JP2000026828A - Adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-pack ordinary-temperature-curable adhesive composition which is reduced in the emission of an odor and in the skinning of the surface of the curing agent, can be rapidly cured even when it is applied in a small amount, namely, when the coating thickness is small, and can exhibit excellent properties such as adhesive strength, elasticity, and flexibility after being cured. SOLUTION: There is provided a two-pack adhesive composition comprising agent A comprising 100 pts.wt. epoxy resin, 1-60 pts.wt. inorganic filler, and 0.01-5 pts.wt. tackifier and agent B comprising 100 pts.wt. aliphatic thiol, 0.1-20 pts.wt. cure accelerator, 1-60 pts.wt. inorganic filler, and 0.01-5 pts.wt. tackifier, wherein the mixing ratio of agent A to agent B is such that 0.5-1 pt.wt. aliphatic thioether is present per pt.wt. epoxy resin.

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 has a problem that the coating amount is small, that is, the coating thickness is small and the curing is slow.

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.

[0004] 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. There is a problem that a trace left remains and the adhesive strength is significantly reduced.

[0005]

SUMMARY OF THE INVENTION In order to solve the above-mentioned conventional problems, the present invention has been developed to reduce the odor and the skinning of the surface of the curing agent liquid, and to rapidly apply even a small amount of coating, that is, a thin coating. 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 adhesive strength and elasticity or flexibility after curing.

[0006]

The adhesive composition according to the first aspect of the present invention (hereinafter referred to as "the present invention") is composed of 100 parts by weight of an epoxy resin and 1 to 60 parts of an inorganic filler.
Part A and 0.1 to 20 parts by weight of a curing accelerator, 100 parts by weight of an aliphatic thioether, and inorganic fillers 1 to 6 with respect to 100 parts by weight of an aliphatic thioether.
A two-part mixed adhesive composition comprising 0 parts by weight and an B agent to which 0.01 to 5 parts by weight of an adhesiveness-imparting agent is added, wherein the mixing ratio of the A agent and the B agent is in a weight ratio. Epoxy resin 1
The adhesive composition, wherein the ratio is 0.5 to 1 relative to the aliphatic thioether.

The epoxy resin contained as a main component in the agent A of the adhesive composition according to the present invention is not particularly limited. For example, bisphenol A, bisphenol F, bisphenol AD and the like and epichlorohydrin can be used. 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; novolak-type epoxy resin; glycidylamine-type epoxy resin; glycidyl-ether-type epoxy resin A glycidyl ester type epoxy resin; a urethane-modified epoxy resin having a 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-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 inorganic filler added to the agent A of the adhesive composition according to the present invention contributes to the improvement of physical properties such as the cohesive strength of the cured product and the cost reduction of the adhesive composition.

The above-mentioned inorganic filler is not particularly limited, and examples thereof include 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 inorganic fillers, calcium carbonate which is more preferably used is not particularly limited. For example, colloidal light calcium carbonate, finely divided calcium carbonate, surface-treated colloidal calcium carbonate, 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 diameter 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 two or more kinds may be used in combination.

In the agent A 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. If the amount of the inorganic filler exceeds 60 parts by weight, the viscosity of the obtained A agent becomes too high, and the workability decreases.

The adhesiveness-imparting agent to be added to the agent A of the adhesive composition according to the present invention is not particularly limited. Examples thereof include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent. And the like, and are preferably used. 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, epoxysilanes 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 agent A 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 adhesion-imparting 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 addition amount exceeds 5 parts by weight, the cost will increase even though the adhesion will no longer be improved.

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

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

When an epoxy thioether other than the above-mentioned aliphatic thioether, for example, an aliphatic thioester or an aromatic thioether is used as a curing agent for the epoxy resin, the resulting adhesive composition has a strong odor and a severe skinning on the surface of the curing agent liquid. , It is not practical.

The aliphatic thioether is not particularly restricted but includes, for example, 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.

The curing accelerator added to the agent B of the adhesive composition according to the present invention is not particularly limited. For example, tris (dimethylaminomethyl) phenol, benzyldimethylamine, m-xylylenediene (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-
Polyethylamines such as aminoethylpiperazine and its modified products, diaminoethane and its modified products, diethylenetriamine and its modified products, polyoxypropylene polyamines and its modified products; polyaminoamines (polyaminoimidazoline) and its modified products; Among them, tertiary amines having a good balance between performance and cost are more preferably used, and among tertiary amines, tris (dimethylaminomethyl) phenol is particularly preferably used.

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

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

If the amount of the curing accelerator added is less than 0.1 part by weight per 100 parts by weight of the aliphatic thioether, a sufficient curing promoting effect cannot be obtained.
If the addition amount of the curing accelerator to 20 parts by weight exceeds 20 parts by weight, the heat resistance, water resistance and the like of the cured product are reduced, though the curing speed is no longer improved.

The inorganic filler added to the B agent of the adhesive composition according to the present invention can improve the physical properties such as the cohesive strength of the cured product in the same manner as the inorganic filler added to the A 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 calcium carbonate, clay, talc, silicon oxide,
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-mentioned inorganic fillers may be used alone or in combination of two or more.

In the agent B 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 aliphatic thioether.

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 coagulation and cost reduction of the cured product cannot be sufficiently obtained. If the amount of the inorganic filler to 60 parts by weight exceeds 60 parts by weight, the viscosity of the resulting B agent becomes too high, and the workability decreases.

The adhesiveness-imparting agent added to the agent B of the adhesive composition according to the present invention is not particularly limited. For example, the same adhesive agent that can be added to the agent A may be used.
Various coupling agents such as a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent are exemplified, and are preferably used. 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 limited, but includes, for example, mercaptosilanes, aminosilanes, epoxysilanes and the like which can be added to the agent A. Of these, 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 agent B 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 aliphatic thioether.

When the amount of the adhesion-imparting agent added is less than 0.01 part by weight based on 100 parts by weight of the aliphatic thioether,
If the effect of improving the adhesive strength is not sufficiently obtained, and if the amount of the adhesiveness-imparting agent added to 100 parts by weight of the aliphatic thioether exceeds 5 parts by weight, the cost is increased even though the adhesive strength is no longer improved. Becomes

In the adhesive composition according to the present invention, the mixing ratio of the A agent and the B agent is such that the weight ratio of the epoxy resin 1 which is the main component of the A agent is such that the aliphatic thioether which is the main component of the B agent is mixed. It is necessary that the ratio be 0.5 to 1.

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, or the elasticity and flexibility of the cured product become poor. When the mixing ratio of the aliphatic thioether to the epoxy resin 1 exceeds 1, the adhesive strength and the mechanical strength of the cured product decrease.

The agent A and / or the agent B 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 as long as the achievement of the object of the present invention is not hindered. Even if one or more of various additives such as agents, thixotropic agents, softeners, plasticizers, surfactants, stabilizers, antioxidants, ultraviolet absorbers, flame retardants, and organic solvents are contained. good.

The curing speed regulator is added when, for example, it is desired to delay the curing speed to extend the pot life (pot life), and is not particularly limited. Such various carboxylic acids are mentioned, and are preferably used.

The addition amount of the above-mentioned curing speed regulator is not particularly limited as long as it is appropriately set in accordance with the desired curing speed, and the curing speed adjusting agent is added to 100 parts by weight of the epoxy resin or the aliphatic thioether. It is preferable that the content be 5 parts by weight or less for the regulator.

Epoxy resin or aliphatic thioether 10
If the addition amount of the curing rate regulator to 0 parts by weight exceeds 5 parts by weight, the curing rate becomes too slow, and the fast curability, one of the objects of the present invention, may be impaired.

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

The coloring agent is used as it is, and the agent A and / or
Alternatively, it may be added to Agent B, or may be added to Agent A and / or Agent B, for example, as a paste-like master batch.

The amount of the colorant to be added is not particularly limited as long as it is appropriately set in accordance with the desired degree of coloration, but 10 parts by weight of the colorant per 100 parts by weight of the epoxy resin or the aliphatic thioether. Parts or less.

Epoxy resin or aliphatic thioether 10
Even if the amount of the coloring agent added to 0 parts by weight exceeds 10 parts by weight, the degree of coloring no longer improves.

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

[0056]

Since the adhesive composition according to the present invention uses an aliphatic thioether as a curing agent for an epoxy resin, it has less odor and less skinning on the surface of the curing agent liquid (agent B) and is excellent in workability. Also, since the epoxy resin is cured using a combination of an aliphatic thioether and a curing accelerator such as a tertiary amine,
In the case of a small amount of coating, that is, even when the coating thickness is thin, it cures rapidly. Furthermore, since an adhesion-imparting agent such as a silane coupling agent and an inorganic filler such as calcium carbonate are added, the adhesiveness to various adherends is excellent, and after the curing, the adhesive strength and elasticity are excellent. Alternatively, it exhibits various physical properties such as flexibility.

[0057]

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”.

(Example 1)

(1) Production of Adhesive Composition As shown in Table 1, 100 parts of a bisphenol A type epoxy resin (trade name “Epicoat 828XA”, manufactured by Yuka Shell Epoxy Co.) was mixed with calcium carbonate as an inorganic filler. 40 parts, 1 part of a silane coupling agent as an adhesion-imparting agent and 0.05 parts of a paste pigment as a coloring agent were added, and preliminarily mixed with a mixer. Agent A of the composition was obtained.

As shown in Table 1, polyoxypropylene poly-2-hydroxythiol (trade name “Cup Cure 3-800LC”, A
CI Japan Limited (85 parts), 10 parts of tris (dimethylaminomethyl) phenol as a curing accelerator, 45 parts of calcium carbonate as an inorganic filler, 1 part of a silane coupling agent as an adhesion promoter and 0 parts of paste pigment After adding 0.05 part by weight and preliminarily mixing with a mixer, the mixture was uniformly kneaded by passing through three rolls once to obtain Agent B of the adhesive composition.

(2) Evaluation The performance of the adhesive composition obtained above (odor of Agent B,
The skinning property and curability in a small amount of the agent B) were evaluated by the following methods. The results were as shown in Table 1.

Odor of Agent B: 200 g of Agent B was added to an internal volume of 20
It was sealed in a 0 cc glass bottle, left in an atmosphere at 20 ° C. or 40 ° C. for 7 days, opened, and immediately smelled, and the odor was evaluated according to the following criteria. [Judgment criteria] ○ ‥‥ Low odor × ‥‥ High odor

Skinning property of Agent B: 200 g of Agent B was placed in a 200 cc glass bottle, sealed and sealed at 20 ° C. or 40 ° C.
After being left in an atmosphere at a temperature of 7 ° C. for 7 days, the container was opened and the skinning state on the surface of the agent B was visually observed, and the skinning property was evaluated according to the following criteria. [Judgment criteria] ○ ‥‥ Low skinning × ‥‥ High skinning

Small amount curability: 10 g of Agent A and 10 g of Agent B were weighed and collected in a 100 cc polycup, and immediately mixed with a stirring bar for 1 minute. The time until the stirring bar did not move was measured with a stopwatch. The small amount curability was evaluated according to the following criteria. The measurement was performed in an atmosphere at 20 ° C. [Criteria] ○ ‥‥ 15 minutes or less △ ‥‥ Over 15 minutes, 20 minutes or less × ‥‥ Over 20 minutes, 30 minutes or less

(Example 2) As shown in Table 1, the blending composition of the B agent was 85 parts of "Cup Cure 3-800LC", 10 parts of tris (dimethylaminomethyl) phenol, and 0.1 part of octylic acid as a curing speed regulator. 5 parts, calcium carbonate 4
5 parts, 1 part of silane coupling agent and 0.
Except that the amount was 05 parts, the procedure of Example 1 was repeated to obtain Agent B of the adhesive composition.

(Examples 3 to 7) In the same manner as in Example 1 except that the composition of the agent B was changed to the composition shown in Table 1, Agent B of the adhesive composition was obtained.

(Comparative Example 1) In the preparation of the agent B, an aliphatic thioester (trade name “Epicure QX4”) was used instead of the aliphatic thioether “Cup Cure 3-800LC”.
0 "(manufactured by Yuka Shell Epoxy Co., Ltd.), and the procedure of Example 1 was repeated, except that the composition was changed to the composition shown in Table 1, to obtain Agent B of the adhesive composition.

Comparative Example 2 In the preparation of Agent B, an aromatic thioether (trade name “Epomate QX1”) was used instead of the aliphatic thioether “Cup Cure 3-800LC”.
0 "(manufactured by Yuka Shell Epoxy Co., Ltd.), and the procedure of Example 1 was repeated, except that the composition was changed to the composition shown in Table 1, to obtain Agent B of the adhesive composition.

Comparative Example 3 In the preparation of the agent B, an aromatic thioether (trade name “Epomate QX1”) was used instead of the aliphatic thioether “Cup Cure 3-800LC”.
1 ", manufactured by Yuka Shell Epoxy Co., Ltd.), and the same procedure as in Example 1 was carried out, except that the composition was changed to the composition shown in Table 1, to obtain Agent B of the adhesive composition.

Comparative Example 4 In the preparation of Agent B, an aromatic thioether (trade name “Epomate QX1”) was used instead of the aliphatic thioether “Cup Cure 3-800LC”.
2 ", manufactured by Yuka Shell Epoxy Co., Ltd.), and in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1, to obtain a B agent of the adhesive composition.

The odor and skininess of the ten types of B agents obtained in Examples 2 to 7 and Comparative Examples 1 to 4 were evaluated in the same manner as in Example 1. The curability in a small amount when the agent A obtained in Example 1 was used in combination with the ten types of agent B was evaluated in the same manner as in Example 1. These results were as shown in Table 1.

[0072]

[Table 1]

As is clear from Table 1, the agent B of the adhesive compositions of Examples 1 to 7 according to the present invention was prepared at 20 ° C. or 40 ° C.
After standing for -7 days, there was little odor and skininess. Further, the adhesive compositions of Examples 1 to 7 were all excellent in curability in a small amount.

On the other hand, the agent B of the adhesive composition of Comparative Example 1 using an aliphatic thioester instead of the aliphatic thioether as a curing agent for the epoxy resin was left at 20 ° C. or 40 ° C. for 7 days. In each case, odor and skininess were intense. In addition, the adhesive composition of Comparative Example 1 had poor curability in a small amount.

The agent B of the adhesive compositions of Comparative Examples 2 to 4 in which an aromatic thioether was used instead of the aliphatic thioether as a curing agent for the epoxy resin was used at 20 ° C. or 40 ° C.
After standing for 7 days, the odor and skininess were intense.

[0076]

As described above, the adhesive composition according to the present invention has a low odor and little skinning on the surface of the curing agent liquid, and rapidly cures even when applied in a small amount, that is, even when the applied thickness is thin. Since it has good workability and exhibits various physical properties such as excellent adhesive strength and elasticity or flexibility after curing, it is suitably used as a two-component mixed-room temperature curable adhesive for various industrial or general uses. .

Continued on the front page F-term (reference) 4J036 AA01 DA02 DC01 DC06 DC10 DC38 DD02 FA01 FA03 FA05 FA06 GA08 GA10 GA28 JA06 4J040 EC021 EC061 EC071 EC121 EC161 EC211 EC401 HA196 HA296 HA306 HC01 HC04 HC05 HC08 HC21 HD05 HD41 JA13 KA11 KA30 LA17 MA04 NA12

Claims (1)

[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.
Part A in which parts by weight are added, and aliphatic thioether 1
0.1 to 20 parts by weight of a curing accelerator with respect to 00 parts by weight,
1 to 60 parts by weight of an inorganic filler and 0.01 to an adhesiveness-imparting agent
A two-part mixed adhesive composition comprising a B agent to which 5 parts by weight is added, wherein a mixing ratio of the A agent and the B agent is 0.5 to 0.5 parts by weight of the aliphatic thioether to 1 part of the epoxy resin. 1
An adhesive composition characterized by the following ratio: