Underwater adhesive

Abstract

A compound represented by formula (1). (In formula (1), A and B satisfy the relation of (I) or (II). (I): One of A and B is a group represented by formula (2). (II): A and B both independently represent a group represented by formula (2). D represents hydrogen or a methyl group.)

Description

[Technical Field]

[0001] The present invention relates to underwater adhesives. [Background technology]

[0002] There are not many underwater adhesives that can be used underwater. The underwater adhesives of the prior art have at least one of the following drawbacks: low dry adhesive strength, low underwater adhesive strength, long curing time, the need to heat the adhesive to melt for adhesion, or the need for a solvent to dissolve the adhesive.

[0003] The present inventors have succeeded in synthesizing a polymer compound obtained by polymerizing an ether having amino groups at both ends with thiocarbonyldiimidazole, as well as a polymer compound obtained by polymerizing an ether having amino groups at both ends with an ether having isothiocyanate groups at both ends (Patent Document 1). Adhesives containing such compounds can be used both in dry and aqueous conditions. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent No. 6574259 Summary of the Invention [Problem to be solved by the invention]

[0005] When bonding is performed using the adhesive of Patent Document 1, after the adhesive is brought into contact with the bonded surface of the bonded member and fixed, the fixed adhesive must be melted by heating or welded by ultrasonic treatment, and then cooled. In other words, in Patent Document 1, it is difficult to heat only the adhesive in water or to apply ultrasonic waves to the adhesive in water.

[0006] An object of the present invention is to provide a compound and a polymer thereof which can be rapidly cured in water and have high adhesiveness in water. [Means for solving the problem]

[0007] The present invention encompasses the embodiments described below.

[0008] Item 1. A compound represented by the following formula (1):

[0009] [ka]

[0010] (In formula (1), A and B satisfy the relationship (I) or (II), (I) One of A and B is a group represented by the following formula (2):

[0011] [ka]

[0012] (In formula (2), R1 and R2 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is selected from the following groups:

[0013] [ka]

[0014] R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; k is an integer greater than or equal to 0, l is an integer greater than or equal to 1, and m is an integer greater than or equal to 0), the other of A and B is a group selected from the following (a) to (c), has a structure in which two or more of the following (b) are linked together, or has a structure in which two of the following (c) are linked together, (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, (b)

[0015] [ka]

[0016] (One bonding site on the main chain may be the 1st position, and the other bonding site may be the 2nd, 3rd, or 4th position, and R3 is a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) (c)

[0017] [ka]

[0018] (One of the main chain bonding sites may be at the 1-position, and the other bonding site may be at any of the 2-, 3-, or 4-positions, and R4 represents a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) When the other of A and B has a structure in which two or more of the following (b) are linked together, or a structure in which two of the following (c) are linked together, the linking group is -O- or -C(R a )(R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. (II) Both A and B are independently a group represented by the following formula (2):

[0019] [ka]

[0020] (In formula (2), R1 and R2 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is selected from the following groups:

[0021] [ka]

[0022] R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; k is an integer greater than or equal to 0, l is an integer greater than or equal to 1, and m is an integer greater than or equal to 0), D is hydrogen or methyl. Item 2. The compound according to Item 1, which is obtained by reacting a compound represented by the following formula (9) with a compound represented by the following formula (10):

[0023] [ka]

[0024] (A in formula (9) and B in formula (10) satisfy the relationship (I) or (II). (I) One of A and B is a group represented by the following formula (2):

[0025] [ka]

[0026] (In formula (2), R1 and R2 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is selected from the following groups:

[0027] [ka]

[0028] R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; where k is an integer greater than or equal to 0, l is an integer greater than or equal to 1, and m is an integer greater than or equal to 0).

[0029] the other of A and B is a group selected from the following (a) to (c), has a structure in which two or more of the following (b) are linked together, or has a structure in which two of the following (c) are linked together, (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, (b)

[0030] [ka]

[0031] (One bonding site on the main chain may be the 1st position, and the other bonding site may be the 2nd, 3rd, or 4th position, and R3 is a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) (c)

[0032] [ka]

[0033] (One of the main chain bonding sites may be at the 1-position, and the other bonding site may be at any of the 2-, 3-, or 4-positions, and R4 represents a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) When the other of A and B has a structure in which two or more of the following (b) are linked together, or a structure in which two of the following (c) are linked together, the linking group is -O- or -C(R a )(R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. (II) Both A and B are independently a group represented by the following formula (2):

[0034] [ka]

[0035] (In formula (2), R1 and R2 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is selected from the following groups:

[0036] [ka]

[0037] R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; where k is an integer greater than or equal to 0, l is an integer greater than or equal to 1, and m is an integer greater than or equal to 0). D is hydrogen or methyl.

[0038] Item 3. The compound according to Item 1 or 2, wherein the formula (2) is a group represented by the following formula (2a):

[0039] [ka]

[0040] (In the formula, R5 and R6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, and the substituents of R5 and R6 are each a carbon atom. number a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group, or a halogen atom; l is an integer from 1 to 5) Item 4. A is a group represented by formula (2a),

[0041] [ka]

[0042] (In the formula, R5 and R6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, and the substituents of R5 and R6 are each a carbon atom. number a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group, or a halogen atom; l is an integer from 1 to 5) Item 3. The compound according to item 1 or 2, wherein B is (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms.

[0043] Item 5.A has a structure in which two of the (c) are linked together, Item 3. The compound according to item 1 or 2, wherein B is a group represented by formula (2a):

[0044] [ka]

[0045] (In the formula, R5 and R6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, and the substituents of R5 and R6 are each a carbon atom. number a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group, or a halogen atom; l is an integer from 1 to 5) Item 6. A polymer obtained by polymerizing the compound according to any one of items 1 to 5.

[0046] Item 7. A polymer represented by the following formula (11):

[0047] [ka]

[0048] (In formula (11), A and B satisfy the relationship (I) or (II), (I) One of A and B is a group represented by the following formula (2):

[0049] [ka]

[0050] (In formula (2), R1 and R2 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is selected from the following groups:

[0051] [ka]

[0052] R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; k is an integer greater than or equal to 0, l is an integer greater than or equal to 1, and m is an integer greater than or equal to 0), the other of A and B is a group selected from the following (a) to (c), has a structure in which two or more of the following (b) are linked together, or has a structure in which two of the following (c) are linked together, (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, (b)

[0053] [ka]

[0054] (One bonding site on the main chain may be the 1st position, and the other bonding site may be the 2nd, 3rd, or 4th position, and R3 is a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) (c)

[0055] [ka]

[0056] (One of the main chain bonding sites may be at the 1-position, and the other bonding site may be at any of the 2-, 3-, or 4-positions, and R4 represents a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) When the other of A and B has a structure in which two or more of the following (b) are linked together, or a structure in which two of the following (c) are linked together, the linking group is -O- or -C(R a )(R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. (II) Both A and B are independently a group represented by the following formula (2):

[0057] [ka]

[0058] (In formula (2), R1 and R2 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is selected from the following groups:

[0059] [ka]

[0060] R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; k is an integer greater than or equal to 0, l is an integer greater than or equal to 1, and m is an integer greater than or equal to 0), D is hydrogen or a methyl group; n is the degree of polymerization of the repeating unit.) Item 8. An adhesive comprising the compound according to any one of items 1 to 5 or the polymer according to any one of items 6 to 7.

[0061] Item 9. An adhesive comprising the compound according to any one of items 1 to 5 and a compound having two or more thiol groups.

[0062] Item 10. A step of applying an adhesive containing the compound according to any one of items 1 to 5 to a surface of an adherend; and A step of irradiating the applied adhesive with light to harden the adhesive. A bonding method comprising:

[0063] Item 11. The adherend is a first adherend, Item 11. The bonding method according to any one of items 10, further comprising, after the step of applying the adhesive, a step of contacting a second member to the adhesive so that the adhesive is disposed between the first member to be bonded and the second member to be bonded, and, after the step of contacting the second member to be bonded, irradiating the applied adhesive with light to cure the adhesive.

[0064] Item 12. A step of mixing the compound according to any one of items 1 to 5 with a compound having two or more thiol groups; and applying the mixture to the surface of the member to be bonded and allowing the mixture to harden A bonding method comprising:

[0065] Item 13. The bonding method according to Item 11 or 12, wherein the curing step is carried out in water, an aqueous solution, an aqueous suspension, or a high humidity environment.

[0066] Item 14. The bonding method according to any one of Items 10 to 13, wherein the bonded members are made of a material selected from the group consisting of metal, glass, wood, and synthetic resin.

[0067] Item 15. Use of the compound according to any one of items 1 to 5 for producing an adhesive. [Effects of the Invention]

[0068] The compound of the present invention can be rapidly cured in water and can be used as an underwater adhesive having high underwater adhesiveness. [Brief explanation of the drawings]

[0069] [Figure 1] FIG. 2 is an explanatory diagram illustrating the function of each part of the polymer according to an embodiment of the present invention. [Figure 2] (A) Schematic of underwater adhesion testing of two different materials. (B) Graph of adhesive strength for various materials. [Figure 3] Adhesion strength of samples bonded using three different processes. [Figure 4] (A) Structural formula of the monomer used in Test Example 3. (B) Graph of adhesive strength in water for each monomer. [Figure 5] Graph of underwater adhesion strength between TUac-EG3 and T-Cy2 immediately after adhesion and 24 hours later. [Figure 6] Comparison of water absorption between TUac-EG3 and T3EG. [Figure 7] Dependence of underwater adhesion on the type of crosslinker. [Figure 8] Dependence of underwater adhesion on curing time. [Figure 9] Monomer dependence of underwater adhesion. [Figure 10] Time-dependent underwater adhesion test. [Figure 11] Time-dependent seawater adhesion test. [Figure 12] Substrate dependence of underwater adhesion. DETAILED DESCRIPTION OF THE INVENTION

[0070] As used herein, the singular forms (a, an, the) include both the singular and the plural unless otherwise expressly stated herein or clearly contradicted by context. In this specification, the term "comprise" is a concept that encompasses "consist essentially of" and "consist only of." In the numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range can be arbitrarily combined with the upper or lower limit of another numerical range. Furthermore, in the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from an example. Furthermore, in this specification, a numerical value connected with "~" means a numerical range that includes the numbers before and after "~" as the upper and lower limits. As used herein, "(meth)acrylic acid" means acrylic acid and / or methacrylic acid.

[0071] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments.

[0072] According to an aspect of the present invention, there is provided a compound represented by the following formula (1):

[0073] [ka]

[0074] In formula (1), A and B satisfy the relationship (I) or (II), (I) One of A and B is a group represented by the following formula (2):

[0075] [ka]

[0076] (In formula (2), R1 and R2 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is selected from the following groups:

[0077] [ka]

[0078] R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; k is an integer greater than or equal to 0, l is an integer greater than or equal to 1, and m is an integer greater than or equal to 0), the other of A and B is a group selected from the following (a) to (c), has a structure in which two or more of the following (b) are linked together, or has a structure in which two of the following (c) are linked together, (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, (b)

[0079] [ka]

[0080] (One bonding site on the main chain may be the 1st position, and the other bonding site may be the 2nd, 3rd, or 4th position, and R3 is a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) (c)

[0081] [ka]

[0082] (One of the main chain bonding sites may be at the 1-position, and the other bonding site may be at any of the 2-, 3-, or 4-positions, and R4 represents a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) When the other of A and B has a structure in which two or more of the following (b) are linked together, or a structure in which two of the following (c) are linked together, the linking group is -O- or -C(R a )(R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms.

[0083] (II) Both A and B are each independently a group represented by the following formula (2):

[0084] [ka]

[0085] (In formula (2), R1 and R2 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is selected from the following groups:

[0086] [ka]

[0087] R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; k is an integer greater than or equal to 0, l is an integer greater than or equal to 1, and m is an integer greater than or equal to 0), D is hydrogen or methyl.

[0088] In formula (2), R1 and R2 are each independently preferably a substituted or unsubstituted alkylene group having 2 to 12 carbon atoms, more preferably a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms, and even more preferably a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms. More preferably, R1 and R2 are each independently a methylene group (-CH2-) or an ethylene group (-CH2-CH2-), and more preferably, R1 and R2 are both a methylene group (-CH2-) or an ethylene group (-CH2-CH2-).

[0089] The R1 and R2 substituents are carbon number Examples of the alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms, cyclohexyl groups, phenyl groups, and halogens (fluorine, chlorine, bromine, iodine, etc.).

[0090] In formula (2), k is preferably 0 to 3, more preferably 0 to 2, and more preferably 0 or 1.

[0091] In the formula (2), l is preferably 1 to 5, more preferably 1 to 4, and more preferably 1 to 3.

[0092] In formula (2), m is preferably 0 to 3, more preferably 0 to 2, and more preferably 0 or 1.

[0093] In some embodiments, in formula (2), k and m are 0 or 1, and l is 1-5.

[0094] In some embodiments, in formula (2), k and m are 0 or 1, and l is an integer of 1 to 5; R1 and R2 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is -R5-O-R6-; and R5 and R6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms.

[0095] In some embodiments, formula (2) is a group represented by formula (2a): A group represented by formula (2a).

[0096] [ka]

[0097] (wherein R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, and l represents an integer of 1 to 5). R5 and R6 are each independently preferably a substituted or unsubstituted alkylene group having 2 to 12 carbon atoms, more preferably a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms, and even more preferably a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms.

[0098] The R5 and R6 substituents are carbon number Examples of the alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms, cyclohexyl groups, phenyl groups, and halogens (fluorine, chlorine, bromine, iodine, etc.).

[0099] In some embodiments, in formula (2), k and m are 0 or 1, and l is an integer of 1 to 5; R1 and R2 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is -R5-O-R6-; and R5 and R6 are each independently -C p H 2p It is a divalent group represented by - (where p is an integer of 1 to 3).

[0100] In a preferred embodiment, the compound represented by formula (1) is such that A and B satisfy the relationship (I) or (II), (I) One of A and B is a group represented by the following formula (2a):

[0101] [ka]

[0102] (wherein R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, and l represents an integer of 1 to 5). the other of A and B is a group selected from the following (a) to (c), has a structure in which two or more of the following (b) are linked together, or has a structure in which two of the following (c) are linked together, (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, (b)

[0103] [ka]

[0104] (One bonding site on the main chain may be the 1st position, and the other bonding site may be the 2nd, 3rd, or 4th position, and R3 is a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) (c)

[0105] [ka]

[0106] (One of the main chain bonding sites may be at the 1-position, and the other bonding site may be at any of the 2-, 3-, or 4-positions, and R4 represents a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) When the other of A and B has a structure in which two or more of the following (b) are linked together, or a structure in which two of the following (c) are linked together, the linking group is -O- or -C(R a )(R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. (II) Both A and B are independently a group represented by the following formula (2a):

[0107] [ka]

[0108] (wherein R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, and l represents an integer of 1 to 5), D is hydrogen or methyl.

[0109] In formula (2a), R5 and R6 are each independently preferably a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms, more preferably a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, even more preferably a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, and even more preferably a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms.

[0110] The R5 and R6 substituents are carbon number Examples of the alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms, cyclohexyl groups, phenyl groups, and halogens (fluorine, chlorine, bromine, iodine, etc.).

[0111] (a) The substituted or unsubstituted alkylene group having 1 to 16 carbon atoms is preferably a substituted or unsubstituted alkylene group having 2 to 12 carbon atoms, more preferably a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms, and even more preferably a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms.

[0112] (a) The substituent of the alkylene group having 1 to 16 carbon atoms is number Examples of the substituents include linear or branched alkyl groups having 1 to 6 carbon atoms, cyclohexyl groups, phenyl groups, and halogens (fluorine, chlorine, bromine, iodine, etc.). The number of the substituents in (a) the substituted or unsubstituted alkylene group having 1 to 16 carbon atoms is preferably 1 to 3.

[0113] In the group represented by formula (3) in (b), when R3 is a substituted alkyl group having 1 to 6 carbon atoms, the substituent is number Examples of the alkyl group include linear or branched alkyl groups of 1 to 6 carbon atoms, and halogens (fluorine, chlorine, bromine, iodine, etc.).

[0114] In some embodiments, the group represented by formula (3) in (b) is a group represented by formula (3a):

[0115] [ka]

[0116] (wherein R3 is a hydrogen atom or 1 to 4 identical monovalent alkyl groups having 1 to 6 carbon atoms). In the group represented by formula (4) in (c), when R4 is a substituted alkyl group having 1 to 6 carbon atoms, the substituent is number Examples of the alkyl group include linear or branched alkyl groups of 1 to 6 carbon atoms, and halogens (fluorine, chlorine, bromine, iodine, etc.).

[0117] In some embodiments, the group represented by formula (4) in (c) is a group represented by formula (4a):

[0118] [ka]

[0119] (wherein R4 is a hydrogen atom or 1 to 4 monovalent alkyl groups having 1 to 6 carbon atoms) In some embodiments, when the other of A and B has a structure in which two or more (b) are linked, the group represented by formula (3) in b) is a group represented by the following formula (3a), and the linking group is -O- or -C(R a )(R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms.

[0120] [ka]

[0121] (wherein R3 is a hydrogen atom or 1 to 4 identical monovalent alkyl groups having 1 to 6 carbon atoms). In some embodiments, when the other of A and B has a structure in which two or more (b)s are linked, the structure in which two or more (b)s are linked is a structure represented by the following formula (5) or (6).

[0122] [ka]

[0123] In some embodiments, when the other of A and B has a structure in which two or more (c) are linked, the group represented by formula (4) of (c) is a group represented by the following formula (4a), and the linking group is -O- or -C(R a )(R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms.

[0124] [ka]

[0125] (wherein R4 is a hydrogen atom or 1 to 4 identical monovalent alkyl groups having 1 to 6 carbon atoms). In some embodiments, when the other of A and B has a structure in which two or more (c)s are linked, the structure in which two or more (c)s are linked is a structure represented by the following formula (7) or (8).

[0126] [ka]

[0127] D can be hydrogen or a methyl group. In some embodiments, D is hydrogen. In some embodiments, D is a methyl group.

[0128] In some embodiments, the compound represented by formula (1) is a compound obtained by polymerizing a compound represented by the following formula (9) and a compound represented by the following formula (10):

[0129] [ka]

[0130] A in formula (9) and B in formula (10) satisfy the relationship (I) or (II), (I) One of A and B is a group represented by the following formula (2):

[0131] [ka]

[0132] (In formula (2), R1 and R2 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is selected from the following groups:

[0133] [ka]

[0134] R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; k is an integer greater than or equal to 0, l is an integer greater than or equal to 1, and m is an integer greater than or equal to 0), the other of A and B is a group selected from the following (a) to (c), has a structure in which two or more of the following (b) are linked together, or has a structure in which two of the following (c) are linked together, (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, (b)

[0135] [ka]

[0136] (One bonding site on the main chain may be the 1st position, and the other bonding site may be the 2nd, 3rd, or 4th position, and R3 is a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) (c)

[0137] [ka]

[0138] (One of the main chain bonding sites may be at the 1-position, and the other bonding site may be at any of the 2-, 3-, or 4-positions, and R4 represents a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) When the other of A and B has a structure in which two or more of the following (b) are linked together, or a structure in which two of the following (c) are linked together, the linking group is -O- or -C(R a )(R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. (II) Both A and B are each independently a group represented by the following formula (2):

[0139] [ka]

[0140] (In formula (2), R1 and R2 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is selected from the following groups:

[0141] [ka]

[0142] R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; where k is an integer greater than or equal to 0, l is an integer greater than or equal to 1, and m is an integer greater than or equal to 0). D is hydrogen or methyl.

[0143] In formula (2), R1 and R2 are each independently preferably a substituted or unsubstituted alkylene group having 2 to 12 carbon atoms, more preferably a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms, and even more preferably a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms. More preferably, R1 and R2 are each independently a methylene group (-CH2-) or an ethylene group (-CH2-CH2-), and more preferably, R1 and R2 are both a methylene group (-CH2-) or an ethylene group (-CH2-CH2-).

[0144] The R1 and R2 substituents are carbon number Examples of the alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms, cyclohexyl groups, phenyl groups, and halogens (fluorine, chlorine, bromine, iodine, etc.).

[0145] In formula (2), k is preferably 0 to 3, more preferably 0 to 2, and more preferably 0 or 1.

[0146] In the formula (2), l is preferably 1 to 5, more preferably 1 to 4, and more preferably 1 to 3.

[0147] In formula (2), m is preferably 0 to 3, more preferably 0 to 2, and more preferably 0 or 1.

[0148] In some embodiments, in formula (2), k and m are 0 or 1, and l is 1-5.

[0149] In some embodiments, in formula (2), k and m are 0 or 1, and l is an integer of 1 to 5; R1 and R2 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is -R5-O-R6-; and R5 and R6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms.

[0150] In some embodiments, formula (2) is a group represented by formula (2a): A group represented by formula (2a).

[0151] [ka]

[0152] (wherein R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, and l represents an integer of 1 to 5). R5 and R6 are each independently preferably a substituted or unsubstituted alkylene group having 2 to 12 carbon atoms, more preferably a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms, and even more preferably a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms.

[0153] The R5 and R6 substituents are carbon number Examples of the alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms, cyclohexyl groups, phenyl groups, and halogens (fluorine, chlorine, bromine, iodine, etc.).

[0154] In some embodiments, in formula (2), k and m are 0 or 1, and l is an integer of 1 to 5; R1 and R2 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is -R5-O-R6-; and R5 and R6 are each independently -C p H 2p It is a divalent group represented by - (where p is an integer of 1 to 3).

[0155] In a preferred embodiment, A in formula (9) and B in formula (10) satisfy the relationship (I) or (II), (I) One of A and B is a group represented by the following formula (2a):

[0156] [ka]

[0157] (Wherein R5 and R6 are each independently -C p H 2p - (wherein p is an integer of 1 to 3, and l is an integer of 1 to 5). the other of A and B is a group selected from the following (a) to (c), has a structure in which two or more of the following (b) are linked together, or has a structure in which two of the following (c) are linked together, (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, (b)

[0158] [ka]

[0159] (One bonding site on the main chain may be the 1st position, and the other bonding site may be the 2nd, 3rd, or 4th position, and R3 is a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) (c)

[0160] [ka]

[0161] (One of the main chain bonding sites may be at the 1-position, and the other bonding site may be at any of the 2-, 3-, or 4-positions, and R4 represents a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) When the other of A and B has a structure in which two or more of the following (b) are linked together, or a structure in which two of the following (c) are linked together, the linking group is -O- or -C(R a )(R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. (II) Both A and B are independently a group represented by the following formula (2a):

[0162] [ka]

[0163] (Wherein R5 and R6 are each independently -C p H 2p - (wherein p is an integer of 1 to 3, and l is an integer of 1 to 5). (a) The substituted or unsubstituted alkylene group having 1 to 16 carbon atoms is preferably a substituted or unsubstituted alkylene group having 2 to 12 carbon atoms, more preferably a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms, and even more preferably a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms.

[0164] (a) The substituent of the alkylene group having 1 to 16 carbon atoms is number Examples of the substituents include linear or branched alkyl groups having 1 to 6 carbon atoms, cyclohexyl groups, phenyl groups, and halogens (fluorine, chlorine, bromine, iodine, etc.). The number of the substituents in (a) the substituted or unsubstituted alkylene group having 1 to 16 carbon atoms is preferably 1 to 3.

[0165] In the group represented by formula (3) in (b), when R3 is a substituted alkyl group having 1 to 6 carbon atoms, the substituent is number Examples of the alkyl group include linear or branched alkyl groups of 1 to 6 carbon atoms, and halogens (fluorine, chlorine, bromine, iodine, etc.).

[0166] In some embodiments, the group represented by formula (3) in (b) is a group represented by formula (3a):

[0167] [ka]

[0168] (wherein R3 is a hydrogen atom or 1 to 4 identical monovalent alkyl groups having 1 to 6 carbon atoms). In the group represented by formula (4) in (c), when R4 is a substituted alkyl group having 1 to 6 carbon atoms, the substituent is number Examples of the alkyl group include linear or branched alkyl groups of 1 to 6 carbon atoms, and halogens (fluorine, chlorine, bromine, iodine, etc.).

[0169] In some embodiments, the group represented by formula (4) in (c) is a group represented by formula (4a):

[0170] [ka]

[0171] (wherein R4 is a hydrogen atom or 1 to 4 monovalent alkyl groups having 1 to 6 carbon atoms) The compound obtained by polymerizing the compound represented by the formula (9) and the compound represented by the formula (10) may or may not contain a compound other than the compound represented by the formula (9) and the compound represented by the formula (10) as a monomer component.

[0172] In some embodiments, the compound obtained by polymerizing the compound represented by the formula (9) and the compound represented by the formula (10) contains only the compound represented by the formula (9) and the compound represented by the formula (10) as monomer components.

[0173] In some embodiments, when the other of A and B has a structure in which two or more (b) are linked, the group represented by formula (3) in b) is a group represented by the following formula (3a), and the linking group is -O- or -C(R a )(R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms.

[0174] [ka]

[0175] (wherein R3 is a hydrogen atom or 1 to 4 identical monovalent alkyl groups having 1 to 6 carbon atoms). In some embodiments, when the other of A and B has a structure in which two or more (b)s are linked, the structure in which two or more (b)s are linked is a structure represented by the following formula (5) or (6).

[0176] [ka]

[0177] In some embodiments, when the other of A and B has a structure in which two or more (c) are linked, the group represented by formula (4) of (c) is a group represented by the following formula (4a), and the linking group is -O- or -C(R a )(R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms.

[0178] [ka]

[0179] (wherein R4 is a hydrogen atom or 1 to 4 identical monovalent alkyl groups having 1 to 6 carbon atoms). In some embodiments, when the other of A and B has a structure in which two or more (c)s are linked, the structure in which two or more (c)s are linked is a structure represented by the following formula (7) or (8).

[0180] [ka]

[0181] D can be hydrogen or a methyl group. In some embodiments, D is hydrogen. In some embodiments, D is a methyl group.

[0182] In some embodiments of the compound represented by formula (1) above, A is a group represented by formula (2), k and m are 0 or 1, and l is an integer of 1 to 5, R1 and R2 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, X is -R5-O-R6-, R5 and R6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, and B is (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms.

[0183] In some embodiments of the compound represented by formula (1), A is a group represented by formula (2a), and R5 and R6 are each independently -C p H 2p -(however, p is an integer of 1 to 3), l is an integer of 1 to 5, and B is (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms.

[0184] In formula (2a), preferably, R1 and R2 are each independently a methylene group (-CH2-) or an ethylene group (-CH2-CH2-), and more preferably, R1 and R2 are both a methylene group (-CH2-) or an ethylene group (-CH2-CH2-).

[0185] In the formula (2a), l is preferably 1 to 4, and more preferably 1 to 3.

[0186] (a) The substituted or unsubstituted alkylene group having 1 to 16 carbon atoms is preferably a substituted or unsubstituted alkylene group having 2 to 12 carbon atoms, more preferably a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms, even more preferably a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms, and even more preferably an alkylene group having 2 to 6 carbon atoms. (a) The substituent of the alkylene group having 1 to 16 carbon atoms is number Examples of the substituents include linear or branched alkyl groups having 1 to 6 carbon atoms, cyclohexyl groups, phenyl groups, and halogens (fluorine, chlorine, bromine, iodine, etc.). The number of the substituents in (a) the substituted or unsubstituted alkylene group having 1 to 16 carbon atoms is preferably 1 to 3.

[0187] In certain embodiments, in formula (2a), R1 and R2 are methylene groups, l is 1 to 3, and (a) is an alkylene group having 2 to 6 carbon atoms.

[0188] In certain embodiments, in formula (2a), R1 and R2 are methylene groups, l is 1 to 2, and (a) is an alkylene group having 2 carbon atoms.

[0189] In some embodiments of the compound represented by formula (1), A has a structure in which two of the (c) are linked together, and B is a group represented by formula (2).

[0190] [ka]

[0191] (In the formula, R1 and R2 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is selected from the following groups:

[0192] [ka]

[0193] R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; where k is an integer greater than or equal to 0, l is an integer greater than or equal to 1, and m is an integer greater than or equal to 0).

[0194] The structure in which two or more (c) are linked together is preferably a structure represented by the following formula (7) or (8).

[0195] [ka]

[0196] In a specific embodiment, the structure in which two or more (c) of A are linked together is a structure represented by formula (7) or (8), B is a group represented by formula (2a), R5 and R6 are methylene groups or ethylene groups, and 1 is 1 to 3.

[0197] In a specific embodiment, the structure in which two or more (c) of A are linked together is a structure represented by formula (7), B is a group represented by formula (2a), R5 and R6 are methylene groups, and 1 is 1 to 2.

[0198] According to another aspect of the present invention, there is provided a polymer obtained by polymerizing the compound represented by the above formula (1).

[0199] According to another aspect of the present invention, there is provided a polymer represented by the following formula (11):

[0200] [ka]

[0201] (In formula (11), A and B satisfy the relationship (I) or (II), (I) One of A and B is a group represented by the following formula (2):

[0202] [ka]

[0203] (In formula (2), R1 and R2 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is selected from the following groups:

[0204] [ka]

[0205] R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; k is an integer greater than or equal to 0, l is an integer greater than or equal to 1, and m is an integer greater than or equal to 0), the other of A and B is a group selected from the following (a) to (c), has a structure in which two or more of the following (b) are linked together, or has a structure in which two of the following (c) are linked together, (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, (b)

[0206] [ka]

[0207] (One bonding site on the main chain may be the 1st position, and the other bonding site may be the 2nd, 3rd, or 4th position, and R3 is a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) (c)

[0208] [ka]

[0209] (One of the main chain bonding sites may be at the 1-position, and the other bonding site may be at any of the 2-, 3-, or 4-positions, and R4 represents a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted.) When the other of A and B has a structure in which two or more of the following (b) are linked together, or a structure in which two of the following (c) are linked together, the linking group is -O- or -C(R a )(R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. (II) Both A and B are independently a group represented by the following formula (2):

[0210] [ka]

[0211] (In formula (2), R1 and R2 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; X is selected from the following groups:

[0212] [ka]

[0213] R5 and R6 each independently represent a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; where k is an integer greater than or equal to 0, l is an integer greater than or equal to 1, and m is an integer greater than or equal to 0).

[0214] D is hydrogen or a methyl group.

[0215] n is the degree of polymerization of the repeating unit.

[0216] Although the applicant does not wish the present invention to be bound by any particular hypothesis or theory, it is believed that when the compound represented by formula (1) is polymerized, as shown in Figure 1, the ether provides flexibility to the entire molecule, the thiourea structural unit has the ability to bond to the surface of the adherend, such as a glass substrate, and the structural unit derived from (meth)acrylic acid contributes to the rapid curing of the polymer. Note that polymers and adhesives that satisfy the constituent requirements defined in the present invention, even if they do not completely conform to such a theory, are included within the technical scope of the present invention.

[0217] Therefore, a polymer obtained by polymerizing a compound represented by formula (1) can be used as an adhesive. The adhesive may consist solely of a polymer obtained by polymerizing a compound represented by formula (1), or may contain additives other than the polymer as long as the adhesive properties are not impaired. When an adhesive according to an embodiment of the present invention contains additives other than the polymer obtained by polymerizing a compound represented by formula (1), such an adhesive can be called an adhesive composition. The object of the invention is to provide a compound and a polymer thereof that can be rapidly cured in water and have high underwater adhesion.

[0218] In some embodiments, the compound represented by formula (1) can be polymerized and cured quickly by irradiation with light, and therefore an adhesive containing such a compound can be used as a one-component adhesive.

[0219] In some embodiments, a compound of formula (1) and a compound having two or more thiol groups can be used as a two-component adhesive, where the two or more thiol groups act as crosslinkers for the compound of formula (1).

[0220] The (meth)acrylate groups at both ends of a compound represented by formula (1) (R1 is a hydrocarbon group in which some of the carbons in the main chain may be substituted) condense with the thiol groups of a compound having two or more thiol groups (R2 is a hydrocarbon group in which some of the carbons in the main chain may be substituted) via a thiol-ene reaction to form a polymer. The thiol-ene reaction is known as the polymerization reaction of an alkene and a thiol. As shown in Scheme A below, for example, when an alkene of formula (12) reacts with a compound having two thiol groups of formula (13) in the presence of a catalyst, the alkene polymerizes to form a three-dimensional network of formula (14), which then hardens. Such catalysts are known, and any base or nucleophilic catalyst that promotes the thiol-ene reaction can be used, with preferred examples including amine catalysts. In the thiol-ene reaction, the carbon-carbon double bond of the alkene of formula (12) reacts with the thiol group of the compound of formula (13) in a 1:1 ratio. Therefore, when an adhesive is produced by condensing a compound represented by formula (1) with a compound having two or more thiol groups, the adhesive can be produced even if the equivalent ratio (C=C:SH) of the carbon-carbon double bond of the alkene of formula (12) to the thiol group of the compound of formula (13) is in the range of 1:10 to 10:1, but 1:3 to 3:1 is more preferable, and 1:1 is most preferable.

[0221] [ka]

[0222] In some embodiments, the compound represented by formula (1) can be polymerized using a polymerization initiator and used as an adhesive. As such a polymerization initiator, any known polymerization initiator that can be used for polymerizing meth(acrylic) ester monomers can be used. Such polymerization initiators include peroxide-based polymerization initiators, azo polymerization initiators, photopolymerization initiators, and combinations thereof. Examples of peroxide initiators include, but are not limited to, benzoyl peroxide, 1,1-bis-t-hexylperoxy-3,3,5-trimethylcyclohexane, and 3,5,5-trimethylhexanoyl peroxide. Examples of azo initiators include, but are not limited to, 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, and the like. The photopolymerization initiator is a polymerization initiator that initiates polymerization upon irradiation with light such as an electron beam, ultraviolet light, visible light, or near-infrared light, and such photopolymerization initiators are known in the art. The photopolymerization initiator may be a self-cleavage type photopolymerization initiator or a hydrogen abstraction type photopolymerization initiator. Examples of the self-cleaving photopolymerization initiator include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, titanocene compounds, acetophenone compounds, phenylglyoxylate compounds, and benzoin ether compounds. Examples of hydrogen abstraction type photopolymerization initiators include, but are not limited to, oxime ester compounds, benzophenone compounds, thioxanthone compounds, anthraquinone compounds, and benzyl compounds.

[0223] The adhesive of the present invention can be used to bond members made of a wide range of materials. Even materials that are considered difficult to bond can be bonded effectively. Examples of materials for the bonded members include metal, glass, wood, and resin. Metals also include metal compounds, such as alloys and metal oxides. Resins include natural resins and synthetic resins. The adhesive of the present invention can be used for bonding not only in the atmosphere but also underwater. "Underwater" includes underwater, aqueous solutions, and aqueous suspensions. Underwater bonding here includes bonding the surfaces of two bonded members that have water on their surfaces due to a high humidity environment without a drying process. In other words, it includes bonding the surfaces of bonded members that are wet with water.

[0224] The adhesive of the present invention can be naturally cured, but the curing process can be accelerated by irradiation with light, so that it can be quickly and easily cured underwater. Furthermore, the adhesive of the present invention can bond without melting by heating, and does not require the complicated process of partially heating the adhesive in water as in the case of hot melt, and does not require a solvent, so it has a small environmental impact.

[0225] Furthermore, after bonding, the adhesive of the present invention not only maintains its adhesion in the atmosphere, but also in water. The polymer of the present invention has lower hygroscopicity than a polymer not having a structural unit derived from (meth)acrylic acid. Therefore, it can maintain high underwater adhesion even when placed in water for a long period of time. For example, the adhesive of the present invention can maintain an underwater adhesion strength of 80% or more 24 hours after application to the surface of the adherend compared to the adhesion strength in water immediately after application to the surface of the adherend. To the inventors' knowledge, the underwater adhesion strength of the adhesive of the present invention significantly exceeds that of commercially available adhesives, both in terms of underwater adhesion strength immediately after application to the surface of the adherend and in terms of underwater adhesion after a period of time has elapsed since application to the surface of the adherend. Furthermore, after bonding, the adhesive of the present invention can maintain its adhesion even in seawater. For example, the adhesive of the present invention can maintain an adhesive strength in seawater 24 hours after application to the surface of the bonded member at 80% or more of the adhesive strength in seawater immediately after application to the surface of the bonded member.

[0226] The adhesive of the present invention can be suitably used as a repair agent, coating, or lining agent, taking advantage of its rapid curing properties, adhesive properties, and stability in contact with water. In particular, the adhesive of the present invention can be used as a so-called fully underwater adhesive that has high underwater adhesion even when the entire process from application to curing is carried out underwater, and therefore can be applied to various fields requiring fully underwater adhesion, such as repairing equipment such as ships, submarines, power generation equipment, and undersea cables, and repairing pool tanks.

[0227] The adhesive of the embodiment of the present invention can be used to bond members to each other.

[0228] In some embodiments, a bonding method using an adhesive according to an embodiment of the present invention includes applying the adhesive to a surface of a workpiece to be bonded and irradiating the applied adhesive with light to cure the adhesive. The irradiated light is preferably visible light, and the wavelength of the visible light is preferably 360 to 830 nm, more preferably 360 to 760 nm.

[0229] The bonding method may further include a step of fixing the applied adhesive after the applying step and before the curing step. The step of contacting the adhesive with the surface of the bonded member and fixing it can be performed by known means. For example, this fixing may be performed using a dedicated fixing device.

[0230] In certain embodiments, the bonded members comprise a first bonded member and a second bonded member, and the bonding method may include the steps of applying an adhesive to a bonded surface of the first bonded member, contacting the second bonded member with the adhesive after the adhesive applying step so that the adhesive is disposed between the first bonded member and the second bonded member, and curing the adhesive by irradiating the applied adhesive with light after the contacting step. If the bonding method further includes a fixing step, the first bonded member and the second bonded member with the adhesive disposed therebetween can be fixed by pressing one of them toward the other, or by sandwiching the first bonded member and the second bonded member with a fixture and pressing them from both sides.

[0231] In some embodiments, the bonding method includes the steps of mixing a compound represented by formula (1) above with a compound having two or more thiol groups, applying the mixture to the surface of a member to be bonded, and curing the mixture.

[0232] The bonding method may further include a step of fixing the applied adhesive after the applying step. The step of contacting the adhesive with the surface of the adherend and fixing it can be performed by known means. For example, this fixing may be performed using a dedicated fixing device.

[0233] The applying, fixing, and curing steps can each be independently carried out in air or underwater. In a preferred embodiment, the applying, fixing, and curing steps can be carried out underwater. The bonding method of the present invention can be carried out entirely underwater, from application of the adhesive to the bonded surface of the bonded member to curing.

[0234] The adhesive of the present invention can also be polymerized and cured by heating and used for adhesion. When the adhesive is heated and melted in the atmosphere and applied to the adherend surface, the adhesive can also be heated and melted and applied to the adherend surface of the adherend member.

[0235] The polymer of the present invention exhibits the above-mentioned excellent properties by having the repeating units, and therefore, even if other repeating units are introduced or the side chains are modified using known means within the scope of the present invention, these polymers are within the scope of the present invention. Furthermore, even if the polymer of the present invention is used alone, it exhibits excellent properties as an adhesive, and therefore, even if desired additives are added to control the properties using known means within the scope of the present invention, the composition to which the additives have been added is within the scope of the present invention. [Example]

[0236] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0237] [Production Example 1: Synthesis of TUac-EG3] As the monomer of Production Example 1, TUac-EG3 was synthesized according to the route shown in Scheme 1 below.

[0238] [ka]

[0239] In the first step, triethylene glycol (1) bearing amino groups at both ends and 2.0 molar equivalents of triethylamine were added to chloroform and cooled to 0°C. Under an argon atmosphere, 2.0 equivalents of carbon disulfide were added dropwise to the reaction mixture, which was then stirred vigorously while being returned to room temperature for 2 hours. The mixture was then cooled to 0°C again, and 2.0 equivalents of ethyl chloroformate were added dropwise. The mixture was stirred vigorously for 30 minutes. After 30 minutes, the mixture was returned to room temperature and stirred for another 2 hours. The reaction mixture was washed with water and brine, followed by drying over sodium sulfate. The solvent was then removed. The mixture was then thermally decomposed at 120°C for 2 hours under vacuum. After pyrolysis, the product was purified using a column to obtain NCS-EG3 (2).

[0240] The second step was the synthesis of aminoethanol acrylate salt. Boc-aminoethanol (3) was dissolved in methylene chloride solvent, and 2.0 equivalents of acryloyl chloride dissolved in methylene chloride at 0°C under an argon atmosphere was slowly added dropwise to the reaction mixture. The mixture was vigorously stirred at 0°C for 2 hours and at room temperature for 1 hour. After the reaction, the mixture was washed with saturated sodium bicarbonate and dried over sodium sulfate. The solvent was then removed and purified using a column to obtain the intermediate Boc-aminoethanol acrylate. The resulting intermediate was dissolved in methylene chloride solvent, and 16 equivalents of trifluoroacetic acid were added at 0°C under an argon atmosphere and stirred for 24 hours. After the reaction, the mixture was dried in vacuo to obtain the paste-like aminoethanol acrylate salt (4).

[0241] In the final step, 6.0 equivalents of aminoethanol acrylate salt (4) was dissolved in tetrahydrofuran. 12 equivalents of triethylamine was added under an argon atmosphere at 0°C and stirred for 5 minutes. Then, NCS-EG 3 (2) was added and stirred for 3 hours. After the reaction was completed, the solvent was removed and the mixture was purified by column chromatography to obtain the desired TUac-EG3 (5).

[0242] [Production Example 2: Synthesis of T-Cy2] As the monomer of Production Example 2, T-Cy2 was synthesized according to the route shown in Scheme 2 below.

[0243] [ka]

[0244] The first step was the synthesis of aminoethylene glycol acrylate salt. Boc-aminoethylene glycol (6) was dissolved in methylene chloride solvent, and 2.0 equivalents of acryloyl chloride dissolved in methylene chloride at 0°C under an argon atmosphere was slowly added dropwise to the reaction mixture. The mixture was vigorously stirred at 0°C for 2 hours and at room temperature for 1 hour. After the reaction, the mixture was washed with saturated sodium bicarbonate and dried over sodium sulfate. The solvent was then removed and purified using a column to obtain the intermediate Boc-aminoethylene glycol acrylate. The resulting intermediate was dissolved in methylene chloride solvent, and 16 equivalents of trifluoroacetic acid were added at 0°C under an argon atmosphere and stirred for 24 hours. After the reaction, the mixture was dried in vacuo to obtain a paste-like aminoethylene glycol acrylate salt (7).

[0245] In the second step, 6.0 equivalents of aminoethylene glycol acrylate salt were dissolved in tetrahydrofuran. Under an argon atmosphere, 12 equivalents of triethylamine were added and stirred for 5 minutes at 0°C. Then, commercially available NCS-Cy2 (8) was added and stirred for 24 hours. After the reaction was complete, the solvent was removed and the mixture was purified using a column to obtain T-Cy2 (9).

[0246] [Production Example 3: Synthesis of Uac-EG3] As the monomer of Production Example 3, Uac-EG3 was synthesized according to the following Scheme 3.

[0247] [ka]

[0248] 1,8-Diamino-3,6-dioxaoctane (10) was dissolved in tetrahydrofuran and cooled to 0 °C under argon. 2.8 equivalents of isocyanatoethyl acrylate (11) were added dropwise and stirred at room temperature for 30 minutes. After stirring, the reaction solution was added dropwise to vigorously stirred diethyl ether, yielding a white precipitate. The precipitate was collected by filtration and dried in vacuo for 24 hours to yield Uac-EG3 (12) as a white solid.

[0249] [Production Example 4: Synthesis of U-Cy2] As the monomer of Production Example 4, U-Cy2 was synthesized according to the route shown in Scheme 4 below.

[0250] [ka]

[0251] 3.0 equivalents of the aminoethylene glycol acrylate salt synthesized in Preparation Example 2 were dissolved in a tetrahydrofuran solution. 6.0 equivalents of triethylamine were added at 0°C under an argon atmosphere and stirred for 5 minutes. Then, commercially available NCO-Cy2 (13) was added and stirred for 24 hours. After the reaction was completed, the solvent was removed and the mixture was purified using a column to obtain U-Cy2 (14).

[0252] [Identification of synthesized monomers] The chemical structures of the monomers synthesized in Production Examples 1 to 4 are as follows: 1 H NMR, 13 The results were confirmed using CNMR. 20 mg of the monomer sample was dissolved in 0.7 mL of chloroform-d and heavy water-d2. All measurements were performed at room temperature. NMR TUac-EG3 1HNMR (500 MHz, CDCl3-d, δ): 7.18 (br 1H), 6.95 (br, 1H), 6.45 (d, J = 17.2 Hz, 2H), 6.15 (dd, J = 17.5, 10.6 Hz, 9. 8 ( 2H), 2H), 4.35 (t, J = 5.2 Hz, 4H), 3.90–3.62 (m, 16H) 13 CNMR (126 MHz, CDCl3-d, δ):182.9, 166.6, 131.8, 128.1, 70.1, 70.0, 63.3, 44.4, 44.1 ·T-Cy2 1 HNMR (500 MHz, CDCl3-d, δ):6.51–6.42 (m, 5H), 6.16 (dd, J = 17.5, 10.6 Hz, 2H), 5.89–5.87 (m, 2H), 4.53–3.10H (m, 2.9), 8pm) 13 CNMR (126 MHz, CDCl3-d, δ):181.3, 166.2, 131.6, 128.1, 70.7, 69.2, 63.5, 63.4, 53.7, 44.5, 49.0, 3.3.8, 3.8.7. 29.3, 28.2·Uac-EG3 1 HNMR (500 MHz, D2O.d2, δ):6.33 (d, J = 17.2 Hz, 2H), 6.10 (dd, J = 17.5, 10.6 Hz, 2H), 5.89 (d, J = 10.3 Hz, 2H (5.4), J = 4.4. 3.56–3.47 (m, 8H), 3.34 (t, J = 5.2 Hz, 4H), 3.20 (t, J = 5.2 Hz, 4H) 13 CNMR (126 MHz, D2O-d2, δ):168.6, 160.5, 132.5, 127.5, 69.8, 69.6, 64.3, 39.5, 38.8 ·Cy2 1 HNMR (500 MHz, CDCl3-d, δ):6.43 (dd, J = 17.5, 1.4 Hz, 2H), 6.15 (dd, J = 17.0, 10.5 Hz, 2H), 5.86 (d, J = 10.3 Hz, 2H), 5.16 (br, 4H), 4.30 (s, 4H), 3.80-3.34 (m, 14H), 1.95-0.94 (m, 20H) 13 CNMR (126 MHz, CDCl3-d, δ):166.3, 158.3, 131.4, 128.2, 71.2, 69.0, 63.7, 63.6, 49.6, 40.4, 33.8, 32.2, 30.1, 28.2

[0253] [Production Example 5: Synthesis of TUac-C8] As the monomer of Production Example 5, TUac-C8 was synthesized according to the route shown in Scheme 5 below.

[0254] [ka]

[0255] In the first step, 1,8-diaminooctane (15) was added to 2.0 molar equivalents of aqueous sodium hydroxide and cooled to 0 °C. Under an argon atmosphere, 2.0 equivalents of carbon disulfide were added dropwise to the reaction mixture, which was then stirred vigorously for 2 hours while being warmed to room temperature. The mixture was then cooled to 0 °C again, and 2.0 equivalents of ethyl chloroformate were added dropwise. The mixture was stirred vigorously for 30 minutes. After 30 minutes, the mixture was warmed to room temperature and stirred for another 2 hours. The reaction mixture was extracted with chloroform, washed with brine, and dried over sodium sulfate. The solvent was then removed. The mixture was then thermally decomposed at 120 °C for 2 hours under vacuum. After pyrolysis, the product was purified using a column to obtain NCS-C8 (16).

[0256] 6.0 equivalents of the aminoethanol acrylate salt (4) synthesized in Preparation Example 1 were dissolved in a tetrahydrofuran solution. 12 equivalents of triethylamine were added at 0°C under an argon atmosphere and stirred for 5 minutes. NCS-C8 (16) was then added and stirred for 24 hours. After the reaction was completed, the solvent was removed and the mixture was purified using a column to obtain TUac-C8 (17).

[0257] [Production Example 6: Synthesis of TUac-Bn] As the monomer of Production Example 6, TUac-Bn was synthesized according to the route shown in Scheme 6 below.

[0258] [ka]

[0259] In the first step, xylylenediamine (18) was added in a molar ratio of 1:2 and 2.0 equivalents of triethylamine to tetrahydrofuran and cooled to 0 °C. Under an argon atmosphere, 2.0 equivalents of carbon disulfide were added dropwise to the reaction mixture, which was then stirred vigorously while being returned to room temperature for 2 hours. The mixture was then cooled to 0 °C again, and 2.0 equivalents of ethyl chloroformate were added dropwise. The mixture was stirred vigorously for 30 minutes. After 30 minutes, the mixture was returned to room temperature and stirred for another 2 hours. The reaction mixture was washed with water and then brine, and dried over sodium sulfate. The solvent was then removed. The mixture was then pyrolyzed under vacuum at 120 °C for 2 hours. After pyrolysis, the product was purified using a column to obtain NCS-Bn (19).

[0260] 6.0 equivalents of the aminoethanol acrylate salt (4) synthesized in Preparation Example 1 were dissolved in a tetrahydrofuran solution. 12 equivalents of triethylamine were added at 0°C under an argon atmosphere and stirred for 5 minutes. NCS-Bn (19) was then added and stirred for 24 hours. After the reaction was completed, the solvent was removed and the mixture was purified using a column to obtain TUac-Bn (20).

[0261] [Identification of synthesized monomers] The chemical structures of the monomers synthesized in Production Examples 5 and 6 are as follows: 1 H NMR, 13The results were confirmed using CNMR. 20 mg of the monomer sample was dissolved in 0.7 mL of chloroform-d. All measurements were performed at room temperature. NMR TUac-C8 1 HNMR (500 MHz, CDCl3-d, δ):6.55-6.43 (m, 6H), 6.14 (dd, J = 17.2, 10.3 Hz, 2H), 5.90 (dd, J = 10.6, 1.4 Hz, 2H), 4.36 (t, J = 5.2 Hz, 4H), 3.86 (s, 4H), 3.38 (s, 4H), 1.61-1.56 (m, 4H), 1.34 (d, J = 17.2 Hz, 9H) 13 CNMR (126 MHz, CDCl3-d, δ):182.0, 166.8, 132.0, 127.9, 63.2, 44.2, 44.1, 28.8, 28.7, 26.6 TUac-Bn 1 HNMR (500 MHz, CDCl3-d, δ):7.64 (br, 3H), 7.30 (t, J = 8.0 Hz, 1H), 7.16-7.10 (m, 3H), 6.45 (dd, J = 17.2, 1.1 Hz, 2H), 6.14 (dd, J = 17.2, 10.3 Hz, 2H), 5.87 (dd, J = 10.6, 1.4 Hz, 2H), 4.93 (s, 4H), 3.92 (s, 4H), 3.18 (s, 4H) 13 CNMR (126 MHz, CDCl3-d, δ):183.1, 165.9, 138.6, 131.7, 129.1, 128.0, 126.7, 121.5, 62.8, 48.3, 43.1

[0262] Production Example 7: Tripropylene glycol diacrylate (TPA)

[0263] [ka]

[0264] Tripropylene glycol diacrylate (TPA) (21) was a commercially available product.

[0265] Production Example 8: Synthesis of T3EG The synthesis of T3EG was carried out using triethylene glycol with amino groups at both ends as the monomer and 0.95 equivalents of thiocarbonyldiimidazole in a molar ratio with dimethylformamide as the solvent (reaction time: 6 hours at 80°C under an argon atmosphere). The reaction mixture was added dropwise to vigorously stirred methanol, resulting in a paste-like insoluble material. The insoluble material and the supernatant were separated by decantation and dissolved in chloroform. This was then added dropwise to methanol again, and the resulting precipitate was separated. This procedure was repeated twice more. The resulting paste-like insoluble material was dried in vacuum at 80°C for 24 hours to obtain T3EG (22) as a yellowish, transparent resin.

[0266] [ka]

[0267] The chemical structure of T3EG is 1 H NMR, 13 The properties were confirmed using C NMR. 20 mg of the polymer sample was dissolved in 0.7 mL of dimethyl sulfoxide-d6. All measurements were performed at room temperature. 1 H NMR (500 MHz, DMSO-d6, δ): 2.78 (br, CH2NH2), 3.45-3.59 (br, (S)NHCH2), 7.49 (br, C(S)NH), 13C NMR (500 MHz, DMSO-d6, δ): 44.03, 69.054, 70.11, 183.34. The degree of polymerization and number-average molecular weight of the polymer were calculated from the integral ratio of the peak derived from the methylene adjacent to the terminal amino group to the peak derived from NH in 1H NMR. The degree of polymerization predicted from the monomer charge ratio was 50. The weight-average molecular weight of T3EG was calculated to be 9500 using a Zimm plot based on multi-angle light scattering measurements.

[0268] [Production Example 9: Synthesis of T-EG3] As the monomer of Production Example 9, T-EG3 was synthesized according to the route shown in Scheme 7 below.

[0269] [ka]

[0270] In the first step, NCS-EG3 (2), prepared by the previously reported method, was added to tetrahydrofuran, and 4.0 equivalents of 2-(2-aminoethoxy)ethanol was added dropwise. The mixture was stirred at room temperature for approximately 2 hours. The reaction mixture was then concentrated and purified by column chromatography to obtain di-OH-EG3 (23). The second step was the synthesis of T-EG3. The resulting di-OH-EG3 (23) was dissolved in tetrahydrofuran, and 4 equivalents of triethylamine were added. 3 equivalents of acryloyl chloride were slowly added dropwise to the reaction mixture at 0°C under an argon atmosphere, and the mixture was vigorously stirred at -40°C for 3 hours. After the reaction, the solvent was removed and the mixture was purified using a column to obtain the desired product, T-EG3 (24).

[0271] [Production Example 10: Synthesis of T-C8] As a monomer for Production Example 10, T-C8 was synthesized according to the route shown in Scheme 8 below.

[0272] [ka]

[0273] In the first step, NCS-C8 (16), prepared by the previously reported method, was added to tetrahydrofuran solvent, and 4.0 equivalents of 2-aminoethylethanol was added dropwise at 0 °C. The mixture was then allowed to warm to room temperature and stirred for approximately 15 hours. The reaction mixture was then concentrated and purified using a column chromatography to obtain di-OH-C8 (25). The second step was the synthesis of T-C8. The resulting di-OH-C8 (25) was dissolved in tetrahydrofuran, and 5 equivalents of triethylamine were added. Four equivalents of acryloyl chloride were then slowly added dropwise to the reaction mixture at 0°C under an argon atmosphere, followed by vigorous stirring at -40°C for 3 hours. After the reaction, the solvent was removed and the mixture was purified using a column to obtain the desired product, T-C8 (26).

[0274] [Identification of synthesized monomers] The chemical structures of the monomers synthesized in Production Examples 9 and 10 are as follows: 1 H NMR, 13 The results were confirmed using CNMR. 20 mg of the monomer sample was dissolved in 0.7 mL of chloroform-d1. All measurements were performed at room temperature. NMR di-OH-EG3 1 HNMR (500 MHz, DMSO-d6, δ):7.52 (s, 6H), 4.57 (t, J = 5.3 Hz, 2H), 3.54-3.42 (m, 28H) 13 CNMR (151 MHz, DMSO-d6, δ):183.1, 72.6, 70.1, 69.5, 69.4, 60.7, 44.1 T-EG3 1 HNMR (600 MHz, CDCl3-d1, δ): 7.05 (d, J = 121.0 Hz, 2H), 6.44 (d, J = 17.6 Hz, 2H), 6.18-6.13 (m, 2H), 5.87 (s, 2H), 4.33 (t, J = 4.6 Hz, 4H), 3.75-3.61 (m, 24H) 13 CNMR (151 MHz, CDCl3-d1, δ):182.6, 166.1, 131.4, 128.1, 70.0, 68.9, 67.9, 67.2, 63.4, 53.5, 44.6 di-OH-C8 1HNMR (600 MHz, DMSO-d6, δ): 7.39 (d, J = 92.4 Hz, 4H), 4.59 (t, J = 5.3 Hz, 2H), 3.52-3.34 (m, 20H), 1.46 (t, J = 6.1 Hz, 4H), 1.27 (s, 8H) 13 CNMR (151 MHz, DMSO-d6, δ):183.5, 72.6, 69.4, 60.7, 44.0, 29.2, 26.9 T-C8 1 HNMR (600 MHz, CDCl3-d1, δ):6.46 (d, J = 17.6 Hz, 2H), 6.29-6.15 (m, 3H), 5.90 (d, J = 10.3 Hz, 2H), 4.35 (t, J = 4.0 Hz, 4H), 3.76-3.42 (m, 16H), 1.63-1.58 (m, 6H), 1.35 (s, 8H) 13 CNMR (151 MHz, CDCl3-d1, δ):182.3, 166.2, 131.5, 128.1, 70.2, 69.2, 63.1, 44.7, 41.5, 30.6, 28.8, 26.5

[0275] Test Example 1: Underwater adhesion test between two substrates of different materials Methods and Materials To confirm the adhesiveness of the synthesized molecules in water, the following procedure A was carried out entirely in deionized water. Here, the first substrate is a glass substrate.

[0276] The second substrate was made of glass, stainless steel, wood, aluminum (Al), polypropylene (PP), or polytetrafluoroethylene (PTFE).

[0277] (Operation A): The TUac-EG3 monomer synthesized in Production Example 1 was placed on the second substrate, and a 10 μm diameter glass spacer was mixed in. The first substrate was then placed on top of the second substrate so that the thickness of the monomer was 10 μm. Light with a wavelength of 365 nm was irradiated for 10 seconds. This operation was carried out at 20°C. During this light irradiation process, the monomer polymerized and hardened into a polymer, completely adhering the two substrates. In this way, an adhesive test specimen was obtained, bonded with the polymer sandwiched between them.

[0278] In this way, the entire process of applying adhesive, sandwiching, and curing was carried out underwater, which was called fully underwater adhesion.

[0279] A lap tensile shear test was used to quantitatively evaluate adhesive strength. This test method is well known. The test piece was pulled at a rate of 1 mm / min to obtain a stress-strain curve. The stress (N) at the time of fracture was calculated as a function of the contact area (mm 2 ) to calculate the adhesive strength (MPa).

[0280] (result) TUac-EG3 exhibited underwater adhesion to all substrates. Among these samples, it showed stronger underwater adhesion to materials with high surface energy, such as stainless steel, aluminum, and wood (Figure 2A, B).

[0281] Test Example 2: Process dependency test of adhesive strength Methods and Materials In order to evaluate the process dependency of adhesive strength, adhesive strength was measured for samples produced by the following three processes.

[0282] D (Dry adhesion): The same procedure as in Procedure A of the underwater adhesion test in Test Example 1 was carried out in a dry state. An adhesion test piece was prepared by sandwiching TUac-EG3 in a dry state and irradiating it with light. A tensile test was carried out at room temperature using this.

[0283] W (underwater adhesion): The same procedure as in Procedure A of the underwater adhesion test was carried out underwater. An adhesion test piece was prepared by sandwiching TUac-EG3 underwater and irradiating it with light. A tensile test was carried out at room temperature using this.

[0284] S (Adhesion in seawater): The same procedure as in Procedure A of the underwater adhesion test was carried out in seawater. TUac-EG3 was sandwiched between the specimens and irradiated with light to prepare an adhesion test specimen. This specimen was used to carry out a tensile test at room temperature.

[0285] In addition, a 100 g weight was attached to the samples bonded in seawater to check whether they could maintain their bonded state in seawater.

[0286] Furthermore, for comparison, a similar experiment was conducted using a commercially available epoxy-based underwater adhesive (manufactured by Cemedine Co., Ltd., product name: Underwater Epoxy).

[0287] (result) The results of the process dependency test for adhesive strength are summarized in Figure 3. These results show that TUac-EG3 exhibits greater adhesive strength than commercially available epoxy adhesives in all three processes, D, W, and S, and that it also exhibits high adhesive strength in seawater, which is expected in practical situations such as repairing the bottom of a ship. Furthermore, it was confirmed that the adhesive state could be maintained in seawater even after one month (data not shown).

[0288] Test Example 3: Underwater adhesion test Methods and Materials Using each of the monomers shown in FIG. 4A, an underwater adhesion test was carried out according to Procedure A of Test Example 1.

[0289] (result) All thiourea monomers (TUac-EG3, T-Cy2, TUac-C8, TUac-Bn) showed underwater adhesion. However, TUac-EG3 and T-Cy2 had similar underwater adhesive strength, and showed particularly high values ​​among thiourea adhesives (Figure 4B). Furthermore, Uac-EG3 is a water-soluble white solid, so when underwater adhesion was attempted, it dissolved in water and was not possible to perform underwater adhesion. U-Cy2 showed underwater adhesion, but T-Cy2 showed underwater adhesion that was more than three times stronger. Furthermore, TPA is water-insoluble. melt Although it was possible to cure in water, it did not exhibit underwater adhesion.

[0290] Test Example 4: Evaluation of adhesive strength durability Methods and Materials Procedure A was performed in water using the same procedure as in the underwater adhesion test in Test Example 1, and slide glasses with TUac-EG3 and T-Cy2 sandwiched between them were prepared and used as samples. The prepared samples were left to stand in deionized water at room temperature for 24 hours, and then the adhesive strength was evaluated.

[0291] (result) Both TUac-EG3 and T-Cy2 maintained high underwater adhesion strength even after 24 hours (Figure 5). Furthermore, the adhesion strength of TUac-EG3 decreased by approximately 50% after 24 hours, whereas that of T-Cy2 was maintained at over 80%, demonstrating that T-Cy2 has superior durability.

[0292] Test Example 5. Swelling test Methods and Materials The water absorbency of TUac-EG3 and T3EG of Patent No. 6574259 was evaluated. Specifically, each polymer was first synthesized in a dry state. Then, it was immersed in deionized water and the mass was measured at specific intervals. The mass change (%) was calculated by dividing the difference in mass before and after immersion by the mass before immersion and multiplying by 100. This mass change was taken as the amount of water absorbed and used as an index for evaluating water absorbency.

[0293] (result) It was found that TUac-EG3 of the present invention swells by only 4%, while T3EG swells by 20% (Figure 6). Therefore, TUac-EG3 of the present invention overcomes the problem of moisture absorption. Overcoming this problem of water absorption has made it possible to maintain adhesive strength for a long period of time. It is thought that T-Cy2, which has a cyclohexyl structure, further suppresses swelling.

[0294] Test Example 6: Adhesion test Methods and Materials To confirm the underwater adhesion of the two-component adhesive without the use of light, the following procedure B was carried out entirely in deionized water.

[0295] Here, the first and second substrates may be the same or different. In this test example, glass substrates were used as the first and second substrates. The two liquids are named Liquid A and Liquid B, respectively, and are described below.

[0296] (Liquid A): Thiourea adhesive of either TUac-EG3 or T-Cy2 (Solution B): A mixture of branched thiol (either Tri-SH (27) or Hexa-SH (28)) and amine catalyst (hexylamine) (29).

[0297] [ka]

[0298] (Operation B): A mixture of Liquid A and Liquid B, with equal amounts of C=C and SH, was placed on the second substrate, and a 10 μm diameter glass spacer was added. The first substrate was then placed on top of the second substrate so that the thickness of the mixture was 10 μm, and the substrate was secured in place with clips. This process was carried out at 20°C. The substrate was then left in water for a certain period of time, during which a three-dimensional network was formed by the reaction of thiol and ene, resulting in hardening. In this way, an adhesive test specimen was obtained, with the polymer sandwiched between the two.

[0299] (result) It was found that all combinations of TUac-EG3 / Tri-SH, TUac-EG3 / Hexa-SH, T-Cy2 / Tri-SH, and T-Cy2 / Hexa-SH exhibited underwater adhesion. Thus, by using a two-component adhesive, underwater adhesion was possible without the use of light. This expands the versatility of thiourea acrylate adhesives, allowing them to bond opaque materials together.

[0300] Test Example 7. Dependence of underwater adhesion on the type of crosslinking agent The dependence of underwater adhesion on the type of crosslinker was investigated. Tri-SH (27) and Hexa-SH (28) were used as crosslinkers, and each was mixed at 1 equivalent relative to the C=C of the T-Cy2 monomer. Adhesion test specimens were prepared according to the method in Test Example 6. The results of the tensile shear test in Test Example 1 (except that the tensile speed was 5 mm / min) showed that Hexa-SH had higher underwater adhesion than Tri-SH (Figure 7).

[0301] Test Example 8. Curing time dependency The underwater adhesive strength was investigated at various times after mixing T-Cy2 and the crosslinker Hexa-SH. The results of the adhesive test, which followed the tensile shear test in Test Example 1 (except that the tensile speed was 5 mm / min), showed that the adhesive strength converged to a nearly constant value after about 3 hours (Figure 8).

[0302] Test Example 9. Dependence of underwater adhesion on the ratio of two liquids The underwater adhesion of a two-component crosslinking agent, a branched thiol (Hexa-SH), and an amine catalyst (hexylamine) was investigated when the equivalent weight relative to each monomer was varied. Each adhesive test piece was prepared according to the method of Test Example 6. The results of the adhesion test, which followed the tensile shear test of Test Example 1 (except that the tensile speed was 5 mm / min), showed that Hexa-SH exhibited the highest underwater adhesion when its C=C ratio was 1:1. Furthermore, the underwater adhesion strength of hexylamine reached its maximum when it was 50 mol% relative to the C=C ratio of the monomer, indicating that it was the most suitable (Table 1).

[0303] [Table 1]

[0304] Test Example 10. Monomer dependence of underwater adhesion Here, a two-component adhesive was used, and adhesive test specimens were prepared according to the method of Test Example 6. The monomers used in (Liquid A) were T-Cy2, T-EG3, and T-C8, respectively. (Liquid B) was a mixed solution of Hexa-SH and hexylamine. Adhesion tests were conducted in accordance with the tensile shear test of Test Example 1 (except that the tensile speed was 5 mm / min). All adhesives demonstrated underwater adhesion, with the adhesive produced using T-Cy2 demonstrating the highest underwater adhesion (Figure 9).

[0305] Test Example 11. Underwater adhesion time dependency test The following test was conducted to evaluate the underwater durability of the adhesive. A two-component adhesive was used, and adhesive test specimens were prepared according to the method described in Test Example 6. T-Cy2 was used as the monomer for Liquid A. Liquid B from Test Example 6 was used for Liquid B. The prepared samples were left in deionized water at room temperature for 1, 3, 10, and 30 days, and then subjected to the tensile shear test described in Test Example 1 (except that the tensile speed was 5 mm / min). The results are shown in Figure 10. These results demonstrate that the underwater adhesive of the present invention maintains sufficient adhesive strength even after prolonged exposure to water. Furthermore, the adhesive strength of the two commercially available two-component epoxy adhesives decreased over time, whereas the two-component adhesive prepared using T-Cy2 (hereinafter simply referred to as "two-component T-Cy2") exhibited the highest adhesive strength and excellent durability. Furthermore, the two-component T-Cy2 exhibited strong and durable adhesion even in seawater (Figure 11).

[0306] Test Example 12. Substrate Dependence The two-component T-Cy2 exhibits adhesion to substrates other than glass. To confirm the substrate dependency of adhesion, adhesive test specimens were prepared according to the method of Test Example 6 using substrates of various materials instead of two pieces of glass, and the underwater adhesive strength was examined by a tensile test under the same conditions as the tensile shear test of Test Example 1 (except that the tensile speed was 5 mm / min). The two-component T-Cy2 exhibited stronger underwater adhesion to materials with high surface energy, such as stainless steel (SUS stainless steel plate), titanium oxide, wood, and PMMA (Figure 12).

[0307] Test Example 13. Instantaneous adhesion of two-component mixtures We decided to use light to shorten the curing time of a two-component mixed adhesive. Here, we mixed liquids A and C. Liquid A was the same as in Test Example 6, and liquid C was newly prepared as follows. (Liquid C): A mixture of branched thiol (Hexa-SH(28)) and a commercially available photopolymerization initiator (2,2-dimethoxy-2-phenylacetophenone, Tokyo Chemical Industry Co., Ltd.). The first and second substrates were glass substrates. A mixture of Liquid A and Liquid C, with equal amounts of C=C and SH, was placed on the second substrate, and the first substrate was placed on top of it and fixed with clips. This operation was carried out at 20°C. After that, light was irradiated, and a three-dimensional network was formed by the reaction of thiol and ene, which hardened the mixture. In this way, an adhesive test piece was obtained, with the polymer sandwiched between them.

[0308] (result) It was found that T-Cy2 / Hexa-SH exhibited underwater adhesive strength comparable to that achieved without light (Test Example 7). However, the adhesive only required one minute to harden. Thus, even though it is a two-part adhesive, it can be rapidly hardened as needed.

Claims

1. A compound represented by the following formula (1): 【Chemistry 1】 (In formula (1), A and B satisfy the relationship (I) or (II), (I) One of A and B is a group represented by the following formula (2): 【Chemistry 2】 (In formula (2), R 1 and R 2 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, X is selected from the following groups: 【Transformation 3】 R 5 and R 6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; k is an integer of 0 or greater, l is an integer of 1 or greater, and m is an integer of 0 or greater). the other of A and B is a group selected from the following (a) to (c), has a structure in which two or more of the following (b) are linked together, or has a structure in which two of the following (c) are linked together, (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, (b) 【Chemistry 4】 (One of the main chain bonding sites may be at the 1-position, and the other bonding site may be at the 2-position, 3-position, or 4-position. R 3 are a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups, substituted or unsubstituted, having 1 to 6 carbon atoms. (c) 【Transformation 5】 (One of the main chain bonding sites may be at the 1-position, and the other bonding site may be at the 2-position, 3-position, or 4-position. R 4 are a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups, substituted or unsubstituted, having 1 to 6 carbon atoms. When the other of A and B has a structure in which two or more of the following (b) are linked together, or a structure in which two of the following (c) are linked together, the linking group is -O- or -C(R a ) (R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. (II) Both A and B are independently a group represented by the following formula (2): 【Transformation 6】 (In formula (2), R 1 and R 2 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, X is selected from the following groups: 【Transformation 7】 R 5 and R 6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; k is an integer of 0 or greater, l is an integer of 1 or greater, and m is an integer of 0 or greater). D is hydrogen or methyl.

2. The compound according to claim 1, which is obtained by reacting a compound represented by the following formula (9) with a compound represented by the following formula (10): 【Transformation 8】 (A in formula (9) and B in formula (10) satisfy the relationship (I) or (II). (I) One of A and B is a group represented by the following formula (2): 【Chemistry 9】 (In formula (2), R 1 and R 2 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, X is selected from the following groups: 【Chemistry 10】 R 5 and R 6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; k is an integer of 0 or more, l is an integer of 1 or more, and m is an integer of 0 or more). the other of A and B is a group selected from the following (a) to (c), has a structure in which two or more of the following (b) are linked together, or has a structure in which two of the following (c) are linked together, (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, (b) 【Chemistry 11】 (One of the main chain bonding sites may be at the 1-position, and the other bonding site may be at the 2-position, 3-position, or 4-position. R 3 are a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups, substituted or unsubstituted, having 1 to 6 carbon atoms. (c) 【Chemistry 12】 (One of the main chain bonding sites may be at the 1-position, and the other bonding site may be at the 2-position, 3-position, or 4-position. R 4 are a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups, substituted or unsubstituted, having 1 to 6 carbon atoms. When the other of A and B has a structure in which two or more of the following (b) are linked together, or a structure in which two of the following (c) are linked together, the linking group is -O- or -C(R a ) (R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. (II) Both A and B are independently a group represented by the following formula (2): 【Chemistry 13】 (In formula (2), R 1 and R 2 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, X is selected from the following groups: 【Chemistry 14】 R 5 and R 6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; k is an integer of 0 or more, l is an integer of 1 or more, and m is an integer of 0 or more). D is hydrogen or methyl.

3. The compound according to claim 1, wherein the formula (2) is a group represented by the following formula (2a): 【Chemistry 15】 (In the formula, R 5 and R 6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, and R 5 and R 6 The substituent is a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group, or a halogen atom; and l is an integer from 1 to 5.

4. A is a group represented by formula (2a), 【Chemistry 16】 (In the formula, R 5 and R 6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, and R 5 and R 6 The substituent is a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group, or a halogen atom; and l is an integer from 1 to 5. The compound according to claim 1, wherein B is (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms.

5. A has a structure in which two of the (c) are linked together, The compound according to claim 1, wherein B is a group represented by formula (2a). 【Chemistry 17】 (In the formula, R 5 and R 6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, and R 5 and R 6 The substituent is a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group, or a halogen atom; and l is an integer from 1 to 5.

6. A polymer obtained by polymerizing the compound according to any one of claims 1 to 5.

7. A polymer represented by the following formula (11): [Chemistry 18] In formula (11), A and B satisfy the relationship (I) or (II), (I) One of A and B is a group represented by the following formula (2): 【Chemistry 19】 (In formula (2), R 1 and R 2 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, X is selected from the following groups: 【Chemistry 20】 R 5 and R 6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; k is an integer of 0 or greater, l is an integer of 1 or greater, and m is an integer of 0 or greater). the other of A and B is a group selected from the following (a) to (c), has a structure in which two or more of the following (b) are linked together, or has a structure in which two of the following (c) are linked together, (a) a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, (b) 【Chemistry 21】 (One of the main chain bonding sites may be at the 1-position, and the other bonding site may be at the 2-position, 3-position, or 4-position. R 3 are a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups, substituted or unsubstituted, having 1 to 6 carbon atoms. (c) 【Chemistry 22】 (One of the main chain bonding sites may be at the 1-position, and the other bonding site may be at the 2-position, 3-position, or 4-position. R 4 are a hydrogen atom or 1 to 4 identical or different monovalent alkyl groups, substituted or unsubstituted, having 1 to 6 carbon atoms. When the other of A and B has a structure in which two or more of the following (b) are linked together, or a structure in which two of the following (c) are linked together, the linking group is -O- or -C(R a ) (R b )- and R a and R b are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. (II) Both A and B are independently a group represented by the following formula (2): 【Chemistry 23】 (In formula (2), R 1 and R 2 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, X is selected from the following groups: 【Chemistry 24】 R 5 and R 6 are each independently a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, R is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms; k is an integer of 0 or greater, l is an integer of 1 or greater, and m is an integer of 0 or greater). D is hydrogen or a methyl group; n is the degree of polymerization of the repeating unit.

8. An adhesive comprising the compound according to any one of claims 1 to 5.

9. An adhesive comprising the compound according to any one of claims 1 to 5 and a compound having two or more thiol groups.

10. applying an adhesive comprising the compound according to any one of claims 1 to 5 to the surface of a workpiece to be bonded; A step of irradiating the applied adhesive with light to harden the adhesive. A bonding method comprising:

11. the adherend is a first adherend, 11. The bonding method according to claim 10, further comprising, after the step of applying the adhesive, a step of contacting a second member to be bonded with the adhesive so that the adhesive is disposed between the first member and the second member to be bonded, and after the step of contacting the second member to be bonded, irradiating the applied adhesive with light to cure the adhesive.

12. A step of mixing the compound according to any one of claims 1 to 5 with a compound having two or more thiol groups; and applying the mixture to the surface of the member to be bonded and allowing the mixture to harden A bonding method comprising:

13. 12. The method of claim 11, wherein the curing step is carried out in water, an aqueous solution, an aqueous suspension, or a high humidity environment.

14. The adhesive method of claim 12, wherein the curing step is carried out in water, an aqueous solution, an aqueous suspension, or a high humidity environment.

15. 11. The bonding method according to claim 10, wherein the bonded members are made of a material selected from the group consisting of metal, glass, wood, and synthetic resin.

16. Use of a compound according to any one of claims 1 to 5 for producing an adhesive.

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