azo compound is not particularly limited and can be appropriately adjusted according to the required adhesion and release properties of the cured product obtained by curing the adhesive composition. 【0077】 The mixing ratio of compound (1) to at least one selected from azo compound (2), azo compound (3), and azo compound (4) is not particularly limited and can be appropriately adjusted according to the required adhesion and release properties of the cured product obtained by curing the adhesive composition. 【0078】The adhesive composition of this embodiment may contain a solvent capable of dissolving compound (1), azo compound (2), azo compound (3), and azo compound (4). That is, the adhesive composition of this embodiment may contain a solution of compound (1) dissolved in a solvent, and a solution of at least one selected from azo compound (2), azo compound (3), and azo compound (4) dissolved in a solvent. A cured product made of the adhesive composition of this embodiment can also be obtained by mixing these solutions to form a coating liquid, applying the coating liquid to a substrate, and drying it. 【0079】 Examples of solvents include N,N-dimethylformamide, acetonitrile, and tetrahydrofuran. 【0080】 In this embodiment, the adhesive composition is obtained by mixing compound (1) with at least one selected from azo compound (2), azo compound (3), and azo compound (4), through which a reaction proceeds between compound (1) and at least one selected from azo compound (2), azo compound (3), and azo compound (4), resulting in a cured product of the adhesive composition. 【0081】 The adhesive of the second embodiment of the present disclosure is preferably a two-component curing adhesive comprising a first component comprising a compound (A) represented by the following formula (A1) or (A2), and a second component comprising an azo compound (B) represented by the following formula (B1) or (B2). 【0082】 【0083】 In formula (A1), X １ is N, CR ｘ１ , B, P=O, or SiR ｘ２ And R ｘ１ and R ｘ２ Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and multiple Z １ Each of these is independently a hydroxyl group, an amino group, an isocyanate group, or an isothiocyanate group, and n1 is a number from 1 to 6. 【0084】 In formula (A1), X １ It is preferable that it is N. Multiple Z １An amino group or an isothiocyanate group is preferred. n1 is preferably 1 to 4, and more preferably 1 or 2. 【0085】 【0086】 In formula (A2), X ２ is N ＋ , C, or Si, and multiple Z ２ Each of these is independently a hydroxyl group, an amino group, an isocyanate group, or an isothiocyanate group, and n2 is a number from 1 to 6. 【0087】 In formula (A2), multiple Z ２ An amino group or an isothiocyanate group is preferred. n2 is preferably 1 to 4, and more preferably 1 or 2. 【0088】 【0089】 In formula (B1), multiple Z ３ Each of these is independently a hydroxyl group, an amino group, an isocyanate group, or an isothiocyanate group, L ５ and L ６ Each of these is an alkylene group having 2 to 6 carbon atoms, X ３ and X ４ Each is independently -O- or -NH-, and R １ ~R ４ Each of these is an alkyl group having 1 to 3 carbon atoms. 【0090】 In formula (B1), multiple Z ３ The amino group or isothiocyanate group is preferred. ５ and L ６ Each of these is preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. ３ and X ４ Each of these is independently preferably -NH-. １ ~R ４ A C1 or C2 alkyl group is preferred, and a methyl group is more preferred. 【0091】 【0092】 In formula (B2), multiple Z ４Each of these is independently a hydroxyl group, an amino group, an isocyanate group, or an isothiocyanate group, L １１ and L １２ Each is independently - (CH ２ ) ｓ -NR Ｌ１ - (CH ２ ) ｔ It is a group represented by -, where s and t are independently numbers from 2 to 6, R Ｌ１ Y is an alkyl group having 1 to 3 carbon atoms. ７ and Y ８ Each of these is independently a urethane bond, a thiourethane bond, a urea bond, or a thiourea bond, L ９ and L １０ Each of these is an alkylene group having 2 to 6 carbon atoms, X ５ and X ６ Each is independently -O- or -NH-, and R ５ ~R ８ Each of these is an alkyl group having 1 to 3 carbon atoms, and b2 is a number between 2 and 10. 【0093】 In formula (B2), multiple Z ４ The group is preferably an amino group or an isothiocyanate group. The numbers s and t are preferably 2 or 3, and more preferably 3. Ｌ１ A C1 or C2 alkyl group is preferred, and a methyl group is more preferred. ７ and Y ８ A thiourethane bond or a thiourea bond is preferred. ９ and L １０ Each of these is preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. ５ and X ６ Each of these is independently preferably -NH-. ５ ~R ８ A C1 or C2 alkyl group is preferred, and a methyl group is more preferred. 【0094】 The adhesive of the present disclosure preferably has one of the compound (A) and the azo compound (B) having a hydroxyl group or an amino group, and the other having an isocyanate group or an isothiocyanate group. 【0095】 In the first agent, the content of compound (A) is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and even more preferably 90 to 100% by mass, relative to the total mass of the first agent. When the content of compound (A) in the first agent is within the above range, the curing reaction proceeds easily. 【0096】 In the second agent, the content of azo compound (B) is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and even more preferably 90 to 100% by mass, relative to the total mass of the second agent. When the content of azo compound (B) in the second agent is within the above range, the curing reaction proceeds easily. 【0097】 The adhesive of this disclosure preferably further contains an ultraviolet absorber in at least one of the first or second component. It is more preferable that the second component contains an ultraviolet absorber. Examples of ultraviolet absorbers are not particularly limited, but include malonic acid ester compounds, acrylic acid ester compounds, triazine compounds, benzophenone compounds, benzotriazole compounds, phenyl benzoate compounds, phenyl salicylate compounds, anilide oxalate compounds, and the like. 【0098】 Examples of malonic acid ester compounds include dimethyl 2-(4-(dimethylamino)benzylidene)malonate and dimethyl (4-methoxyphenyl)malonate. 【0099】 Examples of cyanoacrylate ester compounds include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. 【0100】Examples of triazine compounds include 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-{4-(octyl-2-methylethanol)oxy-2-hydroxyphenyl Examples include roxyphenyl-4,6-{bis(2,4-dimethylphenyl)}-1,3,5-triazine, 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. 【0101】 Examples of benzophenone compounds include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone. Examples of benzotriazole compounds include 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol and 2-(2H-benzotriazole-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol. 【0102】 Examples of phenyl benzoate compounds include phenyl salicylate, p-tert-butylphenyl salicylate, and p-(1,1,3,3-tetramethylbutyl)phenyl salicylate. 【0103】 Examples of phenyl salicylate compounds include phenyl salicylates, 3-hydroxyphenylbenzoate, and phenylene-1,3-dibenzoate. 【0104】 Examples of oxalic acid anilide compounds include 2-ethoxy-2'-ethyloxalanilide and 2-ethoxy-2'-dodecyloxalanilide. 【0105】 In the first agent, the content of the ultraviolet absorber is preferably 0.1 to 3% by mass, and more preferably 0.5 to 2% by mass, relative to the total mass of the first agent. When the content of the ultraviolet absorber in the first agent is within the above range, it is easier to suppress the decomposition of the cured product by ultraviolet light. 【0106】 In the second agent, the content of the ultraviolet absorber is preferably 0.5 to 5% by mass, and more preferably 0.5 to 3% by mass, relative to the total mass of the second agent. When the content of the ultraviolet absorber in the second agent is within the above range, the decomposition of the azo compound by ultraviolet light is easily suppressed. 【0107】 In yet another embodiment, in the adhesive of the second embodiment, the formula (A1) (CH ２ ) ｎ１ (CF ２ ) ｍ１ Or (Si(CH ３ ) ２ -O) ｍ１ The first agent substituted with (CH) of formula (A2). ２ ) ｎ２ (CF ２ ) ｍ２ Or (Si(CH ３ ) ２ -O) ｍ２ It may also be a two-component curing adhesive having a first component substituted with . m1 and m2 are each independently a number from 1 to 6. 【0108】 [Cured product] A cured product according to one embodiment of the present invention is a cured product of the adhesive composition of the above embodiment, and is represented by the following general formula (5). 【0109】 (However, E is carbon, nitrogen, silicon, boron, phosphoryl group, amino group, phenyl group, cyclohexyl group, difluoromethylene group, or dialkylsiloxy group. n2 is the valency of E. R ５ is -a-(b-c) ｎ３It is represented as -d (where n3 is an integer greater than or equal to 2). a is an alkylene group having 1 or more carbon atoms, which may have a functional group. b is at least one selected from a urethane bond, a thiourethane bond, a urea bond, and a thiourea bond. c is an organic group having 1 or more carbon atoms, and at least some of the plurality of said organic groups have an azo group. d is a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. R ５ They may be the same or different from each other. 【0110】 In other words, the cured product of this embodiment consists of a compound (1) represented by the above general formula (1), an azo compound (2) represented by the above general formula (2), an azo compound (3) represented by the above general formula (3), and an azo compound (4) represented by the above general formula (4), all linked together via at least one bond selected from urethane bonds, thiourethane bonds, urea bonds, and thiourea bonds. 【0111】 In the general formula (5) above, a is an alkylene group having 1 or more carbon atoms. The alkylene group may have substituents. Specifically, a may be -CH ２ -CH ２ -ien-CH ２ -C(CH ３ ) H-, -CH ２ -C(CH ３ ) ２ -ien-CH ２ -CH ２ Examples include -O-, etc. 【0112】 In the above general formula (1), b is at least one selected from urethane bonds, thiourethane bonds, urea bonds, and thiourea bonds. 【0113】 The urethane bond is represented by the following formula (42). 【0114】 【0115】 The thiourethane bond is represented by the following formula (43). 【0116】 【0117】The urea bond is represented by the following formula (44). 【0118】 【0119】 The thiourea bond is represented by the following formula (45). 【0120】 【0121】 In the general formula (5) above, c is an organic group having one or more carbon atoms, and at least some of the plurality of such organic groups have an azo group. Examples of c having an azo group include -CH ２ -CH ２ -N = N - CH ２ -CH ２ -ien-CH ２ -CH ２ -C(CH ３ ) ２ -N = N - C(CH ３ ) ２ -CH ２ -CH ２ - are examples. Examples of c that do not have an azo group include -CH ２ -CH ２ -ien-CH ２ -CH ２ -O-CH ２ -CH ２ - are some examples. 【0122】 The cured product according to this embodiment consists of, for example, a compound having a repeating unit represented by the following formula (46), a compound having a repeating unit represented by the following formula (47), and the like. 【0123】 【0124】 【0125】In the cured product of this embodiment, b, which is at least one selected from urethane bonds, thiourethane bonds, urea bonds, and thiourea bonds in the compound represented by the above general formula (5), has adhesive properties. Furthermore, in the cured product of this embodiment, the azo group in the compound represented by the above general formula (5) releases nitrogen gas upon microwave irradiation. That is, when the cured product of this embodiment is irradiated with microwaves, the azo group decomposes and nitrogen gas is released. As a result, the interface between the cured adhesive product and the adherend is destroyed, and at the same time, the cured product decomposes into low molecular weight fragments with low adhesive properties that can be easily removed. This reduces the adhesive properties of the cured product, allowing it to be easily peeled off the adherend. 【0126】 According to the cured product of this embodiment, the shear peel strength is significantly reduced by creating a molecular structure that releases nitrogen gas upon microwave irradiation, allowing the cured product to be easily peeled off the adherend. As a result, the components of the cured product remaining on the surface of the adherend after peeling can be easily cleaned, making the adherend reusable. 【0127】 The microwaves irradiated onto the cured material in this embodiment preferably have a wavelength of 1 mm to 1000 mm, more preferably 10 mm to 500 mm, and even more preferably 100 mm to 200 mm. When the wavelength of the microwaves is above the lower limit and below the upper limit, the microwaves are efficiently absorbed by the cured material, and the shear peel strength of the cured material can be reduced in a short time. 【0128】 The microwaves irradiated onto the cured material in this embodiment preferably have a frequency of 0.3 GHz to 300 GHz, more preferably 0.6 GHz to 30 GHz, and even more preferably 1.5 GHz to 3 GHz. When the wavelength of the microwaves is above the lower limit and below the upper limit, the microwaves are efficiently absorbed by the cured material, and the shear peel strength of the cured material can be reduced in a short time. 【0129】The microwaves irradiated onto the cured material in this embodiment preferably have an intensity of 50 W to 2000 W, more preferably 100 W to 1500 W, and even more preferably 200 W to 1000 W. If the microwave intensity is above the lower limit, the required microwave irradiation time can be shortened. If the microwave intensity is below the upper limit, the microwave generator does not need to be large and no additional safety equipment is required. 【0130】 In this embodiment, the time for irradiating the cured material with microwaves is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 30 seconds to 3 minutes. If the microwave irradiation time is above the lower limit, the cured material is less likely to be dismantled by unintended microwave irradiation. If the microwave irradiation time is below the upper limit, the time required for dismantling due to microwave irradiation is short, and on-site work time can be reduced. 【0131】 [Method for producing a cured product] A method for producing a cured product according to one embodiment of the present invention includes the step of reacting a compound (1) represented by the above general formula (1) with at least one selected from the azo compound (2) represented by the above general formula (2), the azo compound (3) represented by the above general formula (3), and the azo compound (4) represented by the above general formula (4). 【0132】 To react compound (1) with at least one selected from azo compound (2), azo compound (3), and azo compound (4), these compounds are mixed and maintained at a predetermined temperature in a nitrogen atmosphere in the presence of a catalyst. Alternatively, the compounds may be dissolved in a solvent and maintained at a predetermined temperature in a nitrogen atmosphere in the presence of a catalyst. 【0133】 Examples of catalysts that can be used include diazabicycloundecene, triazabidiclodecene, and tetramethylguanidine. 【0134】The reaction temperature for reacting compound (1) with at least one selected from azo compound (2), azo compound (3), and azo compound (4) is preferably 0°C to 100°C, and more preferably 10°C to 40°C. If the reaction temperature is above the lower limit, the effect of the cured product is less likely to be inhibited by condensation of moisture in the air. If the reaction temperature is below the upper limit, nitrogen gas is less likely to be released from the cured product, reducing the adhesion. 【0135】 The curing time for a mixture of compound (1) and at least one compound selected from azo compound (2), azo compound (3), and azo compound (4) is preferably 5 minutes or more and 120 minutes or less, and more preferably 10 minutes or more and 60 minutes or less. If the curing time is greater than or equal to the lower limit, the mixture will harden before the cured material can be applied to the predetermined position on the adherend, which reduces the likelihood of a decrease in workability. If the curing time is less than or equal to the upper limit, no separate temporary fixing is required until the mixture hardens. 【0136】 According to the method for producing the cured product of this embodiment, the cured product of the above-described embodiment can be obtained. 【0137】 The cured product of the adhesive according to the second embodiment of this disclosure is obtained by mixing and reacting the first agent and the second agent. The curing temperature is not particularly limited, but is preferably, for example, room temperature (25°C). The cured product is in a glassy state at room temperature and preferably satisfies the condition that storage modulus (G') > loss modulus (G''). Furthermore, the cured product has a glass transition temperature (T ｇ It is preferable that the material is in a rubbery state at or above the specified temperature and that the storage modulus (G') > loss modulus (G''). The storage modulus (G') and loss modulus (G'') are measured using a shear-type dynamic viscoelasticity measuring system (rheometer) or a dynamic mechanical analyzer (DMA). Specifically, they are measured by the method described in the examples. The ratio expressed as loss modulus (G'') / storage modulus (G') at room temperature (25°C) is preferably 0.001 to 1.0, and more preferably 0.01 to 1.0. When the ratio is within the above range, it is easier to maintain a glassy state at room temperature, maintain adhesive strength, and produce a cured product that is less prone to cracking. 【0138】 The cured product of this disclosure preferably has urethane bonds, thiourethane bonds, urea bonds, or thiourea bonds. These bonds are formed by the reaction of the first agent and the second agent. 【0139】 The glass transition temperature (T) of a cured product as measured by differential scanning calorimetry (DSC). ｇ The temperature is preferably 30 to 70°C, and more preferably 33 to 65°C. 【0140】 [Method of Use of Adhesive] The adhesive of this disclosure functions as an adhesive when the first agent and the second agent are mixed and cured to form a cured product. Furthermore, the adhesive of this disclosure can be peeled off from the adherend by irradiating the cured product of the adhesive with microwaves to generate nitrogen gas and reduce the molecular weight of the cured product. That is, the method of use of the adhesive of this disclosure includes irradiating the cured product of the adhesive with microwaves to generate nitrogen gas and reduce the molecular weight of the cured product. The above-described conditions can be used as the microwave irradiation conditions. Furthermore, it is preferable that the method of use of the adhesive of this disclosure includes washing and removing the reduced molecular weight cured product. The washing solution is not particularly limited, but a washing solution containing an organic solvent is preferred. The organic solvent is not particularly limited, but examples include alcohol-based solvents such as methanol, ethanol, and isopropyl alcohol; ketone-based solvents such as acetone; ester-based solvents such as ethyl acetate; amide-based solvents such as N,N-dimethylformamide and 2-pyrrolidone; and aromatic solvents such as toluene. The cured product after depolymerization is in a fluid state at room temperature, and it is preferable that the storage modulus (G') < loss modulus (G''). For the cured product after depolymerization, the ratio expressed as loss modulus (G'') / storage modulus (G') at room temperature (25°C) is preferably 1.0 to 1000, and more preferably 1.0 to 100. When the ratio is within the above range, it becomes easier to remove with a cleaning solution, and the recyclability of the adherend is improved. 【0141】 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. 【0142】[Synthesis of Diisothiocyanates] At 0°C, 100 mL of tetrahydrofuran is mixed with 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and 60 mL of carbon disulfide (CS ２ To the first solution containing ) dissolved in 200 mL of tetrahydrofuran (THF), a second solution containing 100 mmol of diamine (N,N-bis(3-aminopropyl)methylamine) dissolved in 200 mL of tetrahydrofuran (THF) was added dropwise. The mixture was heated to room temperature (25°C) and stirred for 8 hours. This carried out the reaction shown in the following chemical equation (48). Subsequently, the mixture was evaporated using a rotary evaporator until the volume of THF was reduced to 50 mL. Next, 500 mL of diethyl ether was added to the mixture to precipitate the by-product. The by-product was filtered and thoroughly washed with diethyl ether. The filtrate and washing solution were concentrated using a rotary evaporator, and the product and by-product were separated by column chromatography using chloroform 95% - acetonitrile 5% as the eluent. After concentrating the solution containing the product using a rotary evaporator, the solvent was evaporated using a vacuum pump to obtain the product. The yield was 88%. The Fourier transform infrared (FT-IR) spectrum of the obtained product was measured. A JASCO Model FT / IR-4100 Fourier transform infrared spectrometer was used for the FT-IR spectrum measurement. The measurement was performed in attenuated total internal reflection mode at 4 cm. －１ The FT-IR spectrum was recorded at the following resolution. The results are shown in Figure 1. Regarding the obtained product, １ H-NMR spectrum and １３ The C-NMR spectrum was measured. １ H-NMR spectrum and １３ For the 13C-NMR spectra, a JEOL model JNM-ECA 500II spectrometer operating at 500 MHz and 125 MHz, respectively, was used. The chemical shift (δ in ppm) was used as an internal reference, with the non-deuterated solvent residue as the reference. The results are shown in Figure 2. From the results shown in Figures 1 and 2, the obtained product was confirmed to be a diisothiocyanate. 【0143】 【0144】 [Synthesis of Oligomers] A solution was prepared by dissolving 4.8 mmol of diisothiocyanate obtained in the above-described synthesis of diisothiocyanate in 20 mL of acetonitrile. To this solution, 2.7 mmol of (E)-2,2'-(diazen-1,2-diyl)bis(N-(2-hydroxyethyl)-2-methylpropanamide) and 1.44 mmol of 2,3,4,6,7,8,9,10-octahydropyrimide[1,2-a]azepine (DBU) were added. The solution was then stirred at 40°C for 24 hours. This carried out the reaction shown in the following chemical equation (49). The solution was then concentrated to 10 mL and precipitated in 200 mL of diethyl ether. The mixture was centrifuged to obtain a viscous liquid. The liquid was dried to obtain the product. The yield was 83%. The Fourier transform infrared (FT-IR) spectrum of the obtained product was measured in the same manner as in the synthesis of diisothiocyanate. The results are shown in Figure 1. The obtained product was measured in the same manner as in the synthesis of diisothiocyanate, １ H-NMR spectrum and １３ The 13C-NMR spectrum was measured. The results are shown in Figure 2. From the results shown in Figures 1 and 2, it was confirmed that the obtained product is a diisothiocyanate containing azo and thiourethane bonds. From the results shown in Figure 2, it was confirmed that the obtained product is an oligomer. １ H NMR (500 MHz, DMSO-d6) δ 9.18 (-OC(=S)-NH-), 7.70 (-C(=O)-NH-), 4.41-4.35 (-CH2-OC(=S)-NH-), 3. 67-3.65 (-CH2-NCS), 3.48-3.42 (-OC(=S)-NH-CH2-), 3.16-3.12 (-C(=O)-NH- CH2-), 2.45-2.43 (-CH2-CH2-NCS), 2.34-2.19 (-N(CH3)-CH2), 2.10-2.05 (-N- CH3), 1.78-1.52 (-OC(=S)-NH-CH2-CH2-), 1.30-1.27 (-C(CH3)2-C(=O)-NH-). 【0145】 【0146】[Example 1] 0.5 mmol to 2.0 mmol of a derivative of 2,2',2''-triaminotriethylamine represented by the following formula (50) and 1.0 mmol of an azo compound represented by the following formula (51) were mixed and reacted to obtain a cured product consisting of a compound having repeating units represented by the above formula (46). 【0147】 【0148】 【0149】 [Example 2] 0.5 mmol to 2.5 mmol of 2,2',2''-triaminotriethylamine represented by the following formula (52) and 1.0 mmol of an azo compound represented by the following formula (53) were mixed and reacted to obtain a cured product (cured material) consisting of a compound having repeating units represented by the above formula (47). In the figure, the adhesive of Example 2 is also shown as Sample 2. 【0150】 【0151】 【0152】 [Comparative Example 1] 【0153】 【0154】Hexanediocytic acid (30 mmol), 2-aminoethanol (66 mmol), and 1-hydroxybenzotriazole (HOBt, 66 mmol) were dissolved in 100 mL of dichloromethane. The solution was cooled to 0°C, and N,N'-diisopropylcarbodiimide (DIPC, 66 mmol) was added dropwise. The reaction mixture was stirred at room temperature for 24 hours. After the reaction was complete, the precipitated material was filtered and washed with dichloromethane. The crude product was recrystallized in a mixture of toluene (80 mL) and ethanol (40 mL) to obtain N,N'-bis(2-hydroxyethyl)adipamide as a white crystalline solid. 4.8 mol of 3-isothiocyanate-N-(3-isothiocyanatetopropyl)-N-methylpropane-1-amine (represented by formula (48)), synthesized by the method described above, was dissolved in 20 mL of acetonitrile, and the synthesized N,N'-bis(2-hydroxyethyl)adipamide (2.7 mmol) and DBU (1.44 mmol) were added to it. The reaction mixture was stirred at 40°C for 24 hours. The solution was then concentrated under reduced pressure to approximately 10 mL and added to 200 mL of diethyl ether to precipitate the product. The resulting mixture was centrifuged, and the separated viscous oligomer was recovered and dried under vacuum at 30°C to obtain the compound represented by the above formula that does not contain azo bonds. １ H NMR (500 MHz, DMSO-d6) δ 9.19 (-OC(=S)-NH-), 8.00-7.97(-C(=O)-NH-), 4.32-4.29(-CH2-OC(=S)-NH-), 3.68-3.67(-CH2-NCS), 3.47-3.31(-OC (=S)-NH-CH2-), 3.22-3.12 (-C(=O)-NH-CH2-), 2.56-2.55 (-CH2-CH2-NCS), 2.33-2.23 (-N(CH3)-CH2-), 2.11-2.05 (-N-CH3 and -CH2-C(=O)-NH-), 1.86-1.63 (-OC(=S)-NH-CH2-CH2-), 1.61-1.57 (-CH2-CH2-C(=O)-), 1.47-1.44 (-CH2-CH2-CH2-C(=O)-). 【0155】 【0156】Next, 0.5 mmol to 2.5 mmol of 2,2',2''-triaminotriethylamine represented by formula (52) was mixed with 1.0 mmol of the obtained azo compound, and these compounds were reacted to obtain a cured product (cured material) consisting of a compound having repeating units represented by the above formula. In the formula, n was 5 to 6. 【0157】 [Evaluation] (Confirmation of nitrogen gas generation) Thermogravimetric-mass spectrometry (TG-MS) was performed on the cured product made from the compound obtained in Example 1. For TG-MS, Mettler-Toledo Model TGA / DTA8122, Shimadzu Model Nexus GC-2030, and GCMS Model QP2020 NX were used. TG-MS was performed under a helium gas flow rate of 250 mL / min and a heating rate of 20 °C / min in the temperature range of 25 °C to 200 °C. The results are shown in Figure 3. From the results shown in Figure 3, nitrogen gas generation was confirmed from the point when the cured product was heated to about 120 °C. On the other hand, almost no oxygen gas generation was confirmed. 【0158】 (Measuring Adhesion Strength 1) The adhesion strength of the cured product made from the compound obtained in Example 2 was measured. The cured product made from the compound obtained in Example 2 was bonded to two substrates by sandwiching it between them. A 1.0 mm thick polymethyl methacrylate (PMMA) substrate was used. The area of ​​the cured product between the two substrates was 0.7 to 0.9 cm². ２ The thickness was set to 10 to 30 μm. For measuring the adhesive strength, a Shimadzu EZ-LX type tester or a Shimadzu Autograph ags-x series tester was used. The tensile speed was set to 5 mm / min. The results are shown in Figure 4. From the results shown in Figure 4, it was found that the adhesive strength of the cured product obtained by mixing the isothiocyanate group derived from the azo compound with the amino group derived from 2,2',2''-triaminotriethylamine in a ratio of 1:1.25 was the highest. 【0159】(Measuring Adhesion Strength 2) The adhesion strength of the cured product made from the compound obtained in Example 2 was measured. The isothiocyanate group derived from the azo compound was mixed with the amino group derived from 2,2',2''-triaminotriethylamine in a ratio of 1:1.25. The cured product made from the compound obtained in Example 2 was bonded to two substrates by sandwiching it between them. The substrates used were made of wood, gypsum, polystyrene, polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), iron, stainless steel, and glass, with a thickness of 0.1 to 10 mm. The area of ​​the cured product between the two substrates was 0.7 to 0.9 cm². ２ The thickness was set to 10 to 30 μm. For measuring the adhesive strength, a Shimadzu EZ-LX type tester or a Shimadzu Autograph ags-x series tester was used. The tensile speed was set to 5 mm / min. The results are shown in Figure 5. From the results shown in Figure 5, it was found that the cured product made from the compound obtained in Example 2 showed an adhesive strength of 1 MPa or more on all substrates, and that the adhesive strength was particularly high on substrates made of stainless steel and substrates made of glass. 【0160】(Measuring Adhesion Strength 3) The adhesion strength of the cured product made from the compound obtained in Example 2 was measured. 1.25 mmol of 2,2',2''-triaminotriethylamine was mixed with 1.0 mmol of the azo compound. The cured product made from the compound obtained in Example 2 was bonded to two glass substrates (1.0 mm thick) by sandwiching them between them. As a comparative example, two glass substrates (1.0 mm thick) were bonded with other adhesives, and the adhesion strength of these adhesives was measured. Other adhesives used included Sikasil IG-25 HM Plus (silicone adhesive, manufactured by Sika), Sikasil SG-550 (silicone adhesive, manufactured by Sika), J-B Weld Epoxy (epoxy adhesive, manufactured by J-B Weld), Loccite ​​Super Glue (acrylic adhesive, manufactured by Loccite), and Gorilla Glue (polyurethane adhesive, manufactured by Gorilla Glue). The total area of ​​all cured material and adhesive between the two glass substrates was 0.7 to 0.9 cm². ２ The thickness was set to 10 to 30 μm. For measuring the adhesive strength, a Shimadzu EZ-LX type tester or a Shimadzu Autograph ags-x series tester was used. The tensile speed was set to 5 mm / min. The results are shown in Figure 6. From the results shown in Figure 6, it was found that the cured product made from the compound obtained in Example 2 had higher adhesive strength than the other adhesives. 【0161】 (Removability Evaluation) The removable properties of the cured product made from the compound obtained in Example 2 were evaluated. The cured product made from the compound obtained in Example 2 was placed on one surface of a 1.0 mm thick glass substrate, and the area covered by the cured product was 0.7 to 0.9 cm². ２An adhesive layer with a thickness of 10 to 30 μm was formed. This adhesive layer was irradiated with microwaves with a wavelength of 122 mm, a frequency of 2.45 MHz, and an intensity of 500 W, and the peel strength of the adhesive layer was measured as the irradiation time progressed. The peel strength of the adhesive layer was measured using a Shimadzu EZ-LX type tester or a Shimadzu Autograph ags-x series tester. The tensile speed was set to 5 mm / min. The results are shown in Figure 7. From the results shown in Figure 7, it was confirmed that when the adhesive layer was irradiated with microwaves for more than 3 minutes, the peel strength decreased to about 1 / 3 of the initial (0 minutes) value. In other words, it was confirmed that the adhesive layer could be easily peeled off the glass substrate by irradiating the adhesive layer with microwaves for more than 3 minutes. In addition, when the adhesive layer was irradiated with microwaves, numerous bubbles could be visually observed on the adhesive surface between the glass substrate and the adhesive layer. 【0162】 (Evaluation of Adhesion Strength) Figure 8 shows the evaluation of adhesive strength using the adhesive of Example 2. The test materials used were metals (steel, stainless steel), inorganic materials (glass, aluminosilicate ceramic, mortar, gypsum board), wood (cedar, cypress, Douglas fir), and plastics (polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polystyrene (PS)). The adhesive of this disclosure was found to exhibit practical adhesive strength on all of the adherends, including plastics, wood, inorganic materials, and metals. Adhesion strengths of 11.9 MPa, 11.8 MPa, and 11.0 MPa were achieved for Douglas fir, glass, and stainless steel, respectively. For mortar, gypsum board, cedar, and cypress, fracture occurred inside the material before delamination, indicating that the adhesive strength of these materials is sufficiently high. 【0163】(Evaluation of Peeling Force) Figure 9 shows the adhesive strength of the adherend before microwave irradiation using the adhesive of Example 2. Two glass plates were joined with the adhesive of the present disclosure, and the resulting sample was irradiated with 100 W microwaves from a distance of 12 mm from the sample surface. This irradiation was performed non-contact, using a 5 mm thick polytetrafluoroethylene (PTFE) barrier sandwiched between air gaps of 2 mm and 5 mm thickness. Figure 10 shows the state of the sample in Figure 9 after microwave irradiation. Within 15 minutes after microwave irradiation, the cured product of the adhesive of the present disclosure lost its adhesive strength due to the reduction of molecular weight, making it unable to support the weight, and the adhesive surface separated. It was found that when irradiated with 1000 W microwaves, the time until separation was shortened to 84 seconds. 【0164】 (Evaluation of re-adhesion) Figure 11 shows an example in which the cured adhesive of the present disclosure was depolymerized by irradiating the bonding surface with microwaves, removed with ethanol, and then the adhesive of the present disclosure was applied to the removed cross-section and bonded to another cross-section. As shown in Figure 11, it was found that the cured adhesive was depolymerized by microwaves and could be easily removed with ethanol, and that the adhesive could be re-bonded by reapplying it to the removed cross-section. In other words, it was found that the adhesive of the present disclosure is easy to remove, the component can be re-bonded, and the recyclability of the component is improved. 【0165】 Figure 12 shows the change in nitrogen gas generation with microwave irradiation time. As shown in Figure 12, it was found that the number and size of nitrogen gas bubbles increase as the microwave irradiation time increases. It was found that when nitrogen gas is generated, the adhesive strength is lost as the molecules become smaller, as shown in the following equation. 【0166】 【0167】 As shown in Table 1 below, Example 2, which has an azo bond, was compared with Comparative Example 1, which does not have an azo bond. In Comparative Example 1, no nitrogen gas generation was observed upon microwave irradiation. 【0168】 【0169】Figure 13 shows the evaluation results of the rheological properties. After 5 minutes of microwave irradiation, both the storage modulus (G') and the loss modulus (G'') decreased rapidly, with the loss modulus (G'') exceeding the storage modulus (G'). This indicates a transition from a crosslinked network to a fluid state. The resulting fluid residue could be easily removed with 75% ethanol, and the adhesive surface returned to its original clean state. Thus, microwave-induced delamination was found to enable the reuse of parts without damaging the surface. The storage modulus (G') and loss modulus (G'') were measured using a shear-type dynamic viscoelasticity measurement system (rheometer) or a dynamic mechanical analyzer (DMA). Specifically, the measurements were performed using an Anton Paar MCR-302 rheometer equipped with an 8 mm parallel plate structure. A cylindrical sample (8 mm in diameter) was subjected to vibrational shear at a fixed frequency of 1 Hz and a strain amplitude of 0.01%, and the temperature was swept from 0 to 80°C at a rate of 3°C / min. 【0170】 Figure 14 shows the change in adhesive strength over microwave irradiation time. In Example 2, the adhesive strength of the cured adhesive decreased as the microwave irradiation time increased. From this, it was found that the adhesive strength was lost because nitrogen gas was generated from the cured material due to microwave irradiation and the molecules were broken down into smaller molecules. 【0171】 Figure 15 shows the stability under high temperature, low temperature, hard conditions, and ultraviolet irradiation conditions. Under ultraviolet irradiation conditions, the solar power simulator (1000 W / m²) was used. ２ The stability under simulated sunlight was investigated by exposure to AM 1.5G. The adhesive strength rapidly decreased to zero within 48 hours. However, when a mixture of UV absorbers (2-(4-(dimethylamino)benzylidene) dimethyl malonate (1.5 wt%) and 2-cyano-3,3-diphenylacrylate ethyl (1.5 wt%)) was added to the second component of the adhesive in Example 2, the decrease in adhesive strength under simulated sunlight was suppressed. 【0172】According to the present invention, an adhesive composition, a cured product, and a method for producing a cured product can be provided, in which the shear peel strength is significantly reduced by using a molecular structure that releases nitrogen gas upon microwave irradiation, and the adherend can be reused because the adhesive can be easily cleaned after peeling.

Claims

1. An adhesive composition comprising the compound (1) represented by the following general formula (1) and at least one selected from the azo compound (2) represented by the following general formula (2), the azo compound (3) represented by the following general formula (3), and the azo compound (4) represented by the following general formula (4). (However, n1 is the valence of A. A is carbon, nitrogen, silicon, boron, a phosphoryl group, an amino group, a phenyl group, a cyclohexyl group, a difluoromethylene group, or a dialkylsiloxy group. R １ is an organic group having 1 or more carbon atoms and contains a hydroxyl group, an amino group, an isothiocyanate group or an isocyanate group. R １ may be the same as or different from each other.) (However, B １ is an organic group having 1 or more carbon atoms, and the organic group has an azo group. R ２ is an organic group having 1 or more carbon atoms and contains a hydroxyl group, an amino group, an isothiocyanate group or an isocyanate group. R ２ may be the same as or different from each other.) (However, C １ is CH, nitrogen or silicon. R ３ is an organic group having 1 or more carbon atoms, the organic group has an azo group and contains a hydroxyl group, an amino group, an isothiocyanate group or an isocyanate group. R ３ may be the same as or different from each other.) (However, D is carbon, a nitrogen cation having a counter anion or silicon. R ４ is an organic group having 1 or more carbon atoms, the organic group has an azo group and contains a hydroxyl group, an amino group, an isothiocyanate group or an isocyanate group. R ４ may be the same as or different from each other.) 2. A cured product of the adhesive composition described in claim 1, the cured product being represented by the following general formula (5). (However, E is carbon, nitrogen, silicon, boron, phosphoryl group, amino group, phenyl group, cyclohexyl group, difluoromethylene group, or dialkylsiloxy group. n2 is the valency of E. R ５ is -a-(b-c) ｎ３ It is represented as -d (where n3 is an integer greater than or equal to 2). a is an alkylene group having 1 or more carbon atoms, which may have a functional group. b is at least one selected from a urethane bond, a thiourethane bond, a urea bond, and a thiourea bond. c is an organic group having 1 or more carbon atoms, and at least some of the plurality of said organic groups have an azo group. d is a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. R ５ They may be the same or different from each other.

3. A method for producing a cured product, comprising the step of reacting a compound (1) represented by the following general formula (1) with at least one selected from an azo compound (2) represented by the following general formula (2), an azo compound (3) represented by the following general formula (3), and an azo compound (4) represented by the following general formula (4). (However, n1 is the valence of A. A is carbon, nitrogen, silicon, boron, phosphoryl group, amino group, phenyl group, cyclohexyl group, difluoromethylene group, or dialkylsiloxy group. R １ R is an organic group having one or more carbon atoms, and includes a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. １ They may be the same or different from each other. (However, B １ R is an organic group having one or more carbon atoms, and the organic group has an azo group. ２ R is an organic group having one or more carbon atoms, and includes a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. ２ They may be the same or different from each other. (However, C １ R is CH, nitrogen, or silicon. ３ R is an organic group having one or more carbon atoms, and the organic group has an azo group and includes a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. ３ They may be the same or different from each other. (However, D is carbon, a nitrogen cation with a counter-anion, or silicon. R ４ R is an organic group having one or more carbon atoms, and the organic group has an azo group and includes a hydroxyl group, an amino group, an isothiocyanate group, or an isocyanate group. ４ They may be the same or different from each other.

4. A two-component curing adhesive comprising a first component containing a compound (A) represented by the following formula (A1) or (A2), and a second component containing an azo compound (B) represented by the following formula (B1) or (B2). In formula (A1), X １ is N, CR ｘ１ , B, P=O, or SiR ｘ２ And R ｘ１ and R ｘ２ Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and multiple Z １ Each of these is independently a hydroxyl group, an amino group, an isocyanate group, or an isothiocyanate group, and n1 is a number from 1 to 6. In formula (A2), X ２ is N ＋ , C, or Si, and multiple Z ２ Each of these is independently a hydroxyl group, an amino group, an isocyanate group, or an isothiocyanate group, and n2 is a number from 1 to 6. In formula (B1), multiple Z ３ Each of these is independently a hydroxyl group, an amino group, an isocyanate group, or an isothiocyanate group, L ５ and L ６ Each of these is an alkylene group having 2 to 6 carbon atoms, X ３ and X ４ Each is independently -O- or -NH-, and R １ ~R ４ Each of these is an alkyl group having 1 to 3 carbon atoms. In formula (B2), multiple Z ４ Each of these is independently a hydroxyl group, an amino group, an isocyanate group, or an isothiocyanate group, L １１ and L １２ Each is independently - (CH ２ ) ｓ -NR Ｌ１ - (CH ２ ) ｔ It is a group represented by -, where s and t are independently numbers from 2 to 6, R Ｌ１ Y is an alkyl group having 1 to 3 carbon atoms. ７ and Y ８ Each of these is independently a urethane bond, a thiourethane bond, a urea bond, or a thiourea bond, L ９ and L １０ Each of these is an alkylene group having 2 to 6 carbon atoms, X ５ and X ６ Each is independently -O- or -NH-, and R ５ ~R ８ Each of these is an alkyl group having 1 to 3 carbon atoms, and b2 is a number between 2 and 10.

5. The two-component curing adhesive according to claim 4, wherein one of the compound (A) and the azo compound (B) has a hydroxyl group or an amino group, and the other has an isocyanate group or an isothiocyanate group.

6. The two-component curing adhesive according to claim 4, wherein at least one of the first or second component further comprises an ultraviolet absorber.

7. A cured product of a two-component curing adhesive according to claim 4, obtained by mixing the first agent and the second agent and curing the mixture.

8. The cured product according to claim 7, having urethane bonds, thiourethane bonds, urea bonds, or thiourea bonds.

9. A method for using the two-component curing adhesive according to claim 4, comprising irradiating the cured product of the two-component curing adhesive according to claim 4 with microwaves to generate nitrogen gas and reduce the molecular weight of the cured product.

10. A method for using a two-component curing adhesive according to claim 9, comprising washing and removing the low-molecular-weight cured product.

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