JP2000303052A - Adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a two-component mixing type, cold setting adhesive compsn. which generates little odor of the curing agent and little film formation on the liq. surface, cures rapidly when a small amt. is applied, that is, when a thin film is formed by the application and furnishes various properties such as excellent (hot) water resistance, adhesion strength and impact resistance after curing. SOLUTION: This two-component mixing type adhesive compsn. comprises a main ingredient having 100 pts.wt. of an epoxy resin with an addition of 1-60 pts.wt. of an inorg. filler and 0.01-5 pts.wt. of an adhesion providing agent, and a curing agent having 100 pts.wt. of an aliph. thioether with an addition of 0.1-50 pts.wt. of an alicyclic polyamine, 0.1-20 pts.wt. of a curing accelerator, 1-60 pts.wt. of an inorg. filler and 0.01-5 pts.wt. of an adhesion proving agent. The mixing ratio of the main ingredient to the curing agent is determined so that the wt. ratio of the aliph. thioether to the epoxy resin is 0.5-1:1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-part mixture type cold-setting adhesive composition.

[0002]

2. Description of the Related Art Conventionally, a two-component type cold-setting epoxy resin-based adhesive composition or a urethane resin-based adhesive composition has been widely used as an industrial or general adhesive. However, such a two-part cold-setting adhesive composition of a two-component type has a problem that the coating amount is small, that is, the coating thickness is small and the curing is slow. In order to respond to the above problems, for example, by using a fast-curing curing agent such as an aliphatic thioether, the two-component mixed epoxy resin-based adhesive composition is imparted with fast-curing properties. However, in general, fast-curing 2
The liquid-mixed epoxy resin-based adhesive composition has a problem that the (warm) water resistance after curing is not sufficient.

To cope with the above problems, when polyamidoamine is used as a curing agent for an epoxy resin, for example, although the (hot) water resistance after curing is improved, the curability at the time of applying a small amount is not satisfactory. Problems remain.

On the other hand, in recent years, for example,
No. 298584, a one-part type moisture-curable urethane-based adhesive composition as disclosed in JP-A-298584, which has been adjusted to a fast-curing type which can be initially cured at room temperature for about 2 hours, is subjected to high-frequency heating. A system that cures in a short time of about 15 to 30 seconds by applying it has been actively adopted as a joining method of building members such as ceramic siding.

[0005] However, in the case of a system in which rapid curing is performed by high-frequency heating, a large amount of equipment investment is required when the system is introduced, and a large amount of carbon dioxide gas is generated during a rapid curing reaction by high-frequency heating, so that foaming occurs in a cured product. There is a problem that a trace left remains and the adhesive strength is significantly reduced.

[0006]

SUMMARY OF THE INVENTION In order to solve the above-mentioned conventional problems, the present invention reduces the odor of the curing agent and the skinning of the surface of the liquid, so that even when the coating amount is small, that is, even when the coating thickness is thin, the curing agent is rapidly formed. It is an object of the present invention to provide a two-part mixture type room temperature curable adhesive composition which cures and exhibits various properties such as excellent (hot) water resistance, adhesive strength and impact resistance after curing.

[0007]

The adhesive composition according to the invention described in claim 1 (hereinafter referred to as "first invention")
Inorganic fillers 1 to 6 per 100 parts by weight of epoxy resin
0 to 100 parts by weight of an aliphatic thioether and 0.1 to 50 parts by weight of an alicyclic polyamine, and 0.1 to 50 parts by weight of a hardening accelerator. A two-pack type adhesive composition comprising 1 to 20 parts by weight, a curing agent to which 1 to 60 parts by weight of an inorganic filler and 0.01 to 5 parts by weight of an adhesiveness-imparting agent are added; And a curing agent, wherein the weight ratio of the epoxy resin to the epoxy resin is 0.5 to 1 of the aliphatic thioether.

The invention according to claim 2 (hereinafter referred to as “second
The adhesive composition according to the present invention is characterized in that, in the adhesive composition according to the first invention, the alicyclic polyamine is an alicyclic polyamine containing no phenol.

The first invention and the second invention (hereinafter referred to as "the present invention")
The epoxy resin contained as a main component in the main component of the adhesive composition according to the present invention is not particularly limited. For example, bisphenol A, bisphenol F, bisphenol AD, or the like is reacted with epichlorohydrin. Bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin and hydrogenated products thereof; phenol novolak type epoxy resin; glycidylamine type epoxy resin; glycidyl ether type epoxy resin; glycidyl Ester type epoxy resin; urethane-modified epoxy resin having urethane bond;
Nitrogen-containing epoxy resins obtained by epoxidizing metaxylenediamine, hydantoin, and the like; rubber-modified epoxy resins containing polybutadiene rubber (BR), acrylonitrile-butadiene copolymer rubber (NBR), and the like; However, a bisphenol A type epoxy resin having a good balance between performance and cost is more preferably used.

The above epoxy resins may be used alone or in combination of two or more.

The above-mentioned bisphenol A type epoxy resin has various properties from liquid to semi-solid or solid at normal temperature depending on its molecular weight. In the first invention, bisphenol A liquid at normal temperature is used. The epoxy resin alone may be used, or a bisphenol A epoxy resin that is liquid at room temperature and a bisphenol A epoxy resin that is semi-solid or solid at room temperature may be used in combination.

The ratio of the bisphenol A epoxy resin liquid at room temperature to the semi-solid or solid bisphenol A epoxy resin at room temperature is not particularly limited. It is preferable that the solid or solid bisphenol A epoxy resin / the liquid bisphenol A epoxy resin at room temperature ≦ 1.

When the ratio of the semi-solid or solid bisphenol A type epoxy resin at room temperature / the liquid bisphenol A type epoxy resin at room temperature (weight ratio) exceeds 1, the viscosity of the obtained adhesive composition may be too high. In addition, the curing speed may be too slow, resulting in reduced workability and reduced cured product adhesive strength.

The inorganic filler added to the main component of the adhesive composition according to the present invention contributes to improvement of physical properties such as improvement of cohesive strength of the cured product, reduction of the cost of the adhesive composition, and the like.

The inorganic filler is not particularly restricted but includes, for example, various inorganic fillers such as calcium carbonate, clay, talc, silicon oxide, titanium oxide and asbestos. Among them, calcium carbonate having a good balance between performance and cost is more preferably used.

The above-mentioned inorganic fillers may be used alone or in combination of two or more.

Among the above-mentioned inorganic fillers, calcium carbonate that is more preferably used is not particularly limited. Examples thereof include colloidal light calcium carbonate, finely divided calcium carbonate, surface-treated colloidal calcium carbonate, and surface-treated finely divided carbonate. Various calcium carbonates such as calcium and heavy calcium carbonate are exemplified, and are preferably used.

Here, the colloidal light calcium carbonate is
Light calcium carbonate in a special dispersed state,
It has a mean particle size of about 1 to 10 μm and an apparent specific gravity of about 0.2 g / ml.

Here, the finely divided calcium carbonate is obtained by further pulverizing the colloidal light calcium carbonate, and has an average particle diameter of about 0.07 to 0.15 μm and a particle size of 0.2 to 0.25 μm.
It has an apparent specific gravity of about 5 to 0.4 g / ml.

Further, the surface-treated colloidal light calcium carbonate or the surface-treated fine calcium carbonate refers to the colloidal light calcium carbonate or the finely divided calcium carbonate obtained by subjecting the surface of the colloidal light calcium carbonate or the finely divided calcium carbonate to a hydrophobic treatment with a fatty acid or rosin.

The above calcium carbonate may be used alone or in combination of two or more.

In the main component of the adhesive composition according to the present invention, it is necessary that 1 to 60 parts by weight of the inorganic filler is added to 100 parts by weight of the epoxy resin.

If the amount of the inorganic filler is less than 1 part by weight per 100 parts by weight of the epoxy resin, the effect of improving the cohesive strength of the cured product and the effect of reducing the cost cannot be sufficiently obtained.
Conversely, if the amount of the inorganic filler exceeds 60 parts by weight based on 100 parts by weight of the epoxy resin, the viscosity of the obtained base material becomes too high and the workability decreases.

The adhesiveness-imparting agent added to the main component of the adhesive composition according to the present invention contributes to improving the adhesiveness of the obtained adhesive composition to various adherends.

The above-mentioned adhesiveness-imparting agent is not particularly limited, and examples thereof include various coupling agents such as a silane coupling agent, a titanium coupling agent and an aluminum coupling agent, and are preferably used. But,
Among them, a silane coupling agent having a good balance between performance and cost is more preferably used.

The above-mentioned adhesiveness imparting agents may be used alone or in combination of two or more.

The silane coupling agent is not particularly restricted but includes, for example, epoxy silanes such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane; γ-mercapto Mercaptosilanes such as propyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; γ
Aminosilanes such as-(2-aminoethyl) aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane, etc., are preferably used. Among them, epoxysilanes having excellent storage stability of a mixture with an epoxy resin are preferred. Are more preferably used.

The above silane coupling agents may be used alone or in combination of two or more.

In the main component of the adhesive composition according to the present invention, it is necessary that 0.01 to 5 parts by weight of the above-mentioned adhesiveness-imparting agent is added to 100 parts by weight of the epoxy resin.

If the amount of the adhesive agent is less than 0.01 part by weight per 100 parts by weight of the epoxy resin, the effect of improving the adhesive strength cannot be sufficiently obtained.
If the amount of the above-mentioned adhesiveness-imparting agent relative to 0 parts by weight exceeds 5 parts by weight, the cost will increase even though the adhesive strength no longer improves.

The aliphatic thioether contained as a main component in the curing agent of the adhesive composition according to the present invention functions as a curing agent for the epoxy resin, which is a main component in the above-mentioned main component.

By using an aliphatic thioether as a curing agent for an epoxy resin, it becomes possible to obtain an adhesive composition having less odor of the curing agent and less skinning on the liquid surface.
In addition, by using an aliphatic thioether in combination with a curing accelerator described later, it is possible to obtain an adhesive composition that can be rapidly cured even in the case of a small amount of application, that is, in the case of a small application thickness.

When a curing agent other than the above-mentioned aliphatic thioether, for example, an aliphatic thioester, an aromatic thioether, an aliphatic polyamine, a heterocyclic polyamine, a polyamidoamine, or the like is used as a curing agent for the epoxy resin, a curing agent for the resulting adhesive composition is obtained. , The odor and the skin on the liquid surface become intense,
Poor practicality.

The aliphatic thioether is not particularly limited, and examples thereof include polyoxypropylene poly-2-hydroxythiol and ethylene glycol type di (poly) hydroxythiol.
It is preferably used, and among them, polyoxypropylene poly 2-hydroxy thiol having a good balance between performance and cost is more preferably used.

The above aliphatic thioethers may be used alone or in combination of two or more.

In the curing agent of the adhesive composition according to the present invention, an alicyclic polyamine is added as a curing agent together with the aliphatic thioether.

By including an alicyclic polyamine in the curing agent, the cured product of the resulting adhesive composition can be used to withstand (warm).
The aqueous properties are significantly improved. Here, the term "(warm) water resistance" means warm water resistance or water resistance.

The alicyclic polyamine is not particularly restricted but includes, for example, isophorone diamine,
N-aminoethylpiperazine, diaminoethane, diethylenetriamine, polyoxypropylenepolyamine, and modified products thereof, and the like are preferably used.

The alicyclic polyamines may be used alone or in combination of two or more.

In the second invention, it is necessary to use, as the alicyclic polyamine added to the curing agent, an alicyclic polyamine containing no phenol, among the above-mentioned various alicyclic polyamines.

The use of an alicyclic polyamine containing no phenol as the alicyclic polyamine not only significantly improves the (hot) water resistance of the cured product of the obtained adhesive composition, but also improves the odor of the curing agent. Also, the skinning property of the liquid surface is improved, and a curing agent having more excellent storage stability can be obtained.

The alicyclic polyamines containing no phenol may be used alone or in combination of two or more.

In the curing agent for the adhesive composition according to the present invention, based on 100 parts by weight of the aliphatic thioether,
It is necessary that 0.1 to 50 parts by weight of the alicyclic polyamine is added.

If the amount of the alicyclic polyamine is less than 0.1 part by weight based on 100 parts by weight of the aliphatic thioether, the (hot) water resistance of the cured product of the obtained adhesive composition is not sufficiently improved. Conversely, if the addition amount of the alicyclic polyamine exceeds 50 parts by weight with respect to 100 parts by weight of the aliphatic thioether, the curing rate of the obtained adhesive composition, particularly the curing rate at the time of applying a small amount, becomes slow.

The curing accelerator added to the curing agent of the adhesive composition according to the present invention comprises the epoxy resin contained as a main component in the main component and the aliphatic resin contained as a main component in the curing agent. It contributes to promoting the curing of the adhesive composition by the reaction with the thioether and the alicyclic polyamine.

The curing accelerator is not particularly restricted but includes, for example, tris (dimethylaminomethyl) phenol, benzyldimethylamine, m-xylylenedi (dimethylamine), N, N'-dimethylpiperazine, N Tertiary amines such as -methylpyrrolidine and N-methylhydroxypiperidine; m-xylylenediamine and its modified products, isophoronediamine and its modified products, N-aminoethylpiperazine and its modified products,
Diaminoethane and its modified products, diethylenetriamine and its modified products, polyoxypropylene polyamines and polyamines such as its modified products; polyaminoamine (polyaminoimidazoline) and its modified products, etc., which are preferably used. Tertiary amines having a good balance between cost and cost are more preferably used.
Tris (dimethylaminomethyl) among the primary amines
Phenol is particularly preferably used.

The curing accelerators may be used alone or in combination of two or more.

In the curing agent for the adhesive composition according to the present invention, 100 parts by weight of the aliphatic thioether is used.
It is necessary that 0.1 to 20 parts by weight of the curing accelerator is added.

When the amount of the curing accelerator is less than 0.1 part by weight based on 100 parts by weight of the aliphatic thioether,
A sufficient curing acceleration effect cannot be obtained, and conversely, the amount of the curing accelerator added is 20 parts by weight based on 100 parts by weight of the aliphatic thioether.
If the amount is more than 10 parts by weight, the cured product of the obtained adhesive composition will have reduced (warm) water resistance, adhesive strength, etc., even though the curing speed will no longer be improved.

The inorganic filler added to the curing agent of the adhesive composition according to the present invention can improve the physical properties such as the cohesive strength of the cured product, similarly to the case of the inorganic filler added to the main agent. It contributes to cost reduction of the adhesive composition and the like.

The inorganic filler is not particularly limited. For example, the same inorganic fillers as those which can be added to the base material include calcium carbonate, clay, talc, silicon oxide, and the like.
Various inorganic fillers such as titanium oxide and asbestos are exemplified and are preferably used. Among them, the various calcium carbonates having a good balance between performance and cost are more preferably used.

The above inorganic fillers may be used alone or in combination of two or more.

In the curing agent for the adhesive composition according to the present invention, based on 100 parts by weight of the aliphatic thioether,
It is necessary that 1 to 60 parts by weight of the inorganic filler is added.

If the amount of the inorganic filler is less than 1 part by weight based on 100 parts by weight of the aliphatic thioether, the effect of the cohesive force and cost reduction of the cured product cannot be sufficiently obtained. If the amount of the inorganic filler to be added is more than 60 parts by weight, the viscosity of the obtained curing agent becomes too high, and the workability is reduced.

The adhesion-imparting agent added to the curing agent of the adhesive composition according to the present invention may be used in the same manner as in the case of the adhesion-imparting agent added to the main agent. It contributes to the improvement of the adhesion to the body.

The above-mentioned adhesiveness-imparting agent is not particularly limited, but examples thereof include various silane coupling agents, titanium coupling agents, aluminum coupling agents and the like similar to those which can be added to the main component. Coupling agents are mentioned and are preferably used. Among them, silane coupling agents having a good balance between performance and cost are more preferably used.

The above-mentioned adhesiveness-imparting agents may be used alone or in combination of two or more.

The silane coupling agent is not particularly restricted but includes, for example, mercaptosilanes, aminosilanes, epoxysilanes and the like which can be added to the main ingredient. Among them, mercaptosilanes and aminosilanes, which are excellent in storage stability of a mixture with an aliphatic thioether, are more preferably used.

The above silane coupling agents may be used alone or in combination of two or more.

In the curing agent for the adhesive composition according to the present invention, based on 100 parts by weight of the aliphatic thioether,
It is necessary that 0.01 to 5 parts by weight of the above-mentioned adhesiveness imparting agent is added.

If the amount of the adhesion-imparting agent is less than 0.01 part by weight per 100 parts by weight of the aliphatic thioether, the effect of improving the adhesive strength cannot be sufficiently obtained. If the amount of the adhesive agent exceeds 5 parts by weight, the cost will increase even though the adhesive strength is no longer improved.

In the adhesive composition according to the present invention, the mixing ratio of the above-mentioned main agent and the above-mentioned curing agent is, by weight ratio, the ratio of the epoxy resin 1 which is the main component of the main agent to the epoxy resin 1 which is the main component of the curing agent. When the aliphatic thioether is 0.5 to
It is necessary that the ratio of the aliphatic thioether to the epoxy resin 1 is 0.5 to 0.1.
The ratio becomes 7.

When the mixing ratio of the aliphatic thioether to the epoxy resin 1 is less than 0.5, the curing of the adhesive composition does not proceed sufficiently, the adhesive strength of the cured product, the impact resistance, etc. Becomes insufficient, and conversely, epoxy resin 1
When the mixing ratio of the aliphatic thioether with respect to 1 exceeds 1, the (hot) water resistance, heat and humidity resistance, etc. of the cured product decrease.

The main component and / or the curing agent of the adhesive composition according to the present invention may contain, if necessary, a curing speed regulator, a coloring agent, a reinforcing agent, and a thickening agent within a range not to impair the achievement of the object of the present invention. , Thixotropic agent (thixotropic agent), softener, plasticizer, surfactant, stabilizer, antioxidant, ultraviolet absorber, flame retardant,
One or more of various additives such as an organic solvent may be contained.

The curing speed adjusting agent is added when it is desired to extend the pot life (pot life) after mixing the main agent and the curing agent, for example, by delaying the curing speed, and is particularly limited. Although not limited thereto, for example, various carboxylic acids such as octylic acid may be mentioned, and are preferably used.

The amount of the curing rate modifier added is not particularly limited as long as it is appropriately set in accordance with the desired curing rate, but is not particularly limited, and is preferably 100 parts by weight of the epoxy resin and / or the aliphatic thioether. It is preferable that the curing rate adjusting agent is 5 parts by weight or less.

If the amount of the above-mentioned curing rate modifier is more than 5 parts by weight per 100 parts by weight of the epoxy resin and / or the aliphatic thioether, the curing rate becomes too slow, which is one of the objects of the present invention. May be impaired.

The coloring agent is added when it is desired to color the main agent and the curing agent in different colors, for example, in order to easily determine whether or not the main agent and the curing agent are properly mixed. Yes, ordinary pigments and dyes are preferably used.

The above-mentioned coloring agent is used as it is as the main agent and / or
Alternatively, it may be added to the curing agent, or may be added to the main agent and / or the curing agent, for example, as a paste-like master batch.

The amount of the coloring agent to be added is not particularly limited as long as it is appropriately set according to the desired degree of coloring, but is not limited to 100 parts by weight of the epoxy resin and / or the aliphatic thioether. It is preferable that the content of the coloring agent is 10 parts by weight or less.

Even if the amount of the coloring agent is more than 10 parts by weight based on 100 parts by weight of the epoxy resin and / or the aliphatic thioether, the coloring degree is no longer improved.

The method for producing the main agent or the curing agent of the adhesive composition according to the present invention is not particularly limited. A predetermined amount of each component to be contained in the main agent or the curing agent is weighed, and a mixer such as a mixer or a kneader is used. After pre-mixing, if necessary, the desired base agent or curing agent can be obtained by uniformly kneading using, for example, a three-roll mill.

[0073]

The adhesive composition according to the first invention comprises an epoxy resin as a main component, and a specific amount of the epoxy resin to which a specific amount of an inorganic filler and an adhesion-imparting agent are added; An aliphatic thioether as a main component, a specific amount of the aliphatic thioether, a specific amount of an alicyclic polyamine, a curing accelerator, an inorganic filler and a curing agent to which an adhesion promoter is added, and Since the mixing ratio of the above main agent and the curing agent is a specific ratio by weight, after curing, it exhibits excellent physical properties such as excellent (hot) water resistance, adhesive strength, impact resistance, etc. The odor of the agent and the skinning of the liquid surface are small, and it cures rapidly even when applied in a small amount, that is, even when the applied thickness is thin.

The adhesive composition according to the second invention is the adhesive composition according to the first invention, wherein the alicyclic polyamine containing no phenol is used as the alicyclic polyamine added to the curing agent. Since it is used, after curing, it exhibits even more excellent (warm) water resistance, and the odor of the curing agent and the skinning property of the liquid surface are further reduced.

[0075]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”, and “%” means “parts” unless otherwise specified.
It means "% by weight".

(Example 1)

(1) Production of Adhesive Composition As shown in Table 1, 100 parts of bisphenol A type epoxy resin (trade name “Epicoat 828XA”, manufactured by Yuka Shell Epoxy Co., Ltd.) which is liquid at room temperature was filled with an inorganic material. 40 parts of calcium carbonate as an agent, 1 part of a silane coupling agent as an adhesion-imparting agent, and paste pigment 0.05 as a coloring agent
The mixture was preliminarily mixed with a mixer, and then kneaded uniformly by passing through three rolls once to obtain a main component of the adhesive composition.

As shown in Table 1, polyoxypropylene poly-2-hydroxythiol (trade name “Cup Cure 3-800LC”, B
TR Japan Limited (55 parts), 25 parts of “Sunmide I-544” (phenol content: 0%, Sanwa Chemical Co., Ltd.) as an alicyclic polyamine, and tris (dimethylaminomethyl) as a curing accelerator ) Phenol 1
0 parts, 45 parts of calcium carbonate as an inorganic filler, 1 part of a silane coupling agent as an adhesion-imparting agent, and 0.05 part of a paste pigment as a coloring agent, and after premixing with a mixer, three rolls are applied once. And knead it evenly,
A curing agent for the adhesive composition was obtained.

(2) Evaluation The performance of the adhesive composition obtained above (odor of curing agent,
The following methods were used to evaluate the skinning properties of the curing agent, the curability in a small amount, and the hot water resistance of the cured product. The results were as shown in Table 1.

Odor of the curing agent: 200 g of the curing agent was placed in a 200 cc glass bottle and sealed,
After being left in an atmosphere at a temperature of 7 ° C. for 7 days, the bottle was opened, the odor was immediately smelled, and the odor was evaluated according to the following criteria. [Judgment criteria] ○ ‥‥ Low odor × ‥‥ High odor

Skinning property of curing agent: 200 g of curing agent was placed in a 200 cc glass bottle, sealed, left to stand in an atmosphere of 20 ° C. or 40 ° C. for 7 days, and then opened to open the skin on the surface of the curing agent. The state of tension was visually observed, and the skin tension was evaluated according to the following criteria. [Judgment criteria] ○ ‥‥ Low skinning × ‥‥ High skinning

A small amount of curability: 10 g of the main agent and 10 g of a curing agent were weighed and collected in a 100 cc polycup, immediately mixed with a stirring bar for 1 minute, and the time until the stirring bar stopped moving was measured with a stopwatch. The small amount curability was evaluated according to the criteria. The measurement was performed in an atmosphere at 20 ° C. [Criterion] ◎ ‥‥ Excellent curability (curing time: less than 10 minutes) ○ ‥‥ Good curability (curing time: 10 minutes or more, 2
(Less than 0 minutes) × ‥‥ Poor curability (curing time: 20 minutes or more)

Warm water resistance of the cured product: 10 g of the main agent and 10 g of the curing agent were weighed and collected in a polycup having an internal volume of 100 cc.
Immediately after stirring and mixing, the mixture was poured into a mold having a size of 50 mm square and 5 mm thick, and cured in an atmosphere at 20 ° C. for 7 days to obtain a square plate-shaped cured product. Then, after immersing the cured product in hot water at 60 ° C. for 14 days, the hardness of the surface of the cured product was measured using a durometer D type in accordance with JIS K-7215 “Durometer hardness test method for plastics”. ,
Warm water resistance was evaluated according to the following criteria. [Criteria] ◎ ‥‥ Excellent hot water resistance (hardness: 60 or more) ○ ‥‥ Good hot water resistance (hardness: 20 or more, less than 60) × ‥‥ Poor hot water resistance (hardness: Less than 20)

(Example 2) As shown in Table 1, in the production of the curing agent, the product name "Ankamine M" was used instead of 25 parts of "Sunmide I-544" as the alicyclic polyamine.
A curing agent was obtained in the same manner as in Example 1, except that 25 parts of "CA" (phenol content: 8%, manufactured by BTR Japan Limited) was added. The main ingredient used in Example 1 was used as it was.

(Comparative Example 1) As shown in Table 1, in the production of a curing agent, without adding an alicyclic polyamine,
As an aliphatic thioether, "Cup Cure 3-800L"
C ”to 85 parts, 10 parts of tris (dimethylaminomethyl) phenol as a curing accelerator, 1 part of octylic acid as a curing speed regulator, and 4 parts of calcium carbonate as an inorganic filler.
5 parts, 1 part of a silane coupling agent and 0.05 part of a paste pigment as an adhesion-imparting agent were added, and preliminarily mixed with a mixer.
A curing agent for the adhesive composition was obtained. The main ingredient used in Example 1 was used as it was.

Comparative Example 2 As shown in Table 1, in the production of a curing agent, an alicyclic polyamine “Sanamide I-54” was used.
In the same manner as in Example 1 except that 25 parts of an aliphatic polyamine (trade name “Ankamine AD”, phenol content 50%, manufactured by BTR Japan Limited) was added instead of 25 parts of “4”, a curing agent was used. I got The main ingredient used in Example 1 was used as it was.

Comparative Example 3 As shown in Table 1, in the production of a curing agent, an alicyclic polyamine "Sanamide I-54" was used.
A curing agent was obtained in the same manner as in Example 1 except that 25 parts of a modified aliphatic polyamine (trade name “Sunmide X-983”, manufactured by Sanwa Chemical Co., Ltd.) was added instead of 25 parts of “4”. The main ingredient used in Example 1 was used as it was.

Comparative Example 4 As shown in Table 1, in the production of a curing agent, an alicyclic polyamine “Sanamide I-54” was used.
A curing agent was obtained in the same manner as in Example 1 except that 25 parts of a heterocyclic diamine (trade name “Epomate RX-3”, manufactured by Yuka Shell Epoxy) was added instead of 25 parts of “4”. The main ingredient used in Example 1 was used as it was.

Comparative Example 5 As shown in Table 1, in the production of a curing agent, an alicyclic polyamine “Sanamide I-54” was used.
4) Instead of 25 parts, a heterocyclic diamine (trade name “Epomate B-002W”, manufactured by Yuka Shell Epoxy) 2
A curing agent was obtained in the same manner as in Example 1 except that 5 parts were added. The main ingredient used in Example 1 was used as it was.

Comparative Example 6 As shown in Table 1, in the production of a curing agent, an alicyclic polyamine "Sanamide I-54" was used.
A curing agent was obtained in the same manner as in Example 1 except that 25 parts of polyamidoamine (trade name "Versamide V-125", manufactured by Henkel) was added instead of 25 parts of "4".
The main ingredient used in Example 1 was used as it was.

The performances of the seven types of adhesive compositions obtained in Example 2 and Comparative Examples 1 to 6 (the odor of the curing agent, the skinning property of the curing agent, the curability in a small amount, the hot water resistance of the cured product) ) Was evaluated in the same manner as in Example 1. Table 1 shows the results.
Was as shown in FIG.

[0092]

[Table 1]

As is clear from Table 1, the adhesive composition of Example 1 in which the alicyclic polyamine containing no phenol was added to the curing agent had a low odor and skininess of the curing agent, and a small amount of curability. And after curing, exhibited excellent warm water resistance.

The adhesive composition of Example 2 in which an alicyclic polyamine containing 8% by weight of phenol was added to the curing agent, the odor of the curing agent after standing for 7 days in an atmosphere of 40 ° C. Although the skinning property was inferior, the odor and the skinning property of the curing agent after being left in an atmosphere at 20 ° C. for 7 days are small, the curing property in a small amount is good, and after curing, excellent warm water resistance Demonstrated.

On the other hand, the adhesive composition of Comparative Example 1 in which the alicyclic polyamine or other polyamine was not added to the curing agent had a low odor and skininess of the curing agent, and was excellent in a small amount of curability. However, the hot water resistance after curing was poor.

The adhesive compositions of Comparative Examples 2 to 4 in which an aliphatic polyamine, a modified aliphatic polyamine or a heterocyclic diamine was added to the curing agent without adding an alicyclic polyamine were used. Although the curability and the warm water resistance after curing were good, the odor and skininess of the curing agent were poor.

Furthermore, the adhesive compositions of Comparative Examples 5 and 6, in which a heterocyclic diamine or polyamidoamine was added without adding an alicyclic polyamine to the curing agent, had good hot water resistance after curing. However, the odor and skininess of the curing agent were poor, and the curability of a small amount was also poor.

[0098]

As described above, the adhesive composition according to the present invention hardens rapidly even when it is applied in a small amount, that is, when the applied thickness is small, in which the odor of the curing agent and the skinning of the liquid surface are small. Excellent workability during use. In addition, after curing, it exhibits excellent properties such as excellent (hot) water resistance, adhesive strength and impact resistance. It is suitably used as an adhesive.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J036 AD01 AF01 AG00 AH00 DC05 DC06 DC10 DC13 DC38 DD01 DD02 DD03 HA11 JA06 4J040 EC061 EC071 EE052 HA136 HA196 HA306 HA356 HB07 HC04 HC05 HC24 HD05 HD35 HD36 HD37 JA13 KA16 KA17 KA42 LA05 LA08 LA11

Claims (2)

[Claims] 1 to 60 parts by weight of an inorganic filler and 0.01 to 5 parts by weight of an adhesion-imparting agent based on 100 parts by weight of an epoxy resin.
A base material to which parts by weight are added, and an aliphatic thioether 1
0.1 to 50 parts by weight of an alicyclic polyamine, 0.1 to 20 parts by weight of a curing accelerator, 1 to 100 parts by weight,
A two-part mixed adhesive composition comprising 60 parts by weight and a curing agent to which 0.01 to 5 parts by weight of an adhesion-imparting agent is added, wherein the mixing ratio of the main agent and the curing agent is in a weight ratio. An adhesive composition, wherein the ratio of the aliphatic thioether to the epoxy resin 1 is 0.5 to 1. 2. The adhesive composition according to claim 1, wherein the alicyclic polyamine is a phenol-free alicyclic polyamine.