JPS61148280A - Epoxy resin adhesive - Google Patents

Abstract

PURPOSE:To provide the titled adhesive, composed of an epoxy resin, a thiol- containing highly crosslinked polysulfide polymer, a (modified) primary amine and a tertiary amine, having low viscosity, bonding firmly to wet concrete surface, and curable rapidly at a low temperature. CONSTITUTION:The objective adhesive is composed of (A) an epoxy resin having >=2 epoxy groups in the molecule, (B) a highly crosslinked polysulfide polymer crosslinked with >=5mol% crosslinking agent (preferably polyfunctional alkyl halide) and having >=2 thiol groups in the molecule [preferably a polymer of formula (R is alkyl constaining 0-3 ether groups and 0-2 thiol groups; x is 1-3; n is 1-20) having an average molecular weight of 300-7,000] (C) a (modified) primary amine (e.g. diethylenetriamine), and (D) a tertiary amine (e.g. N,N-dimethyldodecylamine).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an epoxy resin adhesive. More specifically, it is an epoxy resin adhesive that has low viscosity, strongly adheres to wet concrete surfaces, and quickly hardens at low temperatures.

[Prior Art] Epoxy resins have excellent adhesive properties, chemical resistance, durability, etc., and are therefore widely used as paints, electrical parts, adhesives, and the like. Epoxy resin adhesives adhere well to many materials such as metal, glass, ceramics, wood, concrete, and plastic, and are used as adhesives for electrical and electronic parts, civil engineering and construction adhesives, and aircraft adhesives. ing. In particular, epoxy resin has good alkali resistance, and when mixed with an appropriate hardening agent or modifier, a hardened product with toughness and flexibility can be obtained, and it also blends well with concrete. It is used as an adhesive for crack injection repair, an adhesive for repairing floating concrete, a protective coating for concrete floors, an adhesive for tiles, and an adhesive for joining old and new concrete. However, conventional commercially available civil engineering and construction adhesives cure slowly at low temperatures, especially below 5°C, and have strong adhesion to dry concrete surfaces, but do not adhere well to wet concrete surfaces. There was a tendency for power to decrease significantly.

When it comes to adhesives for civil engineering and construction, the viscosity of the adhesive has a major effect on workability and adhesion. Epoxy resin adhesives with low viscosity have good workability and penetrate into small cracks in concrete, improving adhesion. Normally, in order to reduce the viscosity of epoxy resins, it is common to mix reactive or non-reactive diluents, but mixing diluents can improve the strength of the cured product, water resistance, heat resistance, and chemical resistance. This is not a preferable method because it reduces the For this reason, there has been a desire for an epoxy resin adhesive that does not contain a diluent, has low viscosity, and has strong adhesive strength as a higher performance epoxy resin adhesive.

A mixture of epoxy resin and polyamide resin is known as an epoxy resin adhesive that adheres to concrete. However, polyamide resin has a high viscosity, and it has been difficult to obtain an epoxy resin adhesive with low viscosity that adheres well to wet concrete surfaces.

Furthermore, epoxy resin adhesives containing polyamide resins are slow to cure at temperatures below 5° C., and there are many problems in using polyamide resins as winter epoxy resin adhesives.

Furthermore, epoxy resin adhesives using polyamines as a curing agent are known as adhesives for concrete. but,
Polyamine-based epoxy resin adhesives have difficulty achieving the desired performance unless the amount of polyamine-based curing agent mixed with the epoxy resin base resin is strictly controlled. Moreover, they are greatly affected by water and humidity, so they cannot be used under high humidity. When used, curing problems often occurred. Furthermore, polyamine-based epoxy resin adhesives also harden slowly at temperatures below 5° C., and there are many problems in using polyamine-based epoxy resin adhesives as winter epoxy resin adhesives.

It is known that when a polysulfide polymer with a crosslinking agent content of 2 mol% is used as an epoxy resin adhesive composition, an epoxy resin adhesive with low viscosity and good adhesion to wet concrete surfaces can be obtained. However, an epoxy resin adhesive composition containing a polysulfide polymer with a crosslinking agent content of 2 mol % has the disadvantage that curing is slow at low temperatures, and curing is too slow when used in extremely cold seasons.

As a method to increase the curing speed of epoxy resin 1
- A method of blending a polythiol compound with an epoxy resin is known. For example, when a polyalkylene glycol type polythiol compound or an ester type polythiol compound is used as an epoxy resin composition, curing becomes faster. However, epoxy resin adhesives containing polyalkylene glycol-type polythiol compounds have extremely poor water-resistant adhesion properties, making it impossible to use them as adhesives for wet concrete surfaces. Furthermore, epoxy resin adhesives containing ester-type polythiol compounds are extremely sensitive to alkalis, and their cured products dissolve in alkaline solutions. Since the surface of concrete is alkaline with a pH of 11 or higher, epoxy resin adhesives containing ester-type polythiol compounds cannot be used as adhesives for concrete.

[Problems to be Solved by the Invention] As a result of repeated studies on epoxy resin adhesives that have low viscosity, strongly adhere to wet surfaces of concrete, and quickly harden at low temperatures, the inventors found that 5 mol. When a highly crosslinked polysulfide polymer crosslinked with a crosslinking agent of % or more and primary amines or modified primary amines and tertiary amines are used as an epoxy resin adhesive composition, it has a low viscosity and is strong on wet concrete surfaces. It has been discovered that an epoxy resin adhesive that adheres and quickly cures at low temperatures can be obtained, and the present invention has been achieved.

[Means for solving problems] The present invention has the following configuration.

(A) an epoxy resin having at least two epoxy groups in the molecule; (B) a highly crosslinked polysulfide polymer having at least two thiol groups in the molecule crosslinked with 5 mol% or more of a crosslinking agent; An epoxy resin adhesive comprising (C) primary amines or modified primary amines and (D) tertiary amines.

The epoxy resin of the present invention has at least two or more epoxy groups in the molecule, and includes, for example, bisphenol A, bisphenol AD, halogenated bisphenol A1 bisphenol F, halogenated bisphenol F rsorcinol, hydroquinone, pyrocatechol,
4. ．． Epoxy resins obtained by adding epichlorohydrin to polyhydric phenols such as 4'-dihydroxybisphenol and 1,5-dihydroxynaphthalene, and epoxy resins obtained by adding epichlorohydrin to polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin. , epoxy resins obtained by adding epichlorohydrin to oxybenzoic acid, phthalic acid, etc., epoxy resins obtained by oxidizing butadiene derivatives, cyclohexene derivatives, etc. with an appropriate peroxidant, epichlorohydrin to amines such as aniline, xylene diamine, etc. There are epoxy resins obtained by adding .

The polysulfide polymer of the present invention is a polysulfide polymer having a total of two or more thiol groups in the molecule, and is synthesized, for example, by the reaction of bis(dichloroethyl) formal, sodium polysulfide, and a suitable crosslinking agent.

Furthermore, the polysulfide polymer of the present invention is crosslinked with a crosslinking agent in an amount of 5 mol % or more based on the polymer. If the crosslinking agent content is 5 mol % or more, the adhesive will not slow down in curing even at low temperatures, and can be used freely even in extremely cold seasons. The crosslinking agent is 5
If it is less than mol %, curing will be delayed at low temperatures, making it undesirable to use it in extremely cold seasons.

Furthermore, as a preferable polysulfide polymer used in the present invention, the general formula % formula % (wherein R is an alkyl group containing 0 to 3 ether groups and 0 to 2 thiol groups, and the average of X is 1 .0-3
．． 0, n is 1 to 20), the average molecular weight is 300 to 7000, and the content of the crosslinking agent is 5 to 100 mol%.

More preferably, the general formula % formula % (However, RSR' is an alkyl group containing 0 to 2 thiol groups, and the average of X is 1.5 to 2.5, m, p
is O or 1, n is 1 to 20), and usually has an average molecular weight of 500 to 20.
2000, and the content of the crosslinking agent used is 20 to 60 mol%.

As the crosslinking agent used in the polysulfide polymer used in the present invention, polyfunctional alkyl halides are mainly used, and trivalent or tetravalent aliphatic hydrocarbon groups or aromatic hydrocarbon groups are used in the polysulfide polymer. Forms crosslinking points.

The hydrocarbon group forming the crosslinking point is CH2CT (C
H2-.

CH2CH2CHCH2-9 CH20CH20CH2CH2- CH3CH2CCH2OCH2OCH2CH2-.

CH20CH20CH2CH2- CH20CH20CH2CH2- CH3C-CH2OCH2OC)12CH2.

CH20CH20CH2C82- etc. can be mentioned.

In the present invention, in addition to the highly crosslinked polysulfide polymer, primary amines or modified primary amines and tertiary amines are mixed together in the epoxy resin.

Examples of the primary amines used in the present invention include:
Aliphatic primary amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine, isophoronediamine, cyclohexylamine, 1,2-diaminocyclohexane, 1
, 3-bis(aminomethyl)cyclohexane, bis(4
Alicyclic primary amines such as -amino-3-methylcyclohexyl)methane, m-xylene diamine, aniline,
Examples include primary amines having an aromatic ring such as p,p'-diaminodiphenylmethane, m-phenylenediamine, 4,4'-methylenedianiline, and benzylamine.

Examples of the modified primary amines used in the present invention include diethylenetriamine, triethylenetetramine,
, 3-bis(aminomethyl)cyclohexane, 1,2-
Diaminocyclohexane, m-xylene diamine, p+
r) Epoxy-modified primary amines obtained by modifying primary amines such as '-diaminodiphenylmethane with glycidyl allyl ether, glycidyl butyl ether, glycidyl phenyl ether, etc., or diethylenetriamine, triethylenetetramine, bishexamethylenetriamine, m-xylene diamine , 1,2-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, aniline, p,p''-diaminodiphenylmethane, and other dehydrated condensates obtained by reacting primary amines with phenols and aldehydes. Illustrated.

Examples of the tertiary amines used in the present invention include:
N, N-dimethyldodecylamine, N.

Aliphatic tertiary amines such as N, N', N'-tetramethylhexamethylene diamine, N-methylpiperidine,
Examples include alicyclic tertiary amines such as N,N'-dimethylpiperazine, aromatic tertiary amines such as benzyldimethylamine, dimethylaminomethylphenol, and 2,4.6-tris(dimethylaminomethyl)phenol. be done.

In addition, the amines used in the present invention include compounds in which a primary amino group and a tertiary amino group are present in the same molecule;
For example, 1-(2-aminoethyl)piperazine, N,
N-dimethyl-p-phenylenediamine, N,N-dimethylamino-n-propylamine, etc. can be used in place of the mixture of primary and tertiary amines. Moreover, a compound in which a primary amino group and a tertiary amino group are present in the same molecule can also be used instead of primary amines.

In the present invention, the amount of polysulfide polymer blended in the epoxy resin varies depending on the type of epoxy resin, but is usually 5 parts by weight per 100 parts by weight of the epoxy resin.
~100 parts by weight, preferably 10 to 70 parts by weight.

In the present invention, the blending amount of amines varies depending on the type of amine, but usually, the amount of primary amines or modified primary amines is 3 to 3 parts by weight per 100 parts by weight of the epoxy resin.
0 parts by weight, and the tertiary amines are used in an amount of 2 to 20 parts by weight per 100 parts by weight of the epoxy resin.

In the epoxy resin adhesive of the present invention, acidic compounds such as methyltetrahydrophthalic anhydride, boron trifluoride monoethylamine complex salt, 2-ethylhexanoic acid, etc. can be blended as a pot life control agent, if necessary. . The blending amount of these acidic compounds varies depending on the desired pot life, but usually epoxy resin 1
0.5 to 5.0 parts by weight per 00 parts by weight.

In the epoxy resin adhesive of the present invention, if necessary, zinc powder, aluminum powder, carbon black, glass fiber, titanium oxide, iron oxide, silica, coal tar, talc, calcium carbonate, pennite, etc. Filler extenders such as polyethylene powder, mica, pigments, reinforcing materials, etc. can be added.

[Effects of the Invention] The epoxy resin adhesive of the present invention is characterized in that primary amines or modified primary amines and tertiary amines are blended together with the epoxy resin and the highly crosslinked polysulfide polymer. do.

Epoxy resin adhesives containing only primary amines or modified primary amines hardly cure on wet concrete surfaces and cannot be used as adhesives for concrete; Although the final adhesive strength of the epoxy resin adhesive formulated in 2009 is quite high, the speed at which adhesive strength develops on wet concrete surfaces is slow, and moreover, it tends to be greatly affected by moisture on the concrete surface.

When combined with primary amines or modified primary amines and tertiary amines, it has the remarkable effect of forming an excellent adhesive with low viscosity, strong adhesion to wet concrete surfaces, and rapid curing at low temperatures. occurs.

Because the adhesive of the present invention has such excellent properties, it can be widely used as an adhesive for industrial and civil engineering/construction purposes, and is particularly suitable for adhering wet surfaces to concrete during the severe cold season.

[Example] Next, the present invention will be explained with reference to Examples and Comparative Examples.

Example 1 Polysulfide polymer containing 40 mol% of trichloropropane as a crosslinking agent in 100 parts by weight of bisphenol A type epoxy resin (Mikata Petrochemical Epoxy ■, trade name "EPOMTK R-130", epoxy equivalent: 183-193) 35 parts by weight, 10 parts by weight of pentaethylene hexamine, and 5 parts by weight of 2,4゜6-tris(dimethylaminomethyl)phenol were mixed and soaked in water at 20°C for one day to make a mortar that was sufficiently moistened with water. Glued. Place the bonded mortar at room temperature and humidity (20℃±1℃, humidity 90-100%)
After curing for a predetermined period of time under these conditions, the bending adhesive strength was measured. The results are summarized in Table 1. Furthermore, the tensile shear adhesive strength to a cold rolled steel plate after curing at 5° C. for 24 hours was measured. The results are summarized in Table 1.

Example 2 In Example 1, 1,3-bis(aminomethyl)cyclohexane was used instead of pentaethylene hexazine.
0 parts by weight was mixed, and the bending adhesive strength to mortar (wet conditions) and the tensile shear adhesive strength to cold rolled steel plates after curing at 5° C. for 24 hours were measured. The results are summarized in Table 1.

Example 3 In Example 1, instead of pentaethylene hexazine, 10 parts by weight of m-xylene diamine was mixed to improve the bending adhesive strength to mortar (tW wet condition) and cold hardening after curing at 5°C for 24 hours. The tensile shear adhesive strength to rolled steel plates was measured. The results are summarized in Table 1.

Reference Example 1 100 parts by weight of glycidylphenyl ether and 100 parts by weight of triethylenetetramine were mixed and stirred at room temperature for 4 hours to obtain an adduct of glycidylphenyl ether and triethylenetetramine (hereinafter referred to as modified triethylenetetramine).

Example 4 In Example 1, instead of pentaethylene hexazine, 10 parts by weight of modified triethylenetetramine was mixed to increase the bending adhesive strength to mortar (wet conditions) and 5°C.
After curing for 24 hours, the tensile shear adhesive strength to a cold rolled steel plate was measured. The results are summarized in Table 1.

Comparative Example 1 100 parts by weight of bisphenol A type epoxy resin (Mikata Petrochemical Epoxy ■, trade name "EPOMIK R-130", epoxy equivalent: 183-193) was mixed with 9 parts by weight of diethylenetriamine, and the mixture was bent and bonded to mortar. The tensile shear adhesion strength to a cold-rolled steel plate after curing for 24 hours at 5° C. was measured. The results are summarized in Table 1.

Reference Example 2 After thoroughly mixing 96 parts by weight of phenol and 136 parts by weight of m-xylene diamine, 35% formalin (30 parts by weight as formaldehyde) was added dropwise, and the mixture was reacted at 80°C for 4 hours. After the dropwise addition was completed, the reaction was further carried out at 90° C. for 4 hours. After the reaction was completed, the mixture was dehydrated under reduced pressure to obtain a dehydrated condensate of phenol, formaldehyde, and m-xylene diamine (hereinafter referred to as phenol-modified xylene diamine).

Example 5 Bisphenol A type epoxy resin (Mikata Petrochemical Epoxy ■, trade name "EPOMIK R-130", epoxy equivalent = 183-193) i00 parts by weight, polysulfide polymer containing 40 mol% of trichloropropane as a crosslinking agent 30 parts by weight, 10 parts by weight of phenol-modified xylene diamine, and 10 parts by weight of 2.4.6-)lis(dimethylaminomethyl)phenol were mixed, and the mortar was sufficiently soaked in water at 20°C for one day. was glued.

Place the bonded mortar at room temperature and humidity (20°C ± 1°C, humidity 90°C).
~100%) conditions for a predetermined period of time, and the bending adhesive strength was measured. The results are summarized in Table 1. After curing at 5° C. for 24 hours, the tensile shear adhesive strength to a cold rolled steel plate was measured. The results are summarized in Table 1.

Reference Example 3 After thoroughly mixing 108 parts by weight of 0-cresol and 142 parts by weight of 1,3-bis(aminomethyl)cyclohexane,
35% formalin (30 parts by weight as formaldehyde) was added dropwise and reacted at 80° C. for 5 hours. After the dropwise addition was completed, the reaction was further carried out at 90° C. for 5 hours. After the reaction is completed, dehydration is performed under reduced pressure to obtain 0-cresol, formaldehyde, 1,
A dehydrated condensate of 3-bis(aminomethyl)cyclohexane (hereinafter referred to as cresol-modified bis(aminomethyl)cyclohexane) was obtained.

Example 6 In Example 5, 10 parts by weight of cresol-modified bis(aminomethyl)cyclohexane was mixed instead of the phenol-modified xylene diamine, and the mixture was cured for 24 hours at 5° C. to increase bending adhesive strength to mortar (wet conditions). The tensile shear adhesive strength of the sample was measured on a cold rolled steel plate. The results are summarized in Table 1.

Example 7 In Example 5, 10 parts by weight of N,N-dimethyl-p-phenylene diamine was mixed instead of the phenol-modified xylene diamine, and the adhesive strength was increased by bending to the mortar (wet conditions) and 5°C*24 hours. The tensile shear adhesive strength to the subsequent cold-rolled steel plate was measured. The results are summarized in Table 1.

Example 8 In Example 5, 10 parts by weight of m-phenylene diamine was mixed instead of the phenol-modified xylene diamine to increase the bending adhesive strength to the mortar (wet conditions) and 5.
The tensile shear adhesive strength to the cold rolled steel plate was measured after 24 hours at °C.

The results are summarized in Table 1.

Example 9 In Example 5, 1 p, p'-diaminodiphenylmethane was used instead of the phenol-modified xylene diamine.
0 parts by weight was mixed, and the bending adhesive strength to mortar (wet conditions) and the tensile shear adhesive strength to cold rolled steel plates after curing at 5° C. for 24 hours were measured. The results are summarized in Table 1.

Reference Example 4 After thoroughly mixing 94 parts by weight of phenol and 228 parts by weight of 1,2-diaminocyclohexane, 35% formalin (
60 parts by weight of formaldehyde) was added dropwise to the mixture, and the mixture was reacted at room temperature for 4 hours. After the dropwise addition was completed, the reaction was further carried out at 80° C. for 2 hours. After the reaction was completed, the mixture was dehydrated under reduced pressure to obtain a dehydrated condensate of phenol, formaldehyde, and 1,2-diaminocyclohexane (hereinafter referred to as phenol-modified diaminocyclohexane).

Comparative Example 2 40 parts by weight of phenol-modified diaminocyclohexane was mixed with 100 parts by weight of bisphenol A type epoxy resin (Mikata Petrochemical Epoxy ■, trade name "EPOMIK R-130", epoxy equivalent = 183-193), and a mortar was prepared. flexural bond strength (wet conditions) and 24°C at 5°C.
The tensile shear adhesive strength to the cold rolled steel plate after time curing was measured. The results are summarized in Table 1.

Example 10 75 parts by weight of a polysulfide polymer containing 40 mol% of trichloropropane as a crosslinking agent, 15 parts by weight of m-xylene diamine, and 10 parts by weight of 2,4.6-)lis(dimethylaminomethyl)phenol were mixed. was used as a hardening agent. As the main agent, bisphenol A type epoxy resin (Mikata Petrochemical Epoxy ■, product name "EPOMTK R-"
130'', epoxy equivalent: 183-193) was used.

The mixing ratio of the base resin and curing agent was fixed at 271, and the bending adhesive strength to mortar (wet conditions) was measured in the same manner as in Example 1. The results are summarized in Table 2.

Example 11 In Example 10, the blending amount of m-xylene diamine was changed to 35 parts by weight, and the bending adhesive strength to mortar (wet conditions) was measured. The results are summarized in Table 2.

Example 12 60 parts by weight of a polysulfide polymer containing 40 mol% of trichloropropene as a crosslinking agent, 20 parts by weight of benzylamine, and 20 parts by weight of 2,4.6-)lis(dimethylaminomethyl)phenol were mixed and cured. It was used as a drug. As the main agent, bisphenol A type epoxy resin (Mikata Petrochemical Epoxy ■, product name "EPOMIK R-130" is used)
", epoxy equivalent: 183 to 193). The mixing ratio of the main resin and curing agent was fixed at 271, and the bending adhesive strength to mortar (wet conditions) was measured in the same manner as in Example 1. The results are shown in Table 1. Summarized in 2.

Example 13 In Example 12, the blending amount of Hensylamine was changed to 10 parts by weight, and the bending adhesive strength to mortar (wet conditions) was measured. The results are summarized in Table 2.

Example 14 Polysulfide polymer containing 40 mol% of trichloropropane as a crosslinking agent in 100 parts by weight of bisphenol A type epoxy resin (Mikata Petrochemical Epoxy ■, trade name "EPOMTK R-130", epoxy equivalent: 183-193) 35 parts by weight and 15 parts by weight of N,N-dimethyl-p-phenylenediamine were mixed, and the bending adhesive strength to mortar (wet conditions) was measured in the same manner as in Example 1.

The results are summarized in Table 2.

Comparative Example 3 In Example 10, the blending amount of m-xylene diamine was reduced to zero, and the bending adhesive strength to mortar (wet conditions) was measured. The results are summarized in Table 2.

Comparative Example 4 In Example 10, the blending amount of 2,4.6-)lis(dimethylaminomethyl)phenol was set to zero, and the bending adhesive strength to mortar (wet conditions) was measured. The results are summarized in Table 2.

Comparative Example 5 In Example 12, the amount of benzylamine blended was set to zero, and the bending adhesive strength to mortar (wet conditions) was measured. The results are summarized in Table 2.

Comparative Example 6 In Example 12, the blending amount of 2,4,6-tris(dimethylaminomethyl)phenol was set to zero, and the bending adhesive strength to mortar (wet conditions) was measured. The results are summarized in Table 2.

Comparative Example 7 35 parts by weight of phenol-modified xylene diamine was mixed with 100 parts by weight of bisphenol A type epoxy resin (Mikata Petrochemical Epoxy ■, trade name "EPOMIK R-130", epoxy equivalent: 183-193), and a mortar was prepared. The bending adhesion strength under wet conditions was measured. The results are summarized in Table 2. Commissioner of the Patent Office Michibe Uga 1, Indication of the case 1981 Patent application No. 270620M2, Title of the invention] - Po4 Niji resin adhesive 3, Person who made the amendment Relationship Patent Application Appointment Address 3-6, Nihonbashi Honseki-cho, Chuo-ku, Tokyo Name Higashi Thiokol Co., Ltd. Ne1 Representative Director? Yoshimizu Kitayu 4, Agent address: 2-2-5 Nihonbashi Muromachi, Chuo-ku, Tokyo, Date of amendment order: Voluntary action 6, Number of inventions increased by amendment No. 7, Subject of amendment: Description Column 8 of “Detailed Description of the Invention”
, Details of amendment (1) Page 9, line 12 r-CH2CHCH20CHz 0CH2CHCH2-
Correct J.

(2) On page 11, line 6, "Thoramine, tetraethylenepentamine, pentae" is corrected to "Thoramine, tetraethylenepentamine, methylaminopropylamine, pentae."

(3) On page 11, line 15, “Primary class with an aromatic ring such as niline, benzylamine, etc.” was replaced with “Primary class with an aromatic ring such as niline, N-benzylethylenediamine, benzylamine, etc.” “Mikata Petrochemical Epoxy ■ " is corrected to "Mikata Petrochemical Industry ■".

Claims (1)

[Claims] (A) an epoxy resin having at least two epoxy groups in the molecule; (B) a highly crosslinked polysulfide polymer having at least two thiol groups in the molecule crosslinked with 5 mol% or more of a crosslinking agent; An epoxy resin adhesive comprising (C) primary amines or modified primary amines and (D) tertiary amines.