Degradable crosslinking agent

Abstract

Provided is a degradable crosslinking agent having high solubility in a solvent. The present invention relates to a decomposable cross-linking agent comprising a compound represented by formula (1). In formula (1), n > = 0, k > = 0, m > = 0, p1 > = 1, p2 > = 1, and p3 > = 1. R1, R2, and R3 independently represent a single bond, or a C1-500 hydrocarbon having or not having a substituent or a heteroatom. Q1, Q2, and Q3 are each independently selected from the group consisting of a hydroxyl group, an amino group, a thiol group, a hydrazide group, a carboxylic acid group, an anhydride group, a vinyl group, an allyl group, an acrylate group, a methacrylate group, a crotonate group, an isoprene group, an acrylamide group, a methacrylamide group, a crotonamido group, an epoxy group, an oxetanyl group, an oxazoline group, an isocyanate group, a carbodiimide group, and a hydroxymethyl group; and one or more reactive functional groups selected from the group consisting of a silanol group, a hydroxysilyl group, and an alkoxysilyl group. X1a, X1b, X2a, X2b, X3a, X3b, X4a, and X4b are each independently an oxygen atom, a sulfur atom, a single bond, a hydrocarbon group having 1-20 carbon atoms and having or not having a substituent, or-Nb-(B is a hydrogen atom or a hydrocarbon group), and one or more of X1a, X1b, X2a, X2b, X3a, X3b, X4a, and X4b are an oxygen atom, a sulfur atom, or-Nb-(B is a hydrogen atom or a hydrocarbon group). A1-A8 are carbonyl groups or single bonds, at least one of A1 and A2 is a carbonyl group, at least one of A3 and A4 is a carbonyl group, at least one of A5 and A6 is a carbonyl group, and at least one of A7 and A8 is a carbonyl group. Z independently represent a divalent or higher group including a siloxane structure, or a C1-500 hydrocarbon group having or not having a heteroatom. [Chemical Formula 1]

Description

Technical Field

[0001] The present invention relates to decomposable cross-linking agents. Background Art

[0002] Plastic products are used in a variety of fields, including daily necessities, automobiles, and electronic devices, due to their moldability, durability, and lightweight properties. However, they are difficult to decompose after disposal. In recent years, the development of biodegradable polymers that can be easily decomposed has been underway to protect the global environment.

[0003] As one type of degradable polymer, a polymer having a diacylhydrazine structure is disclosed (see Patent Documents 1, 2, and 3). These polymers exist stably in the air due to their diacylhydrazine structure and are rapidly decomposed by reaction with an oxidizing agent such as sodium hypochlorite.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2011-236381

[0007] Patent Document 2: International Publication No. 2021 / 131003

[0008] Patent Document 3: Japanese Patent Application Laid-Open No. 2011-052075 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] The diacylhydrazine compounds used as raw materials for the polymers described in Patent Documents 1 and 2, and the diacylhydrazine-containing polymers described in Patent Document 3, have low solubility in solvents, severely limiting their compositional limitations when combined with resins, polymerization initiators, and the like. Furthermore, even when they exhibit relatively high solubility in solvents, they dissolve only in high-boiling aprotic polar solvents and strong acids, resulting in significant environmental impact and limitations in applications such as coatings that require drying to remove the solvent. The present invention aims to provide a decomposable crosslinking agent with high solubility in solvents.

[0011] Means for solving problems

[0012] The present inventors have discovered that the solubility in a solvent can be improved by including a specific structure in a hydrazine derivative, thereby completing the present invention.

[0013] That is, the present disclosure (1) is a decomposable cross-linking agent composed of a compound represented by the following formula (1).

[0014] [Chemistry 1]

[0015]

[0016] (In formula (1),

[0017] n≥0, k≥0, m≥0, p1≥1, p2≥1, p3≥1.

[0018] ·R 1 、R 2 、R 3 Each independently represents a single bond, or a hydrocarbon having 1 to 500 carbon atoms which may have a substituent or a heteroatom.

[0019] Q 1 , Q 2 , Q 3 Each of the reactive functional groups is independently selected from the group consisting of a hydroxyl group, an amino group, a thiol group, a hydrazide group, a carboxylic acid group, an acid anhydride group, a vinyl group, an allyl group, an acrylate group, a methacrylate group, a crotonate group, an isoprenyl group, an acrylamide group, a methacrylamide group, a crotonamide group, an epoxy group, an oxetane group, an oxazoline group, an isocyanate group, a carbodiimide group, a hydroxymethyl group, a silanol group, a hydroxysilyl group, and an alkoxysilyl group.

[0020] ·X 1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b are independently an oxygen atom, a sulfur atom, a single bond, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, or -NB- (B is a hydrogen atom or a hydrocarbon group), X 1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b One or more of them are oxygen atoms, sulfur atoms, or -NB- (B is a hydrogen atom or a hydrocarbon group).

[0021] ·A 1 ~A 8 is a carbonyl group or a single bond, A 1 and A 2 At least one of A is a carbonyl group, 3 and A 4 At least one of A is a carbonyl group, 5 and A 6 At least one of A is a carbonyl group, 7 and A 8 At least one of them is a carbonyl group.

[0022] Z are each independently a divalent or higher valent group containing a siloxane structure, or a hydrocarbon group having 1 to 500 carbon atoms which may have a heteroatom.

[0023] The present disclosure (2) is a decomposable crosslinking agent as described in the present disclosure (1), wherein p1≥2, p2≥2, or p3≥2, and the two or more Q 1 Each other, Q 2 Each other or Q 3 They are reactive functional groups different from each other.

[0024] The present disclosure (3) is the decomposable cross-linking agent according to the present disclosure (1) or (2), wherein p1=1, p2=1, or p3=1.

[0025] The present disclosure (4) is the decomposable crosslinking agent according to the present disclosure (1) or (2), which has at least one decomposition site represented by the following formula (2).

[0026] -X 5 -C 1 -NH-NH-C 2 -X 6 -(2)

[0027] (In formula (2), X 5 、X 6 are different from each other and are each an oxygen atom, a sulfur atom, a single bond, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or -NB- (B is a hydrogen atom or a hydrocarbon group). 1 、C 2 is a carbonyl group or a single bond, C 1 and C 2 At least one of them is a carbonyl group.)

[0028] The present disclosure (5) is a decomposable crosslinking agent as described in the present disclosure (1) or (2), wherein X 1a or X 1b For oxygen atoms.

[0029] The present disclosure (6) is the decomposable crosslinking agent as described in the present disclosure (1) or (2), wherein n≧1.

[0030] Disclosure (7) The decomposable crosslinking agent according to Disclosure (1) or (2), wherein n ≥ 1,

[0031] X 1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b At least one of them is an oxygen atom,

[0032] At least one of them is a single bond or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and

[0033] At least one is -NB- (B is a hydrogen atom or a hydrocarbon group).

[0034] This disclosure (8) is the decomposable cross-linking agent according to this disclosure (1) or (2), wherein the molecular weight is 2000 or less.

[0035] The present disclosure (9) is the decomposable crosslinking agent as described in the present disclosure (1) or (2), wherein k≧1.

[0036] The present disclosure (10) is a composition comprising the decomposable crosslinking agent according to the present disclosure (1) or (2), and one or more selected from the group consisting of a curable resin, a polymerization initiator, and a solvent.

[0037] The present disclosure (11) is the composition as described in the present disclosure (10), which does not substantially contain a solvent having a boiling point exceeding 150°C.

[0038] The present disclosure (12) is a degradable cross-linked product, which is composed of the composition described in the present disclosure (10).

[0039] The present disclosure (13) is the decomposable cross-linked product according to the present disclosure (12), which can be decomposed by an oxidizing agent.

[0040] The present disclosure (14) is a method for decomposing a decomposable cross-linked product, comprising the step of bringing the decomposable cross-linked product described in the present disclosure (12) into contact with an aqueous solution containing an oxidizing agent at a temperature of 100° C. or lower.

[0041] Effects of the Invention

[0042] The decomposable cross-linking agent of the present invention has excellent solubility in solvents. DETAILED DESCRIPTION

[0043] <<Decomposable cross-linking agent>>

[0044] The decomposable cross-linking agent of the present invention is a decomposable cross-linking agent composed of a compound represented by the following formula (1).

[0045] [Chemistry 2]

[0046]

[0047] In formula (1),

[0048] n≥0, k≥0, m≥0, p1≥1, p2≥1, p3≥1.

[0049] ·R 1 、R2 、R 3 Each independently represents a single bond, or a hydrocarbon having 1 to 500 carbon atoms which may have a substituent or a heteroatom.

[0050] Q 1 , Q 2 , Q 3 Each of the reactive functional groups is independently selected from the group consisting of a hydroxyl group, an amino group, a thiol group, a hydrazide group, a carboxylic acid group, an acid anhydride group, a vinyl group, an allyl group, an acrylate group, a methacrylate group, a crotonate group, an isoprenyl group, an acrylamide group, a methacrylamide group, a crotonamide group, an epoxy group, an oxetane group, an oxazoline group, an isocyanate group, a carbodiimide group, a hydroxymethyl group, a silanol group, a hydroxysilyl group, and an alkoxysilyl group.

[0051] ·X 1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b are independently an oxygen atom, a sulfur atom, a single bond, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, or -NB- (B is a hydrogen atom or a hydrocarbon group), X 1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b One or more of them are oxygen atoms, sulfur atoms, or -NB- (B is a hydrogen atom or a hydrocarbon group).

[0052] ·A 1 ~A 8 is a carbonyl group or a single bond, A 1 and A 2 At least one of A is a carbonyl group, 3 and A 4 At least one of A is a carbonyl group, 5 and A 6 At least one of A is a carbonyl group, 7 and A 8 At least one of them is a carbonyl group.

[0053] Z are each independently a divalent or higher valent group containing a siloxane structure, or a hydrocarbon group having 1 to 500 carbon atoms which may have a heteroatom.

[0054] The decomposable crosslinking agent of the present invention is characterized in that one or more of the two or more Xs in formula (1) is an oxygen atom or -NB- (B is a hydrogen atom or a hydrocarbon group).

[0055] It should be noted that the term "cross-linking agent" in a narrow sense sometimes refers to a chemical substance that forms chemical bonds between polymers or within a polymer. However, in this specification, in addition to chemical substances that form chemical bonds between polymers or within a polymer, it also refers to chemical substances that can form chemical bonds between their own molecules.

[0056] <n, m, k in formula (1)>

[0057] In formula (1), n ​​and m are both 0 or more, and are each independently preferably 1 to 50, and more preferably 1 to 5. When n is 1 or more, the decomposability of the decomposable crosslinking agent is improved due to the presence of two or more hydrazine structures (-A-NH-NH-A-), and in addition to X 1a 、X 1b In addition to the options of X 2a 、X 2b The solubility in the solvent is finely adjusted by the selection of n and m. The upper limit of n and m is not particularly limited, but when it exceeds 50, the solubility in the solvent tends to decrease.

[0058] In formula (1), k is 0 or greater, preferably 1 or greater, and more preferably 2 or greater. When k is 1 or greater, three-dimensional crosslinking can be achieved using the decomposable crosslinking agent of the present invention. The upper limit of k is not particularly limited and can be 200 or less. When k exceeds 200, solubility in solvents tends to decrease.

[0059] <p1, p2, p3 in formula (1)>

[0060] In formula (1), p1, p2, and p3 are all 1 or more, and are each independently preferably 1 to 4, and more preferably 1 to 2. When p1 ≥ 2, p2 ≥ 2, or p3 ≥ 2, the decomposable crosslinking agent of the present invention facilitates three-dimensional crosslinking, and the strength and reliability of the crosslinked product are improved. When p1 ≥ 2, p2 ≥ 2, or p3 ≥ 2, and there are two or more Q 1 Each other, Q 2 Each other or Q 3 Different reactive functional groups facilitate the selection of various curable resins and crosslinking processes as crosslinking agents. Furthermore, when only specific reactive functional groups are crosslinked, the reactive functional groups not used in the crosslinking reaction can contribute to improved adhesion and solubility, among other physical properties. When p1 = 1, p2 = 1, or p3 = 1, solubility in solvents and decomposition rates are further enhanced.

[0061] <R in formula (1) 1 、R 2 、R 3 >

[0062] In formula (1), R 1 、R 2 、R 3 Each of the substituents is independently a single bond, or a hydrocarbon group having 1 to 500 carbon atoms which may have a substituent or a heteroatom. In the case of a hydrocarbon group, the number of carbon atoms is 1 to 500, preferably 1 to 100, more preferably 1 to 10, from the viewpoint of decomposition rate. Examples of the substituent include an alkoxy group, a phenoxy group, a halogen atom, a tertiary amino group, and a sulfo group.

[0063] The hydrocarbon group has a saturated or unsaturated hydrocarbon group as the main skeleton, and can be any structure of a branched or linear structure. In addition, the skeleton formed by the hydrocarbon group can adopt a cyclic structure. The hydrocarbon group can have heteroatoms such as N, S, and O. The heteroatoms can be present in the main chain of the hydrocarbon group or in the side chain. As structures having heteroatoms, ether bonds, carbamate bonds, urea bonds, -NH- in which hydrogen atoms can be replaced, silicone bonds, ester bonds, thioether bonds, carbonate bonds, etc. can be cited. The methylene groups other than the terminal groups in the hydrocarbon group can be substituted by 1 to 4 heteroatoms or arylene groups or heteroarylene groups selected from N, S, O, etc. The hydrogen atoms in the hydrocarbon group can be substituted by cyano, nitro, halogen or phenyl. Among them, R is preferred. 1 、R 2 、R 3 The structure of hydroxybenzoic acid does not contain disulfide bonds. This is because disulfide bonds sometimes generate sulfonic acid when oxidized.

[0064] Examples of the hydrocarbon group include straight-chain hydrocarbons such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and nonylene; branched-chain hydrocarbons such as isopropylene, isobutylene, 2,2-dimethylpropylene, and 2-ethyl-2-methylpropylene; cyclic hydrocarbons such as cyclohexylene, cyclopentylene, norbornene, phenylene, and naphthylene; PEG chains; and groups in which these groups become trivalent or tetravalent groups.

[0065] <Q in formula (1) 1 , Q 2 , Q 3 >

[0066] In formula (1), Q 1 , Q 2 , Q 3The reactive functional groups are independently selected from the group consisting of a hydroxyl group, an amino group, a thiol group, a hydrazide group, a carboxylic acid group, an acid anhydride group, a vinyl group, an allyl group, an acrylate group, a methacrylate group, a crotonate group, an isoprenyl group, an acrylamide group, a methacrylamide group, a crotonamide group, an epoxy group, an oxetane group, an oxazoline group, an isocyanate group, a carbodiimide group, a methylol group, a silanol group, a hydroxysilyl group, and an alkoxysilyl group. The type of these reactive functional groups can be selected optimally according to the application and process.

[0067] <X in formula (1)>

[0068] In formula (1), X 1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b are independently an oxygen atom, a sulfur atom, a single bond, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, or -NB- (B is a hydrogen atom or a hydrocarbon group). 1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b It is called X inside.

[0069] When X is a hydrocarbon group, the number of carbon atoms is 1 to 20, preferably 1 to 10, more preferably 1 to 6, from the viewpoint of ease of handling and easiness of cross-linking reaction.

[0070] The hydrocarbon group has a saturated or unsaturated hydrocarbon group as the main skeleton. The hydrocarbon group can be any structure of a branched or straight chain. In addition, the skeleton formed by the hydrocarbon group can adopt a cyclic structure.

[0071] The hydrocarbon group may have heteroatoms such as N, S, or O in the molecular chain. Methylene groups other than the terminal ones in the hydrocarbon group may be substituted with 1 to 4 heteroatoms selected from N, S, and O, or with arylene or heteroarylene groups. Hydrogen atoms in the hydrocarbon group may be substituted with cyano, nitro, halogen, or phenyl groups.

[0072] Specific examples of hydrocarbon groups include straight-chain hydrocarbons such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and nonylene; branched hydrocarbons such as 2,2-dimethylpropylene and 2-ethyl-2-methylpropylene; and cyclic hydrocarbons such as 1,4-cyclohexylene, cyclopentylene, norbornene, phenylene, and naphthylene. Among these, methylene and phenylene are preferred.

[0073] When X is -NB-, B is a hydrogen atom or a hydrocarbon group. When B is a hydrocarbon group, from the perspective of decomposition rate, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5. The hydrocarbon group B has a saturated or unsaturated hydrocarbon group as the main skeleton, and can be either branched or linear. The hydrocarbon group skeleton can also be cyclic.

[0074] Furthermore, the hydrocarbon group B may have heteroatoms such as N, S, or O in the molecular chain. Methylene groups other than the terminal groups in the hydrocarbon group may be substituted with 1 to 4 heteroatoms selected from N, S, and O, or with arylene or heteroarylene groups. Hydrogen atoms in the hydrocarbon group may be substituted with cyano, nitro, halogen, or phenyl groups.

[0075] Specific examples of B as a hydrocarbon group include straight-chain hydrocarbons such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and nonylene; branched hydrocarbons such as 2,2-dimethylpropylene and 2-ethyl-2-methylpropylene; cyclic hydrocarbons such as 1,4-cyclohexylene, cyclopentylene, norbornene, phenylene, and naphthylene; PEG chains; and groups in which these groups are trivalent or tetravalent. Among these, straight-chain hydrocarbons are preferred.

[0076] In formula (1), by making one or more of X an oxygen atom, a sulfur atom, or -NB- (B is a hydrogen atom or a hydrocarbon group), the overall solubility in the solvent is improved. In addition, by selecting the two or more Xs present, the solubility in the solvent can be fine-tuned. From the perspective of excellent solubility in the solvent, X is preferably 1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b Any one of them is an oxygen atom, more preferably X 1a or X 1b For oxygen atoms.

[0077] Furthermore, in formula (1), it is preferred that n≥1, X 1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b At least one of them is an oxygen atom, at least one is a single bond, or a hydrocarbon group with 1 to 20 carbon atoms which may or may not have a substituent, and at least one is -NB- (B is a hydrogen atom or a hydrocarbon group). In formula (1), it is preferred that n ≥ 1, and in X1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a and X 4b At least three of the following are present: an oxygen atom, a sulfur atom, a single bond, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, and -NB- (B is a hydrogen atom or a hydrocarbon group). By making three or more Xs have different structures, the solubility in the solvent can be improved.

[0078] The degradable cross-linking agent preferably has different structures at both ends of the hydrazine structure (-A-NH-NH-A-). This structure is represented by the following formula (2).

[0079] -X 5 -C 1 -NH-NH-C 2 -X 6 -(2)

[0080] In formula (2), X 5 、X 6 are different from each other and are each an oxygen atom, a sulfur atom, a single bond, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or -NB- (B is a hydrogen atom or a hydrocarbon group). 1 、C 2 is a carbonyl group or a single bond, C 1 and C 2 At least one of X is a carbonyl group. 5 、X 6 The combination of is preferably a combination of an oxygen atom and a single bond or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a combination of an oxygen atom and -NB- (B is a hydrogen atom or a hydrocarbon group).

[0081] In addition, the combination of X at both ends of the hydrazine structure (-A-NH-NH-A-), that is, X 1a 、X 1b Combination of X 2a 、X 2b Combination of X 3a 、X 3b Combination of X 4a 、X 4b The combination of can be the same as each other, also can be different from each other. By designing these combinations, the solubility in the solvent can be fine-tuned. As an example of the case where the combination is different, X can be cited. 1a is an oxygen atom, X 1b is a single bond or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, X 2a is an oxygen atom, X2b It is -NB- (B is a hydrogen atom or a hydrocarbon group).

[0082] <A in formula (1) 1 ~A 8 >

[0083] In formula (1), A 1 ~A 8 is a carbonyl group or a single bond, A 1 and A 2 At least one of A is a carbonyl group, 3 and A 4 At least one of A is a carbonyl group, 5 and A 6 At least one of A is a carbonyl group, 7 and A 8 At least one of them is a carbonyl group.

[0084] When one of the two A's on both sides of -NH-NH- is a carbonyl group, the decomposition rate by the oxidant tends to increase. When both are carbonyl groups, the decomposition product tends to dissolve easily in a solution containing the oxidant.

[0085] <Z in formula (1)>

[0086] In formula (1), two or more Zs present are independently a divalent or higher valent group containing a siloxane structure, or a hydrocarbon group having 1 to 500 carbon atoms which may have a heteroatom.

[0087] When Z is a divalent or higher group containing a siloxane structure, the group containing a siloxane structure includes a -Si-O- bond as the main skeleton. The main skeleton may be any of a linear structure, a branched structure, and a cyclic structure. The number of silicon atoms in the group containing a siloxane structure is preferably 2 to 400, more preferably 4 to 200, and even more preferably 8 to 150.

[0088] In the siloxane structure, hydrogen atoms bonded to silicon atoms may be substituted. Specific examples of the substituent include alkyl groups, alkoxy groups, phenoxy groups, halogen atoms, amino groups, sulfo groups, cyano groups, and nitro groups.

[0089] Specific examples of the group containing a siloxane structure include dimethyl silicone, diethyl silicone, ethylmethyl silicone, polymethylsilsesquioxane, and modified silicones containing heteroatoms such as N, S, O, and P by modifying their terminal and / or side chain hydrocarbon groups.

[0090] When Z is a hydrocarbon group having 1 to 500 carbon atoms with or without heteroatoms, the number of carbon atoms is more preferably 1 to 200, and even more preferably 2 to 30, from the perspective of decomposition rate and crosslinking density. The hydrocarbon group has a saturated or unsaturated hydrocarbon group as the main skeleton, and may be either branched or linear. Furthermore, the skeleton formed by the hydrocarbon group may have a cyclic structure. The hydrocarbon group may have heteroatoms such as N, S, and O. Heteroatoms may be present in the main chain of the hydrocarbon group or in the side chain. Examples of structures containing heteroatoms include ether bonds, carbamate bonds, urea bonds, -NH- bonds where hydrogen atoms may be substituted, silicone bonds, ester bonds, thioether bonds, and carbonate bonds. Non-terminal methylene groups in the hydrocarbon group may be substituted with 1 to 4 heteroatoms selected from N, S, O, or arylene or heteroarylene groups. Hydrogen atoms in the hydrocarbon group may be substituted with hydroxyl, cyano, amino, nitro, halogen, or phenyl groups. However, it is preferred that the structure of Z does not contain a disulfide bond. This is because disulfide bonds can sometimes generate sulfonic acids due to oxidizing agents.

[0091] Examples of the hydrocarbon group include straight-chain hydrocarbons such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and nonylene; branched-chain hydrocarbons such as isopropylene, isobutylene, 2,2-dimethylpropylene, and 2-ethyl-2-methylpropylene; cyclic hydrocarbons such as cyclohexylene, cyclopentylene, norbornene, phenylene, naphthylene, and pyridylene; PEG chains; and groups in which these groups become trivalent or tetravalent groups.

[0092] <Molecular weight>

[0093] The molecular weight of the decomposable crosslinking agent is not particularly limited, but is preferably 20,000 or less, more preferably 400 to 2000, and even more preferably 700 to 2000. Within these molecular weight ranges, the balance between decomposability and crosslinking density tends to be improved, while a molecular weight exceeding 20,000 tends to reduce solubility in solvents.

[0094] <Method for Synthesizing a Degradable Crosslinking Agent>

[0095] The method for synthesizing the decomposable cross-linking agent is not particularly limited, and examples thereof include: the reaction of a hydrazide compound, a semicarbazide compound, or a carbazate compound with a carbonate compound, an isocyanate compound, an acid anhydride, an acid halide, or a cyclic ester compound; the reaction of hydrazine with a carboxylate; the reaction of hydrazine with a carbonate compound; the reaction of hydrazine with an isocyanate compound, etc.

[0096] Examples of hydrazide compounds used in the above-mentioned synthesis methods include lactic acid hydrazide, methacrylic acid hydrazide, sebacic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, salicylic acid dihydrazide, and trimellitic acid trihydrazide. Examples of carbonate compounds include allyl N-succinimidyl carbonate and C,C'-(oxydi-2,1-ethanediyl)bis-N-succinimidyl carbonate. Examples of isocyanate compounds include 2-isocyanatoethyl methacrylate, hexamethylene diisocyanate, toluene diisocyanate, and polymethylene polyphenyl polyisocyanate. Examples of semicarbazide compounds include N-allylhydrazinecarboxamide, N,N'-1,6-hexanediylbis[hydrazinecarboxamide], 4,4'-isophoronebis(semicarbazide), and 4,4'-(1,3-phenylenebismethylene)bis(semicarbazide). Examples of carbazate compounds include allyl carbazate and C,C'-(oxydi-2,1-ethanediyl)biscarbazate. Examples of acid anhydrides include methacrylic anhydride, succinic anhydride, and pyromellitic dianhydride. Examples of acid halides include acryloyl chloride, sebacoyl dichloride, adipoyl dichloride, phthaloyl dichloride, salicyloyl dichloride, and trimesoyl trichloride. Examples of cyclic ester compounds include propiolactone, butyrolactone, and valerolactone. Examples of carboxylic acid esters include ethyl lactate, methyl parahydroxybenzoate, monomethyl succinate, diethyl adipate, and trimethyl trimellitate.

[0097] <Composition>

[0098] The composition of the present invention comprises the above-mentioned decomposable crosslinking agent and one or more selected from the group consisting of a curable resin, a polymerization initiator, and a solvent. The amount of the decomposable crosslinking agent in the composition is preferably 0.1 to 99% by weight, more preferably 1 to 50% by weight.

[0099] <Curing Resin>

[0100] The curable resin is not particularly limited as long as it has a structure capable of reacting with and crosslinking the reactive functional groups of the decomposable crosslinking agent. Examples thereof include acrylic resins, phenolic resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, silicone resins, isocyanate compounds, and polyimides. The curable resin may be a thermosetting resin or a photocurable resin. The amount of the curable resin in the composition is preferably 0.1 to 95% by weight, more preferably 1 to 50% by weight.

[0101] <Polymerization Initiator>

[0102] The polymerization initiator is not particularly limited as long as it is a compound capable of catalyzing the polymerization of the curable resin, and either a thermal polymerization initiator or a photopolymerization initiator can be used. Examples of the polymerization initiator include free radical generators such as alkylphenone compounds, benzoin compounds, benzophenone compounds, oxime ester compounds, and phosphine compounds; base generators such as oxime ester compounds, ammonium compounds, benzoin compounds, dimethoxybenzylcarbamate compounds, and o-nitrobenzylcarbamate compounds; acid generators such as onium salts, halogen-containing compounds, diazomethane compounds, sulfone compounds, and sulfonic acid compounds; tin compounds such as dibutyltin dilaurate and dibutyltin diacetate; bismuth compounds such as bismuth octoate; titanium compounds such as tetraoctyl titanate and ethyl titanium acetoacetate; zirconium compounds such as zirconium monoacetoacetate and zirconium tetraacetoacetate; amines such as triethylenediamine and 1,4-diazabicyclo[2,2,2]octane (DABCO), platinum compounds such as chloroplatinic acid and alkenylsiloxane platinum complexes, iron complexes, cobalt complexes, and nickel complexes. The amount of the polymerization initiator in the composition is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the curable resin.

[0103] <Solvent>

[0104] Examples of the solvent include water and organic solvents. Examples of the organic solvent include ether solvents, amide solvents, hydrocarbon solvents, alcohol solvents, ester solvents, aldehyde solvents, ketone solvents, solvents containing carbon atoms and heteroatoms, and the like.

[0105] Examples of ether solvents include propylene glycol monomethyl ether, anisole, 4-methylanisole, diisopropyl ether, diethyl ether, dibutyl ether, tetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, and tert-butyl methyl ether. Examples of amide solvents include dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, and cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, tert-butylbenzene, trifluoromethylbenzene, nitrobenzene, and chlorobenzene. Examples of alcohol solvents include ethanol, propanol, butanol, ethylene glycol, and propylene glycol monomethyl ether. Examples of ester solvents include ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate. Examples of aldehyde solvents include formaldehyde and acetaldehyde. Examples of ketone solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of solvents containing carbon atoms and heteroatoms include acetonitrile and dimethyl sulfoxide. The amount of the solvent in the composition is preferably 1 to 99% by weight, more preferably 20 to 80% by weight.

[0106] The solvents listed above can be used alone or in combination of two or more. In addition, the boiling point of the solvent is preferably below 150°C, more preferably below 130°C, and even more preferably below 110°C. When the boiling point is within these ranges, the solvent can be removed by heating for a relatively short time. Preferably, the composition does not substantially contain a solvent with a boiling point exceeding 150°C. Here, "substantially does not contain a solvent with a boiling point exceeding 150°C" means that the amount in the composition is less than 1% by weight.

[0107] <Degradable cross-linked product>

[0108] The degradable cross-linked product of the present invention is obtained by curing a composition comprising a degradable cross-linking agent and at least one selected from the group consisting of a curable resin, a polymerization initiator, and a solvent. The method for producing the degradable cross-linked product from the composition can be any method that promotes polymerization and cross-linking of the curable resin. Those skilled in the art will be able to appropriately select light irradiation conditions, heating conditions, and other conditions based on the types of degradable cross-linking agent, curable resin, and polymerization initiator contained in the composition. For example, when forming the degradable cross-linked product into a three-dimensional molded article, methods such as injection molding, compression molding, transfer molding, three-dimensional printing, and photolithography can be employed.

[0109] In addition, when forming a coating film composed of a decomposable crosslinked product, the composition can be applied to a substrate to form a coating film, and the coating film can be subjected to light irradiation or heating. The material and shape of the substrate are not particularly limited, and examples include resins, inorganic materials, paper, and cloth. Examples of resins include polyesters such as polyethylene terephthalate, polyethylene naphthalate, polylactic acid, polyhydroxybutyric acid, and polybutylene succinate; polyolefins such as polyethylene, polypropylene, and polymethylpentene; polyamides such as cycloolefins, polystyrene, polytetrafluoroethylene, PMMA, nylon 6, and nylon 66; polycarbonates, polyvinyl acetate, polyvinyl alcohol, polyimides, ABS resins, cellulose, cellulose acetate, silk fibroin, keratin, and the like. Examples of inorganic materials include glass, metals such as Ni, Cu, Cr, Fe, and Si, their oxides, and composite materials.

[0110] Examples of the method for coating the composition on a substrate include bar coating, spin coating, spray coating, dip coating, nozzle coating, gravure coating, reverse roll coating, die coating, air knife coating, blade coating, rod coating, curtain coating, knife coating, conveyor roll coating, extrusion coating, impregnation coating, kiss coating, calendar coating, and extrusion coating.

[0111] The curing conditions of the composition applied to the substrate are not particularly limited. When curing is performed by light irradiation, for example, 100 to 2000 mJ / cm 2When curing by heating, the heating temperature is preferably 40 to 300°C, more preferably 80 to 120°C. In addition, the heating time is preferably 0.5 to 180 minutes, more preferably 0.5 to 10 minutes.

[0112] The thickness of the cured coating film is not particularly limited, but is preferably 0.01 to 900 μm, more preferably 0.02 to 100 μm, and even more preferably 0.05 to 10 μm. Within this range, the strength of the coating film and its adhesion to the substrate can be maintained.

[0113] <Method for Decomposing Degradable Cross-linked Product>

[0114] The method for decomposing a decomposable cross-linked product of the present invention includes the step of bringing the decomposable cross-linked product into contact with an aqueous solution containing an oxidizing agent at 100° C. or lower.

[0115] <Oxidant>

[0116] The oxidizing agent is not particularly limited as long as it is an oxidizing agent other than molecular oxygen. Examples thereof include sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, ammonium hypochlorite, hydrogen peroxide, peracetic acid, m-chloroperbenzoic acid, perbenzoic acid, ammonium hypobromite, calcium hypobromite, potassium hypobromite, sodium hypobromite, and ozone. These may be used alone or in combination of two or more. Among these, water-soluble salts such as sodium hypochlorite and sodium hypobromite, and ozone water are preferred. These oxidizing agents are preferably reacted in the form of a decomposition solution mixed with an alkaline aqueous solution such as sodium hydroxide solution, an organic solvent, a surfactant, and the like. The concentration of the oxidizing agent in the aqueous solution is preferably 0.001 to 50% by weight, more preferably 0.01 to 3% by weight.

[0117] The temperature for contacting the degradable cross-linked product with the aqueous solution containing the oxidant is 100°C or less, preferably 15 to 50°C. The time for contacting the degradable cross-linked product is preferably 60 minutes or less, more preferably 10 minutes or less. If necessary, the cross-linked product may be shaken or stirred during the reaction with the oxidant. The specific method for contacting the degradable cross-linked product with the aqueous solution containing the oxidant is not particularly limited, and examples thereof include immersing the degradable cross-linked product in the aqueous solution containing the oxidant, spraying or dripping the aqueous solution containing the oxidant onto the degradable cross-linked product, and the like.

[0118] <Decomposition products>

[0119] When n≥1 in the above formula (1), the decomposable cross-linked product reacts with the oxidizing agent to generate a decomposition product represented by the following formula:

[0120] XZ(X) k -X.

[0121] Here, Z and k are the same as those in formula (1), and X is the same as X in formula (1). 1a、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b When X is a hydrocarbon group or a single bond, the decomposition product is a carboxylic acid group. When X is an oxygen atom, the decomposition product is an alcohol. When X is -NB- (B is a hydrogen atom or a hydrocarbon group), the decomposition product is an amine. When X is a sulfur atom, the decomposition product is a thiol. In the decomposable crosslinking agent, when two or more Xs are different from each other, the decomposition product may have two or more selected from the group consisting of a carboxylic acid group, a hydroxyl group, an amino group, and a thiol group.

[0122] The solubility of the decomposition product in water is preferably 30 g / L or greater, more preferably 60 g / L or greater. The solubility in water is a value measured at 20°C. When a decomposition product with high solubility in water is produced, the decomposition rate of the cross-linked product is excellent. This is believed to be because the decomposition product readily dissolves in the aqueous solution containing the oxidant, preventing the accumulation of the decomposition product from hindering the reaction between the oxidant and the cross-linking agent and promoting the penetration of the aqueous oxidant solution into the cross-linked product. However, the present invention is not limited to this mechanism.

[0123] The decomposition products may include poorly water-soluble products with low solubility in water, such as carboxylic acids, alcohols, amines, or thiols containing Z. The poorly water-soluble products herein include substances with low solubility in water and substances that are completely insoluble in water. Specific examples of poorly water-soluble products include terephthalic acid, 1,10-decanediol, 4,4'-methylenedianiline, and 1,2-ethanedithiol.

[0124] <Application of Degradable Crosslinking Agent>

[0125] The decomposable crosslinking agent of the present invention has excellent solubility in solvents and can therefore be used to crosslink various resins. Examples of applications for crosslinked products using the decomposable crosslinking agent of the present invention include adhesives, pressure-sensitive adhesives, water-absorbing resins, three-dimensional modeling resins, photoresists, release agents, cell culture media, affected area fixation materials, and imprinted molded products.

[0126] Example

[0127] The present invention will be described below with reference to Examples, but the present invention is not limited to the following Examples. Hereinafter, "parts" or "%" means "parts by weight" or "% by weight" respectively, unless otherwise specified.

[0128] (Comparative Example 1)

[0129] In a 30 ml two-necked flask, 1.4 g of pyridine, 10.3 g of acetonitrile, and 0.86 g of allyl acetohydrazide were mixed. 0.82 g of sebacoyl dichloride dissolved in 6.2 g of acetonitrile was added dropwise at below 5°C, and the mixture was stirred at room temperature for 3 hours. The resulting white solid was washed with 30 g of acetonitrile and dried in a vacuum dryer at 40°C to obtain the compound of formula (A) in a yield of 95%.

[0130] [Chemistry 3]

[0131]

[0132] 1H-NMR (DMSO, δppm) 1.25 (8H, S, C8H16), 1.50 (4H, t, C8H16), 2.09 (4H, t, C8H16), 2.17~2.18 (8H, m, C2H4), 4.96 (2H, d, CH=CH2), 5.05 (2H, d, CH=CH2), 5.76~5.87 (2H, m, CH=CH2), 9.66 (2H, S, NHNH), 9.69 (2H, S, NHNH)

[0133] The solvent solubility of the obtained compound of formula (A) was evaluated, and the results are shown in Table 1. When a 3% aqueous sodium hypochlorite solution was added to the powdered compound of formula (A), foaming and decomposition were observed.

[0134] To 40 g of dimethyl sulfoxide, 0.3 g of the compound of formula (A), 0.1 g of poly(methylhydrogensiloxane), and 4.0 mg of a platinum-based catalyst (trade name: CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to obtain a thermosetting composition solution. This solution was applied to a glass substrate to a cured film thickness of 0.1 μm, and then dried at 150°C for 10 minutes to cure, yielding a degradable crosslinked product. While the degradable crosslinked product was insoluble in water, it was observed to foam and be removed from the substrate when immersed in a 3% aqueous sodium hypochlorite solution.

[0135] (Example 1)

[0136] 15.7 g of dimethyl sulfoxide and 0.50 g of sebacic acid dihydrazide were mixed in a Schlenk tube at 80°C, 0.46 g of allyl isocyanate was added dropwise, and the mixture was stirred for 4 hours. The reaction solution, which had been returned to room temperature, was added dropwise to 150 g of acetone. The resulting white solid was further washed with acetone and dried in a vacuum dryer at room temperature to obtain the compound of formula (B) in an 84% yield.

[0137] [Chemistry 4]

[0138]

[0139] 1H-NMR (DMSO, δppm) 1.24 (8H, S, C8H16), 1.49 (4H, t, C8H16), 2.08 (4H, t, C8H16), 3.61~3.64 (4H, m, CH2), 5.01 (2H, d d, CH=CH2), 5.11 (2H, dd, CH=CH2), 5.73~5.83 (2H, m, CH=CH2), 6.41 (2H, t, NH), 7.69 (2H, S, NHNH), 9.39 (2H, S, NHNH)

[0140] The solvent solubility of the obtained compound of formula (B) was evaluated, and the results are shown in Table 1. When a 3% aqueous sodium hypochlorite solution was added to the powdered compound of formula (B), foaming and decomposition were observed.

[0141] To 40 g of dimethyl sulfoxide, 0.3 g of the compound of formula (B), 0.1 g of poly(methylhydrogensiloxane), and 4.0 mg of a platinum-based catalyst (trade name: CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to obtain a thermosetting composition solution. This solution was applied to a glass substrate to a film thickness of 0.1 μm after curing, and then dried at 150°C for 10 minutes to cure, yielding a degradable crosslinked product. While the degradable crosslinked product was insoluble in water, it was confirmed that it foamed and was removed from the substrate when immersed in a 3% aqueous sodium hypochlorite solution.

[0142] (Example 2)

[0143] In a 50 ml eggplant-shaped flask, 22.2 g of dimethyl sulfoxide and 1.00 g of 4,4'-hexylcarbazide were mixed at 40°C, and 1.89 g of N-(allyloxycarbonyloxy)succinimide was added dropwise. The mixture was then stirred at room temperature for 4 hours. The reaction mixture was added dropwise to 300 g of acetonitrile, and the resulting white solid was further washed with acetonitrile and dried in a vacuum dryer at room temperature to obtain the compound of formula (C) in an 89% yield.

[0144] [Chemistry 5]

[0145]

[0146] 1H-NMR (DMSO, δppm) 1.22 (4H, S, C6H12), 1.36 (4H, t, C6H12), 2.95~3.00 (4H, m, C6H12), 4.49~4.51 (4H, m, CH2), 5.19 (2H, d, CH=CH2), 5.28~5.33 (2H, m, CH=CH2), 5.85~5.94 (2H, m, CH=CH2), 6.30 (2H, s, NH), 7.65 (2H, S, NHNH), 8.83 (2H, S, NHNH)

[0147] The solvent solubility of the obtained compound of formula (C) was evaluated, and the results are shown in Table 1. When a 3% aqueous sodium hypochlorite solution was added to the powdered compound of formula (C), foaming and decomposition were observed.

[0148] To 40 g of propylene glycol monomethyl ether, 0.3 g of the compound of formula (C), 0.1 g of poly(methylhydrogensiloxane), and 4.0 mg of a platinum-based catalyst (trade name: CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to obtain a thermosetting composition solution. This solution was applied to a glass substrate to a film thickness of 0.1 μm after curing, and then dried at 130°C for 1 minute to cure, yielding a degradable crosslinked product. While the degradable crosslinked product was insoluble in water, it was confirmed that it foamed and was removed from the substrate when immersed in a 3% aqueous sodium hypochlorite solution.

[0149] (Example 3)

[0150] In a 50 ml eggplant-shaped flask, 22.4 g of dimethyl sulfoxide and 1.00 g of sebacic acid dihydrazide were mixed at room temperature, and 1.90 g of N-(allyloxycarbonyloxy)succinimide was added dropwise. The mixture was stirred for 20 hours. The reaction solution was added dropwise to 230 g of ion-exchanged water. The resulting white solid was further washed with ion-exchanged water and dried in a vacuum dryer at 40°C to obtain the compound of formula (D) in an 88% yield.

[0151] [Chemistry 6]

[0152]

[0153] 1H-NMR (DMSO, δppm) 1.24 (8H, S, C8H16), 1.49 (4H, t, C8H16), 2.07 (4H, t, C8H16), 4.51 (4H, d, CH2), 5.1 9(2H, d, CH=CH2), 5.30 (2H, d, CH=CH2), 5.86~5.95 (2H, m, CH=CH2), 9.04 (2H, S, NHNH), 9.58 (2H, S, NHNH)

[0154] The solvent solubility of the obtained compound of formula (D) was evaluated, and the results are shown in Table 1. When a 3% aqueous sodium hypochlorite solution was added to the powdered compound of formula (D), foaming and decomposition were observed.

[0155] The compound of formula (D) and poly(methylhydrogensiloxane) were mixed in a weight ratio of 3:1, dissolved in isopropyl alcohol to a concentration of 2% by weight, and then diluted with ethyl acetate to a concentration of 1% by weight. One part by weight of a platinum-based catalyst (trade name: CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a thermosetting composition solution. This was applied to a glass substrate to a cured film thickness of 0.1 μm and then dried at 130°C for 1 minute to cure, yielding a degradable crosslinked product. The degradable crosslinked product was insoluble in water, but upon immersion in a 3% aqueous sodium hypochlorite solution, foaming occurred and the product was removed from the substrate.

[0156] The compound of formula (D), pentaerythritol tetrakis(3-mercaptobutyrate), and N-methylpyrrolidone were mixed in a weight ratio of 3:2:5, diluted with a mixed solvent of isopropyl alcohol and propylene glycol monomethyl ether (weight ratio 1:1) to a concentration of 15% by weight, and then 0.2 parts by weight of a photopolymerization initiator (Omnirad 907 manufactured by IGM RESINS) and 0.2 parts by weight of a photopolymerization initiator (Omnirad TPO-H manufactured by IGM RESINS) were added to obtain a photocurable composition solution. The composition was applied to a glass substrate to a film thickness of 2.5 μm after curing, dried at 120°C for 3 minutes, and irradiated with an ultraviolet irradiation device (Ushio Inc. UniCure UVH-1500M) at 500 mJ / cm 2 The decomposable cross-linked product was irradiated with ultraviolet rays of 100 nm to obtain a decomposable cross-linked product. The decomposable cross-linked product was insoluble in water, but when immersed in a 3% sodium hypochlorite aqueous solution, it was confirmed that the product foamed and was removed from the substrate.

[0157] (Example 4)

[0158] In a 100 ml eggplant flask, 10 g of a two-terminal methanol-modified polydimethylsiloxane (KF-6000 manufactured by Shin-Etsu Chemical Co., Ltd.) with a molecular weight of about 1000 was mixed with 16 g of acetone and 6.5 g of triethylamine, 6.0 g of di(N-succinimidyl) carbonate was added, and the mixture was stirred at room temperature for one night. 47 g of chloroform and 3.1 g of 4-pentenoic acid hydrazide were added to the reaction solution, and the mixture was stirred again at room temperature for one night. The reaction solution was transferred to a separatory funnel, 140 g of chloroform was added, and the organic layer was washed three times with 140 g of pure water. After washing, the organic layer was distilled off to obtain a compound having a structure of formula (E) with a yield of 98%. The obtained compound of formula (E) was liquid at 30°C.

[0159] [Chemistry 7]

[0160]

[0161] In the formula, R represents a hydrocarbon group.

[0162] 1H-NMR (CDCl3, δppm) 0.06 (76H, br, CH3), 2.29~2.46 (8H, m, CH2CH2), 4.96~5.10 ( 4H, m, CH=CH2), 5.76~5.94 (2H, m, CH=CH2), 7.74 (2H, br, NHNH), 8.41 (2H, br, NHNH)

[0163] The solvent solubility of the obtained compound of formula (E) was evaluated, and the results are shown in Table 1. When a 3% aqueous sodium hypochlorite solution was added to the compound of formula (E), foaming and decomposition were observed.

[0164] 1.61 g of the compound of formula (E), 0.27 g of pentaerythritol tetrakis(thioglycolate), 60 mg of a polymerization initiator (Omnirad 907 manufactured by IGM RESINS), and 60 mg of a polymerization initiator (Omnirad TPO-H manufactured by IGM RESINS) were added to a mixed solvent of 10 g of toluene and 8 g of isopropyl alcohol and mixed to obtain a photocurable composition solution. The solution was applied onto a PET film substrate to a film thickness of 0.9 μm after curing, dried at 120° C. for 2 minutes, and irradiated with an ultraviolet irradiation device (Ushio Inc. UniCure UVH-1500M) at 500 mJ / cm 2The degradable cross-linked product was irradiated with ultraviolet light to obtain a degradable cross-linked product. The degradable cross-linked product was insoluble in ethanol and water, but when immersed in a solution prepared by diluting Kao Kitchen Haiter containing sodium hypochlorite 5-fold with Solmix AP-1 manufactured by Japan Alcohol Trading Co., Ltd., whose main component is ethanol, foaming was observed and the cross-linked product was removed from the substrate.

[0165] (Example 5)

[0166] In a 100ml eggplant-shaped flask, 3.30g of 1,12-bis(2,5-dioxy-1-pyrrolidinyl)-2,5,8,11-tetraoxadodecane dioic acid, 26g of dimethylformamide, and 1.6g of triethylamine were mixed, 0.88g of succinic acid dihydrazide was added, and the mixture was stirred at room temperature overnight. Subsequently, 0.31g of 4-hydroxybenzohydrazide was added, and the mixture was further stirred at room temperature for 6 hours. 37g of ethyl acetate was added to the reaction mixture, and the mixture was allowed to stand at -10°C overnight to form a precipitate. After removing the organic solvent by decantation, the precipitate was washed twice with 35g of ethyl acetate. Finally, the solvent was distilled off to obtain a compound having the structure of Formula (F) as a white solid with a yield of 79%.

[0167] [Chemistry 8]

[0168]

[0169] 1H-NMR (DMSO, δppm) 2.34 (36H, br, CH2CO), 3.54 (40H, br, CH2O), 3.59 (40H, br, CH2O), 4.10 (40H, br, C H2OCO), 6.81 (4H, d, benzene ring), 7.72 (4H, d, benzene ring), 9.07 (20H, br, NHNH), 9.67 (20H, br, NHNH), 10.02 (2H, br, OH)

[0170] The molecular weight calculated from the proton ratio of 1H-NMR was 3,030.

[0171] The solvent solubility of the obtained compound of formula (F) was evaluated, and the results are shown in Table 1. When a 3% aqueous sodium hypochlorite solution was added to the compound of formula (F), foaming and decomposition were observed.

[0172] 1.0 g of the compound of formula (F), 0.14 g of polyglycerol polyglycidyl ether (GEX-521 manufactured by Nagase ChemteX), 0.06 g of benzyltriethylammonium chloride, 2 g of methanol, and 0.06 g of a leveling agent (BYK-348 manufactured by BYK Chemical Co.) were added to 10 g of ion-exchanged water to obtain a curing composition solution. After coating on a glass petri dish so that the cured film thickness was 5 μm, the mixture was dried and cured at 120°C for 3 hours to obtain a degradable cross-linked product. The degradable cross-linked product was insoluble in ethanol and water, but when immersed in a solution prepared by diluting Kao Kitchen Haiter containing sodium hypochlorite by 2 times with Solmix AP-1 manufactured by Japan Alcohol Trading Co., Ltd., whose main component is ethanol, foaming was observed and the product was removed from the substrate.

[0173] (Example 6)

[0174] In a 200 ml eggplant flask, 2.0 g of 4-hydroxybutyric acid hydrazide was dissolved in 170 g of acetonitrile at 50°C, and 3.4 g of N-allyloxycarbonyloxysuccinimide was added. After stirring at 40°C for 1 hour, the mixture was further stirred at room temperature overnight. After the reaction solution was concentrated using an evaporator, 30 g of chloroform was added, and N-hydroxysuccinimide precipitated as a white solid. N-hydroxysuccinimide was removed by filtration, and the solvent was distilled off again to obtain the compound of formula (G) with a yield of 90%. The obtained compound of formula (G) was liquid at 50°C.

[0175] [Chemistry 9]

[0176]

[0177] 1H-NMR (DMSO, δppm) 1.61~1.68 (2H, m, CH2), 2.12 (2H, t, C=OCH2), 3.89 (2H, q, OCH2), 4.45 (1H, t, OH), 4.51 (2H, q, C=OOCH2), 5.20 (1H, d, C=CH2), 5.30 (1H, d, C=CH2), 5.85~5.96 (1H, m, CH=C), 9.04 (1H, s, NHNH), 9.59 (1H, s, NHNH)

[0178] The solvent solubility of the obtained compound of formula (G) was evaluated, and the results are shown in Table 1. When a 3% aqueous sodium hypochlorite solution was added to the compound of formula (G), foaming and decomposition were observed.

[0179] 0.9 g of a urate-modified hexamethylene diisocyanate (Burnock DN-901S manufactured by DIC Corporation), 1.0 g of a compound of formula (G), and 0.9 g of tetraethylene glycol bis(3-mercaptopropionate) were dissolved in 20 g of a mixed solvent of propylene glycol monomethyl ether and butyl acetate (weight ratio 1:1). 70 mg of a dibutyltin curing catalyst (NEOSTAN NU-810 manufactured by Nitto Kasei Kogyo Co., Ltd.), 40 mg of a photopolymerization initiator (Omnirad 907 manufactured by IGM RESINS Co., Ltd.), and 40 mg of a photopolymerization initiator (Omnirad TPO-H manufactured by IGM RESINS Co., Ltd.) were added to prepare a curable composition solution. The composition was applied to a glass plate to a dry film thickness of 10 μm, dried at 100°C for 120 minutes to cure, and then irradiated with an ultraviolet light source (UniCure UVH-1500M manufactured by Ushio Inc.) at 500 mJ / cm 2 The degradable cross-linked product was irradiated with ultraviolet rays of 1000 nm to obtain a degradable cross-linked product. The degradable cross-linked product was insoluble in water, but when the degradable cross-linked product was immersed in a 3% sodium hypochlorite aqueous solution, it was confirmed that the degradable cross-linked product foamed and was removed from the substrate.

[0180] (Example 7)

[0181] In a 200 ml eggplant-shaped flask, 10.0 g of 2-hydroxyethylcarbazate was added to 38.7 g of 1,2-glycerol carbonate. After stirring at 80°C for 6 days, the mixture was allowed to cool to room temperature and then added dropwise to 300 g of acetonitrile. The top layer was removed, and the remaining viscous liquid was dried in a vacuum dryer at 50°C overnight to obtain the compound of formula (H) in a 46% yield. The resulting compound of formula (H) was liquid at 40°C.

[0182] [Chemistry 10]

[0183]

[0184] 1H-NMR (DMSO, δppm) 3.49~3.58 (2H, m, CH2), 4.00 (2H, t, CH2), 4.35~4.84 (7H, m), 9.04 (2H, br, NHNH)

[0185] The solvent solubility of the obtained compound of formula (H) was evaluated, and the results are shown in Table 1. When a 3% aqueous sodium hypochlorite solution was added to the compound of formula (H), foaming and decomposition were observed.

[0186] 4.0 g of polymethylene polyphenyl polyisocyanate (MILLIONATE MR-200 manufactured by Tosoh Corporation), 2.0 g of the compound of formula (H), 0.2 g of trimethylolpropane, and 50 mg of a dibutyltin-based curing catalyst (NEOSTANN U-810 manufactured by Nitto Kasei Kogyo Co., Ltd.) were mixed to obtain a curing composition solution. This composition was applied to a glass plate to a dry film thickness of 10 μm and cured at 70°C for 150 minutes to obtain a degradable crosslinked product. The degradable crosslinked product was insoluble in THF and water, but when immersed in a solution prepared by diluting a 3% aqueous sodium hypochlorite solution 3-fold with THF, foaming and removal from the substrate were observed.

[0187] (Example 8)

[0188] In a 100 ml eggplant-shaped flask, 2.5 g of 3,5-dihydroxybenzoic acid hydrazide was dissolved in 27.3 g of DMSO at room temperature. 2.3 g of 2-isocyanatoethyl methacrylate (Karenz MOI, manufactured by Resonac) was added and stirred for one day. The reaction mixture was then mixed with 300 g of toluene and the upper layer removed. 280 g of methyl isobutyl ketone was added to the remaining lower layer to precipitate a solid. The solid was filtered, washed with 150 g of methyl isobutyl ketone, and dried in a vacuum dryer at 30°C overnight to obtain the compound of formula (I) in an 82% yield.

[0189] [Chemistry 11]

[0190]

[0191] 1H-NMR (DMSO, δ ppm) 1.88 (3H, s, CH3), 3.33 (2H, q, CH2), 4.08 (2H, t, CH2), 5.67 (1H, br, C=CH2), 6.07 (1H, br, C=CH2), 6.38 (1H, t, benzene ring), 6.55 (1H, t, NH) 6.72 (2H, d, benzene ring), 7.89 (1H, br, NHNH), 9.47 (2H, br, OH), 9.88 (1H, br, NHNH)

[0192] The solvent solubility of the obtained compound of formula (I) was evaluated, and the results are shown in Table 2. When a 3% aqueous sodium hypochlorite solution was added to the compound of formula (I), foaming and decomposition were observed.

[0193] 2.0 g of polyethylene glycol diglycidyl ether (EX-830 manufactured by Nagase ChemteX), 1.0 g of the compound of formula (I), and 0.06 g of benzyltriethylammonium chloride were mixed in 20 g of methanol, and 4 g of N-methylpyrrolidone and 0.05 g of a photopolymerization initiator (Omnirad 907 manufactured by IGM RESINS) were added to obtain a curable composition solution. The above composition was applied to a glass petri dish so that the dry film thickness became 5 μm, dried at 120° C. for 2 minutes, cured, and then irradiated with an ultraviolet irradiation device (Ushio Inc. UniCure UVH-1500M) at 500 mJ / cm 2 The crosslinked product was irradiated with ultraviolet light. It was further cured at 120°C for 2 hours to obtain a degradable crosslinked product. The crosslinked product was insoluble in isopropyl alcohol and water. However, when it was immersed in a 3% sodium hypochlorite aqueous solution diluted 2-fold with isopropyl alcohol, it was confirmed that it foamed and was removed from the substrate.

[0194] (Example 9)

[0195] In a 100 ml eggplant-shaped flask, 2.0 g of 3-mercaptopropionyl hydrazide was dissolved in 26 g of THF, and 3.0 g of poly(hexamethylene diisocyanate) (manufactured by Sigma Aldrich) was added dropwise. The mixture was stirred at room temperature overnight. The precipitated white solid was collected by decantation and dried in a vacuum dryer to obtain a crosslinker having the structure of Formula (J) in a yield of 94%.

[0196] [Chemistry 12]

[0197]

[0198] 1H-NMR (DMSO, δppm) 1.24~1.50 (24H, m, CH2), 2.41 (6H, t, C=OCH2), 2.67 (6H, t, SCH2), 2.9 7~3.10 (12H, m, NCH2), 6.26 (3H, s, NH), 7.67 (3H, s, NH), 8.21 (2H, br, NH), 9.50 (3H, s, NH)

[0199] The solvent solubility of the obtained compound of formula (J) was evaluated, and the results are shown in Table 2. When a 3% aqueous sodium hypochlorite solution was added to the compound of formula (J), foaming and decomposition were observed.

[0200] 1.2 g of the compound of formula (J) and 2.3 g of a reactive silicone oil having acrylate groups at both ends (X-22-2445 manufactured by Shin-Etsu Silicone Co., Ltd.) were dissolved in a mixed solvent of 20 g of N-methylpyrrolidone, 4 g of toluene, and 10 g of methyl ethyl ketone. 0.3 g of a leveling agent (BYK-307 manufactured by BYK Chemical Co., Ltd.), 0.2 g of a photopolymerization initiator (Omnirad 907 manufactured by IGM RESINS Co., Ltd.), and 0.2 g of a photopolymerization initiator (Omnirad TPO-H manufactured by IGM RESINS Co., Ltd.) were added to obtain a curing composition solution. The above composition was applied to a PET film so that the dry film thickness became 0.8 μm, dried at 120° C. for 10 minutes, and then subjected to a 2000 mJ / cm 2 The degradable cross-linked product was cured by UV light of 100 nm. The degradable cross-linked product was insoluble in water, but when immersed in a 3% sodium hypochlorite aqueous solution, it was confirmed that the product foamed and was removed from the substrate.

[0201] (Example 10)

[0202] In a 100 ml eggplant flask, 10 g of polymethyl acrylate (UMM-1001 manufactured by Soken Chemical Co., Ltd.) with a molecular weight of about 1000 and a hydroxyl group at one end, 13 g of acetonitrile, and 5.1 g of triethylamine were mixed, 4.7 g of di(N-succinimidyl) carbonate were added, and the mixture was stirred at room temperature for 1 night. Next, 1.4 g of trimesic acid trihydrazide and 80 g of dimethyl sulfoxide were added, and the mixture was stirred at 60 ° C for 4 hours. The reaction solution was transferred to a separatory funnel, 210 g of ethyl acetate and 210 g of pure water were added, and the water layer was removed. The organic layer was then washed 4 times with 90 g of pure water, and the organic solvent was distilled off. 4 g of the residue was collected, dissolved in 30 g of acetonitrile, 10 g of ethanol was added, and the mixture was concentrated with an evaporator. This process was repeated twice. The purified residue was transferred to a 500 ml eggplant flask and dissolved in 168 g of ethanol and 100 g of acetonitrile. 38 g of hydrazine monohydrate was added in four portions and stirred at room temperature for 4 days. The reaction solution was added dropwise to 140 g of ice-cold isopropanol to precipitate a solid.

[0203] The obtained solid was washed with 40 g of acetonitrile and dried in a vacuum dryer at 50°C for 3 hours. 1.0 g of the dried solid was transferred to a 30 ml eggplant flask, dissolved in 11.1 g of DMSO, 2.3 g of N-allyloxycarbonyloxysuccinimide was added, and stirred at room temperature for 1 night. The reaction solution was added dropwise to 87 g of ion exchange water to precipitate the solid. The obtained solid was dissolved in 6 g of ethanol and added dropwise to 60 g of methyl isobutyl ketone to precipitate the solid again. The obtained solid was dried in a vacuum dryer at 30°C for 1 night to obtain 0.5 g of the compound of formula (K).

[0204] [Chemistry 13]

[0205]

[0206] In the formula, R represents a hydrocarbon group.

[0207] 1H-NMR (DMSO, δppm) 1.4~1.9 (75H, m, CH2), 1.95~2.41 (37H, m, CH), 4.55 (71H, d, OCH2), 5.21 (35H, t, C=CH 2), 5.32 (35H, d, C=CH2), 5.91 (35H, br, C=CH), 8.48 (3H, s, benzene ring), 9.30 (72H, br, NHNH), 10.61 (3H, br, NHNH)

[0208] The solvent solubility of the obtained compound of formula (K) was evaluated, and the results are shown in Table 2. When a 3% aqueous sodium hypochlorite solution was added to the compound of formula (K), foaming and decomposition were observed.

[0209] The compound of formula (K), pentaerythritol tetrakis(thioglycolate), and the compound of formula (I) were mixed in a weight ratio of 3:2:2, diluted with methanol to a concentration of 15% by weight, and then 0.2 parts by weight of a photopolymerization initiator (Omnirad 907 manufactured by IGM RESINS) and 0.2 parts by weight of a photopolymerization initiator (Omnirad TPO-H manufactured by IGM RESINS) were added to obtain a photocurable composition solution. The composition was applied to a glass substrate to a film thickness of 4 μm after curing, dried at 120°C for 1 minute, and irradiated with an ultraviolet ray (UniCure UVH-1500M manufactured by Ushio Inc.) at 500 mJ / cm 2 The decomposable cross-linked product was irradiated with ultraviolet rays of 100 nm to obtain a decomposable cross-linked product. The decomposable cross-linked product was insoluble in water, but when immersed in a 3% sodium hypochlorite aqueous solution, it was confirmed that the product foamed and was removed from the substrate.

[0210] (Example 11)

[0211] In a 100mL three-necked flask, 5.0g of succinic acid dihydrazide was dissolved in 30g of methyl sulfoxide, 15.7g of 2-isocyanato diethyl glutarate was added, and after stirring at room temperature for 1 day, 24.7g of hydrazine monohydrate was added and stirred for another day. The reaction solution was added dropwise to 900g of methanol to precipitate a solid. The obtained solid was washed with 300g of methanol and dried in a vacuum dryer at 40°C for 3 hours. 5g of the dried solid was transferred to a 100mL eggplant-shaped flask, dissolved in 23g of DMSO, 7.3g of N-allyloxycarbonyloxysuccinimide was added, and stirred at room temperature for 1 day. The reaction solution was added dropwise to 550g of acetonitrile, the precipitated solid was washed with 250g of acetonitrile, and dried in a vacuum dryer at 50°C for 3 hours to obtain 2.6g of compound of formula (L).

[0212] [Chemistry 14]

[0213]

[0214] 1H-NMR (DMSO, δppm) 1.68~1.91 (4H, m, CH2), 2.04~2.17 (4H, m, C=OCH2), 2.37 (4H, br, C =OCH2), 4.07~4.13(2H,m,C=OCH), 4.51(8H,br,OCH2), 5.19(4H,d,C=CH2), 5.30(4H,d , C=CH2), 5.89 (4H, br, CH=C), 6.52 (2H, br, NC=ONHC), 7.90 (2H, s, NHNH), 9.03 (2H, br, NHNH), 9.19 (2H, br, NHNH), 9.57 (2H, br, NHNH), 9.64 (2H, br, NHNH), 9.81 (2H, br, NHNH)

[0215] The solvent solubility of the obtained compound of formula (L) was evaluated, and the results are shown in Table 2. When a 3% aqueous sodium hypochlorite solution was added to the compound of formula (L), foaming and decomposition were observed.

[0216] In 4 g of a mixed solvent of methanol and N-methylpyrrolidone (weight ratio 3:1), 0.26 g of the compound of formula (L) and 0.22 g of tetraethylene glycol bis(3-mercaptopropionate) were dissolved, and 8 mg of a photopolymerization initiator (Omnirad 907 manufactured by IGM RESINS) and 8 mg of a photopolymerization initiator (Omnirad TPO manufactured by IGM RESINS) were added to obtain a curable composition. The composition was applied to a glass plate to a dry film thickness of 2 μm and irradiated with an ultraviolet irradiation device (Ushio Inc. UniCure UVH-1500M) at 500 mJ / cm 2 The degradable cross-linked product was insoluble in water, but when the degradable cross-linked product was immersed in a 3% sodium hypochlorite aqueous solution, it was confirmed that foaming occurred and the product was removed from the substrate.

[0217] (Example 12)

[0218] In a 1L eggplant-shaped flask, dissolve 14.5g of N-hydroxysuccinimide in 377g of THF, add 9.5g of isophthalic acid and 24.3g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and stir at room temperature overnight. After concentrating using an evaporator, add 310g of chloroform, transfer to a separatory funnel, and wash the organic layer four times with 200g of ion-exchanged water. Dry the organic layer over 5.8g of magnesium sulfate and concentrate using an evaporator. Add the concentrated solution dropwise to 150g of isopropyl alcohol to precipitate a solid. Dry the resulting solid in a vacuum dryer at 25°C overnight. 15.3 g of the above-mentioned dried solid was added to a 100 mL eggplant flask containing 13.6 g of 6-hydroxyhexanoic acid hydrazide, 18 g of triethylamine, and 40 g of DMF. After stirring at room temperature for one night, the reaction solution was added dropwise to 800 g of acetonitrile to precipitate a white powder. The white powder was filtered, washed with 200 g of acetonitrile, and dried in a vacuum dryer at 50°C for 3 hours. 6 g of the dried white powder was transferred to a 100 mL eggplant flask and dissolved in 36 g of DMF. 8.7 g of triethylamine and 7.3 g of bis(N-succinimidyl) carbonate were added. After stirring at room temperature for 90 minutes, 3.4 g of 2-hydroxyethylcarbazate was added and stirred for another one night. The reaction solution was added dropwise to 800 g of acetonitrile, and the precipitated solid was washed with 200 g of acetonitrile and dried in a reduced pressure dryer at 50° C. for 3 hours to obtain 6.7 g of the compound of formula (M).

[0219] [Chemistry 15]

[0220]

[0221] 1H-NMR (DMSO, δ ppm) 1.31-1.63 (12H, m, CH2), 2.17-2.24 (4H, m, O=CCH2), 3.55 (4H, q, OCH2), 3.99-4.023 (8H, q, O=COCH2), 4.77 (2H, br, OH), 7.62 (1H, t, benzene ring), 8.03 (2H, dd, benzene ring), 8.37 (1H, s, benzene ring), 9.00 (2H, br, NHNH), 9.03 (2H, br, NHNH), 9.99 (2H, br, NHNH), 10.40 (2H, br, NHNH)

[0222] The solvent solubility of the obtained compound of formula (M) was evaluated, and the results are shown in Table 2. When a 3% aqueous sodium hypochlorite solution was added to the compound of formula (M), foaming and decomposition were observed.

[0223] 1.5 g of polymethylene polyphenyl polyisocyanate (MILLIONATE MR-200 manufactured by Tosoh Corporation), 4.0 g of the compound of formula (M), 50 mg of a dibutyltin-based curing catalyst (NEOSTANN U-810 manufactured by Nitto Kasei Kogyo Co., Ltd.), and 5 g of N-methylpyrrolidone were mixed to obtain a curing composition solution. This composition was applied to a glass plate to a dry film thickness of 2 μm and dried at 120°C for 150 minutes to cure, thereby obtaining a degradable crosslinked product. The degradable crosslinked product was insoluble in THF and water, but when immersed in a solution prepared by diluting a 3% aqueous sodium hypochlorite solution 3-fold with THF, foaming and removal from the substrate were observed.

[0224] (Example 13)

[0225] In a 100 ml eggplant flask, 10 g of triol-type polypropylene glycol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) with a molecular weight of approximately 1500 was mixed with 40 g of acetonitrile and 18.2 g of triethylamine, and 15.3 g of bis(N-succinimidyl) carbonate was added and stirred at room temperature for one night. After removing the precipitated solid by filtration, 54 g of chloroform and 100 g of pure water were added to the filtrate to perform a liquid separation operation. After removing the water layer, the solvent was distilled off in a manner to a concentration of 80%. After adding 11 g of acetonitrile and 2.8 g of triethylamine, 0.22 g of 2-hydroxyethylcarbazate was added and stirred at room temperature for 4 hours. After confirming the completion of the reaction by NMR, 1.9 g of α-resorcinol carboxylic acid hydrazide was added and stirred at room temperature for 4 hours. After concentrating the reaction solution with an evaporator, 103 g of chloroform was added and the mixture was transferred to a separatory funnel again. The organic layer was washed twice with 70 g of ion-exchanged water, and then the solvent was distilled off using an evaporator to obtain a decomposable compound having the structure of formula (N) in a yield of 61%.

[0226] [Chemistry 16]

[0227]

[0228] 1H-NMR (DMSO, δppm) 1.05 (77H, d, CH3), 3.32~3.67 (80H, m, CH, CH2), 4.00 (6H, t, O=COCH2), 4.75 (3H, t, OH), 8.97 (3H, br, NHNH), 8.99 (3H, br, NHNH)

[0229] The solvent solubility of the obtained compound of formula (N) was evaluated, and the results are shown in Table 2. When a 3% aqueous sodium hypochlorite solution was added to the compound of formula (N), foaming and decomposition were observed.

[0230] 1.0 g of polymethylene polyphenyl polyisocyanate (MILLIONATE MR-200 manufactured by Tosoh Corporation), 5.0 g of the compound of formula (N), 60 mg of a dibutyltin-based curing catalyst (NEOSTANN U-810 manufactured by Nitto Kasei Kogyo Co., Ltd.), and 0.5 g of methyl isobutyl ketone were mixed to obtain a curing composition solution. This composition was applied to a polyester nonwoven fabric to a dry film thickness of 200 μm, and then heated at 60°C for 10 minutes and then at 40°C for 6 hours to obtain a degradable crosslinked product. The degradable crosslinked product was insoluble in isopropyl alcohol or water, but when immersed in a 3 wt% aqueous solution of sodium dichloroisocyanurate diluted 2-fold with isopropyl alcohol, foaming was observed, leading to removal from the substrate.

[0231] (Evaluation of Solvent Solubility)

[0232] To 2 mg of the decomposable cross-linking agent of Examples 1 to 13 and Comparative Example 1, add 0.5 ml of the solvent described in Tables 1 to 2, stir, and visually confirm dissolution. If there is residual dissolution at room temperature, fully heat it with a heat gun and then visually confirm again. The case of complete dissolution at room temperature is set to 3 points, the case of residual dissolution at room temperature and complete dissolution after heating is set to 2 points, the case of a small amount of residual dissolution after heating is set to 1 point, and the case of a large amount of residual dissolution after heating is set to 0 points. It should be noted that for the decomposable cross-linking agent in a liquid state, the compatibility with the solvent is evaluated. The results are shown in Tables 1 to 2.

[0233] [Table 1]

[0234]

[0235] [Table 2]

[0236]

[0237] The compound of formula (A) of Comparative Example 1 has low solubility in any solvent. The compounds of Examples 1 to 13 show solubility in a variety of solvents. In particular, the compounds of Examples 1 to 7 and Examples 10 to 13 having a -NHNHCOO- structure show high solubility. The compound of Example 9 has a branched structure, so its solubility is slightly worse than that of the compound of Example 3, but it shows a solubility at a usable level. The compounds of Examples 5 and 10 have high molecular weights, so their solubility is slightly worse than that of the compound of Example 3, but they show a solubility at a usable level. The compounds of Examples 7 to 8 have a local presence of reactive functional groups, so their solubility is slightly worse than that of the compound of Example 3, but they show a solubility at a usable level.

[0238] The present disclosure (1) is a decomposable cross-linking agent composed of a compound represented by the following formula (1).

[0239] [Chemistry 17]

[0240]

[0241] (In formula (1),

[0242] n≥0, k≥0, m≥0, p1≥1, p2≥1, p3≥1.

[0243] ·R 1 、R 2 、R 3 Each independently represents a single bond, or a hydrocarbon having 1 to 500 carbon atoms which may have a substituent or a heteroatom.

[0244] Q 1 , Q 2 , Q 3 Each of the reactive functional groups is independently selected from the group consisting of a hydroxyl group, an amino group, a thiol group, a hydrazide group, a carboxylic acid group, an acid anhydride group, a vinyl group, an allyl group, an acrylate group, a methacrylate group, a crotonate group, an isoprenyl group, an acrylamide group, a methacrylamide group, a crotonamide group, an epoxy group, an oxetane group, an oxazoline group, an isocyanate group, a carbodiimide group, a hydroxymethyl group, a silanol group, a hydroxysilyl group, and an alkoxysilyl group.

[0245] ·X 1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b are independently an oxygen atom, a sulfur atom, a single bond, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, or -NB- (B is a hydrogen atom or a hydrocarbon group), X1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b One or more of them are oxygen atoms, sulfur atoms, or -NB- (B is a hydrogen atom or a hydrocarbon group).

[0246] ·A 1 ~A 8 is a carbonyl group or a single bond, A 1 and A 2 At least one of A is a carbonyl group, 3 and A 4 At least one of A is a carbonyl group, 5 and A 6 At least one of A is a carbonyl group, 7 and A 8 At least one of them is a carbonyl group.

[0247] Z are each independently a divalent or higher valent group containing a siloxane structure, or a hydrocarbon group having 1 to 500 carbon atoms which may have a heteroatom.

[0248] The present disclosure (2) is a decomposable crosslinking agent as described in the present disclosure (1), wherein p1≥2, p2≥2, or p3≥2, and the two or more Q 1 Each other, Q 2 Each other or Q 3 They are reactive functional groups different from each other.

[0249] The present disclosure (3) is the decomposable cross-linking agent according to the present disclosure (1), wherein p1=1, p2=1, or p3=1.

[0250] This disclosure (4) is the decomposable crosslinking agent according to any one of the disclosures (1) to (3), which has at least one decomposition site represented by the following formula (2).

[0251] -X 5 -CO 1 -NH-NH-CO 2 -X 6 -(2)

[0252] (In formula (2), X 5 、X 6 are different from each other and are each an oxygen atom, a sulfur atom, a single bond, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or -NB- (B is a hydrogen atom or a hydrocarbon group). 1 、C 2 is a carbonyl group or a single bond, C 1 and C2 At least one of them is a carbonyl group.)

[0253] The present disclosure (5) is a decomposable crosslinking agent as described in any one of the present disclosures (1) to (4), wherein X 1a or X 1b For oxygen atoms.

[0254] The present disclosure (6) is the decomposable cross-linking agent according to any one of the present disclosures (1) to (5), wherein n≧1.

[0255] The present disclosure (7) is the decomposable crosslinking agent according to any one of the present disclosures (1) to (6), wherein n ≥ 1,

[0256] X 1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b At least one of them is an oxygen atom,

[0257] At least one of them is a single bond or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and

[0258] At least one is -NB- (B is a hydrogen atom or a hydrocarbon group).

[0259] This disclosure (8) is the decomposable cross-linking agent according to any one of the disclosures (1) to (7), wherein the molecular weight is 2000 or less.

[0260] The present disclosure (9) is the decomposable cross-linking agent according to any one of the present disclosures (1) to (8), wherein k≧1.

[0261] The present disclosure (10) is a composition comprising the decomposable crosslinking agent according to any one of the present disclosures (1) to (9), and one or more selected from the group consisting of a curable resin, a polymerization initiator, and a solvent.

[0262] The present disclosure (11) is the composition as described in the present disclosure (10), which does not substantially contain a solvent having a boiling point exceeding 150°C.

[0263] The present disclosure (12) is a degradable cross-linked product composed of the composition described in the present disclosure (10) or (11).

[0264] The present disclosure (13) is the decomposable cross-linked product according to the present disclosure (12), which can be decomposed by an oxidizing agent.

[0265] The present disclosure (14) is a method for decomposing a decomposable cross-linked product, comprising the step of bringing the decomposable cross-linked product described in the present disclosure (12) or (13) into contact with an aqueous solution containing an oxidizing agent at a temperature of 100° C. or lower.

Claims

1. A decomposable crosslinking agent, comprising a compound represented by the following formula (1): [Chemistry 1] In formula (1), n ≥ 0, k ≥ 0, m ≥ 0, p 1 ≥ 1, p 2 ≥ 1, p 3 ≥ 1; ·R 1 、R 2 、R 3 Each of them is independently a single bond, or a hydrocarbon having 1 to 500 carbon atoms which may have a substituent or a heteroatom; Q 1 , Q 2 , Q 3 each independently representing at least one reactive functional group selected from the group consisting of a hydroxyl group, an amino group, a thiol group, a hydrazide group, a carboxylic acid group, an acid anhydride group, a vinyl group, an allyl group, an acrylate group, a methacrylate group, a crotonate group, an isoprenyl group, an acrylamide group, a methacrylamide group, a crotonamide group, an epoxy group, an oxetane group, an oxazoline group, an isocyanate group, a carbodiimide group, a hydroxymethyl group, a silanol group, a hydroxysilyl group, and an alkoxysilyl group; ·X 1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b are independently an oxygen atom, a sulfur atom, a single bond, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, or -NB-, B is a hydrogen atom or a hydrocarbon group, X 1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b One or more of them are oxygen atoms, sulfur atoms, or -NB-, and B is a hydrogen atom or a hydrocarbon group; ·A 1 ~A 8 is a carbonyl group or a single bond, A 1 and A 2 At least one of A is a carbonyl group, 3 and A 4 At least one of A is a carbonyl group, 5 and A 6 At least one of A is a carbonyl group, 7 and A 8 At least one of is a carbonyl group; Z are each independently a divalent or higher valent group containing a siloxane structure, or a hydrocarbon group having 1 to 500 carbon atoms which may have a heteroatom.

2. The decomposable crosslinking agent according to claim 1, wherein p1≥2, p2≥2, or p3≥2, the presence of two or more Q 1 Each other, Q 2 Each other or Q 3 They are reactive functional groups different from each other.

3. The decomposable crosslinking agent according to claim 1 or 2, wherein p1=1, p2=1, or p3=1.

4. The decomposable cross-linking agent according to any one of claims 1 to 3, which has at least one decomposition site represented by the following formula (2): -X 5 -C 1 -NH-NH-C 2 -X 6 -(2) In formula (2), X 5 、X 6 are different from each other and are respectively an oxygen atom, a sulfur atom, a single bond, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, or -NB-, B is a hydrogen atom or a hydrocarbon group; C 1 、C 2 is a carbonyl group or a single bond, C 1 and C 2 At least one of them is a carbonyl group.

5. The decomposable cross-linking agent according to any one of claims 1 to 4, wherein X 1a or X 1b For oxygen atoms.

6. The decomposable cross-linking agent according to any one of claims 1 to 5, wherein n≥1。 7. The decomposable cross-linking agent according to any one of claims 1 to 6, wherein n≥1， X 1a 、X 1b 、X 2a 、X 2b 、X 3a 、X 3b 、X 4a 、X 4b At least one of them is an oxygen atom, At least one of them is a single bond or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and At least one is -NB-, wherein B is a hydrogen atom or a hydrocarbon group. 8 . The decomposable cross-linking agent according to claim 1 , which has a molecular weight of 2,000 or less.

9. The decomposable cross-linking agent according to any one of claims 1 to 8, wherein k≥1。 10 . A composition comprising the decomposable cross-linking agent according to claim 1 , and at least one selected from the group consisting of a curable resin, a polymerization initiator, and a solvent. The composition according to claim 10 , which comprises substantially no solvent having a boiling point exceeding 150° C.

12. A degradable cross-linked product comprising the composition according to claim 10. The decomposable cross-linked product according to claim 12 , which can be decomposed by an oxidizing agent. A method for decomposing a decomposable cross-linked product, comprising the step of bringing the decomposable cross-linked product according to claim 12 or 13 into contact with an aqueous solution containing an oxidizing agent at a temperature of 100° C. or lower.

Images