JP3253919B2 - Adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition, and more particularly to an adhesive composition having a high adhesive strength and a fast curing property, which is suitable as an adhesive for rubber, metal or plastic. The present invention relates to an adhesive composition which is also excellent in curability, is low in odor and can have a low modulus, is suitable as an adhesive for construction, and a resin composition for a sealing agent which contains a specific resin and has excellent adhesive strength and tensile strength. .

[0002]

2. Description of the Related Art Epoxy resin adhesives exhibit adhesiveness to a wide variety of adherends, such as metals, plastics, wood, glass, concrete, and ceramics. Because of its excellent electrical insulation properties, it is used in various industrial fields. For example, it is used as a structural adhesive for automobiles and aircraft, an adhesive for civil engineering and construction, and the like. In recent years, heat resistance, excellent properties such as electrical insulation, and further less gas generation during curing,
Due to its properties such as low shrinkage, its use in the electric and electronic fields is increasing.

[0003]

Incidentally, it is considered that the adhesive force of the epoxy resin-based adhesive is mainly exhibited by a hydroxyl group generated by a curing reaction.
However, this hydroxyl group has low reactivity (acidity), and it is considered that the adhesive force is developed by physical affinity. Therefore, if a highly reactive functional group that can generate a substituent that is more chemically reactive than a hydroxyl group during curing is introduced into the molecule, it will have higher adhesive strength than conventional epoxy resin-based adhesives. It is expected that a quick-setting adhesive can be obtained. For a two-liquid room temperature-curable epoxy resin adhesive used outdoors, the balance between pot life and curing speed is important. When an aliphatic polyamine is used as a curing agent, there is an advantage that the curing speed is high, but there is a problem that the pot life is short. on the other hand,
When a cycloaliphatic polyamine compound is used, the pot life is long and the calorific value is low, but there is a problem that the curing speed is low and the curing is not performed at a low temperature.

[0004] Therefore, an object of the present invention is to have higher adhesive strength and faster curing than conventional epoxy resin adhesives,
Adhesive composition suitable for use as an adhesive for rubber, metal or plastic, adhesive composition that can achieve both pot life and low-temperature curability and has high adhesiveness, and adheres better than conventional epoxy resin adhesives The adhesive composition suitable for the use of adhesives for civil engineering and construction that is excellent in flexibility, fast curing, flexibility and low odor, and the adhesive containing a specific resin, a sealing agent resin composition excellent in tensile strength and Is to provide.

[0005]

According to the present invention, in order to solve the above problems, all or a part of the oxirane ring of the epoxy compound is represented by the following formula (1):

Embedded image Or a compound (A) obtained by substituting the thiirane ring represented by the formula (I) or a compound (B) having an oxirane ring in the molecule and not containing a thiirane ring, wherein the oxirane ring / thiirane ring Is 90/10 to 10/90.

The present invention further includes the compound (A) or the compound (A) and the compound (B), wherein the content ratio of oxirane ring / thiirane ring is 90/10 to 10/90.
And further, a hydroxyl group, a mercapto group, an amino group,
An object of the present invention is to provide an adhesive composition containing at least one curing agent selected from a compound having a carboxyl group or an isocyanate group and a compound having an acid anhydride structure.

Further, the present invention provides an adhesive composition containing at least one cycloaliphatic polyamine compound when the above-mentioned curing agent contains a compound containing an amino group.

Further, the present invention provides an adhesive composition containing a liquid curing agent having a viscosity at 25 ° C. of 100,000 mPa · s or less.

The viscosity of the compound (A) or the compound (A) and the compound (B) at 25 ° C. is preferably 100,000 mPa · s or less.

When the thiirane content is X and the equivalent ratio of the curing agent to the total of the oxirane ring and the thiirane ring is Y, it is preferable that X and Y have the following relationship. When 10% ≦ X <50% Y = (1−X / 100) ± 0.2 When 50% ≦ X ≦ 90% Y = 0.1 to 0.7

Further, the present invention provides a polysulfide resin,
Urethane resin, silicone resin, modified silicone resin,
And a resin composition for a sealing agent comprising at least one selected from the group consisting of butyl rubber and the adhesive composition.

The present invention also relates to the compound (A) or a total amount of the compound (A) and the compound (B) of 100
Another object of the present invention is to provide a resin composition for a sealing agent containing 10 to 200 parts by weight of an inorganic filler and 10 to 200 parts by weight of a plasticizer with respect to parts by weight.

Hereinafter, the present invention will be described in detail. The present invention includes a first aspect and a second aspect. A first aspect is the above-mentioned compound (A) or an adhesive composition containing the compound (A) and the above-mentioned compound (B) (hereinafter, referred to as “the composition of the present invention”). The second aspect further includes:
A resin composition for a sealing agent comprising at least one of a polysulfide resin, a urethane resin, a silicone resin, a modified silicone resin, and butyl rubber, an inorganic filler and a plasticizer.

The first embodiment of the present invention will be described. The compound (A), which is the main component of the composition of the present invention, is a compound obtained by substituting all or a part of the oxirane ring of the epoxy compound with a thiirane ring. Compound (A-1), which is substituted and has only a thiirane ring, or Compound (A-2), in which only a part of the oxirane ring in the molecule is substituted with a thiirane ring, and which has both a thiirane ring and an oxirane ring There may be.

The epoxy compound used for obtaining the compound (A) includes, for example, the following formulas (a), (b),
In (c), (d), (e) or (f), all the substituents Y are represented by the following formula (2):

Embedded image Or an compound in which Z is an oxygen atom. N is 0 or a number equal to or greater than 0.

[0016]

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[0017]

Embedded image These epoxy compounds may be those in which a hydrogen atom or other group in the molecule is substituted with a halogen atom. For example, the following formula (g):

Embedded image (Wherein, Hal represents a halogen atom). As halogen atoms, bromine, chlorine,
Fluorine and the like.

In the present invention, the compound (A) is a compound of the formula (a), (b), (c), (d), (e), (f) or (g) At least one is
Y is a thiirane ring represented by the above formula (1), and Y other than the thiirane ring is a compound which is an oxirane ring represented by the above formula (2), or at least one of Z is S, and the other Z
Is a compound wherein O is O.

Specific examples of the compound (A) include those represented by the following formula. In each of the following formulas, a compound in which at least one of two or more Y is a thiirane ring represented by the formula (1), and Y other than the thiirane ring is an oxirane ring represented by the formula (2); Or Z
Is a compound wherein at least one is S and the other Z is O. N is 0 or a number equal to or greater than 0.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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The production of the compound (A) can be carried out according to a method of reacting the above-mentioned epoxy compound and an episulfide agent in a polar solvent with vigorous stirring.

The episulfide agent used includes:
For example, potassium thiocyanate (KSCN), thiourea and the like can be mentioned.

As the polar solvent, for example, methanol,
Ethanol, acetone, water, or a mixed solvent thereof can be used. In particular, when KSCN is used as the episulfide agent, the thiirination rate is 50%, that is, the content ratio of oxirane ring / thiirane ring is 1/1.
In order to obtain the compound (A), it is necessary to use 2 /
It is preferable to use one mixed solvent. In order to obtain a compound (A) having a thiirane conversion rate of 100%, that is, a content ratio of oxirane ring / thiirane ring of 0/100, it is preferable to use acetone as a solvent.

The reaction is usually carried out in a temperature range of 10 to 35 ° C.
For example, the reaction can be performed at room temperature for a reaction time of about 10 to 40 hours, for example, about 20 hours. The reaction atmosphere may be air or an inert atmosphere such as nitrogen.

As a specific example of the production of the compound (A),
Taking a method for producing a compound (A) having a thiirane ring using a bisphenol A type epoxy resin as a starting material, the method can be carried out according to a method represented by the following reaction formula. Here, X is S or O.

Embedded image

The compound (B) having an oxirane ring in the molecule contained therein and not containing a thiirane ring is exemplified as the epoxy compound used for obtaining the compound (A) described above. All of the available epoxy compounds are available. Specifically, a compound in which the substituent Y in any of the above formulas as a specific example of the compound (A) is an oxirane ring represented by the formula (2), or
Compounds wherein all Z are O are illustrated. n is 0 or a number greater than or equal to 0. Among these, from the viewpoint of adhesiveness, a bifunctional epoxy compound having two oxirane rings in the molecule is preferable, and an aromatic bifunctional epoxy compound having two oxirane rings in the molecule is more preferable.

The composition of the present invention may contain both the compound (A-1) having only a thiirane ring and the compound (A-2) having both a thiirane ring and an oxirane ring. It may include only one of them. For example, it may be a combination of any of the following components. (I) Composition containing compound (A-1) and compound (B) (ii) Composition containing only compound (A-2) (iii) Compound (A-2) and compound (B) (Iv) Composition containing compound (A-1), compound (A-2) and compound (B) Particularly, in the present invention, when a composition exhibiting high adhesive strength is required Preferably, the composition comprises the combination of the above (iii).

In the composition of the present invention, an oxirane ring /
The content ratio of the thiirane ring is 90/1 in that both a hydroxyl group and a mercapto group can be generated at the time of curing.
It is in the range of 0 to 10/90, and preferably in the range of 50/50 to 90/10, in that a composition exhibiting high adhesive strength can be obtained.

The composition of the present invention comprises the compound (A) or the compounds (A) and (B) and a curing agent.
The two-part adhesive can be prepared separately, and when used as an adhesive, they are mixed at a predetermined ratio to prepare an adhesive. Further, the composition of the present invention,
Compound (A), or compound (A) and compound (B)
Can be mixed with a latent curing agent that exerts a curing action by heating or pressurizing to form a one-part adhesive.

The curing agent used is not particularly limited, and those commonly used as curing agents for epoxy resin-based adhesives can be used. In the present invention, at least one selected from a compound containing a hydroxyl group, a mercapto group, an amino group, a carboxyl group or an isocyanate group, and a compound having an acid anhydride structure is particularly preferable.
Examples of the curing agent include amine curing agents, acid or acid anhydride curing agents, basic active hydrogen compounds, imidazoles,
Examples include polymercaptan-based curing agents, phenolic resins, urea resins, melamine resins, isocyanate-based curing agents, latent curing agents, and ultraviolet curing agents.

Specific examples of the amine curing agent include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, bis (hexamethylene) triamine, 1,3,6-trisaminomethyl. Polyamines such as hexane; polymethylene diamines such as trimethylhexamethylenediamine, polyetherdiamine, diethylaminopropylamine; mensendiamine (M
DA), isophoronediamine (IPDA), bis (4
-Amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine (N-AEP), diaminodicyclohexylmethane, bisaminomethylcyclohexane,
3,9-bis (3-aminopropyl) -2,4,8,1
Cycloaliphatic polyamines such as 0-tetraoxaspiro (5.5) undecane; aliphatic polyamines containing an aromatic ring such as meta-xylylenediamine; aromatics such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and diaminodiethyldiphenylmethane Polyamines and 3,9-bis (3-aminopropyl)-
2,4,8,10-tetraspiro [5.5] undecane and the like. Also, amine adducts (polyamine epoxy resin adducts), polyamine-ethylene oxide adducts, polyamine-propylene oxide adducts,
Cyanoethylated polyamine, ketimine which is a reaction product of an aliphatic polyamine and a ketone; linear diamine, tetramethylguanidine, triethanolamine, piperidine,
Pyridine, benzyldimethylamine, picoline, 2-
(Dimethylaminomethyl) phenol, dimethylcyclohexylamine, dimethylbenzylamine, dimethylhexylamine, dimethylaminophenol, dimethylamino p-cresol, N, N′-dimethylpiperazine,
Piperidine, 1,4-diazadicyclo (2,2,2) octane, 2,4,6-tris (dimethylaminomethyl)
Phenol, liquid polyamide prepared by reacting secondary amines or tertiary amines such as 1.8-diazabicyclo (5.4.0) undecene-1, or dimer acid with polyamines such as diethylenetriamine and triethylenetetramine. And the like.

When the composition of the present invention is blended with at least one of the above-mentioned amine-based curing agents as a curing agent, the resulting composition has a long pot life and can be cured even at low temperatures. A composition having a high speed and a well-balanced pot life and curing time even at a low temperature can be obtained. The cycloaliphatic polyamine compound may be used in combination with another amine-based curing agent, or may be used alone. Specific examples of the cyclic aliphatic polyamine compound include:
Mensendiamine (MDA), isophoronediamine (IPDA), bis (4-amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine (NA)
EP) and the like, ie, 3-aminomethyl-3,
5,5-trimethylcyclohexylamine / bisphenol A diglycidyl ether adduct and the like.

Specific examples of the acid or acid anhydride-based curing agent include polycarboxylic acids such as adipic acid, azelaic acid, and decanedicarboxylic acid, phthalic anhydride, trimellitic anhydride, and ethylene glycol bis (anhydrotrimellitate). Glycerol tris (androtrimellitate), pyromellitic anhydride, aromatic anhydrides such as 3,3 ', 4,4'-benzophenonetetracarboxylic anhydride, maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride Acid, methyltetrahydrophthalic anhydride, methylnadic anhydride, alkenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexenetetracarboxylic anhydride, methylhymic anhydride, trialkyltetrahydrophthalic anhydride , Poly (phenylhexadecane) Acid) anhydrides such as cyclic aliphatic acid anhydrides such as anhydrides, polyadipic anhydrides, polyazelain anhydrides, polysebacic anhydrides, dodecenyl succinic anhydrides, and poly (ethyl octadecane diacid) anhydrides , Chlorendic anhydride, tetrabromophthalic anhydride, halogenated anhydrides such as heptic anhydride, and the like.

Specific examples of the basic active hydrogen compound include:
Dicyandiamide, organic acid dihydrazide and the like can be mentioned.

Specific examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole , 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4
-Methylimidazole, 2-methylimidazolium isocyanurate, 2,4-diamino-6- [2-methylimidazoline- (1)]-ethyl-S-triazine,
2,4-diamino-6- [2-ethyl-4-methylimidazoline- (1)]-ethyl-S-triazine and the like.

Specific examples of the polymercaptan-based curing agent include partial epoxy adducts of 2,2'-bismercaptoethyl ether, pentaerythritol tetrathioglycolate, dipentaerythritol hexathioglycolate, and trimethylolpropandolithioglycol. And esters containing a mercapto group such as polysulfide rubber having a mercapto group at the terminal.

Specific examples of the isocyanate-based curing agent include isocyanate compounds such as toluene diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate, and blocked isocyanate compounds obtained by reacting an isocyanate group with phenol, alcohol, caprolactam, or the like and masking the same. No.

The latent curing agents used for preparing the one-pack type curing agent include amines such as n-hexylamine, monoethylamine, benzylamine, diethylamine, piperidine, triethylamine, aniline, and boron trifluoride. A boron trifluoride-amine complex which is a compound of dicyandiamide or o-tolylbiguanide;
derivatives of dicyandiamide such as α-2,5-dimethylbiguanide, α, ω-diphenylbiguanide, 5-hydroxynaphthyl-1-biguanide; succinic hydrazide,
Adipic hydrazide, isophthalic hydrazide, p-
Acid hydrazides such as oxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide; diaminomaleonitrile or derivatives thereof; melamine derivatives such as diallylmelamine; amine imides synthesized from carboxylic acid esters, dimethylhydrazine and epoxy compounds; ethylenediamine , Salts of diamines such as hexamethylenediamine and piperidine with aliphatic dicarboxylic acids such as sebacic acid, 2,4,4-trimethyl-
Salts of polyamines such as 2,4,7-trihydroxyflavan and polyhydroxyphenols such as N, N'-dimethyl-1,3-propanediamine, phenylphosphonates of polyamines, phenylphosphates of polyamines; sulfones Examples thereof include an ester compound of an acid and a primary alcohol, a monoester or diester of phosphoric acid or a mixture thereof, and an ester compound obtained by an addition reaction between a sulfonic acid and an epoxy compound. Further, an ultraviolet curing agent such as an aromatic diazonium salt and an aromatic sulfonium salt may also be used.

The amount of the curing agent used for curing the composition of the present invention is such that the equivalent ratio is 0.1 to 1.5 with respect to the total of the thiirane ring and the oxirane ring. When the curing agent has an equivalent ratio of less than 0.1 with respect to the total of the thiirane ring and the oxirane ring, the composition does not cure, and when the equivalent ratio exceeds 1.5, the obtained cured product becomes brittle. . In addition, when an adhesive composition that achieves both low-temperature curability in an environment such as 0 ° C. and pot life is preferred, a cycloaliphatic polyamine compound is preferably blended.
In this case, as the curing agent, only the cycloaliphatic polyamine compound may be used, or another curing agent and the cycloaliphatic polyamine compound may be used in combination. When used in combination, the proportion of the cycloaliphatic polyamine compound in the curing agent is from 30 to
90 mol% is preferred.

In the composition of the present invention, the compound (A) or the compound (A) and the compound (B) have a viscosity at 25 ° C. of 100,000 m
Pa · s or less, preferably 30,000 mPa · s or less, and has a viscosity at 25 ° C. of 1000
00 mPa · s or less, preferably 30,000 mPa · s
The adhesive composition containing the following liquid curing agent is excellent in quick-curing property even at room temperature, and is therefore suitable as a low-temperature curing adhesive composition for rubber, metal or plastic, or for civil engineering and construction.

The above-mentioned viscosity at 25 ° C. is 10,000
The compound (A) or the compound (B) of 0 mPa · s or less has an equivalent of 450 g / eq or less or an average equivalent of 45 as an epoxy compound before thiirane modification.
A mixture of combinations in which the amount is 0 g / eq or less is preferable. Among these, epoxy equivalents of 150 to 3
Bisphenol A of 00 or the like is most preferred.

The viscosity at 25 ° C. is 30,000 m
Examples of the liquid curing agent having a Pa · s or less include: ethylenediamines such as triethylenetetramine and tetraethylenepentamine; heterocyclic chemicals such as 1- (2-aminoethyl) piperazine; m-xylylenediamine; and polyamides. Examples include amines and polythiols.

In the first embodiment of the present invention, when the thiirane content in the composition of the present invention is X and the equivalent ratio of the curing agent to the total of the oxirane ring and the thiirane ring is Y, X and Y are as follows: It is preferable to have the relationship shown. Here, the thiirane content means a molar fraction (%) of the thiirane ring in the total of the oxirane ring and the thiirane ring in the compound (A) or the compound (A) and the compound (B). 10% ≦ X <50% Y = (1−X / 100) ± 0.2 50% ≦ X ≦ 90% Y = 0.1 to 0.7 FIG. 1 shows the relationship between X and Y. FIG. In FIG. 1, a hatched portion is a preferable range of X and Y. If the equivalent ratio of the curing agent is larger than this range, the conventional curing agent is expensive, so that the raw material cost increases, which is not preferable. If the equivalent ratio of the curing agent is smaller than this range, the curing reaction does not proceed sufficiently and the composition is not cured, resulting in poor adhesion. In the composition of the present invention, a compound containing only an oxirane ring is used because the contained thiirane ring has high chemical reactivity and —SH generated by ring opening of the thiirane ring contributes to the curing reaction. Compared with the case, the curability can be kept good even if the amount of the curing agent used is smaller than that of the thiirane ring.
However, when X is in the range of 50% or more, although the reason is not clear, the reactivity is saturated and the equivalent ratio of the curing agent used is Y.
= (1−X / 100) ± 0.2 The curing reaction proceeds well if Y = 0.1 to 0.7. More preferably, from the viewpoint of adhesiveness, Y
Is given by Y = (1−X / 100) −0.1.

The composition of the present invention may contain a curing accelerator in addition to the curing agent. Examples of the curing accelerator include phosphites, phenols, tertiary amines, and the like. Among these, the composition of the present invention containing a phosphite is preferred because it does not cause thickening or other problems during storage.

The phosphites used include:
Triphenyl phosphite, tris (nonylphenyl)
Phosphite, triethyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, tris (tridecyl) phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono (Tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, trilauryltrithiophosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol Diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris (2,
Triesters such as 4-di-t-butylphenyl) phosphite and hydrogenated bisphenol A / pentaerythritol phosphite polymer are exemplified. Further, di- or monoesters obtained by partially hydrolyzing these triesters can also be used. These may be used alone or in combination of two or more. Among these, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, hydrogenated bisphenol A. A pentaerythritol phosphite polymer or the like has a particularly high effect of accelerating curing and is preferably used.

Examples of the tertiary amine include benzylmethylamine, triethylamine, dimethylaminomethylphenol, trisdimethylaminomethylphenol, 1,8-
Diazabicyclo [5.4.0] undecene-1,1,4
-Diazabicyclo [2.2.2] octane and the like.

The composition of the present invention includes the compound (A),
Alternatively, in addition to the compound (B) or the curing agent, various additives can be blended as needed. For example, fillers, plasticizers, thixotropic agents, pigments, dyes,
An antioxidant, an antioxidant, an antistatic agent, a flame retardant, an adhesion-imparting agent, a dispersant, a solvent, and the like can be added.

As the filler, those having various shapes can be used. For example, fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, Barium oxide, maglesium oxide; calcium carbonate, magnesium carbonate,
Organic carbonates and inorganic fillers such as zinc carbonate; limestone clay, kaolin clay and calcined clay; carbon black; and fatty acid, resin acid and fatty acid ester-treated products thereof. These may be used alone or in combination of two or more.

As a plasticizer, dioctyl phthalate (D
OP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetyl ricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, adipic acid Butylene glycol polyester and the like. These plasticizers may be used alone or in combination of two or more.

Examples of the antioxidant include butylhydroxytoluene (BHT), butylhydroxyanisole (B
HA) and the like. Antioxidants include, for example, compounds such as hindered phenols.

As the pigment, titanium dioxide, zinc oxide,
Examples thereof include inorganic pigments such as ultramarine, red iron, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate, and organic pigments such as azo pigments and copper phthalocyanine pigments.

Examples of the thixotropic agent include aerosil (manufactured by Nippon Aerosil Co., Ltd.), disparone (manufactured by Kusumoto Kasei Co., Ltd.), calcium carbonate, Teflon, and the like. Examples include quaternary ammonium salts and hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

Examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins and the like.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl methylphosphonate, bromine.
Examples include phosphorus compounds, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.

In the composition of the present invention, the compound (A) as a main component contains at least one thiirane ring in the molecule,
For example, the formula:

Embedded image As shown in an example, in addition to the generation of hydroxyl groups during curing, the thiirane ring opens to generate a thiol group having a higher acidity than the hydroxyl group, and thus exhibits higher adhesive strength than conventional epoxy resin-based adhesives. In addition, since the thiirane ring is more reactive than the oxirane ring, it can exhibit fast curing. In particular, when at least one cycloaliphatic polyamine compound is contained as a curing agent, the pot life (working time) is long even at a low temperature such as 0 ° C., and at the same time, the curing time is not delayed, and the curing property is fast. The properties are good. This is because, due to the steric hindrance of the cycloaliphatic polyamine compound molecule contained as a curing agent, the pot life is kept long, and the reactivity of the thiirane ring is high, so that the cycloaliphatic polyamine compound having steric hindrance can be quickly used. It is thought to react to. In addition, the composition of the present invention in which the average equivalents of the compound (A) and the compound (B), which are the main components, to the curing agent and the viscosity at 25 ° C. is equal to or less than a specific value is excellent in curability even at room temperature, and has an odor. Since the working environment can be favorably maintained, the composition of the present invention
It can be suitably used as an adhesive for civil engineering construction.
Particularly, since the composition of the present invention is excellent in curability, the use of the composition of the present invention as an adhesive for civil engineering and construction can shorten the construction period. Further, due to the reactivity of the thiirane ring, the amount of the curing agent to be used is smaller than in the case of using only the oxirane ring containing no thiirane ring, and the raw material cost can be kept low.

Next, a second embodiment of the present invention will be described. A second aspect of the present invention provides a polysulfide resin, a urethane resin, a silicone resin, a modified silicone resin, and
At least one selected from the group consisting of butyl rubber,
The compound (A) described in the first aspect of the present invention, or a resin composition for a sealing agent containing the compound (A) and the compound (B), and further, the resin composition for a sealing agent In addition, 10 to 200 parts by weight of an inorganic filler, 10 parts by weight of a plasticizer and 10 parts by weight of the compound (A) or the total amount of the compound (A) and the compound (B) are 100 parts by weight.
200 parts by weight of the resin composition for a sealing agent. Hereinafter, the resin composition for a sealing agent according to the second embodiment of the present invention is also referred to as a resin composition for a sealing agent of the present invention.

The polysulfide resin used in the second embodiment of the present invention is a polymer having a reactive mercapto group at the terminal and preferably having-(R-Sx) n- in the main chain. The average value of x is 1.5 to 2.5, and n is 2 to 45
It is. R is a divalent aliphatic group, but an oxygen atom can be interposed between carbon atoms. As the polysulfide resin, one kind or a mixture of two or more kinds may be used. As such a polysulfide resin, a commercially available product can be used, and for example, LP-3 manufactured by Thiokol Chemical Co., Ltd. can be exemplified. When a polysulfide resin is contained in the resin composition for a sealing agent of the present invention, there is an advantage that flexibility is particularly increased, impact resistance is improved, and curing shrinkage is reduced.
The urethane resin is not particularly limited, and a conventionally known urethane resin synthesized from a urethane prepolymer and a polyisocyanate compound can be used. When the resin composition for a sealing agent of the present invention contains a urethane resin,
Particularly, there is an advantage that flexibility and impact resistance are increased.

The silicone resin is a copolymer obtained by copolymerizing a polyfunctional siloxane. In the second embodiment of the present invention, the silicone resin may be used as it is, or may be modified with an organic resin. For example, a modified silicone resin such as alkyd-modified or epoxy-modified may be used. When the resin composition for a sealing agent of the present invention contains a silicone resin, there is an advantage that the flexibility is particularly increased and the weather resistance is improved. When the modified silicone resin is contained in the resin composition for a sealing agent of the present invention, there is an advantage that flexibility and impact resistance are particularly increased. As the butyl rubber, a halogenated butyl rubber may be used. For example, brominated butyl rubber and chlorinated butyl rubber can be exemplified. When the butyl rubber is contained in the resin composition for a sealing agent of the present invention, there is an advantage that the flexibility is particularly increased and the airtightness is improved.

The above-mentioned polysulfide resin, urethane resin, silicone resin, modified silicone resin and butyl rubber may be used alone or in combination of two or more.

In the resin composition for a sealing agent of the present invention, at least one selected from the group consisting of a polysulfide resin, a urethane resin, a silicone resin, a modified silicone resin, and butyl rubber (hereinafter referred to as a polymer), and a compound ( A) or the compounding ratio of the compound (A) and the compound (B) is [at least one selected from the above polymers] / [the compound (A) or the compound (A) and the compound (B)]. = 50 / 50-80 / 20 is preferable, and 60 / 40-70 / 30 is more preferable.
Within this range, it is possible to improve the adhesive strength and tensile strength of the obtained resin composition for a sealing agent, and to add flexibility and other properties inherent to the resin without impairing the mechanical strength. It is.

As the inorganic filler, those having various shapes can be used. For example, fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica;
Zinc oxide, titanium oxide, barium oxide, magresium oxide; calcium carbonate, magnesium carbonate, zinc carbonate; carbon black, and the like. These may be used alone or in combination of two or more. The compounding amount of the inorganic filler is 10 to 200 parts by weight, preferably 50 to 50 parts by weight, based on 100 parts by weight of at least one kind of the polymer and the compound (A) or the total of the compound (A) and the compound (B). １００100 parts by weight. Within this range,
This is because the obtained resin composition for a sealing agent of the present invention has excellent tensile strength without impairing flexibility.

As plasticizers, dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester;
Butyl oleate, methyl acetyl ricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol adipate polyester, and the like. These plasticizers may be used alone or in combination of two or more. The mixing amount of the plasticizer is 10 to 200 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of at least one kind of the polymer and the compound (A) or the total of the compound (A) and the compound (B). It is 150 parts by weight. Within this range, the obtained resin composition for a sealing agent of the present invention can be softened and a low modulus product can be obtained.

The resin composition for a sealing agent of the present invention includes:
A curing agent for the curing reaction of the compound (A) or the compound (B) can be contained in the same manner as in the above-mentioned adhesive composition, and examples of the curing agent include those described in the first embodiment of the present invention. The same ones as those commonly used as curing agents for the exemplified epoxy resin adhesives can be used.

Further, in addition to the above components, various additives can be added to the resin composition for a sealing agent within a range not to impair the object of the present invention. For example, thixotropic agents, pigments, dyes, antioxidants, antioxidants,
An antistatic agent, a flame retardant, an adhesion-imparting agent, a dispersant, a solvent and the like can be added. As these additives, those similar to those exemplified in the first embodiment of the present invention can be exemplified.

The resin composition for a sealing agent of the present invention comprises at least one of the above polymers, the above compound (A), or the compounds (A) and (B), an inorganic filler, a plasticizer, According to the above, a two-component resin composition may be used in which the main agent comprising other additives and the curing agent are separately provided, and the two components are mixed at a predetermined ratio when used. Also, at least one of said polymers
The seed, the compound (A), or the compound (A) and the compound (B), the inorganic filler, the plasticizer, and other additives, if necessary, exert a curing action by heating or pressing. It can also be mixed with a latent curing agent to form a one-pack type resin composition. In the case of a two-pack type, the polymer may be contained in the main component or may be contained in the curing agent.

The resin composition for a sealing agent of the present invention having the above constitution has excellent fast-curing properties, has a strong adhesive property equal to or higher than that of a conventional epoxy resin-based adhesive, and also has excellent tensile strength. The working environment can be kept good with little odor. Further, the cured product after curing can be softened, and a low modulus product can be obtained.

[0071]

The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

Synthesis Example 1 of Compound Containing Thiirane Ring 121 g of potassium thiocyanate was added to 75 ml of ethanol.
And 100 ml of water, and dissolved in a mixed solvent of 85 g of bisphenol A diglycidyl ether. Thereafter, 85 g of bisphenol A diglycidyl ether was further added, and the mixture was vigorously stirred at room temperature for 40 hours. Next, the reaction mixture was extracted with chloroform, washed with water, and dried over magnesium sulfate using magnesium sulfate. The chloroform was distilled off under reduced pressure, followed by drying under reduced pressure to obtain a reaction product. The content ratio of oxirane ring / thiirane ring in the obtained reaction product was measured by NMR and found to be 55/45.

According to this synthesis example, a bisphenol A type epoxy resin (2) (manufactured by Dow Chemical Company, trade name: DER332) was used, and all or a part of the oxirane ring in the bisphenol A type epoxy resin (2) was used. When substituted with a thiirane ring, the content ratio of oxirane ring / thiirane ring is 80/20, 50/50, 30/70 and 1
00/0 compound (hereinafter referred to as (2) 80% modified thiirane, (2) 50% modified thiirane, (2)
30% modified thiirane or thiirane 100 of (2)
% Modified product). Similarly, an aliphatic epoxy resin (3) (trade name: EP, manufactured by Asahi Denka Co., Ltd.)
4080) in which the content ratio of oxirane ring / thiirane ring is 80/20 (hereinafter referred to as thiirane 80 in (3)).
% Modified product).

Synthesis Example 2 of Compound Containing Thiirane Ring A reaction product was obtained in the same manner as in Synthesis Example 1 except that acetone was used as a solvent instead of a mixed solvent of methanol and water. Ring content,
It was 90/10 as measured by NMR.

Synthesis Example 3 of Compound Containing Thiirane Ring A 300 ml methanol solution of 0.25 equivalent of epoxy resin was placed in a 2 liter three-necked flask equipped with a mechanical stirrer. At room temperature, a solution of 0.375 equivalents of thiourea in 300 ml of methanol was added dropwise over 45 minutes.
Next, the mixture was reacted by stirring for 12 hours. Thereafter, the reaction mixture was poured into cold water, and washed three times with a methanol / water mixed solvent. After further dissolving in methylene chloride, the product was washed with water, and methylene chloride was distilled off under reduced pressure, and then dried under reduced pressure to obtain a reaction product. Oxirane ring of the obtained reaction product /
The content of the thiirane ring was measured by NMR and found to be 90/10.

Two metal pieces of the following material having a peel strength of 100 mm × 25 mm × 2 mm were prepared, and the adhesive composition was applied to an area of 12.5 × 25 mm from the end of each metal piece in accordance with JIS K6850. A test piece is prepared by applying an object and overlapping and joining two metal pieces where the adhesive composition has been applied.
The test piece was subjected to a tensile shear test at a speed of 50 mm / min, and the peel strength was measured. Copper plate (JIS C1220) Steel plate (JIS G3141) Aluminum plate (JIS A1050) The same tensile shear test was also performed on vulcanized rubber and polycarbonate. The vulcanized rubber used had the following composition. Vulcanized rubber NR 100 parts by weight CB 40 parts by weight ZnO 5 parts by weight Stearic acid 1 part by weight Sulfur 2.1 parts by weight

Curing Time After the adhesive composition was prepared, it was left at 20 ° C., and the time until tack disappeared (tack free time) was measured as the curing time.

(Examples 1 to 5, Comparative Examples 1 to 5) In each of the examples, an adhesive composition was prepared according to the formulation shown in Table 1, and was subjected to measurement of peel strength and curing time. Table 1 shows the results.

[0079]

[Table 1]

Note Bisphenol A epoxy resin (1): Sumitomo Chemical Co., Ltd., trade name: ELA-128 Bisphenol A epoxy resin (2): Dow Chemical Company, trade name: DER332 aliphatic epoxy resin (3) ): Asahi Denka Co., Ltd. product name:
EP4080 Heterocyclic amine curing agent: Yuka Shell Epoxy Co., Ltd.
Product name: Epomate QX-2: 80% modified thiirane of (2): a compound in which a part of the oxirane ring of bisphenol A type epoxy resin (2) is substituted with a thiirane ring, and a thiirane ring / oxirane ring (2) 50% modified thiirane: a compound obtained by substituting a part of the oxirane ring of the bisphenol A type epoxy resin (2) with a thiirane ring, wherein the thiirane ring / oxirane ring (2) 30% modified thiirane: a compound in which a part of the oxirane ring of bisphenol A type epoxy resin (2) is substituted with a thiirane ring, wherein the thiirane ring / oxirane ring (3) 80% modified thiirane: A part of the oxirane ring of the aliphatic epoxy resin (3) is substituted with a thiirane ring A thiirane ring / epoxy group content of 8
0/20: 100% modified thiirane of (2): a compound in which all oxirane rings of bisphenol A type epoxy resin (2) are substituted with thiirane rings

(Examples 6 to 13, Comparative Examples 7 and 8)
With the composition shown in 2, the adhesive composition was synthesized, cured and adhered.
The sex was evaluated. Curing time After preparing the adhesive composition, leave it at 10 ° C, there is no tack
The time (tack free time) until
Measured.Peel strength 100mm x 25mm x 2mm pure aluminum plate (J
IS A1050) and prepare JIS K6850
12.5 × from the end of each aluminum plate
Apply the adhesive composition to an area of 25 mm,
The places where the adhesive composition was applied on the boards were overlapped and joined.
To make a test piece. About this test piece, 50 mm /
Perform a tensile shear test at a speed of min and measure the peel strength.
Specified. Table 2 shows the results.

[0082]

[Table 2]

Note: Polyamide amine: manufactured by Sanwa Chemical Industry Co., Ltd., trade name: Sunmide 301D (active amine hydrogen equivalent: 150) 30% modified thiirane of (1): bisphenol A type epoxy resin (1) A compound partially substituted with a thiirane ring and having a thiirane ring / oxirane ring content of 30/70. (1) 50% modified thiirane: bisphenol A type epoxy resin (1) A compound partially substituted with a thiirane ring and having a thiirane ring / oxirane ring content ratio of 50/50. (1) 70% modified thiirane: bisphenol A type epoxy resin (1) Compounds partially substituted with thiirane rings and having a thiirane ring / oxirane ring content of 70/30

(Examples 14 to 17, Comparative Examples 9 to 13) With the formulations shown in Table 3 below, adhesive compositions were synthesized, and pot life, curability, and adhesiveness were measured and evaluated. Pot life According to the method described in JIS K 6833, "Test on pot life " for use conditions, the time at which a significant increase in viscosity occurred was measured on a 50 g scale. After setting the adhesive composition at the set temperature (20 ° C., 0 ° C.),
Leave to stand, tack is gone and hardness is 6 with Shore D hardness tester
The time until a hardness of 0 or more was developed was measured. Steel plate with peel strength of 100 mm x 25 mm x 2 mm (JIS G3
142) were prepared, and 12.5 × from each steel sheet end was prepared according to the method described in JIS K 6850.
The adhesive composition was applied to an area of 25 mm ^2, the portions where the adhesive composition was applied to the two steel sheets were overlapped and joined, and left for 5 days at 20 ° C., 0 ° C. and each temperature condition. A test piece was prepared. About this test piece, 50 mm / mi
A tensile shear test was performed at a speed of n, and the peel strength was measured. The results are shown in Table 3 below.

[0085]

[Table 3]

Examples 14 and 16 are examples in which a thiirane 30% modified product was cured with a cycloaliphatic polyamine compound or a modified product thereof. Compared to the case of curing with the polyamidoamine alone of Example 17, the pot life at 0 ° C. is more than doubled, but the curing time hardly changes,
It can be seen that the workability at low temperatures is excellent. Example 15 is
This is an example in which a polyamidoamine and a cycloaliphatic polyamine compound are used in combination as a curing agent. Comparative Examples 9 to 11 are examples in which a bisphenol A type epoxy resin was cured with various curing agents. Curing at 20 ° C. is good, but at 0 ° C., particularly when curing is performed with a cycloaliphatic polyamine compound and a modified cycloaliphatic polyamine compound (Comparative Examples 10 and 1).
1) It is found that curing is slow and the use of these curing agents at low temperatures is not suitable. Even in the case of curing with polyamidoamine (Comparative Example 9), it can be seen that the curing is slow at 0 ° C. and cannot be used at low temperatures. Comparative Examples 9 and 10, 11
When comparing ordinary bisphenol A type epoxy resin, it is understood that the pot life and the curing time are correlated, and that the cyclic aliphatic polyamine-based curing agent having a long pot life also increases the curing time. . Comparative Example 1
No. 2 is an example in which a 100% modified thiirane was cured with a cycloaliphatic polyamine compound, and it can be seen that the peel strength (adhesive strength) is small. Comparative Example 13 is an example in which a 3% modified thiirane was cured with a cycloaliphatic polyamine compound.
Since the curing time at 0 ° C. is as long as 72 hours, it cannot be used at low temperatures.

Note Bisphenol A type epoxy resin (1): Sumitomo Chemical Co., Ltd. Product name: ELA-128 Polyamide amine: Sanwa Chemical Industry Co., Ltd. Product name: SUNMIDE X-2000 (active amine hydrogen equivalent: 90) Cycloaliphatic polyamine compound (isophoronediamine): manufactured by Huls (amine value = 41) Modified cycloaliphatic polyamine compound (3-aminomethyl-3,5,5-trimethylcyclohexylamine / bisphenol A diglycidyl ether adduct) Product name: SUNMIDE IM-544 (active amine hydrogen equivalent = 100) 30% modified thiirane of (1): Part of the oxirane ring of bisphenol A type epoxy resin (1) A compound having a thiirane ring / oxirane ring content of 30 Thiirane 3% modified product of (1): a compound in which a part of the oxirane ring of the bisphenol A type epoxy resin (1) is substituted with a thiirane ring, wherein the content ratio of thiirane ring / oxirane ring is 3 / 97: 100% modified thiirane of (1): a compound in which all oxirane rings of bisphenol A type epoxy resin (1) are substituted by thiirane rings

(Examples 18 to 22, Comparative Examples 14 to 16)
The resin composition for a sealing agent for civil engineering and construction was synthesized with the composition shown in Table 4 below, and the curability, tensile strength, and adhesiveness were evaluated. Curing time After the adhesive composition was prepared, it was left at 20 ° C., and the time until tack disappeared (tack free time) was measured as the curing time. Tensile strength was measured according to the method described in JIS K7113.
As the test piece, a No. 1 test piece was used, and the pulling speed was 50 mm / min. Peel strength was measured according to the method described in JIS K6850.
The adherends used are as follows. Steel plate (JIS G 3142) PVC 3001 manufactured by Mitsubishi Plastics Co., Ltd. Regarding the mortar adhesiveness, the resin composition obtained in the above Examples and Comparative Examples was applied to an area of 12.5 mm × 50 mm from the end of the mortar having a thickness of 10 mm. The coating was applied and a peel test was performed. The results are shown in Table 3 below.

[0089]

[Table 4]

Note: 100% modified thiirane of (1): a compound in which all oxirane rings of bisphenol A type epoxy resin (1) are substituted with thiirane rings Calcium carbonate: manufactured by Maruo Calcium Co., trade name: MS-
700 Silica: manufactured by Nippon Aerosil Co., Ltd., trade name: AEROS
IL200 Epoxy plasticizer: Diglycidyl ether of 1,6-hexanediol Modified silicone resin: Kanebuchi Chemical Industry Co., Ltd., trade name:
SAT200, silyl standard grade Aminosilane tackifier: trade name: AQ-1121 polysulfide resin: manufactured by Nippon Unicar Co., Ltd .: trade name: LP-3 amine catalyst: manufactured by Toray Thiokol, trade name: DMP-3
0 Polyamide amine: manufactured by Sanwa Chemical Industry Co., Ltd., trade name: Sunmide 315 (active amine hydrogen equivalent: 125) Tin catalyst: silyl curing agent: manufactured by Sankyoki Gosei Co., Ltd.
Product name: No.918

[0091]

According to the adhesive composition of the present invention, the compound (A) as the main component contains at least one thiirane ring in the molecule, and in addition to the generation of a hydroxyl group during curing, the thiirane ring is opened. Produces a thiol group having higher acidity than hydroxyl group, so shows higher adhesive strength than conventional epoxy resin-based adhesives, and shows faster curing because thiirane ring is more reactive than oxirane ring Things. Further, the adhesive composition of the present invention containing at least one cycloaliphatic polyamine compound as a curing agent has a long pot life, a short curing time, and a good balance between the pot life and the curing time even at a low temperature of 0 ° C. Good workability. The adhesive composition of the present invention having such properties is
It is suitable for use as an adhesive for rubber, metal or plastic. In particular, the composition of the present invention exhibits a high adhesive strength to aluminum or stainless steel, which has not been able to obtain a sufficient adhesive strength with a conventional epoxy adhesive, and is useful. Further, the adhesive composition of the present invention in which the viscosities of the compounds (A) and (B) are specified values, or the adhesive composition of the present invention further containing a liquid curing agent is excellent in curability even at room temperature. It can be suitably used as a curable adhesive composition. Therefore, the adhesive composition of the present invention is also suitable for use as an adhesive for civil engineering and construction, and its rapid curing property can shorten the construction period. These adhesive compositions can have flexibility in addition to the above-mentioned properties and can be made into a low modulus product. Furthermore, although it is a fast-curing composition, unlike conventional fast-curing compositions, it has less odor, so that a favorable working environment during use can be maintained. Further, the resin composition for a sealing agent of the present invention using a polymer such as a polysulfide resin in combination has the excellent properties of the above-mentioned adhesive composition, further increases flexibility (flexibility), and provides impact resistance and weather resistance. Good airtightness and airtightness. In addition, the resin composition for a sealing agent of the present invention, which contains an inorganic filler and a plasticizer in addition to the above-described polymer, is further excellent in flexibility and excellent in tensile strength without impairing flexibility.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the thiirane content X and the equivalent ratio Y of a curing agent to the total of oxirane rings and thiirane rings.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C09K 3/10 C09K 3/10 FG // C08G 75/08 C08G 75/08 (56) References JP-A-11-209576 ( JP, A) JP-A-11-222582 (JP, A) JP-A-11-116772 (JP, A) JP-A-55-82178 (JP, A) JP-A-8-269043 (JP, A) JP-A-11-60818 (JP, A) JP-A-10-95789 (JP, A) JP-B-49-44583 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09J 101 / 00-201/10 C09K 3/10 C08G 75/00-75/32 C08L 63/00-101/10

Claims (13)

(57) [Claims] (1) All or a part of the oxirane ring of an epoxy compound is represented by the following formula (1): Or a compound (A) obtained by substituting the thiirane ring represented by the formula (I) or a compound (B) having an oxirane ring in the molecule and not containing a thiirane ring, wherein the oxirane ring / thiirane ring The adhesive composition whose content ratio is 90/10 to 10/90. 2. The adhesive composition according to claim 1, wherein the compound (A) is a compound having both a thiirane ring and an oxirane ring in a molecule. 3. The adhesive composition according to claim 1, wherein the compound (A) is a compound having only a thiirane ring in the molecule and not having an oxirane ring. Wherein said epoxy compound is represented by the following formula (a)
The adhesive composition according to claim 1, wherein
(Note, Y is represented by formula (2).) ## STR2 ## 5. The method according to claim 1, wherein the epoxy compound has the following formula (j):
4. The product according to claim 1, which is a condensate with chlorohydrin.
An adhesive composition according to any one of the above. (Note that Y is represented by equation (2).
It is. ) [Formula 3] 6. Further, a hydroxyl group, a mercapto group, an amino group, any of claims 1-5 comprising a compound containing a carboxyl group or isocyanate group, and at least one curing agent selected from compounds having an acid anhydride structure An adhesive composition according to any one of the above. 7. The adhesive composition according to claim 6 , wherein the compound containing an amino group contains at least one cycloaliphatic polyamine compound. 8. A composition having a viscosity at 25 ° C. of 10,000
Claim containing the following liquid curing agent mPa · s 6 or 7
The adhesive composition according to item 1. 9. The compound (A) or the compound (A) and the compound (B) having a viscosity at 25 ° C. of 100,000 mPa · s or less.
The adhesive composition according to any one of 8. 10. thiirane content X, the equivalent ratio of curing agent to the total of oxirane ring and thiirane ring in the case of the Y, X, claims 6-9 in which Y has the relation shown below
The adhesive composition according to any one of the above. When 10% ≦ X <50% Y = (1−X / 100) ± 0.2 When 50% ≦ X ≦ 90% Y = 0.1 to 0.7 11. A rubber adhesive composition according to any one of claims 1 to 10 used for metal or plastic. 12. A polysulfide resin, a urethane resin,
A resin composition for a sealing agent, comprising at least one selected from the group consisting of a silicone resin, a modified silicone resin, and butyl rubber, and the adhesive composition according to any one of claims 1 to 10 . 13. An inorganic filler of 10 to 200 parts by weight and a plasticizer of 10 to 200 parts by weight per 100 parts by weight of the compound (A) or the total amount of the compound (A) and the compound (B). The resin composition for a sealing agent according to claim 12 , comprising: