JP2000303053A - Adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a two-component mixing type, cold setting adhesive compsn. which does not cause crystllization (freezing) of the main ingredient at a low temp., 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 and strength against wet heating as well as excellent 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 contg. 1 wt.% or less of a saponifiable chlorine, 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 0.1-20 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 mixture type epoxy resin-based adhesive composition has a problem in that the (warm) water resistance and the heat and humidity resistance after curing are not sufficient. Further, in the case of a two-part mixture type cold-setting epoxy resin-based adhesive composition, the main agent mainly composed of an epoxy resin crystallizes (freezes) during storage at a low temperature (0 ° C. or lower), for example, in winter. This causes a problem that workability deteriorates.

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 does not cause crystallization (freezing) of the main agent even at a low temperature, and reduces odor of the hardener and skinning of the liquid surface. Even when a small amount of coating is applied, that is, even when the coating thickness is small, it is rapidly cured, and after curing, exhibits various physical properties such as excellent (warm) water resistance and heat and humidity resistance, and excellent adhesive strength and impact resistance. An object of the present invention is to provide a two-part mixture type cold-setting adhesive composition.

[0006]

The adhesive composition according to the invention described in claim 1 (hereinafter referred to as "first invention")
Epoxy resin 1 having a saponified chlorine content of 1% by weight or less
With respect to 100 parts by weight, a main agent added with 1 to 60 parts by weight of an inorganic filler and 0.01 to 5 parts by weight of an adhesion promoter, and with 100 parts by weight of an aliphatic thioether, a curing accelerator of 0.1 part by weight. 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.

Further, the invention according to claim 2 (hereinafter referred to as “second
The adhesive composition according to the first aspect of the present invention is the adhesive composition according to the first aspect, wherein the epoxy resin having a saponified chlorine content of 1% by weight or less is 50 to 90% by weight of a bisphenol A type epoxy resin and It is an epoxy resin containing 50 to 10% by weight of a phenol novolak type epoxy resin and / or a bisphenol F type epoxy resin.

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

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

In the main component of the adhesive composition according to the second invention, as the epoxy resin, 50 to 90% by weight of a bisphenol A type epoxy resin and 50 to 10% by weight of a phenol novolak type epoxy resin and / or a bisphenol F type epoxy resin. Is required to be used.

In the second invention, an epoxy resin containing 50 to 90% by weight of a bisphenol A type epoxy resin is used as the epoxy resin, so that a cured product of the obtained adhesive composition has adhesive strength, impact resistance, It is excellent in performance balance such as resistance to (warm) water and heat and humidity. Here, the term “(warm) water resistance” means “warm water resistance” or “water resistance”.

When the content of the bisphenol A type epoxy resin in the epoxy resin used in the second invention is less than 50% by weight, the adhesive strength of the cured product of the obtained adhesive composition becomes insufficient, and conversely, When the content of the bisphenol A type epoxy resin in the epoxy resin exceeds 90% by weight, the impact resistance of the cured product of the obtained adhesive composition becomes insufficient.

The above-mentioned bisphenol A type epoxy resin may have various properties from liquid to semi-solid or solid at room temperature, depending on its molecular weight. In the second invention, bisphenol A liquid at room 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 combination ratio of the bisphenol A type epoxy resin which is liquid at ordinary temperature and the semi-solid or solid bisphenol A type epoxy resin at ordinary temperature is not particularly limited. It is preferable that the ratio of solid or solid bisphenol A epoxy resin / liquid bisphenol A epoxy resin at room temperature is 1 or less.

If the ratio of the semi-solid or solid bisphenol A-type epoxy resin at room temperature to the liquid bisphenol A-type epoxy resin at room temperature (weight ratio) exceeds 1, the viscosity of the resulting 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.

In the second invention, an epoxy resin containing 50 to 10% by weight of a phenol novolak type epoxy resin and / or a bisphenol F type epoxy resin is used as the epoxy resin.

The phenol novolak type epoxy resin is an epoxy resin obtained by reacting a phenol novolak resin with epichlorohydrin. The epoxy resin is used to improve the (hot) water resistance and the heat and humidity resistance of a cured product of the obtained adhesive composition. Contribute.

The phenol novolak type epoxy resin may be used alone or in combination of two or more.

The bisphenol F type epoxy resin is an epoxy resin obtained by reacting bisphenol F with epichlorohydrin, and contributes to prevention of crystallization (freezing) of the main component of the obtained adhesive composition at a low temperature. .

The bisphenol F type epoxy resin is
They may be used alone or in combination of two or more.

When the content of the phenol novolac type epoxy resin and / or bisphenol F type epoxy resin in the epoxy resin used in the second invention is less than 10% by weight, the heat resistance of the cured product of the obtained adhesive composition is reduced. The effect of improving the wet strength and heat resistance and / or the effect of preventing the crystallization (freezing) of the base material of the obtained adhesive composition at low temperature is not sufficiently obtained, and conversely, the phenol novolak type epoxy resin and / or Alternatively, when the content of the bisphenol F type epoxy resin exceeds 50% by weight, the adhesive strength, impact resistance, (warm) water resistance, and the like of the cured product of the obtained adhesive composition are reduced.

The first invention and the second invention (hereinafter referred to as "the present invention")
), It is necessary that the above-mentioned saponified chlorine content in the epoxy resin is 1% by weight or less.
When two or more epoxy resins are used in combination, the content of each saponified chlorine in each epoxy resin used may be 1% by weight or less, or the saponification of all the epoxy resins used in combination may be sufficient. The average value of the chlorine content may be 1% by weight or less.

When the content of the saponified chlorine in the epoxy resin exceeds 1% by weight, the cured product of the resulting adhesive composition has insufficient (warm) water resistance and heat and humidity resistance.

The inorganic filler added to the main component 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 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, and are preferably used. 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 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.

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 two or more kinds may be used in combination.

In the main component of the adhesive composition according to the present invention, 100 parts by weight of the epoxy resin having a saponified chlorine content of 1% by weight or less (hereinafter, simply referred to as "epoxy resin") is added to the inorganic material. It is necessary that 1 to 60 parts by weight of a filler is added.

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 limited. 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 with less odor of the curing agent and less skinning on the liquid surface.
Also, by using an aliphatic thioether in combination with a curing accelerator described below, it becomes possible to obtain an adhesive composition which can be rapidly cured even when the coating is performed in a small amount, that is, even when the coating thickness is small.

When a curing agent for the epoxy resin other than the above-mentioned aliphatic thioether, for example, an aliphatic thioester or an aromatic thioether, is used, the curing agent of the obtained adhesive composition has a strong odor and a strong skin on the liquid surface. It becomes poor in practicality.

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

The curing accelerator added to the curing agent of the adhesive composition according to the present invention includes 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 accelerating the curing of the adhesive composition by the reaction with the thioether.

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 resulting adhesive composition will have reduced (warm) water resistance, heat and humidity resistance, etc., although 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 component. 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, and the like which can be added to the base material are used.
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.

[0054] 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 of the cured product and the cost reduction effect 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 adhesiveness-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 adhesiveness-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, and examples thereof include various silane coupling agents, titanium coupling agents, and aluminum coupling agents similar to those that 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 as the main component of the main agent to the epoxy resin 1 as 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, or the adhesive strength and impact resistance of the cured product are reduced. 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 rate adjusting agent is added when, for example, it is desired to extend the pot life after mixing the main ingredient and the curing agent by delaying the curing rate, 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 addition amount of the above-mentioned curing rate adjusting agent is not particularly limited as long as it is appropriately set in accordance with a desired curing rate, but is not particularly limited, and is based on 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 curing rate controlling agent 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 in accordance with 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.

When the amount of the coloring agent is more than 10 parts by weight per 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 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.

[0074]

The adhesive composition according to the first invention comprises, as a main component, an epoxy resin having a saponified chlorine content of a specific value or less, and a specific amount of an inorganic filler and adhesion imparting property with respect to a specific amount of the epoxy resin. And a curing agent containing an aliphatic thioether as a main component, and a specific amount of the aliphatic thioether, and a specific amount of a curing accelerator, an inorganic filler and an adhesion promoter added. And the mixing ratio between the main agent and the curing agent is a specific ratio by weight, so that after curing, excellent (warm) water resistance and heat and humidity resistance, and excellent adhesive strength and impact resistance are obtained. In addition to exhibiting various physical properties such as properties, the odor of the curing agent and the skinning of the liquid surface are small, and it is rapidly cured even when applied in a small amount, that is, even when the applied thickness is thin.

The adhesive composition according to the second aspect of the present invention is the adhesive composition according to the first aspect of the present invention, wherein the epoxy resin having a saponified chlorine content of a specific value or less is a specific amount of bisphenol A type epoxy resin and phenol. Since a novolak type epoxy resin and / or an epoxy resin containing a specific amount of a bisphenol F type epoxy resin is used,
After hardening, it exhibits more excellent (warm) water resistance and heat and humidity resistance, and does not crystallize (freeze) the main agent even at low temperatures.

[0076]

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, bisphenol A type epoxy resin (trade name “Epicoat 828”) which is liquid at normal temperature, saponified chlorine content 0.03%, oiled shell epoxy After adding 40 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 to 100 parts, and premixing with a mixer, The roll was passed once and kneaded uniformly to obtain a main component of the adhesive composition.

As shown in Table 1, as an aliphatic thioether, polyoxypropylene poly-2-hydroxythiol (trade name “Cup Cure 3-800LC”, B
With respect to 85 parts of TR Japan Limited, 10 parts of tris (dimethylaminomethyl) phenol as a curing accelerator, 1 part of octylic acid as a curing speed regulator, 45 parts of calcium carbonate as an inorganic filler, and as an adhesion promoter 1 part of a silane coupling agent and 0.05 part of a paste pigment were added and preliminarily mixed by a mixer, and then kneaded uniformly by passing through a single roll once to obtain a curing agent for the adhesive composition.

(2) Evaluation Performance of the adhesive composition obtained above: crystallization resistance (freezing) of the main agent, odor of the curing agent, skinning of the curing agent,
A small amount of curability, warm water resistance, and heat and humidity resistance were evaluated by the following methods. The results were as shown in Table 1.

Crystallization (freezing) resistance of main agent: main agent 200
g in a 200 cc glass bottle and sealed with a stopper.
Alternatively, after left for 60 days in an atmosphere of −20 ° C., the container was opened, the crystallization (freezing) state of the main agent was visually observed, and the crystallization (freezing) resistance was evaluated according to the following criteria. [Evaluation criteria] ○ ‥‥ Almost no crystallization (freezing) × ‥‥ Extremely crystallization (freezing)

Odor of the curing agent: 200 g of the curing agent 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 bottle was opened, the odor was immediately smelled, and the odor was evaluated according to the following criteria. [Judgment criteria] ○ ‥‥ Low odor × ‥‥ High odor

Hardening agent skinning: 200 g of hardening 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, opened, and the skin on the surface of the hardening agent was opened. 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 the curing agent 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 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: 10 g of the base material and 10 g of a curing agent were weighed and collected in a 100 cc polycup, immediately mixed with stirring, and poured into a 50 mm square × 5 mm thick mold at 20 ° C. for 7 days. After curing, a square plate-shaped cured product was obtained. 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”. The 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)

Heat and humidity resistance: 10 g of the main agent and 10 g of the curing agent were weighed and collected in a 100 cc polycup, immediately mixed with stirring, and then 60 mm wide × 100 mm long × 1 thickness thick.
Two 2 mm ceramic siding materials were used as adherends, and the two adherends were butt-adhered to each other in a cross section in the width direction and cured for 7 days in a 20 ° C. atmosphere. Then
After leaving this joined body in an atmosphere of 60 ° C. and 95% RH for 14 days, J
IS A-1408 "Bending test method for architectural boards"
The bending adhesive strength was measured in accordance with the above, and the heat and humidity resistance was evaluated according to the following criteria. [Judgment criteria] ◎ ‥‥ Excellent heat and humidity strength (Bending adhesive strength: 80k)
gf / cm or more) Good heat and moisture resistance (bending adhesive strength: 60k)
gf / cm or more and less than 80 kgf / cm) × ‥‥ Poor heat and moisture resistance (bending adhesive strength: 60 kgf / cm)
less than cm)

(Example 2) As shown in Table 1, a main ingredient was obtained in the same manner as in Example 1 except that the addition amount of calcium carbonate to 100 parts of "Epicoat 828" was changed to 20 parts. In addition, the amount of “Cup Cure 3-800LC” was changed to 7
0 parts, and the amount of calcium carbonate added to this was 35 parts.
A curing agent was obtained in the same manner as in Example 1 except that the curing agent was used.

Example 3 As shown in Table 1, as an epoxy resin, 70 parts of "Epicoat 828", a semi-solid bisphenol A type epoxy resin (trade name "Epicoat 834", a saponified chlorine content at room temperature) were used. 0.1% or less, Yuka Shell Epoxy Co., Ltd.) 10 parts and phenol novolak type epoxy resin (trade name "DER 431", saponified chlorine content 0.77%, Dow Chemical Co., Ltd.) 20 A main agent was obtained in the same manner as in Example 2 except that parts were used.
The curing agent used was the curing agent obtained in Example 2.

Example 4 As shown in Table 1, 70 parts of "Epicoat 828", 10 parts of "Epicoat 834", and a bisphenol F type epoxy resin (trade name "Epicoat 807") which is liquid at normal temperature were used as epoxy resins. A main agent was obtained in the same manner as in Example 2, except that 20 parts of a saponified chlorine content of 1% or less (manufactured by Yuka Shell Epoxy Co., Ltd.) was used.
The curing agent used was the curing agent obtained in Example 2.

(Comparative Example 1) As shown in Table 1, in the production of the main component of the adhesive composition, instead of 100 parts of “Epicoat 828”, a bisphenol A type epoxy resin (product Name "Epicoat 8
28XA ", a saponified chlorine content of 1.67%, manufactured by Yuka Shell Epoxy Co., Ltd.) (100 parts), and a main agent was obtained in the same manner as in Example 1. The curing agent used in Example 1 was used as it was.

Performance of Five Adhesive Compositions Obtained in Examples 1-4 and Comparative Example 1 Crystallization Resistance of Main Agent (Freezing)
The properties, the odor of the curing agent, the skinning property of the curing agent, the curability in a small amount, the hot water resistance, and the heat and humidity resistance｝ were evaluated in the same manner as in Example 1. The results were as shown in Table 1.

[0092]

[Table 1]

As is clear from Table 1, the cured products of the adhesive compositions of Examples 1 to 4 according to the present invention were excellent in both hot water resistance and heat and humidity resistance, and exhibited excellent physical properties. . Similarly, the main components of the adhesive compositions of Examples 1 to 4 hardly crystallized (frozen) even at a low temperature. Furthermore, the curing agents of the adhesive compositions of Examples 1 to 4 also had little odor and little skinning on the liquid surface. Furthermore,
The adhesive compositions of Examples 1 to 4 were also excellent in curability in a small amount. Therefore, it can be said that the adhesive compositions of Examples 1 to 4 have excellent workability.

On the other hand, Comparative Example 1 using an epoxy resin having a saponified chlorine content of more than 1% by weight (a saponified chlorine content of 1.67% by weight) as an epoxy resin as a main component of the main agent. In the adhesive composition, the cured product was poor in both warm water resistance and heat and humidity resistance.

[0095]

As described above, the adhesive composition according to the present invention hardly causes crystallization (freezing) of the base agent even at a low temperature, reduces the odor of the curing agent and the skinning of the liquid surface,
In addition, even when the coating amount is small, that is, even when the coating thickness is small, it is rapidly cured, so that the workability during use is excellent. Further, after curing, it exhibits various properties such as excellent (hot) water resistance and heat and humidity resistance, and excellent adhesive strength and impact resistance. It is suitably used as a liquid mixture type room temperature curable adhesive.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C09J 11/06 C09J 11/06 F term (reference) 4J036 AA01 AA05 AA06 AD08 AF01 BA07 DA02 DD02 FA01 FA13 FA14 FB12 JA06 4J040 EC061 EC071 EE052 HA136 HA196 HA306 HA356 HB07 HC05 HC08 HC09 HD05 HD30 HD35 HD36 HD37 JA13 JB11 KA17 KA42 LA05 LA06 LA07 LA08

Claims (2)

[Claims] 1. An inorganic filler of 1 to 6 parts by weight per 100 parts by weight of an epoxy resin having a saponified chlorine content of 1% by weight or less.
0.1 to 20 parts by weight of a curing accelerator, and 1 to 10 parts by weight of an inorganic filler, based on 100 parts by weight of an aliphatic thioether and 0 parts by weight and 0.01 to 5 parts by weight of an adhesion promoter.
A two-pack type 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 by weight. An adhesive composition, wherein the ratio of the aliphatic thioether to the epoxy resin 1 is 0.5 to 1. 2. An epoxy resin having a saponified chlorine content of 1% by weight or less is a bisphenol A type epoxy resin 50.
Phenol novolak type epoxy resin and / or bisphenol F type epoxy resin
The adhesive composition according to claim 1, wherein the adhesive composition is an epoxy resin containing the resin in an amount of 1% by weight.