JP3382205B2 - Water-based rubber adhesive - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solvent- and water-resistant water-based rubber adhesive mainly for porous materials having a relatively long pot life.

[0002]

BACKGROUND OF THE INVENTION As a method for improving solvent resistance and water resistance of a water-based rubber polymer by crosslinking, crosslinking with a methylol compound, ionic crosslinking with an aqueous solution of a metal compound such as Ca, Zn, Zr or Al, an isocyanate compound Crosslinking using an organic reactive compound such as an epoxy compound as a curing agent is known. The cross-linking method using a methylol compound requires heating, and the ionic cross-linking using a metal ion solution and the method using an organic reactive compound have drawbacks that the pot life is relatively short. The method using a methylol compound also has a problem in that it produces harmful formalin.

[0003]

SUMMARY OF THE INVENTION The present invention has improved the above-mentioned drawbacks and has a long working life (usable time).
It is a water-based rubber adhesive that has low toxicity, solvent resistance and water resistance.

[0004]

[Means for Solving the Problems] When an alkaline earth metal compound is added to a carboxyl group-containing aqueous rubber-based polymer composition, it gels instantly or within a few hours and becomes unusable. The present invention is a carboxyl group-containing aqueous rubber-based polymer composition, an alkaline main agent containing a volatile aqueous amine compound, as a curing agent, an alkaline earth metal carbonate, an alkaline earth metal oxide, an alkali A powdery alkaline earth metal compound selected from hydroxides of earth metals, which is non-reactive with the alkaline earth metal compound, and which is a main rubber-based aqueous compound. The problem is solved by using a curing agent dispersed in an aqueous polymer composition that is compatible with the combined composition.

By adding a volatile aqueous amine compound to the main component of the water-based rubber adhesive, when the main component and the curing agent are mixed, ion dissociation and chemisorption of the alkaline earth metal compound are suppressed, and Dispersing an alkaline earth metal compound in a reactive aqueous polymer solution and using a curing agent in which the surface of the alkaline earth metal compound is coated with a non-reactive polymer enables a long pot life. To do.

Generally, a carboxyl-containing polymer has poor water resistance due to the hydrophilicity of the carboxyl group, and has low solvent resistance due to the polarity of the carboxyl group. Shielding carboxyl groups is an important issue for water-based adhesives. The present invention mainly achieves the problem of cross-linking by chemical adsorption of a carboxyl group and an alkaline earth metal compound, and formation of a salt of a carboxyl group and an alkaline earth metal to shield the carboxyl group. Is.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Main ingredient A carboxyl group-containing aqueous rubber-based polymer composition as a main ingredient is
An emulsion polymer composition containing a carboxyl group-containing rubber-based polymer as a main component and containing auxiliary agents such as an emulsifier and a stabilizer. The carboxyl group-containing aqueous rubber polymer has an acid value of 1 before neutralization.
~ 30 mg KOH / g polymer, preferably 2-10 mg
It is a polymer of KOH / g . The volatile aqueous amine compound added is ammonia, morpholine, N-methylmorpholine,
N ethylmorpholine, NN dimethyl ethanolamine,
It can be selected from NN diethylethanolamine, NN dimethylpropanolamine, and NN diethylpropanolamine.

By the addition of the volatile aqueous amine compound,
Although the main agent is made to have a proper alkalinity, the pH is 7 or more, and it may be in a range that prevents ionic dissociation and chemical adsorption of the powdery alkaline earth metal compound. . Usually 12 or less is sufficient. pH 1
When it is larger than 2, the alkali itself becomes excessive,
The reaction that produces crosslinks is less likely to occur. Preferably,
It is carried out at pH 8-10. The concentration of the polymer of the main agent is related to the pot life, and lowering the concentration can extend the pot life even though there is a limit. If necessary, other polymers, resins, coloring pigments, extender pigments, additives and the like can be added as the main ingredient component after being water-dispersed or water-solubilized. Further, when pure water is added to the main component, the concentration of the carboxyl group-containing aqueous rubber-based polymer composition decreases,
Pot life becomes longer.

(B) Curing agent An aqueous polymer composition which is a dispersion medium of the curing agent, is non-reactive with an alkaline earth metal compound, and is compatible with the main rubber-based aqueous polymer composition. Is a polymer whose polymer does not have an acid group such as a carboxyl group. For example, a non-carboxylic acid-modified rubber-based emulsion polymer, ethylene
Examples thereof include vinyl acetate emulsion copolymers and non-carboxylic acid-modified acrylic emulsion copolymers. It is necessary to select a suitable one having compatibility with the selected aqueous rubber polymer composition of the main component. Generally, it is a polymer composition similar to the carboxyl group-containing aqueous rubber-based polymer composition of the main component.

Curing agents are added to produce crosslinks. The alkaline earth metal compound containing the curing agent as a main component is selected from alkaline earth metal carbonates, oxides, and hydroxides.
From the viewpoint of low toxicity and economy, practically usable alkaline earth metals include Mg, Ca, and Ba.
The particle size of the powder of the alkaline earth metal powder is not limited. The selected alkaline earth metal compound is an aqueous solution containing the selected non-reactive aqueous polymer composition, if necessary, a dispersing agent, an antifoaming agent, etc. are added and dispersed by a usual means. Use a hardener with a concentration and viscosity that are convenient for use.

(C) Compounding of curing agent The amount of the powdery alkaline earth metal compound used as a curing agent is 10% or less of the weight of the main agent. Excessive use only shortens pot life. Usually, 0.5 to 5% of the weight of the main agent is desirable.

(D) Mixing Main Agent and Curing Agent The water-based rubber adhesive according to the present invention is a two-component adhesive agent in which two components of the main agent and the curing agent are mixed before use. 1 to 4 show schematic views for producing this water-based rubber adhesive. FIG. 1 shows the case where the main component is (A) a carboxyl group-containing aqueous rubber-based polymer composition, and (2) a volatile aqueous amine compound is added. The curing agent comprises a powdery alkaline earth metal compound and an aqueous polymer composition which is non-reactive with the alkaline earth metal compound and which is compatible with the main rubber-based aqueous polymer composition. The case where it includes is shown. In FIG. 1, an aqueous polymer composition that is non-reactive with an alkaline earth metal compound and is compatible with the main rubber-based aqueous polymer composition is non-reactive with an alkaline earth metal compound. Of aqueous polymer composition.
The same applies to FIGS. 2 to 4 below.

The two components, the main agent and the curing agent, are stored in separate containers until use. At the time of use, a main agent and a curing agent are mixed to form a water-based rubber adhesive. In order to crosslink, it is necessary to volatilize the amine compound. Therefore, it is necessary to use a volatile amine compound. Further, since both the main agent and the curing agent are aqueous, it is necessary to use an aqueous amine compound. Therefore, in this invention, the volatile aqueous amine compound is added to the main agent or the curing agent.

A volatile aqueous amine compound may or may not be added to the curing agent. FIG. 2 shows a case where a volatile aqueous amine compound is added to the curing agent of FIG. The method of use is the same as in the case of FIG.

Further, the volatile aqueous amine compound may be added to the curing agent without adding the volatile aqueous amine compound to the main agent (FIG. 3). FIG. 3 shows a case where the main component is only the carboxyl group-containing aqueous rubber-based polymer composition (or other additive). The case where the curing agent contains a powdery alkaline earth metal compound, an aqueous polymer composition that is non-reactive with the alkaline earth metal, and a volatile aqueous amine compound is shown. The method of use is the same as in the case of FIG.

Further, FIG. 4 shows a main agent and a curing agent.
An example is shown in which a volatile aqueous amine compound and a dispersant of an alkaline earth metal compound are mixed to form an aqueous rubber adhesive. As a curing agent, a volatile aqueous amine compound may be mixed with a powdery alkaline earth metal compound to form a paste, and the paste may be mixed with a main agent to form an aqueous rubber adhesive. In the example of FIG. 4, the main component is a carboxyl group-containing aqueous rubber-based polymer composition, but a volatile aqueous amine compound may be added to the main component.

[0017]

Example (Evaluation) According to the method of JIS K6850, an aluminum plate and a 180 mesh polyester cloth were adhered, and the tensile shear adhesive strength was measured on the 25 mm × 20 mm bonded surface. The measuring speed is 10 mm / min. The measured value is Kg / (25mm × 20mm).
For the test piece, apply the same adhesive to the aluminum plate,
After drying at 60 ° C. for 40 minutes and subjecting to a primer treatment, a cloth cloth was placed, and an adhesive was applied on the cloth to adhere the cloth. The evaluation was carried out by immersing 5 test pieces, which were left at room temperature for 3 days after applying the adhesive, in predetermined pure water or a solvent for 24 hours, and then measured the tensile shear adhesive strength.

Table 1 shows the adhesive strength (Kg) after being immersed in propylene glycol / methyl ether (PGM) for 24 hours.
/ (25 mm × 20 mm)) is shown in comparison with a comparative example of the original non-crosslinked carboxyl group-containing aqueous rubber-based polymer composition. In the comparative example, no curing agent was added. The adhesive strength is an average value of 5 points. Comparative Examples 2 and 3 were easily disengaged before the measurement and could not be measured.

[0019]

[Table 1]

Table 2 shows the adhesive strength after immersion in pure water for 24 hours in the same manner as in the comparative example. The adhesive strength is an average value of 5 points.

[0021]

[Table 2]

In the above table, the amount of the curing agent used is
It is expressed in% by weight with respect to the main agent. The pot life “> 3 days” indicates that the pot life of 3 days or more was obtained. The pot life “˜1 day” indicates that the pot life is about 1 day, and “∞” indicates that the pot life is infinite.

(Main ingredient) Example 1 Styrene-butadiene latex (Crosslen SA-22: Takeda Pharmaceutical Co., Ltd.)
100 parts by weight, 25 parts by weight of pure water, NN dimethyl.
A latex having a pH of about 9.1 by adding 1 part by weight of ethanolamine.

Example 2. Styrene-butadiene latex (Nipol LX430: manufactured by Nippon Zeon Co., Ltd.) 100
A latex having a pH of about 8.4 by adding 25 parts by weight of pure water and 1 part by weight of NN dimethyl ethanolamine to parts by weight.

Example 3. Acrylonitrile-butadiene latex (Nipol # 1571: Zeon Corporation)
A latex prepared by adding 1 part by weight of NN dimethyl ethanolamine to 100 parts by weight of the product to adjust the pH to 9.1.

Example 4. Styrene-butadiene latex (Crosslane SA-22: Takeda Pharmaceutical Co., Ltd.) 100
A latex prepared by adding 15 parts by weight of pure water and 1 part by weight of N-ethylmorpholine to parts by weight to adjust the pH to 8.8.

Example 5. Styrene-butadiene latex (Nipol LX430: manufactured by Nippon Zeon Co., Ltd.) 100
Add 1 part by weight of N-methyl morpholine to parts by weight, and add p
Latex with H≈8.2.

(Curing agent) Example 6. Styrene-butadiene latex (Crosslen SK-80: Takeda Pharmaceutical Co., Ltd.)
35 parts by weight of pure water, 47.6 parts by weight of pure water and 1.4 parts by weight of NN dimethyl ethanolamine were added to a uniform latex to prepare basic carbonate magnesium (GP-3).
0: 16 parts by weight of Kamijima Chemical Industry Co., Ltd.) was added with stirring and further dispersed by stirring for 60 minutes.

Example 7. To 35 parts by weight of ethylene / vinyl acetate emulsion copolymer (Panflex OM # 4000: manufactured by Kuraray Co., Ltd.), 48 parts by weight of pure water and 1 part by weight of NN dimethyl / ethanolamine were added to form a uniform latex, and a base was added. A dispersion solution obtained by adding 16 parts by weight of magnesium carbonate carbonate (GP-30: manufactured by Kamijima Chemical Industry Co., Ltd.) with stirring, and further stirring and dispersing for 60 minutes.

Example 8. To 35 parts by weight of styrene-butadiene latex (Crosslen SK-80: manufactured by Takeda Yakuhin Co., Ltd.), 48 parts by weight of pure water and 1 part by weight of NN dimethyl ethanolamine were added to form a uniform latex. A dispersion solution in which 16 parts by weight of (first grade) was added with stirring, and the mixture was further dispersed by stirring for 60 minutes.

[0031]

As shown in Tables 1 and 2, the adhesive of the present invention has an extremely long pot life and has good water resistance and solvent resistance. This is a result of the introduction of a crosslinked structure by the reaction between the carboxyl group, which is a hydrophilic group, and the alkaline earth metal compound. The effect is eloquently demonstrated by comparison with the uncrosslinked product containing no curing agent.

[Brief description of drawings]

FIG. 1 is a schematic diagram in which a main agent containing a volatile aqueous amine compound and a curing agent are mixed to prepare an aqueous rubber adhesive.

FIG. 2 is a schematic diagram in which a main agent containing a volatile aqueous amine compound and a curing agent containing a volatile aqueous amine compound are mixed to form an aqueous rubber adhesive.

FIG. 3 is a schematic diagram in which a main agent and a curing agent containing a volatile aqueous amine compound are mixed to form an aqueous rubber adhesive.

FIG. 4 is a schematic diagram in which an aqueous rubber adhesive is prepared by mixing a main agent and a curing agent in which a volatile aqueous amine compound is dispersed in an alkaline earth metal compound as a curing agent.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09J 113/00 C09J 109/00

Claims (5)

(57) [Claims] 1. An alkaline main agent obtained by adding a volatile aqueous amine compound to a carboxyl group-containing aqueous rubber-based polymer composition, and a curing agent selected from carbonates, oxides and hydroxides of alkaline earth metals. An aqueous polymer composition containing one or more powdery alkaline earth metal compounds, which is non-reactive with the alkaline earth metal compound and is compatible with the rubber-based aqueous polymer composition of the main component. A water-based rubber adhesive that uses a curing agent dispersed in an object. 2. The carboxyl group-containing aqueous rubber-based polymer composition according to claim 1, wherein the composition is one or more selected from a styrene / butadiene copolymer, an acrylonitrile / butadiene copolymer, and a butadiene / acrylic copolymer. A water-based rubber adhesive which is the carboxyl group-containing emulsion copolymer composition of. 3. The water-based rubber adhesive according to claim 1, wherein a volatile water-based amine compound is added to the curing agent. 4. A base compound of a carboxyl group-containing aqueous rubber-based polymer composition, and as a curing agent, an alkaline earth metal carbonate, an alkaline earth metal oxide, and an alkaline earth metal hydroxide. One or more powdery alkaline earth metal compounds selected from the group consisting of water-soluble heavy metals which are non-reactive with the above-mentioned alkaline earth metal compounds and which are compatible with the rubber-based water-based polymer composition of the main component. A water-based rubber adhesive that uses a curing agent to which a volatile water-based amine compound has been added, which is dispersed in the coalescence composition. 5. A curing agent which is made into a paste by mixing a volatile aqueous amine compound and a powdery alkaline earth metal compound as a curing agent to a carboxyl group-containing aqueous rubber-based polymer composition, Water-based rubber adhesive.