Polyamide resin, method for producing polyamide resin, and adhesive containing polyamide resin

Abstract

The present invention addresses the problem of providing a polyamide resin which has a structural unit represented by formula (1). (In formula (1), R1 is an alkyl group having 1 to 12 carbon atoms, R2 is an alkyl group having 1 to 12 carbon atoms, X is a group selected from the group consisting of -O-, -CO-, -SO2-, -CH2-, -C(CH3)2-, and -C(CF3)2-, and R3 is a divalent organic group. In a plurality of formulae (1), R1 moieties, R2 moieties, X moieties, and R3 moieties may be the same as or different from each other.) As a means for solving the problem, the present invention provides a polyamide resin which has a structural unit represented by formula (1). (In formula (1), R1 is an alkyl group having 1 to 12 carbon atoms, R2 is an alkyl group having 1 to 12 carbon atoms, X is a group selected from the group consisting of -O-, -CO-, -SO2-, -CH2-, -C(CH3)2-, and -C(CF3)2-, and R3 is a divalent organic group. In a plurality of formulae (1), R1 moieties, R2 moieties, X moieties, and R3 moieties may be the same as or different from each other.)

Description

Polyamide resin, method for producing polyamide resin, and adhesive containing polyamide resin

[0001] The present invention relates to a polyamide resin, a method for producing a polyamide resin, and an adhesive containing the polyamide resin.

[0002] Polyamide resins are materials with excellent heat resistance, chemical resistance, and mechanical properties, and are widely used in applications such as electronic and electrical components and automobiles. Among these, aromatic polyamide resins have high heat resistance and are expected to have excellent adhesion to metals due to their multipoint hydrogen bonding. However, their low solubility in general-purpose organic solvents requires the use of high-boiling-point solvents, limiting their applications and mounting conditions. To date, polyamide resin adhesives have been proposed, for example, as shown in Patent Documents 1 to 4.

[0003] JP 2016-20447 A JP 2017-528543 A JP 2011-184682 A WO 2009 / 139087

[0004] The polyamide resin adhesives proposed in Patent Documents 1 to 4 have low solubility in organic solvents with boiling points below 150° C., particularly in organic solvents with boiling points below 100° C., and therefore require heating at high temperatures and for long periods of time when forming an adhesive film, and improvements have been sought. Furthermore, while these polyamide resin adhesives have excellent adhesive strength at temperatures of 150° C. or less, many of them lose their adhesive strength at high temperatures of 180° C. or more, and improvements have been sought.

[0005] One of the problems to be solved by the present invention is to provide a compound represented by formula (1): (In formula (1), R １ is an alkyl group having 1 to 12 carbon atoms, R ２ represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ a group selected from the group consisting of -, R ３ is a divalent organic group. １, R ２ , X and R ３ and the structural units may be the same or different from each other.

[0006] One of the problems to be solved by the present invention is to provide a compound represented by formula (2): (In formula (2), R １ is an alkyl group having 1 to 12 carbon atoms, R ２ represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ an amine component containing an N-alkyldiamine represented by formula (3): (In formula (3), R ３ is a divalent organic group. １ -OH, halogen, -OR ４１ , -NHR ４２ and Z ２ -OH, halogen, -OR ４３ , -NHR ４４ That is. Z １ and Z ２ When is -OH, Z １ and Z ２ may be dehydrated to form -O-. ４１ ~R ４４ may be the same or different and are alkyl groups having 1 to 6 carbon atoms.

[0007] One of the problems to be solved by the present invention is to provide an adhesive containing a polyamide resin having a repeating unit represented by the above formula (1).

[0008] One of the problems to be solved by the present invention is to provide an adhesive that has excellent solubility in organic solvents having a boiling point of less than 150°C and that can maintain adhesive strength even at high temperatures of 180°C or higher.

[0009] As a result of extensive research to solve the above problems, the inventors have found that the above problems can be solved by a polyamide resin having a structural unit represented by specific formula (1), an adhesive containing the polyamide resin having the structural unit represented by specific formula (1), and a method for producing a polyamide resin, and have thus completed the present invention. That is, the present invention provides the following polyamide resin, adhesive containing the polyamide resin, and method for producing a polyamide resin.

[0010] [Term 1] Formula (1): (In formula (1), R １ is an alkyl group having 1 to 12 carbon atoms, R ２ represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ a group selected from the group consisting of -, R ３ is a divalent organic group. １ , R ２ , X and R ３ may be the same or different. [Item 2] A polyamide resin solution comprising the polyamide resin according to item 1 and a solvent. [Item 3] A polyamide resin solution comprising a polyamide resin represented by formula (2): (In formula (2), R １ is an alkyl group having 1 to 12 carbon atoms, R ２ represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ an amine component containing a diamine represented by formula (3): (In formula (3), R ３ is a divalent organic group. １ -OH, halogen, -OR ４１ , -NHR ４２ and Z２ -OH, halogen, -OR ４３ , -NHR ４４ That is. Z １ and Z ２ When is -OH, Z １ and Z ２ may be dehydrated to form -O-. ４１ ~R ４４ may be the same or different and are alkyl groups having 1 to 6 carbon atoms. [Item 4] A method for producing a polyamide resin, comprising reacting a component containing a dicarboxylic acid component represented by formula (1): (In formula (1), R １ is an alkyl group having 1 to 12 carbon atoms, R ２ represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ a group selected from the group consisting of -, R ３ is a divalent organic group. １ , R ２ , X and R ３ Item 5. An adhesive comprising a polyamide resin having a structural unit represented by the formula (A): SR ２００ (%) = F ２００ / F ２３ ×100...(A) (In formula (A), F ２３ is the tensile shear adhesive strength at 23°C (JIS K 6850:1999), and F ２００ is the tensile shear adhesive strength at 200°C (based on JIS K 6850:1999). ２００ Item 7. The adhesive according to item 4 or 5, wherein R in formula (1) is 90% or more. １ and R ２ is an ethyl group, and the adhesive strength retention rate SR ２００ Item 7. The adhesive according to Item 6, wherein the ratio of the cross-linking coefficient to the cross-linking coefficient is 90% or more.

[0011] According to the present invention, a compound of formula (1): (In formula (1), R １ is an alkyl group having 1 to 12 carbon atoms, R ２ represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ a group selected from the group consisting of -, R ３ is a divalent organic group. １ , R ２ , X and R ３ may be the same or different from each other.

[0012] According to the present invention, a compound of formula (2): (In formula (2), R １ is an alkyl group having 1 to 12 carbon atoms, R ２ represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ an amine component containing an N-alkyldiamine represented by formula (3): (In formula (3), R ３ is a divalent organic group. １ -OH, halogen, -OR ４１ , -NHR ４２ and Z ２ -OH, halogen, -OR ４３ , -NHR ４４ That is. Z １ and Z ２ When is -OH, Z １ and Z ２ may be dehydrated to form -O-. ４１ ~R ４４may be the same or different and are alkyl groups having 1 to 6 carbon atoms.

[0013] The present invention provides an adhesive containing a polyamide resin having a repeating unit represented by formula (1) above.

[0014] The present invention provides an adhesive that has excellent solubility in organic solvents with boiling points of less than 150° C. and that can maintain adhesive strength even at high temperatures.

[0015] Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that the present invention is not limited to the following embodiments, and should be understood to include various modifications that are implemented within the scope of the present invention.

[0016] [Polyamide resin and method for producing same] The polyamide resin of the present invention is a polyamide resin represented by formula (1): (In formula (1), R １ is an alkyl group having 1 to 12 carbon atoms, R ２ represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ a group selected from the group consisting of -, R ３ is a divalent organic group. １ , R ２ , X and R ３ may be the same or different.) The polyamide resin of the present invention is a polyamide resin having a structural unit represented by the following formula: ２ C≡CH)—).

[0017] <Structural Unit Represented by Formula (1)> The structural unit represented by formula (1) is, for example, a structural unit represented by formula (2): (In formula (2), R １ is an alkyl group having 1 to 12 carbon atoms, R ２represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ an amine component containing a diamine represented by formula (3): (In formula (3), R ３ is a divalent organic group. １ -OH, halogen, -OR ４１ , -NHR ４２ and Z ２ -OH, halogen, -OR ４３ , -NHR ４４ That is. Z １ and Z ２ When is -OH, Z １ and Z ２ may be dehydrated to form -O-. ４１ ~R ４４ may be the same or different and are alkyl groups having 1 to 6 carbon atoms.

[0018] (Diamine represented by formula (2)) Formula (2): (In formula (2), R １ is an alkyl group having 1 to 12 carbon atoms, R ２ represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ The diamine represented by the formula (1a) is a group selected from the group consisting of: In addition, X is -O-, -CO- or -CH ２ In the case of -, R １ and R ２ At least one of these is preferably an alkyl group having two or more carbon atoms.

[0019] Examples of the diamine represented by formula (2) include the following compounds (2a) to (2bt), but are not limited to these compounds (2a) to (2bt) as long as they are diamines represented by formula (2).

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028] The diamine represented by formula (2) may be a commercially available product or may be synthesized. The diamine represented by formula (2) may be synthesized, for example, by the method shown in the synthesis examples of raw material compounds described later.

[0029] (Dicarboxylic acid component represented by formula (3)) Formula (3): (In formula (3), R ３ is a divalent organic group. １ -OH, halogen, -OR ４１ , -NHR ４２ and Z ２ -OH, halogen, -OR ４３ , -NHR ４４ That is. Z １ and Z ２ When is -OH, Z １ and Z ２ may be dehydrated to form -O-. ４１ ~R ４４ may be the same or different and are alkyl groups having 1 to 6 carbon atoms. The structure represented by the formula:

[0030] Examples of the dicarboxylic acid component represented by formula (3) include phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-o- Oxydibenzoic acid, 3,3'-oxydibenzoic acid, 3,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylmethane-3,3'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenylsulfone-3,3'-dicarboxylic acid, 4,4'-thiodibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyisophthalic acid Aromatic dibasic acids such as taric acid, 3-hydroxyisophthalic acid, and 2-hydroxyterephthalic acid; oxalic acid, methylmalonic acid, maleic acid, fumaric acid, malic acid, tartaric acid, thiomalic acid, diglycolic acid, adipic acid, octamethylenedicarboxylic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dimethylmalonic acid, 3,3-diethylsuccinic acid, 2,2-dimethylglutaric acid, and 2-methyladipic acid. and alicyclic dibasic acids such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid, and norbornanedicarboxylic acid; and reactive derivatives thereof. Examples of the reactive derivatives include acid halides, esters, amidations, and acid anhydrides.

[0031] <Copolymerization Unit> The polyamide resin of the present invention may contain copolymerization units other than the structural unit represented by formula (1). Examples of copolymerization units that the polyamide resin of the present invention may contain include structural units formed by bonding the structures represented by the above (1a), (1b), and the following formulae (1c) to (1e) via an amide bond (-HN-CO- or >N-CO-), other than the structural unit represented by formula (1). (-HN-) ｐ R ５１ (-NH-) ｑ ...(1c) (-CO-) ｒ R ５２ (-CO-) ｓ ...(1d) (-HN-) ｔ R ５３ (-CO-) ｕ ...(1e) (In formula (1c), R ５１ represents a p+q valent organic group, p is 1 or 2, and q is 1 or 2, and in formula (1d), R ５２ is an organic group having a valence of r+s, r is 1 or 2, and s is 2; in formula (1e), R ５３ is an organic group having a valence of t+u, where t is 1 or 2 and u is 1 or 2.

[0032] R ５１ , R ５２ and R ５３ Examples of the groups independently include an aliphatic hydrocarbon group having 2 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an aromatic heterocyclic group having 6 to 20 carbon atoms and containing N and / or O and / or S.

[0033] The structure represented by formula (1c) is a structure derived from a polyamine compound other than the compound represented by formula (2). Examples of polyamine compounds other than the compound represented by formula (2) include 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 2,6-diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminobenzanilide, and 3,3'-diaminodiphenyl. Methane, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,3'-diaminobenzanilide, 3,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl ether, 3,4'-diaminobenzophenone, 3,4'-diaminobenzanilide, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl ] sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,Aromatic diamines such as 4'-diaminobiphenyl, 4,4'-(p-phenylenediisopropylidene)bisaniline, 4,4'-(m-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, and derivatives in which a substituent has been introduced into the 9,9-bis(4-aminophenyl)fluorene skeleton; aliphatic diamines such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,9-nonanediamine, 1,12-dodecamethylenediamine, and metaxylenediamine; isophoronediamine, norbornanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, alicyclic diamines such as amine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, and piperazine; polyaminephenols such as 2,2-bis(3-amino-4-hydroxyphenyl)propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane; and polyfunctional amines such as 1,2,4-triaminobenzene, 3,4,4'-triaminodiphenyl ether, 1,2,3,4-tetraaminobenzene, 3,3',4,4'-tetraaminodiphenyl ether, and 3,3',4,4'-tetraaminobenzophenone.

[0034] The structure represented by formula (1d) is a structure derived from any of tricarboxylic acids, tetracarboxylic acids, and their reactive derivatives. Examples of tricarboxylic acids, tetracarboxylic acids, and their reactive derivatives include tricarboxylic acids such as trimellitic acid, benzophenone tricarboxylic acid, diphenyl sulfone tricarboxylic acid, diphenyl ether tricarboxylic acid, diphenyl sulfide tricarboxylic acid, and hydrogenated trimellitic acid; one or more polycarboxylic acid compounds selected from the group consisting of pyromellitic acid, hydrogenated pyromellitic acid, benzophenone tetracarboxylic acid, diphenylmethane tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, diphenyl ether tetracarboxylic acid, and diphenyl sulfide tetracarboxylic acid; and one or more tricarboxylic acids, tetracarboxylic acids, and their reactive derivatives selected from the group consisting of the above. Examples of reactive derivatives include acid halides, esters, amidations, and acid anhydrides.

[0035] The structure represented by formula (1e) is a structure derived from any one of a (di)amino(di)carboxylic acid, a reactive derivative thereof, and a lactam. Examples of the (di)amino(di)carboxylic acid, a reactive derivative thereof, and a lactam include one or more (di)amino(di)carboxylic acids, reactive derivatives thereof, and lactams selected from the group consisting of 4-aminobutanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminocapric acid, 11-aminoundodecanoic acid, aminobenzoic acid, diaminobenzoic acid, aminoterephthalic acid, diaminoterephthalic acid, aminoisophthalic acid, diaminoisophthalic acid, ε-caprolactam, ω-enantholactam, ω-undecalactam, ω-laurolactam, α-pyrrolidone, and α-piperidone. Examples of reactive derivatives include acid halides, esters, amidations, and acid anhydrides.

[0036] In the polyamide resin of the present invention, the total content of structural units derived from 4,4'-diaminodiphenyl ether and isophthalic acid, structural units derived from 3,4'-diaminodiphenyl ether and isophthalic acid, and structural units derived from 2,4'-diaminodiphenyl ether and isophthalic acid is preferably less than 20 mol% of all structural units. If the total content of these structural units is 20 mol% or more of all structural units, the solubility of the polyamide resin in organic solvents having a boiling point of less than 100°C may decrease, and the adhesive strength at high temperatures may also decrease.

[0037] <Constitution and Properties of Polyamide Resin> The polyamide resin of the present invention may be composed solely of the structural unit represented by formula (1). Alternatively, in addition to the structural unit represented by formula (1), it may contain one or more of the copolymerized units. The content of the structural unit represented by formula (1) in the polyamide resin is 1 to 100 mol%, preferably 5 to 100 mol%, and more preferably 10 to 100 mol%, relative to all structural units, which are the sum of the structural unit represented by formula (1) and the copolymerized units.

[0038] The number average molecular weight of the polyamide resin of the present invention is not particularly limited, and can be, for example, 3,000 or more, preferably 4,000 or more, more preferably 5,000 or more, and can be, for example, 100,000 or less, preferably 70,000 or less, more preferably 50,000 or less.

[0039] <Uses of Polyamide Resin> The uses of the polyamide resin of the present invention are not particularly limited, and examples thereof include adhesives, paints, sealants, insulating materials, protective materials, molding materials, tubes, films, sheets, filaments, particles, fibers, light-reflective materials, packaging materials, laminates, electric and electronic materials, semiconductor device materials, civil engineering and construction materials, medical supplies, household products, rolls, bearing materials, resin solutions, and resin dispersions.

[0040] When using the polyamide resin of the present invention for the above-mentioned applications, other components can be added to form a polyamide resin composition within the range that does not impair the effects of the polyamide resin of the present invention. Examples of other components include one or more selected from the group consisting of solvents, plasticizers, heat resistance agents, foaming agents, weathering agents, crystal nucleating agents, crystallization accelerators, mold release agents, lubricants, antistatic agents, flame retardants, flame retardant assistants, pigments, dyes, heat stabilizers, UV absorbers, light stabilizers, antioxidants, tackifiers, sealability improvers, anti-fogging agents, impact resistance improvers, pigments, fragrances, and functional additives such as reinforcing materials. The polyamide resin of the present invention can be prepared as a resin solution containing the polyamide resin and a solvent. Alternatively, the polyamide resin of the present invention can be prepared as a resin dispersion containing the polyamide resin and a dispersion medium.

[0041] <Polyamide Resin Solution> The polyamide resin of the present invention may be used in combination with a solvent to form a polyamide resin solution. The solvent constituting the polyamide resin solution is not particularly limited. Examples thereof include one or more solvents selected from the group consisting of saturated hydrocarbon solvents, aromatic hydrocarbon solvents, ester solvents, ketone solvents, alcohol solvents, halogen-based solvents, nitrogen-containing solvents, and highly polar solvents. Examples of suitable solvents include methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetrahydrofuran, dioxane, chloroform, dichloromethane, chlorobenzene, N,N'-dimethylacetamide, N-methyl-2-pyrrolidone, N,N'-dimethylformamide, N-methylcaprolactam, tetramethylurea, N,N'-dimethyl-2-imidazolidinone, γ-butyrolactone, hexamethylene phosphoramide, dimethyl sulfoxide, xylene, toluene, benzene, ethylbenzene, etc. The polyamide resin of the present invention has excellent solubility in organic solvents having a boiling point of less than 150°C, particularly less than 100°C, and therefore can be suitably used as a resin solution.

[0042] <Method for producing polyamide resin> The method for producing the polyamide resin of the present invention is a method for producing a polyamide resin by a method using a compound represented by formula (2): (In formula (2), R １ is an alkyl group having 1 to 12 carbon atoms, R ２ represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ an amine component containing a diamine represented by formula (3): (In formula (3), R ３ is a divalent organic group. １ -OH, halogen, -OR ４１ , -NHR ４２ and Z ２ -OH, halogen, -OR ４３ , -NHR ４４ That is. Z １ and Z ２ When is -OH, Z １ and Z ２ may be dehydrated to form -O-. ４１ ~R ４４ may be the same or different and are alkyl groups having 1 to 6 carbon atoms.

[0043] [Polymerization Method] In the method for producing a polyamide resin of the present invention, the method for reacting at least a polyamine component containing a diamine represented by formula (2) with a component containing a dicarboxylic acid component represented by formula (3) is not particularly limited. Examples include: (i) a method in which a carboxylic acid component containing a dicarboxylic acid component represented by formula (3) is converted into an acid chloride and reacted with a polyamine component containing a diamine represented by formula (2) in an organic solvent or without a solvent; (ii) a method in which a carboxylic acid component containing a dicarboxylic acid component represented by formula (3) is converted into an ester and reacted with a polyamine component containing a diamine represented by formula (2) in an organic solvent or without a solvent in the presence of a metal catalyst; and (iii) a method in which a carboxylic acid component containing a dicarboxylic acid component represented by formula (3) is converted into a carboxylic acid and reacted with a polyamine component containing a diamine represented by formula (2) in an organic solvent or without a solvent in the presence of a carbodiimide catalyst. In the present invention, it is preferable to use a method in which a polycarboxylic acid component containing a compound represented by formula (3) is converted into an acid chloride and reacted with a polyamine component containing a diamine represented by formula (2) in an organic solvent.

[0044] The organic solvent is not particularly limited, and a wide variety of solvents that can dissolve the raw materials used can be used, including, for example, one or more selected from the group consisting of tetrahydrofuran, N,N'-dimethylacetamide, N-methyl-2-pyrrolidone, N,N'-dimethylformamide, N-methylcaprolactam, tetramethylurea, N,N'-dimethyl-2-imidazolidinone, γ-butyrolactone, hexamethylene phosphoramide, dimethyl sulfoxide, xylene, toluene, and the like.

[0045] As the diamine component represented by formula (2), for example, the diamines described above in the section (Diamine represented by formula (2)) can be used. As the dicarboxylic acid component represented by formula (3), for example, the dicarboxylic acid component described above in the section (Dicarboxylic acid component represented by formula (3)) can be used. Furthermore, in the method for producing a polyamide resin of the present invention, each compound that derives the structure represented by formulas (1c) to (1e) contained in the copolymerization unit can be used as a copolymerization component. These components can be used in a reaction amount ratio such that the content of the structural unit represented by formula (1) in the polyamide resin is 1 to 100 mol%, preferably 5 to 100 mol%, and more preferably 10 to 100 mol%, relative to all structural units, which are the sum of the structural unit represented by formula (1) and the copolymerization unit.

[0046] [Adhesive] The adhesive of the present invention is a compound represented by the formula (1): (In formula (1), R １ is an alkyl group having 1 to 12 carbon atoms, R ２ represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ a group selected from the group consisting of -, R ３ is a divalent organic group. １ , R ２ , X and R ３ may be the same or different.) The adhesive of the present invention may further contain a solvent.

[0047] The polyamide resin having a structural unit represented by formula (1) contained in the adhesive of the present invention is the same as the polyamide resin described above in [Polyamide Resin and Production Method Thereof]. The solvent that may be contained in the adhesive of the present invention is the same as the solvent described above in <Polyamide Resin Solution> in [Polyamide Resin and Production Method Thereof].

[0048] The adhesive of the present invention may contain, in addition to a polyamide resin having a structural unit represented by formula (1) and a solvent used as needed, "other components" as needed. Examples of other components include resins, curable compounds, curing catalysts, thixotropic agents, fillers, antioxidants, moisture absorbers, adhesion promoters, curing catalysts, diluents, plasticizers, colorants, flame retardants, tackifiers, anti-sagging agents, mildew inhibitors, preservatives, fillers, and reinforcing materials. These other components may be used alone or in combination of two or more.

[0049] Among the other components, examples of the resin include one or more selected from the group consisting of epoxy resins, phenolic resins, urethane resins, unsaturated polyester resins, polyolefin resins, polyimide resins, acrylic resins, diene resins, polyether resins, etc. For example, when a curable resin such as an epoxy resin is used, a curing agent, a curing accelerator, or a curing catalyst can be used as necessary.

[0050] <Adhesive Strength Retention Rate> The adhesive of the present invention has a bond strength retention rate represented by the formula (A): SR ２００ (%) = F ２００ / F ２３ ×100...(A) (In formula (A), F ２３ is the tensile shear adhesive strength at 23°C (JIS K 6850:1999), and F ２００ is the tensile shear adhesive strength at 200°C (based on JIS K 6850:1999). ２００ is preferably 90% or more, and more preferably 100% or more. Tensile shear adhesive strength at 23°C (JIS K 6850:1999) F ２３ and tensile shear adhesive strength at 200°C (JIS K 6850:1999) F ２００ can be determined by the method described in the Examples below. １ and R ２ is an ethyl group, the adhesive strength retention rate SR ２００ can be 90% or more, in some cases 120% or more, and further in some cases 200% or more.

[0051] The adhesive of the present invention also comprises a compound represented by the formula (B): SR ２５０ (%) = F ２５０ / F ２３ ×100...(B) (In formula (B), F ２３ is the tensile shear adhesive strength at 23°C (JIS K 6850:1999), and F ２５０ is the tensile shear adhesive strength at 250°C (in accordance with JIS K 6850:1999). ２５０ is preferably 50% or more, and more preferably 100% or more. Tensile shear adhesive strength at 250°C (JIS K 6850:1999) F ２５０ can be determined by the method described in the Examples below.

[0052] <Uses of Adhesive> The adhesive of the present invention can be used in a variety of applications. For example, it can be used in semiconductor-related applications, electronic components, electronic materials, electronic devices, pharmaceuticals, food, medical care, cosmetics, optical equipment, chemical-related applications, precision equipment, civil engineering and construction, textiles, clothing, industrial applications, etc. For example, it can be used as an adhesive for electronic circuit board components, semiconductor components, flexible printed circuit boards, coverlay films, bonding sheets, building materials, industrial adhesives, textile adhesives, etc. The adhesive of the present invention can be in the form of a solution, paste, film, or powder.

[0053] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these. Unless otherwise specified, "parts" in each example refers to "parts by mass." In addition, in Table 1, the numerical values ​​in the columns relating to each component represent the "amount blended."

[0054] [Examples and Comparative Examples Related to Polyamide Resin] <Starting Compound Synthesis Example 1> 3,4'-Diaminophenyl ether (25.3 g, 126 mmol), ethanol (200 mL), and di-tert-butyl dicarbonate (65 mL, 283 mmol) were added to a 500 mL recovery flask, and the mixture was stirred at room temperature for 19 hours. The solvent was distilled off under reduced pressure. Then, the mixture was separated by column chromatography (SiO２ The crude product was purified with ethyl acetate (ethyl acetate only) to obtain a brown solid, bis(3,4'-(tert-butoxycarbonyl)aminophenyl)ether [1] (yield: 46.6 g, 92%, melting point (mp) = 125°C to 132°C).

[0055] <Starting Compound Synthesis Example 2> Sodium hydride (approximately 40% mineral mixture) (12.7 g, 317 mmol) was added to a 500 mL recovery flask, and the mixture was washed with dry hexane under a nitrogen stream and decanted three times. The mixture was then dried under reduced pressure, and dry dimethylformamide (DMF) (300 mL) was added under a nitrogen stream and stirred. Bis(3,4'-(tert-butoxycarbonyl)aminophenyl) ether [1] (46.6 g, 116 mmol) obtained in Starting Compound Synthesis Example 1 and dry DMF (200 mL) were dissolved in a 300 mL recovery flask. This solution was added dropwise to a 500 mL recovery flask over 35 minutes under a nitrogen stream. Iodomethane (17.0 mL, 273 mmol) was added dropwise under a nitrogen stream and stirred at room temperature for 4 hours. The reaction was stopped by adding water, extracted with diethyl ether, washed twice with 1 M hydrochloric acid and once with saturated aqueous sodium chloride, and dried over anhydrous magnesium sulfate. Thereafter, the mixture was filtered, the solvent was distilled off under reduced pressure, and the residue was dried under reduced pressure to obtain a brown viscous liquid, bis(3,4'-((tert-butoxycarbonyl)methylamino)phenyl)ether [2] (bis(3,4'-((tert-butoxycarbonyl)methylamino)phenyl)ether: crude yield: 45.7 g, crude yield: 92%).

[0056] <Starting Compound Synthesis Example 3> Bis(3,4'-((tert-butoxycarbonyl)methylamino)phenyl) ether [2] (45.3 g, 106 mmol) obtained in Synthesis Example 2 and dry methylene chloride (400 mL) were placed in a 1 L recovery flask and cooled in an ice-water bath. Then, trifluoroacetic acid (100 mL, 1.61 mol) was added, and the mixture was stirred at room temperature for 19 hours. The mixture was neutralized with 4.1 M aqueous sodium hydroxide solution (400 mL), extracted with methylene chloride, washed twice with water, and dried over anhydrous magnesium sulfate. Then, the mixture was filtered, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (SiO ２ The crude product was purified with a 2:1 mixture of hexane and ethyl acetate to obtain a yellow solid, bis(3,4'-methylaminophenyl)ether [3] (yield: 15.6 g, 65%, melting point mp = 107.1°C to 108.5°C).

[0057] <Starting Compound Synthesis Example 4> 3,4'-Diaminophenyl ether (7.47 g, 37.3 mmol), dry methylene chloride (150 mL), and dry pyridine (10.0 mL, 124 mmol) were placed in a 300 mL recovery flask and stirred while immersed in an ice-water bath. Acetic anhydride (12.0 mL, 127 mmol) was added dropwise, and the mixture was stirred at room temperature for 22 hours. 1 M hydrochloric acid was added, and the precipitated solid was collected by filtration and washed with methylene chloride and water. The solvent was distilled off under reduced pressure to obtain bis(3,4'-acetylaminophenyl)ether [4] (crude yield: 10.2 g, 96%) as a gray solid.

[0058] <Starting Compound Synthesis Example 5> Bis(3,4'-acetylaminophenyl) ether [4] (8.80 g, 31.0 mmol) obtained in Synthesis Example 4 and dry tetrahydrofuran (dry THF) (50.0 mL) were added to a 20 mL recovery flask and stirred while immersed in an ice-water bath. Under a nitrogen stream, 0.9 M borane-THF complex solution (100.0 mL, 90.0 mmol) was added dropwise and stirred for 1 hour. The mixture was stirred at 60°C for 21 hours, and then 6 M hydrochloric acid (30 mL) was added and stirred for 1 hour. The mixture was neutralized with a saturated aqueous sodium bicarbonate solution, extracted with methylene chloride, washed with water, and dried over anhydrous magnesium sulfate. Thereafter, the mixture was filtered, and the solvent was removed under reduced pressure. The residue was purified by column chromatography (SiO ２ The crude product was purified with a 2:1 mixture of hexane and ethyl acetate to obtain bis(3,4'-ethylaminophenyl)ether [5] (yield: 6.79 g, 86%, melting point: mp = 73.4°C to 75.1°C) as a white solid.

[0059] Example A1: A 50 mL pear-shaped flask and a 50 mL pear-shaped flask were dried under reduced pressure using a heat gun while purging with argon. In a glove box, the pear-shaped flask was charged with bis(3,4'-methylaminophenyl)ether [3] (2.28 g, 10.0 mmol) obtained in Synthesis Example 3, dry triethylamine (6.6 mL, 47 mmol), 4-dimethylaminopyridine (DMAP) (625 mg, 5.12 mmol), and dry methylene chloride (6.0 mL). The mixture was stirred in an ice-water bath. Isophthalic acid dichloride (2.36 g, 11.6 mmol) and dry methylene chloride (15.0 mL) were added to the pear-shaped flask and stirred until dissolved. The solution (14.0 mL, 10.8 mmol) from the pear-shaped flask was added dropwise under a nitrogen stream and stirred at 25°C for 24 hours. Dry methanol (4.0 mL) was added under a nitrogen stream, followed by dry methylene chloride (15.0 mL). The resulting solid was dissolved in methylene chloride (15 mL), and the solution was added dropwise to a 90 v / v % aqueous methanol solution (300 mL), followed by filtration to obtain a pale yellow solid polyamide resin (yield: 1.34 g, yield: 37%, number average molecular weight: M ｎ =23,000, weight average molecular weight M ｗ / number average molecular weight M ｎ = 2.11).

[0060] １ HNMR (600MHz, CDCl ３ ) δ7.37 (m, 1nH), 7.24-7.05 (m, 3nH), 7.01-6.94 (m, 1nH), 6.90-6.82 (m, 2nH), 6.78- 6.73 (m, 1nH), 6.72-6.66 (m, 1nH), 6.63-6.52 (m, 3nH), 3.42 (s, 3nH), 3.39 (s, 3nH).

[0061] Example A2: A 50 mL pear-shaped flask and a 50 mL pear-shaped flask were dried under reduced pressure using a heat gun while purging with argon. In a glove box, the pear-shaped flask was charged with bis(3,4'-ethylaminophenyl)ether [5] (2.562 g, 10.0 mmol) obtained in Synthesis Example 5, dry triethylamine (6.6 mL, 47 mmol), and DMAP (637 mg, 5.21 mmol). Dry methylene chloride (6.0 mL) was added under a nitrogen stream, and the mixture was stirred while immersed in an ice-water bath. Isophthalic acid dichloride (4.71 g, 23.2 mmol) was added to the pear-shaped flask, and dry methylene chloride (30.0 mL) was added under a nitrogen stream. The mixture was stirred until dissolved. The solution (14.0 mL, 10.8 mmol) from the pear-shaped flask was added dropwise to the pear-shaped flask under a nitrogen stream for 6 minutes and then stirred at 25°C for 1 day. Dry methanol (4.0 mL) and dry methylene chloride (10.0 mL) were added under a nitrogen stream. The mixture was added dropwise to an 80 v / v % aqueous methanol solution, and filtered to obtain a yellow-green solid polyamide resin (yield: 2.53 g, yield: 66%, number-average molecular weight: M ｎ =9,090, weight average molecular weight M ｗ / number average molecular weight M ｎ = 1.49).

[0062] １ HNMR (600MHz, CDCl ３ ) δ7.42-7.30 (m, 1nH), 7.25-7.07 (m, 3nH), 7.04-6.81 (m, 3nH), 6.80-6.74 (m, 1nH) , 6.73-6.66 (m, 1nH), 6.65-6.52 (m, 3nH), 4.01-3.84 (m, 4nH), 1.27-1.11 (m, 6nH).

[0063] Reference Example A1: A 10 mL recovery flask and a 20 mL pear-shaped flask were dried under reduced pressure using a heat gun while purging with argon. In a glove box, the recovery flask was charged with bis(3,4'-(tert-butoxycarbonyl)aminophenyl)ether [1] (1.60 g, 4.00 mmol) obtained in Synthesis Example 1, dry triethylamine (2.5 mL, 18 mmol), DMAP (246 mg, 2.0 mmol), and dry NMP (N-methyl-2-pyrrolidone) (2.5 mL), followed by stirring in an ice-water bath. Isophthalic acid dichloride (1.08 g, 5.32 mmol) and dry NMP (4.5 mL) were added to the recovery flask and stirred until dissolved. This solution (3.8 mL) was added dropwise to the recovery flask under a nitrogen stream and stirred at 50°C for 20 hours. Dry methanol (2.0 mL) was added under a nitrogen stream, followed by dry NMP (2.1 mL). The precipitate was dropped into methanol (175 mL) for precipitation purification, and then filtered to obtain N-Boc polyamide (yield: 1.11 g, yield: 52%, number average molecular weight: M ｎ =8,120, weight average molecular weight M ｗ / number average molecular weight M ｎ = 1.29).

[0064]

[0065] １ HNMR (600MHz, CDCl ３ ) δ8.03 (s, 1nH), 7.85 (dd, J=7.2and1.8Hz, 2nH), 7.55-7.50 (m, 1nH), 7.42-7.37 (m, 1nH), 7.23 (d, J = 9.0 Hz, 2 nH), 7.07 (d, J = 9.0 Hz, 2 nH), 7.05-7.00 (m, 3 nH), 1.27-1.22 (m, 18 nH).

[0066] Next, N-Boc polyamide (46.1 mg) was placed in a vial and heated at 180°C and -0.1 MPaG for 1 hour. After cooling to room temperature, dry air was introduced to return the pressure to normal, yielding N-H polyamide (30.6 mg).

[0067] IR (KBr) 3423, 1736, 1719, 1656, 1599, 1543, 1509, 1439, 1212, 1149, 877, 722cm －１ .

[0068] [Examples and Comparative Examples Related to Adhesives] <Examples B1-B2, Comparative Examples B1-B3> The adhesive components shown in Table 1 were charged in the mass ratios shown in Table 1 and mixed by stirring to prepare adhesives according to Examples B1-B2 and Comparative Examples B1-B3. The charged amounts of Polyamide Resin A to Polyamide Resin C and PESU are in mg (milligrams), and the charged amounts of Solvent A to Solvent C are in μl (microliters). The adhesive strength retention rate SR of each of the obtained adhesives was ２００ , adhesive strength retention rate SR ２５０ The evaluation of the solvent solubility was calculated / measured as follows. The results are shown in Table 1.

[0069] (Adhesive components) Polyamide resin A: Polyamide resin produced in Example A1 Polyamide resin B: Polyamide resin produced in Example A2 Polyamide resin C: Polyamide resin produced in Reference Example A1 PESU: Polyethersulfone resin Solvent A: Chloroform (boiling point 70°C) Solvent B: N-methyl-2-pyrrolidone (boiling point 202°C) Solvent C: Toluene (boiling point 111°C)

[0070] (Adhesive strength retention rate SR ２００ Two cold-rolled steel plates (25 mm wide x 100 mm long x 1.6 mm thick) were prepared, the surfaces of which had been polished by sandblasting and then degreased with acetone. An adhesive prepared with a solvent was uniformly applied to each cold-rolled steel plate within an area of ​​25 mm x 12.5 mm using a glass rod. After leaving them in an environment of 23°C for 1 hour, they were bonded together and subjected to a pressure of 10 kgf / cm. ２ The test piece was clamped at a pressure of 1000 kJ / min. The clamped test piece was cured in an oven at 250°C for 7 hours, removed, and then allowed to cool in an environment at 23°C for 1 day to obtain a tensile shear adhesion test piece. The prepared test piece was used to measure the tensile shear adhesive strength F at a pulling rate of 50 mm / min and 23°C in accordance with JIS K 6850:1999. ２３ and tensile shear bond strength F at 200 ° C. ２００Then, the following formula (A): SR ２００ (%) = F ２００ / F ２３ × 100 (%) ... (A), the adhesive strength retention rate SR ２００ In Comparative Examples B1 and B2, the polyamide resin was not dissolved in the solvent, and an adhesive could not be prepared. Therefore, the tensile shear adhesive strength could not be measured, and the adhesive strength retention rate SR ２００ In the present invention, SR ２００ A passing score is 90% or above.

[0071] (Adhesive strength retention rate SR ２５０ Two cold-rolled steel plates (25 mm wide x 100 mm long x 1.6 mm thick) were prepared, the surfaces of which had been polished by sandblasting and then degreased with acetone. An adhesive prepared with a solvent was uniformly applied to each cold-rolled steel plate within an area of ​​25 mm x 12.5 mm using a glass rod. After leaving them in an environment of 23°C for 1 hour, they were bonded together and subjected to a pressure of 10 kgf / cm. ２ The test piece was clamped at a pressure of 1000 kJ / min. The clamped test piece was cured in an oven at 250°C for 7 hours, removed, and then allowed to cool in an environment at 23°C for 1 day to obtain a tensile shear adhesion test piece. The prepared test piece was used to measure the tensile shear adhesive strength F at a pulling rate of 50 mm / min and 23°C in accordance with JIS K 6850:1999. ２３ and tensile shear adhesive strength F at 250 ° C. ２５０ Then, the following formula (B): SR ２５０ (%) = F ２５０ / F ２３ × 100 (%) ... (B), the adhesive strength retention rate SR ２５０ In Comparative Examples B1 and B2, the polyamide resin was not dissolved in the solvent, and an adhesive could not be prepared. Therefore, the tensile shear adhesive strength could not be measured, and the adhesive strength retention rate SR ２５０ It was not possible to calculate this, so it was marked as "-".

[0072] (Solvent Solubility Evaluation) The solvent solubility of the obtained adhesive was evaluated by visually observing the state of the adhesive. If the adhesive was uniformly dissolved in the solvent and no turbidity occurred, it was rated A; if the adhesive was uniformly dissolved in the solvent but turbidity occurred, it was rated B; and if the polyamide resin was not dissolved in the solvent, it was rated C. In the present invention, ratings A and B are acceptable, and rating C is unacceptable.

[0073]

[0074] As can be seen from Table 1, all of the adhesives containing the polyamide resin of the present invention had a high adhesive strength retention rate (SR) ２００ The adhesive strength retention rate (SR) of the polyamide resins of the present invention is over 100%, which indicates that the adhesive has excellent adhesive strength even at high temperatures. The adhesive also has excellent solvent solubility. Furthermore, the adhesive using the polyamide of Example A1 having an N-methylamide bond has an adhesive strength retention rate (SR) of 100%. ２５０ The adhesive strength retention rate (SR) also exceeded 100%. On the other hand, the adhesive containing the polyamide resin having no N-alkylamide bond obtained in Reference Example A1 and the adhesive containing polyethersulfone were not soluble in chloroform having a boiling point of 70°C. Furthermore, the adhesive obtained by dissolving polyethersulfone in a mixed solvent of N-methyl-2-pyrrolidone having a boiling point of 202°C and toluene having a boiling point of 111°C (boiling point 111°C) passed the solvent solubility evaluation, but the adhesive strength retention rate (SR) ２００ was less than 100%, and the adhesive strength at high temperatures was poor.

[0075] Although the present invention has been described in detail above, various changes can be made in the above configuration without departing from the scope of the present invention. Accordingly, all matter contained in the above description or shown in the accompanying drawings should be interpreted as illustrative only.

Claims

1. Formula (1): (In formula (1), R １ is an alkyl group having 1 to 12 carbon atoms, R ２ represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ a group selected from the group consisting of -, R ３ is a divalent organic group. １ , R ２ , X and R ３ may be the same or different.) A polyamide resin having a structural unit represented by the following formula:

2. A polyamide resin solution comprising the polyamide resin according to claim 1 and a solvent.

3. Formula (2): (In formula (2), R １ is an alkyl group having 1 to 12 carbon atoms, R ２ represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ and an amine component containing a diamine represented by formula (3): (In formula (3), R ３ is a divalent organic group. １ -OH, halogen, -OR ４１ , -NHR ４２ and Z ２ -OH, halogen, -OR ４３ , -NHR ４４ That is. Z １ and Z ２ When is -OH, Z １ and Z ２ may be dehydrated to form -O-. ４１ ~R ４４ may be the same or different and are alkyl groups having 1 to 6 carbon atoms.

4. Formula (1): (In formula (1), R １ is an alkyl group having 1 to 12 carbon atoms, R ２ represents an alkyl group having 1 to 12 carbon atoms, and X represents -O-, -CO-, or -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ a group selected from the group consisting of -, R ３ is a divalent organic group. １ , R ２ , X and R ３ may be the same or different from each other.

5. The adhesive of claim 4, further comprising a solvent.

6. Formula (A): SR ２００ (%) = F ２００ / F ２３ ×100...(A) (In formula (A), F ２３ is the tensile shear adhesive strength at 23°C (JIS K 6850:1999), and F ２００ is the tensile shear adhesive strength at 200°C (based on JIS K 6850:1999). ２００ The adhesive according to claim 4 or 5, wherein the ratio of the total surface area to the total surface area is 90% or more.

7. R in formula (1) １ and R ２ is an ethyl group, and the adhesive strength retention rate SR ２００ The adhesive of claim 6, wherein the tensile strength is 90% or more.

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