JPH10237404A - Chloroprene rubber latex adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive having excellent high temperature adhesiveness, by compounding a chloroprene rubber latex containing no gel, a tackifier resin emulsion and a metal oxide emulsion. SOLUTION: This adhesive composition comprises 100 pts.wt. of a chloroprene rubber latex having a G value represented by formula I of zero, wherein G is wt.% of the insoluble part of a chloroprene rubber latex, Wi is the weight of a film prepared from the chloroprene rubber latex and W0 is a weight (g) of the insoluble part of the chloroprene film measured by preparing a 5% chloroform solution of the film and passing the solution through a 200 mesh wire filter followed by drying and weighting the residue on the filter; an amount satisfying formula II of a tackifier resin such as a hydrocarbon resin derived from petroleum, wherein Wt is the pts.wt. of the tackifier resin and T is a softening point ( deg.C) of the tackifier resin; and 0.1 to 5 pts.wt. of an emulsion of a metal oxide such as zinc oxide. The chloroprene rubber latex to be used is obtained by subjecting to emulsion polymerization 100 pts.wt. of chloroprene monomer and 0.1 to 10 pts.wt. of a vinyl monomer having a carboxyl group using an emulsifying and dispersing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chloroprene rubber latex adhesive composition. More specifically, by containing a latex of chloroprene rubber, a tackifier resin emulsion and a metal oxide emulsion containing no gel component, the adhesiveness immediately after lamination is excellent while maintaining sufficient tackiness, and the strength over time. The present invention relates to an adhesive composition having improved heat resistance and good heat resistance.

[0002]

2. Description of the Related Art A method for producing a copolymer latex of chloroprene and a carboxyl group-containing vinyl monomer such as acrylic acid or methacrylic acid is disclosed in Japanese Patent Application Laid-Open No. 61-12771.
No. 0, JP-A-62-257918 and the like.
In addition, water-soluble polymers such as polyvinyl alcohol are emulsified
A method for producing an adhesive latex used as a dispersant and an adhesive using the same are described in JP-B-52-13.
983 and JP-B-61-29968.

[0003]

However, the chloroprene rubber latex produced by these methods has the following problems.

(1) In a conventional adhesive latex, a gel component is formed to increase the molecular weight in order to improve heat resistance, so that sufficient adhesive can be obtained at the cost of maintaining adhesion and room-temperature adhesive strength. Physical properties could not be obtained. Also, an attempt was made to improve heat resistance by crosslinking with a metal oxide such as a carboxyl group-containing vinyl monomer.
The properties expected from the protective colloid properties of the emulsifier used could not be exhibited.

(2) When an emulsifier having good latex stability in a high pH range, such as an alkali metal rosin acid salt, is produced using an emulsifier, tackification, which is an essential component of a chloroprene-based adhesive, is provided. Since rubber precipitates due to a slight change in pH when a resin, a metal oxide or the like is compounded, the pH must be adjusted very carefully, which is troublesome in operation.

(3) When manufactured using a water-soluble polymer such as polyvinyl alcohol, the latex exhibits excellent stability due to its protective colloid properties, but has a water resistance when used as an adhesive. Is significantly reduced.

The present invention has been made in view of the above problems, and has as its object to provide adhesive properties such as room temperature adhesive strength, high temperature adhesive strength, and water resistance, which cannot be obtained with conventional chloroprene rubber latex adhesives. In particular, it is an object of the present invention to provide an adhesive composition having good latex stability, excellent adhesiveness immediately after lamination, excellent adhesiveness immediately after lamination, improved strength over time, and excellent heat resistance.

[0008]

Means for Solving the Problems Based on such background, the present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention. That is, the present invention is, (a) the following equation (1) _{G (%) = (W 0} / W i) × 100 (1) ( wherein, G is chloroform-insoluble portion (%), W _i is a chloroprene rubber latex Is the weight (g) of the film formed by casting, and W ₀ is the dry weight (g) of the insoluble matter that cannot be filtered through a 200-mesh wire gauze after dissolving the film in chloroform to a concentration of 5%. The chloroprene rubber latex adhesive composition comprises chloroprene rubber latex in which G is 0, (b) a tackifier resin emulsion, and (c) a metal oxide emulsion. In particular, when the chloroprene rubber latex is a copolymer of a chloroprene monomer and a carboxyl group-containing vinyl monomer, the physical properties can be further improved by crosslinking the metal oxide. Additionally, the tackifying resin is the following equation (2) _{0.6 ≧ W t /T≧0.2 (2)} ( wherein, W _t is the weight of the tackifier resin to the chloroprene rubber 100 parts by weight (in terms of solid content ), T is the softening point (° C.) of the tackifying resin.) In a chloroprene rubber latex which satisfies), the adhesive holding power can be maximized, and by combining with a metal oxide serving as a curing agent, The other adhesive properties can be sufficiently satisfied.

Hereinafter, the present invention will be described in detail.

Chloroprene rubber latex in [0010] the present invention, the following equation (1) _{G (%) = (W 0} / W i) × 100 (1) ( wherein, G is chloroform-insoluble portion (%), W _i chloroprene weight of the film formed by casting a rubber latex (g), W ₀ is the dry weight (g of this after the film is dissolved so that the concentration of 5% in chloroform, insoluble matter that can not be filtered through a 200-mesh metal gauze G shown in ()) is 0. Here, G = 0 means that the gel content of the chloroprene rubber in the latex is 0.
When G is not 0, the interdiffusion between the adhesive interfaces does not proceed well, the adhesive force as the adhesive becomes insufficient, and the adhesiveness, the room temperature peel strength, the heat resistance, the water resistance and the like are inferior. .

The method for polymerizing the chloroprene rubber latex of the present invention is not particularly limited, and includes a chloroprene monomer, a carboxyl group-containing vinyl monomer, and optionally other copolymerizable ethylenically unsaturated monomers. The body may be subjected to radical emulsion polymerization. In the emulsion polymerization, water, a monomer, an emulsifying / dispersing agent, a polymerization initiator, a chain transfer agent, and the like may be emulsified according to a known method, and polymerization may be performed at a predetermined temperature. Each raw material may be added all at once, sequentially added, or dividedly added. In particular, a copolymer of a chloroprene monomer and a carboxyl group-containing vinyl monomer is suitable because of its excellent high-temperature adhesion and good adhesion to various adherends.
Examples of the copolymerizable carboxyl group-containing vinyl monomer include, for example, unsaturated fatty acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, and crotonic acid, and among these, methacrylic acid is preferable. And
With respect to 100 parts by weight of chloroprene, 0.1 part of methacrylic acid was added.
1 to 10 parts by weight, preferably 0.5 to 4 parts by weight is used. If necessary, copolymerizable ethylenically unsaturated monomers include, for example, copolymerization of normal chloroprene such as ethylene, styrene, methyl methacrylate, acrylonitrile, 2,3-dichlorobutadiene and 1-chlorobutadiene. The monomer used in the above is suitably used in an amount of 20 parts by weight or less.

The emulsifying / dispersing agent used in the polymerization is not particularly limited, and examples thereof include alkali metal salts of rosin acid, sulfonic acid type and sulfate ester type anionic emulsifiers, and nonionic type emulsifiers. Alkyl sulfonate, alkyl aryl sulfonate, alkyl sulfate, alkyl aryl sulfate, condensate of sodium naphthalene sulfonate and formaldehyde, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol, sorbitan fatty acid ester, polyoxyethylene acyl Esters and the like. In the case of a copolymer of a chloroprene monomer and a carboxyl group-containing vinyl monomer, an alkali metal salt and triethanolamine salt of alkyl diphenyl ether disulfonic acid, an alkali metal salt and triethanolamine salt of dodecylbenzenesulfonic acid, Alkali metal salts and triethanolamine salts of lauryl sulfate are preferably used in emulsion polymerization under acidic conditions. The optimum range of the amount of the emulsifying / dispersing agent varies depending on the type of each emulsifying / dispersing agent. Is preferred.

Examples of the polymerization initiator include known free radical-forming substances, for example, peroxides such as potassium persulfate and ammonium persulfate, and inorganic or organic peroxides such as hydrogen peroxide and t-butyl hydroperoxide. Can be used. These may be used alone or in a redox system in combination with a reducing substance such as thiosulfate, thiosulfite, or organic amine.

The polymerization can be carried out at a temperature of 0 to 80 ° C., preferably 5 to 50 ° C.

Examples of the chain transfer agent include molecular weight regulators such as alkyl mercaptans, halogenated hydrocarbons, alkyl xanthogen disulfides and sulfur. The polymerization terminator is not particularly limited as long as it is a commonly used terminator. For example, phenothiazine, 2,6-t-butyl-4-methylphenol, hydroxylamine and the like can be used. The addition may be performed at the time when the conversion reaches a predetermined conversion. Polymerization conversion rate is 50 to 10
0% is preferable, and when residual monomers are present, monomer removal may be performed.

In order to further improve the latex stability of the chloroprene rubber latex of the present invention, a method of adding an emulsifying / dispersing agent in addition to the emulsifying / dispersing agent used in the emulsion polymerization is used. Examples of the timing of adding the emulsifying / dispersing agent include a method of adding all at the time of polymerization preparation, a method of adding during polymerization, and a method of adding at the end of polymerization, and are not particularly limited. % When it reaches%. The amount to be used is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the charged monomer. Within this range, it is possible to satisfy the securing of latex stability and the maintenance of good water resistance when used as an adhesive. As the emulsifying / dispersing agent, alkali metal salts of rosin acid, sulfonic acid type, sulfate type anionic emulsifier, nonionic type emulsifier, for example, alkyl sulfonate, alkyl aryl sulfonate, alkyl sulfate, Alkylaryl sulfates, condensates of sodium naphthalene sulfonate and formaldehyde, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenols,
Sorbitan fatty acid esters, polyoxyethylene acyl esters and the like can be mentioned.

The tackifier resin emulsion used in the present invention is not particularly limited as long as it is uniformly dissolved in the adhesive composition of the present invention. Examples thereof include rosin resins, terpene phenol resins, terpene resins, and cumarone.・ Indene resin, styrene resin, alkylphenol resin,
An aqueous emulsion such as a xylene resin or a petroleum hydrocarbon resin can be used. In particular, petroleum hydrocarbon resins are preferably used because they exhibit good adhesive properties. The petroleum hydrocarbon resin has a softening point of 70 to 150 obtained by polymerizing a fraction having a boiling point of 140 to 220 ° C among the cracked fractions obtained by thermal cracking of petroleum with a Friedel-Crafts polymerization catalyst.
° C as a hydrocarbon resin. As a specific example of a petroleum hydrocarbon resin, Tosoh's trade name Petcol L
X, 120, 140, Nippon Petrochemical's trade name Neopolymer 80, L-90, 100, 120, 130, Toho Chemical Industry's trade names High Resin # 75, # 90, # 120, #
130, # 140, and the like. These resin emulsions are represented by the following formula (2): 0.6 ≧ W _t /T≧0.2 (2) (where W _t is the weight part of the tackifying resin with respect to 100 weight parts of chloroprene rubber (in terms of solid content) ), T is the softening point (° C.) of the tackifying resin. That is,
When the resin has a high softening point, a larger amount is used, and when the resin has a low softening point, a smaller amount is used. However, (2)
When the formula is less than 0.2, the curing reaction between the chloroprene rubber and the metal oxide takes precedence, whereby the interdiffusion of the adhesive interface is suppressed, and sufficient tackiness cannot be maintained. On the other hand, if it exceeds 0.6, the curing properties of the chloroprene rubber and the metal oxide are hindered due to the influence of a large amount of tackifier resin, and the adhesive properties become insufficient. As described above, the value within the range of the expression (2) is preferable because the adhesiveness can be sufficiently secured and the adhesion performance can be further improved by crosslinking with the metal oxide. The tackifier resin may be added by dissolving it in an organic solvent in advance, but is preferably added in the form of an emulsified emulsion.

In the present invention, the metal oxide is a group II-
An oxide of a Group III metal cation, such as magnesium oxide, calcium oxide, or zinc oxide. In particular, zinc oxide is preferably used because the curing reaction proceeds at an appropriate rate and sufficient crosslinking can be exhibited. These metal oxides are chloroprene rubber polymer 1
0.1 to 5 parts by weight is added to 00 parts by weight. Within this range, sufficient tackiness can be ensured, and the adhesive performance can be further improved. As the addition method, a method of adding in the form of an emulsified emulsion is preferable.

The chloroprene rubber latex adhesive composition according to the present invention is as described above, and comprises a composition obtained by mixing a predetermined ratio of a chloroprene rubber latex containing no gel component, a tackifier resin emulsion and a metal oxide emulsion. After applying to the body, usually 40-90
Dry at 5 ° C. for 5 to 10 minutes and attach. If necessary, thickeners such as polyoxyethylene and polyvinyl alcohol, antioxidants, preservatives, antifreezing agents, film-forming aids, p
An appropriate amount of an H regulator or the like may be blended.

The adhesive composition of the present invention having the above constitution has good adhesive properties such as room temperature adhesive strength, high temperature adhesive strength and water resistance and latex stability which cannot be obtained with conventional latex adhesives. In particular, the adhesiveness is maintained, the adhesiveness immediately after lamination is excellent, the strength over time is improved, and the heat resistance is good.

[0021]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

The compounding stability, mechanical stability, room temperature peel strength of the adhesive compositions obtained in the following Examples and Comparative Examples
The high temperature peel strength, heat creep test and water resistance were measured and evaluated by the following methods.

<Blending stability> The presence of rubber precipitates was visually observed by blending with chloroprene rubber latex.

；: No rubber deposition was observed. X: Precipitation of rubber was observed.

<Mechanical Stability> The mechanical stability of the adhesive composition was measured and evaluated as a rubber solidification rate (%) using a Marlon test method.

<Normal temperature peel strength> SBR rubber plate (Showa Rubber, 150 mm × 25
mm) and No. 9 cotton canvas (150 mm × 25 mm) each with an adhesive composition of about 625 g / m.
^{After 2} (wet) coating, the coating was heated and dried at 60 ° C. for 10 minutes, and pressed with a hand roller. The specimen was cured in a constant temperature chamber at 23 ° C. for 1 hour and for 7 days.
The 180 ° peel strength of the test piece was measured at 23 ° C. and a tensile speed of 200 mm / min using a Tensilon type tensile tester.

<High-Temperature Peel Strength> A test piece prepared in the same manner as in the measurement of the normal-temperature peel strength was used at 80 ° C. and a tensile speed of 200.
The 180 ° peel strength was measured using a Tensilon type tensile tester under the condition of mm / min.

<Heat resistance creep test> SBR (Showa Rubber, 150 × 25 mm) surface finished with No. 60 polishing cloth
After applying 625 g / m ² of the adhesive composition to one side of the film by a brush, it was dried by heating at 60 ° C. for 10 minutes, and the hatched portion was covered with a polyethylene sheet as shown in FIG. As shown in (2), the hatched portion was cut off and pressed with a hand roller so that the bonded portion became 25 × 25 mm. The test piece was prepared by curing at 23 ° C. for 3 days in a constant temperature room. One end of the test piece is hung into a thermostat so as to perform 180 ° peeling, and a 200 g weight is attached so as not to give an impact to the other end, and the temperature in the thermostat is maintained at 80 ° C. The adhesive softened and could not withstand the load of the weight, and the time (minute) when the weight dropped was measured, and the heat creep test was performed. The last time is 60 minutes, and when it does not fall, it is indicated by "60 minutes or more". In addition, when the sheet did not drop but did shift, the length (mm) of the shift after 60 minutes was measured.

<Water Resistance> A test piece prepared in the same manner as in the measurement of peel strength at room temperature was immersed in pure water at 23 ° C. for 3 days, and then excess water was immediately wiped off at 23 ° C. and a pulling speed of 200 mm.
/ Min using a Tensilon type tensile tester at 18
The 0 ° peel strength was measured.

Example 1 97 parts by weight of chloroprene, 3 parts by weight of methacrylic acid,
0.75 parts by weight of n-dodecyl mercaptan, 5 parts by weight of sodium alkyl diphenyl ether disulfonate (Perex SSH (trademark), manufactured by Kao), 0.01 parts by weight of sodium hydrosulfite, 0.2 parts by weight of triethanolamine and pure water 95 parts by weight was charged to a 10-liter autoclave with a stirrer at 80% volume, 10 ° C.,
In a nitrogen atmosphere, a 0.35% by weight aqueous solution of potassium persulfate was continuously dropped. 2,6-t-butyl-4-methylphenol 0.05 as a polymerization terminator at a conversion of 98%
Chloroprene rubber copolymer latex A
(Solid content 52% by weight) was obtained. The properties of the obtained latex were G = 0 (gel content, chloroform-insoluble part G
(%) = (W ₀ / W _i ) × 100, a sample latex was cast to form a film, and the weight (W _i (g)) of the sample was measured. Place in a flask and soak at 23 ° C for 24 hours. Then 2
After filtration through a 00 mesh wire mesh and washing with chloroform,
The residue is dried at 110 ° C. and the weight (W ₀ (g)) is measured. ) And a solution viscosity of 2500 mPa · s (solution viscosity of a chloroprene polymer dissolved in chloroform to a concentration of 10%. B-type viscometer (No. 3 rotor, 1
2 rpm, 25 ° C., 60 sec. ) Measurement. )Met.

The obtained copolymer latex A and a tackifier resin emulsion (rosin ester resin, superester E-720, softening point 100 ° C., solid content 50% by weight,
Arakawa Chemical) and zinc oxide emulsion (AZ-SW,
(50% solids by Osaki Kogyo)
The mixture was stirred and mixed at a ratio of 0: 1 (solid content conversion, weight ratio) to obtain an adhesive composition.

Table 1 shows the evaluation results of the composition stability, mechanical stability, room temperature peel strength, high temperature peel strength, heat creep and water resistance of the prepared adhesive composition.

From the results in Table 1, the stability, the peel strength at room temperature,
It was found that high temperature peel strength, heat creep, and water resistance were excellent. Regarding the room temperature peel strength, the strength immediately after lamination was good and a sufficient improvement in strength was recognized after 7 days.

[0034]

[Table 1]

Example 2 The tackifier resin emulsion of Example 1 was used as a Harrier Star D
It was changed to S-70E (rosin ester resin, softening point 70 ° C, solid content 50% by weight, manufactured by Harima Chemicals). Copolymer latex A, tackifier resin emulsion (Hariester DS-70E) and zinc oxide emulsion (AZ-S)
The mixing ratio of W) was changed to 100: 20: 1 (solid content conversion, weight ratio) to obtain an adhesive composition.

Table 1 shows the evaluation results of the composition stability, mechanical stability, room temperature peel strength, high temperature peel strength, heat creep and water resistance of the prepared adhesive composition.

From the results shown in Table 1, the stability, peel strength at room temperature,
It was found that high temperature peel strength, heat creep, and water resistance were excellent. Regarding the room temperature peel strength, the strength immediately after lamination was good and a sufficient improvement in strength was recognized after 7 days.

Example 3 In Example 1, the mixing ratio of the copolymer latex A, the tackifier resin emulsion (Superester E-720) and the zinc oxide emulsion (AZ-SW) was 100: 15: 1 (solid content conversion). , Weight ratio) to obtain an adhesive composition.

Table 1 shows the evaluation results of the composition stability, mechanical stability, room temperature peel strength, high temperature peel strength, heat creep and water resistance of the prepared adhesive composition.

From the results shown in Table 1, the stability was good.
Although room temperature peel strength, high temperature peel strength, heat creep, and water resistance were inferior to those of Example 1, practical values were shown.

Example 4 In Example 1, the mixing ratio of the copolymer latex A, the tackifier resin emulsion (Superester E-720) and the zinc oxide emulsion (AZ-SW) was 100: 70: 1 (solid content conversion). , Weight ratio) to obtain an adhesive composition.

Table 1 shows the evaluation results of the composition stability, mechanical stability, room temperature peel strength, high temperature peel strength, heat creep and water resistance of the prepared adhesive composition.

From the results shown in Table 1, the stability was good.
Although room temperature peel strength, high temperature peel strength, heat creep, and water resistance were inferior to those of Example 1, practical values were shown.

Example 5 In Example 1, a rosin ester resin (Super Ester E-720) was prepared by using a petroleum hydrocarbon resin emulsion (trade name: Petcol LX (softening point: 98 ° C., manufactured by Tosoh) with a solid content of 50%). (Water-based emulsion) and the mixing ratio of copolymer latex A, petroleum-based hydrocarbon resin emulsion (petocol LX) and zinc oxide emulsion (AZ-SW) to 100: 20: 2 (solid content, weight ratio). The adhesive composition was changed.

The evaluation results of the composition stability, mechanical stability, room temperature peel strength, high temperature peel strength, heat creep and water resistance of the prepared adhesive composition are shown in Table 2.

From the results shown in Table 2, the stability, the peel strength at room temperature,
It was found that high temperature peel strength, heat creep, and water resistance were excellent.

[0047]

[Table 2]

Example 6 In Example 5, the mixing ratio of the copolymer latex A, petroleum hydrocarbon resin emulsion (Petokol LX) and zinc oxide emulsion (AZ-SW) was 100: 40: 0.5 (solid content). (Equivalent, weight ratio) to obtain an adhesive composition.

Table 2 shows the evaluation results of the composition stability, mechanical stability, room temperature peel strength, high temperature peel strength, heat creep and water resistance of the prepared adhesive composition.

From the results shown in Table 2, the stability, the peel strength at room temperature,
It was found that high temperature peel strength, heat creep, and water resistance were excellent.

Example 7 In Example 5, a petroleum-based hydrocarbon resin emulsion (a water-based emulsion produced by Tosoh, trade name Petcoal LX (softening point 98 ° C.) having a solid content of 50%) was treated with Petcole 140HM3 (Tosoh, (Softening point 133 ° C.) was changed to an aqueous emulsion prepared with a solid content of 50%, and the mixing ratio of copolymer latex A, petroleum hydrocarbon resin emulsion (Petokol 140HM3), and zinc oxide emulsion (AZ-SW) was 100. The ratio was changed to 30: 2 (solid content conversion, weight ratio) to obtain an adhesive composition.

Table 2 shows the evaluation results of the composition stability, mechanical stability, room temperature peel strength, high temperature peel strength, heat creep and water resistance of the prepared adhesive composition.

From the results shown in Table 2, the stability, the peel strength at room temperature,
It was found that high temperature peel strength, heat creep, and water resistance were excellent.

Example 8 97 parts by weight of chloroprene, 3 parts by weight of methacrylic acid,
1.5 parts by weight of n-dodecyl mercaptan, 5 parts by weight of sodium alkyldiphenyl ether disulfonate (Perex SSH (trademark), manufactured by Kao), 0.01 parts by weight of sodium hydrosulfite, 0.2 parts by weight of triethanolamine and pure water 85 parts by weight with stirrer 1
An 80% autoclave was charged in an 80% volume, and a 0.35% by weight aqueous solution of potassium persulfate was continuously added dropwise at 40 ° C. in a nitrogen atmosphere. With a conversion of 98%,
0.05 parts of 6-t-butyl-4-methylphenol was added to obtain a chloroprene rubber copolymer latex. The properties of the obtained latex were G = 0 and the solution viscosity was 220 mPa · s.

The mixing ratio of the obtained copolymer latex to the petroleum hydrocarbon resin emulsion (Petokol LX) and zinc oxide emulsion (AZ-SW) used in Example 5 was 100: 20: 2 (solid content conversion). , Weight ratio) to obtain an adhesive composition.

Table 2 shows the evaluation results of the composition stability, mechanical stability, room temperature peel strength, high temperature peel strength, heat creep and water resistance of the prepared adhesive composition.

From the results shown in Table 2, the stability, the normal temperature peel strength,
The water resistance was excellent, and it was found that the value was usable for high temperature peel strength and heat creep.

Comparative Example 1 In Example 1, a zinc oxide emulsion (AZ-S
Without adding W), an adhesion test was conducted with an adhesive composition having a mixing ratio of the copolymer latex A and the tackifier resin emulsion (superester E-720) of 100 to 40 (solid content, weight ratio). went.

Table 1 shows the evaluation results of the composition stability, mechanical stability, room temperature peel strength, high temperature peel strength, heat creep and water resistance of the prepared adhesive composition.

From the results shown in Table 1, the peel strength at normal temperature and water resistance were good, but the peel strength at high temperature and heat creep were very poor.

Comparative Example 2 In Example 1, the mixing ratio between the copolymer latex A and the zinc oxide emulsion (AZ-SW) was 100: 1 (solid content conversion, weight ratio) without adding the tackifier resin emulsion. An adhesive test was performed using an adhesive composition consisting of

Table 1 shows the evaluation results of the composition stability, mechanical stability, room temperature peel strength, high temperature peel strength, heat creep and water resistance of the prepared adhesive composition.

From the results shown in Table 1, the heat-resistant creep was good, but the normal-temperature peel strength, high-temperature peel strength, and water resistance were very poor.

Comparative Example 3 97 parts by weight of chloroprene, 3 parts by weight of methacrylic acid,
0.2 parts by weight of n-dodecyl mercaptan, 5 parts by weight of sodium alkyldiphenyl ether disulfonate (Perex SSH (trademark), manufactured by Kao), 0.01 parts by weight of sodium hydrosulfite, 0.2 parts by weight of triethanolamine and pure water 95 parts by weight with stirrer 1
An 80% volume was charged into a 0.1-liter autoclave, and a 0.35% by weight aqueous solution of potassium persulfate was continuously added dropwise at 10 ° C. in a nitrogen atmosphere. With a conversion of 98%,
0.05 parts by weight of 6-t-butyl-4-methylphenol was added to obtain a chloroprene rubber copolymer latex. The properties of the obtained latex were measured in the same manner as in Example 1, and G = 70 and the solution viscosity was 4150 mPa ·
s.

The obtained copolymer latex, a tackifier resin emulsion (Superester E-720) and a zinc oxide emulsion (AZ-SW) were added in a ratio of 100: 40.
The mixture was stirred and mixed in a ratio of 1 (solid content conversion, weight ratio) to obtain an adhesive composition.

The compounding stability and mechanical stability of the prepared adhesive composition, the normal temperature peel strength, the high temperature peel strength of the adhesive composition,
The evaluation results of heat creep and water resistance are shown in Table 1.

From the results shown in Table 1, the stability was good.
However, room temperature peel strength, high temperature peel strength, heat creep, and water resistance were poor.

[0068]

As described above, the chloroprene rubber latex adhesive composition obtained according to the present invention has an adhesive property such as room temperature adhesive strength, high temperature adhesive strength, water resistance and the like, and latex stability which cannot be obtained by conventional latex. Wood, leather, cloth, especially because it is an adhesive composition that has good adhesiveness, maintains adhesive holding power, has excellent adhesiveness immediately after lamination, has improved strength over time, and has good heat resistance. It is suitable as an adhesive for various uses such as rubber, plastic, and metal.

[Brief description of the drawings]

FIG. 1 is a test piece of styrene-butadiene rubber used for a heat creep test.

FIG. 2 is a test piece of styrene-butadiene rubber used for a heat creep test.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09J 193/04 C09J 193/04

Claims (6)

[Claims] 1. A (a) the following equation (1) _{G (%) = (W 0} / W i) × 100 (1) ( wherein, G is chloroform-insoluble portion (%), W _i is a chloroprene rubber latex The weight (g) of the film formed by casting, W ₀ is the dry weight (g) of the insoluble matter which cannot be filtered through a 200-mesh wire net after dissolving the film in chloroform to a concentration of 5%. A) a chloroprene rubber latex wherein G is 0, (b) a tackifier resin emulsion, and (c) a metal oxide emulsion. 2. The chloroprene rubber latex adhesive composition according to claim 1, wherein the chloroprene rubber latex is a copolymer of a chloroprene monomer and a carboxyl group-containing vinyl monomer. 3. The chloroprene rubber latex is a copolymer of a chloroprene monomer and a carboxyl group-containing vinyl monomer obtained by using an emulsifying / dispersing agent for imparting latex stability. The chloroprene rubber latex adhesive composition according to any one of claims 1 to 2. 4. The chloroprene rubber latex adhesive composition according to claim 1, wherein the emulsifying / dispersing agent for imparting latex stability is a water-soluble salt of alkyl diphenyl ether disulfonic acid. 5. The tackifying resin is the following equation (2) _{0.6 ≧ W t /T≧0.2 (2)} ( wherein, W _t is the weight of the tackifier resin to the chloroprene rubber 100 parts by weight (solid The chloroprene rubber latex adhesive composition according to any one of claims 1 to 4, which satisfies the following formula: (value in terms of minutes) and T is the softening point (° C) of the tackifying resin. 6. The chloroprene according to claim 1, wherein the tackifier resin is selected from a phenolic resin, a terpene resin, a rosin derivative resin and a petroleum hydrocarbon resin. Rubber latex adhesive composition.