JPH05279406A - Production of copolymer latex and composition containing the same - Google Patents

Abstract

PURPOSE:To suppress occurrence of a fine solidification material and efficiently obtain a copolymer latex having good polymerization stability by subjecting an aliphatic conjugated diene based monomer to emulsion polymerization with a copolymerizable monomer in the presence of a specific compound. CONSTITUTION:(A) A monomer mixture consisting of A1: 10-80wt.% aliphatic conjugated diene based monomer (preferably 1,3-butadiene) A2: 0.5-10wt.% ethylenically unsaturated carboxylic acid monomer (e.g. acrylic acid) and A3: 10-89.5wt.% copolymerizable monomer (e.g. methyl methacrylate) is subjected to emulsion polymerization in the presence of (B) 0.1-30 pts.wt., preferably 0.5-15 pts.wt. cyclic unsaturated hydrocarbon having one unsaturated bond in the ring, preferably cyclopentene, 4-methylcyclopentene, 4-methylcyclohexene, etc., having <=140 deg.C boiling point and unreacted component B is recovered to provide the objective copolymer latex. The copolymer latex is used for an adhesive composition, paper coating composition, carpet backing adhesive composition, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing a copolymer latex, and an adhesive composition, a paper coating composition, and a carpet lining for the copolymer latex obtained by the method. The present invention relates to an adhesive composition and an adhesive composition for rock fiber base material.

[0002]

2. Description of the Related Art So-called butadiene copolymer latex containing butadiene as a main component has been widely used as a binder in the field of paper coating, back sizing of carpets, or for rock fiber base materials. It is well known that

The performance required of the binder in each application is diverse, and it is common to change the composition and structure of the butadiene-based copolymer latex in accordance with the performance.

These copolymer latices are generally produced by emulsion polymerization. At this time, a slight difference is observed depending on the composition of the monomer mixture constituting the copolymer latices and the kinds and amounts of various additives. However, there is a problem that a fine coagulated product is generated in the copolymer latex.

[0005] Such a fine solidified substance adheres to the reactor, has various adverse effects on the reaction process, and causes various harmful effects in each end use.

That is, in the field of paper coating, if there are many such solidified substances, problems such as streak troubles during blade coating, applicator stains, stains during calendar processing, and blanket piling during printing occur.

Further, these copolymer latexes are
Adhesives for carpet backing such as tufted carpets and needle punched carpets, cushion materials for automobiles,
It is also used as an adhesive for rock fiber bases used in applications such as civil engineering mats and industrial filters, but even in that case, the fine coagulated substance in the copolymer latex adversely affects the adhesive strength and water resistance. Exert.

[0008] As described above, the fine coagulated substance in the copolymer latex accompanies the fouling of the reactor and causes various adverse effects in each end use. Therefore, it is usually removed by a filtration step or the like.

However, since the filtration step is complicated and the amount of the fine coagulated substance to be removed is limited, it is difficult to completely remove the fine coagulated substance and the productivity is inevitably reduced. Was there.

Further, in the field of paper coating, it has been recommended to speed up the coating speed when preparing coated paper from the viewpoint of rationalization, and for paper coating which is more suitable for high speed coating than in the past. A composition is sought.

Further, not only the coating speed but also the printing speed for coated paper has been increased, and high-speed printing suitability superior to the conventional one has been demanded.

That is, the paper coating composition is required to have excellent fluidity and mechanical stability during high-speed coating,
Coated paper is required to have excellent printing strength, blister resistance and printing gloss.

It is known that the copolymer latex which is one component of the coating color has a great influence on these performances.

Further, these copolymer latexes are
Often the odor, especially due to the alkyl mercaptans used as chain transfer agents, can be problematic. This odor reduces the commercial value of the final product,
There is a need for a copolymer latex that produces less odor.

[0015]

[Means for Solving the Problems] As a result of intensive studies on the above problems, the inventors of the present invention suppressed the generation of fine coagulation by emulsion polymerization in the presence of a specific compound, and A copolymer latex having good stability can be efficiently obtained. By using the copolymer latex, the fluidity and mechanical stability at the time of paper coating are excellent, and the odor of coated paper and the time of printing can be obtained. A paper coating composition having improved printing strength, printing gloss and blister resistance, as well as an adhesive composition for carpet backing and an adhesive for rock fiber base material, which has improved adhesive strength and water odor resistance It has been found that a composition is obtained and the invention has been reached.

That is, the present invention comprises 10 to 80% by weight of an aliphatic conjugated diene monomer, 0.5 to 10% by weight of an ethylenically unsaturated carboxylic acid monomer, and 10 to 10% by weight of another monomer copolymerizable therewith. Emulsion polymerization of 89.5% by weight in the presence of a cyclic unsaturated hydrocarbon having one unsaturated bond in the ring, a method for producing a copolymer latex, and a copolymer weight obtained by the method. Provided are an adhesive composition, a paper coating composition, a carpet backing adhesive composition and a rock fiber base adhesive composition which are prepared by using the united latex.

The present invention will be described in detail below.

Examples of the aliphatic conjugated diene-based monomer in the present invention include 1,3-butadiene and 2-methyl-1,3-
Butadiene, 2,3-dimethyl-1,3-butadiene,
2-chloro-1,3-butadiene, substituted linear conjugated pentadienes, substituted and side chain conjugated hexadienes and the like can be mentioned, and one kind or two or more kinds can be used. Particularly, 1,3-butadiene is preferable.

Examples of the ethylenically unsaturated carboxylic acid monomer include mono- or dicarboxylic acids (anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.

Other monomers copolymerizable with the above-mentioned aliphatic conjugated diene monomer and ethylenically unsaturated carboxylic acid monomer include alkenyl aromatic monomer and unsaturated carboxylic acid alkyl ester monomer. And unsaturated monomers containing a hydroxyalkyl group, vinyl cyanide monomers, unsaturated carboxylic acid amide monomers, and the like.

As the alkenyl aromatic monomer, styrene, α-methylstyrene, methyl α-methylstyrene,
Vinyltoluene and divinylbenzene and the like,
One kind or two or more kinds can be used. Particularly preferred is styrene.

Examples of unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl malate, dimethyl. Itaconate, monomethyl fumarate, monoethyl fumarate, 2-ethylhexyl acrylate and the like can be mentioned, and one kind or two or more kinds can be used. Methyl methacrylate is particularly preferable.

Examples of unsaturated monomers containing a hydroxyalkyl group include β-hydroxyethyl acrylate and β-hydroxyethyl acrylate.
-Hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate,
Hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, di- (ethylene glycol) maleate,
Di- (ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis (2-hydroxyethyl)
Maleate, 2-hydroxyethylmethyl fumarate and the like can be mentioned, and one kind or two or more kinds can be used. In particular, β-hydroxyethyl acrylate is preferable.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and α-ethylacrylonitrile.
One kind or two or more kinds can be used. Acrylonitrile is particularly preferable.

As the unsaturated carboxylic acid amide monomer,
Acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N,
N-dimethylacrylamide and the like can be mentioned, and one kind or two or more kinds can be used. Particularly preferred is acrylamide.

The above monomer composition is composed of 10 to 80% by weight of the aliphatic conjugated diene monomer, 0.5 to 10% by weight of the ethylenically unsaturated carboxylic acid monomer, and another monomer which can be copolymerized therewith. The body is 10 to 89.5% by weight.

If the amount of the aliphatic conjugated diene monomer is less than 10% by weight, the printing strength and the adhesive property will be poor, and if it exceeds 80% by weight, the water resistance will tend to be poor. If the amount of the ethylenically unsaturated carboxylic acid monomer is less than 0.5% by weight, the mechanical stability is poor, and if it exceeds 10% by weight, the viscosity of the latex tends to increase, which is not preferable. If the amount of the other copolymerizable monomer is less than 10% by weight, the water resistance tends to be inferior, and if it exceeds 89.5% by weight, the printing strength and the adhesiveness tend to be poor, such being undesirable.

The chain transfer agent used in the present invention includes
Alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan, xanthogen compounds such as dimethylxanthogen disulfide, diisopropylxanthogen disulfide, α- Methylstyrene dimer, terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide,
Thiuram-based compounds such as tetramethylthiuram monosulfide, 2,6-di-t-butyl-4-methylphenol, phenol-based compounds such as styrenated phenol, allyl compounds such as allyl alcohol, dichloromethane, dibromomethane, carbon tetrachloride , Halogenated hydrocarbon compounds such as carbon tetrabromide, α-benzyloxystyrene, α-benzyloxyacrylonitrile, vinyl ethers such as α-benzyloxyacrylamide, triphenylethane, pentaphenylethane, acrolein, methacrolein, α-benzyl Roxystyrene, thioglycolic acid, thiomalic acid, 2-ethylhexyl thioglycolate and the like can be mentioned, and one or more can be used.

The amount of these chain transfer agents used is not particularly limited and can be appropriately adjusted depending on the performance required for the copolymer latex, but preferably 0.05 to 100 parts by weight of the monomer mixture. 10 parts by weight.

Most of the cyclic unsaturated hydrocarbons having one unsaturated bond in the ring used in the present invention remain unreacted after the polymerization, and it is necessary to recover the unreacted product. Therefore, those having a boiling point of 140 ° C. or lower are preferable.
Specific examples include cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene, 1-methylcyclohexene and the like.

The amount of the above compound used in the present invention is 0.1 to 30 parts by weight based on 100 parts by weight of the monomer mixture. If the amount is less than 0.1 parts by weight, the effect of the present invention is insufficiently expressed, and if the amount exceeds 30 parts by weight, the amount of the compound remaining as an unreacted product relatively increases, and the energy required for recovery increases. Not preferable. Preferably 0.5
~ 15 parts by weight.

The method of adding various components in the present invention is not particularly limited, and any of a batch addition method, a divided addition method and a continuous addition method can be adopted. Further, in the emulsion polymerization, a commonly used emulsifier, polymerization initiator, electrolyte, polymerization accelerator, chelating agent and the like can be used.

Further, in the present invention, any one-step polymerization, two-step polymerization, multi-step polymerization or the like can be adopted, but emulsion polymerization is particularly preferred by the following method.

That is, in the first stage, 3 to 40% by weight, preferably 5 to 30% by weight of the monomers are polymerized with respect to all the monomers, and the first stage polymerization conversion is 50% or more, Preferably, the remaining monomer is added at the time when it reaches 70% or more to substantially complete the polymerization. In addition, in the above production method, it is particularly preferable to use the total amount of the ethylenically unsaturated carboxylic acid monomer in the first stage.

As the emulsifier, anionic salts such as sulfuric acid ester salts of higher alcohols, alkylbenzene sulfonates, alkyldiphenyl ether sulfonates, aliphatic sulfonates, aliphatic carboxylates, sulfuric acid ester salts of nonionic surfactants, etc. Surfactants or nonionic surfactants such as polyethylene glycol alkyl ester type, alkyl phenyl ether type, and alkyl ether type are used in one kind or in two or more kinds.

As the initiator, water-soluble initiators such as potassium persulfate, ammonium persulfate and sodium persulfate, redox initiators or oil-soluble initiators such as benzoyl peroxide can be used.

By adopting the above-mentioned production method, it is possible to suppress the generation of fine coagulation products and obtain a copolymer latex having good polymerization stability. Since a cyclic unsaturated hydrocarbon having one unsaturated bond is not preferable in the final use from the viewpoint of working environment hygiene, in the present invention, after the copolymer latex is polymerized by the production method, an unreacted product is obtained. Is substantially removed (0.5 parts by weight or less, more preferably 0.1 parts by weight or less, based on 100 parts by weight of the copolymer latex (solid content)).

As a method for removing the compound, a known method,
For example, it can be removed by steam distillation, vacuum distillation, blowing of an inert gas, or the like.

Further, the present invention provides various adhesive compositions containing the copolymer latex produced by the above-mentioned method. For example, a paper coating composition,
It can be used as an adhesive composition for carpet backing, an adhesive composition for rock fiber base material, an adhesive composition for tire cord, an adhesive composition for wood, an adhesive composition for leather, and the like.

The paper coating composition of the present invention is prepared as an aqueous dispersion of the copolymer latex, together with a pigment and, if necessary, other binder.

At this time, the copolymer latex of the present invention is 2 to 100 parts by weight, preferably 5 to 30 parts by weight, and the other binders are 0 to 100 parts by weight in terms of solid content.
30 parts by weight can be used.

Here, as the pigment, kaolin clay,
Talc, barium sulfate, titanium oxide, calcium carbonate,
Examples thereof include inorganic pigments such as aluminum hydroxide, zinc oxide and satin white, and organic pigments such as polystyrene latex, which may be used alone or in combination.

Other binders include starch, oxidized starch, modified starch such as esterified starch, natural binders such as soybean protein and casein, or synthetic latex such as polyvinyl alcohol, polyvinyl acetate latex and acrylic latex. Is used.

To prepare the paper coating composition of the present invention,
Further other auxiliaries such as dispersants (sodium pyrophosphate, sodium polyacrylate, sodium hexametaphosphate, etc.), antifoaming agents (polyglycol, fatty acid ester, phosphate ester, silicone oil, etc.), leveling agents (funnel oil, Dicyandiamide, urea, etc.),
Preservatives, water resistance agents (formalin, hexamine, melamine resins, urea resins, glyoxal, etc.), release agents (calcium stearate, paraffin emulsion, etc.), fluorescent dyes, color water retention agents (carboxymethyl cellulose, sodium alginate, etc.) It is added as needed.

The method for applying the paper coating composition of the present invention to a coated paper is known in the art, for example, an air knife coater,
It is carried out by a coating machine such as a blade coater, a roll coater or a bar coater. After coating, the surface is dried and finished by calendering.

The adhesive composition for carpet backing of the present invention is obtained by blending the above-mentioned copolymer latex with a filler and / or other additives. At that time, usually 0 filler is added to 100 parts by weight of the copolymer latex in terms of solid content.
~ 800 parts by weight can be used.

Examples of the filler include calcium carbonate, aluminum hydroxide, hollow glass spheres, clay, talc, silica and carbon black, which can be used alone or in combination.

Other additives include pH adjusters, emulsifiers, stabilizers, vulcanizing agents, vulcanization accelerators, antioxidants, dispersants, defoamers, preservatives and thickeners which are generally added. , Colorants,
Examples thereof include crosslinking agents and crosslinking aids.

In the adhesive composition for a rock fiber base material of the present invention, in addition to the above-mentioned copolymer latex, generally added fillers, emulsifiers, stabilizers, antioxidants, ultraviolet deterioration inhibitors, A vulcanizing agent, a vulcanization accelerator, a dispersant, a defoaming agent, a preservative, a thickener, a coloring agent, a cross-linking agent, a cross-linking aid and the like can be added.

[0050]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. In the examples, parts and percentages are by weight. The physical properties in the examples were measured by the following methods.

Stains on the reactor After polymerization, the deposits on the inner wall of the reactor after the polymerization were visually observed. ◯: Very low Δ: Low ×: High

[0052] The fine coagulum number μm~50μm present in fine coagulum in the latex was observed by a microscope ○: very little △: less ×: more is evaluated in this 3 stage.

Gel content A latex film is prepared by drying at room temperature. After accurately weighing about 1.0 g of latex film, put it in 400 cc of toluene, leave it for 48 hours to dissolve it, filter through a 300-mesh wire net, dry it, and weigh the toluene insoluble content (gel) on the wire net to calculate the gel content. To do.

Polymerization Example 1 of Copolymer Latex In a 10 liter autoclave, 100 parts of water, 0.3 part of sodium dodecylbenzenesulfonate, 0.2 part of sodium hydrogen carbonate, 1.0 part of potassium persulfate and one stage shown in Table 1 or Table 2 were used. The first monomer mixture, the chain transfer agent, and the cyclic unsaturated hydrocarbon having one unsaturated bond in the ring were charged and the first stage polymerization was carried out at 65 ° C. When the conversion rate of the first-stage emulsion polymerization reached 70%, the second-stage monomer mixture, the chain transfer agent, and the unsaturated hydrocarbon were continuously added for 7 hours to carry out the second-stage polymerization. .. Then, to complete the polymerization,
The reaction was further continued for 3 hours to complete the polymerization. The polymerization conversion rates were all 98% or more. The copolymer latex thus obtained was adjusted to pH 8 with sodium hydroxide, and then unreacted monomers and unsaturated hydrocarbons remaining as unreacted products were removed by steam distillation to obtain a copolymer latex 1 ~ 1
Got 5.

In the table, the amount on the left side is the first stage and the amount on the right side is the second stage across "/".

Preparation of Paper Coating Composition Copolymer latices 1 to 15 were used to prepare 60% solids based on the following formulations, and pure water was used to prepare the paper coating compositions. It was The mechanical stability and fluidity of the obtained paper coating composition were measured.

(Formulation) Kaolin clay 80 parts Calcium carbonate 20 parts Modified starch 6 parts Copolymer latex 12 parts (solid content)

Commercially available high-quality paper (64 g / m ² ) was coated and dried using a coating bar so that the coating amount of the above composition would be 10 g / m ^{2 on} one side, and the roll temperature was 50.
Super calendering was carried out under conditions of ℃ and linear pressure of 70 to 80 kg / cm to obtain coated paper. The obtained coated paper was measured for RI Wet Pick, RI Dry Pick, blister resistance, print gloss and odor.

Mechanical Stability The above paper coating composition was kneaded between a metal roll and a rubber roll by using a Patastabil tester, mechanically sheared, and the time (minutes) until a coagulated product was generated on the rubber roll was determined. taking measurement. ○: 30 minutes or more △: 20 minutes or more and less than 30 minutes ×: less than 20 minutes

The viscosity of the paper coating composition is measured at a rotation speed of 4000 rpm using Bob F in a fluidity Hercules high shear viscometer. The lower the viscosity, the better the fluidity.

RI Wet Pick The degree of picking when printed with dampening water with a RI printing machine is judged with the naked eye, and five grades from 1st grade (the best one) to 5th grade (the worst) Evaluated by law. The average value of 6 times is shown.

Evaluation was performed in the same manner as in the above-mentioned RI Wet Pick, except that RI Dry Pick dampening water was not used.

Blister resistance It is the minimum temperature when the coated double-sided printing paper is humidity-controlled (about 6%) and thrown into a heated oil bath to generate blisters.

Printing Gloss A RI press is used to perform a constant speed printing using a commercially available red ink for offset printing to prepare a sample. The gloss of the printed surface of the sample is measured according to the method of JIS P-8142. The larger the number, the better the gloss.

A coated paper was obtained in the same manner as the above coating method except that the coating amount of the odorous paper coating composition was 20 g / m ^{2 on} one side. A test piece of 10 cm x 10 cm is prepared from the obtained coated paper, three test pieces are placed in a glass bottle capable of being sealed and left at 50 ° C for 1 hour, and then the stopper is removed to determine the degree of odor. did. ×: Smell △: Slightly sigma ○: Almost no odor

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

Polymerization Example 2 of Copolymer Latex 100 parts of water, 0.6 parts of sodium dodecylbenzene sulfonate, 0.3 parts of sodium hydrogen carbonate, 0.8 parts of potassium persulfate and a first stage monomer shown in Table 4 in a 10 liter autoclave. Mixture, chain transfer agent, 1 unsaturated bond in the ring
A cyclic unsaturated hydrocarbon having two components was charged and the first stage polymerization was carried out at 60 ° C. When the conversion in the first stage reached 75%, the monomer mixture in the second stage, the chain transfer agent, and the unsaturated hydrocarbon were continuously added for 6 hours, and the second stage polymerization was carried out at 70 ° C. Then, in order to complete the polymerization, the reaction was continued for another 3 hours to complete the polymerization. The polymerization conversion rates were all 98% or more. The obtained copolymer latex was adjusted to pH 8 with sodium hydroxide, and then unreacted monomers and unsaturated hydrocarbons remaining as unreacted products were removed by steam distillation to obtain a copolymer latex 16 ~ 22 was obtained.

Preparation of Adhesive Composition for Carpet Backing Copolymer latices 16-22 were each adjusted to pH 8.5 with aqueous sodium hydroxide solution. To 100 parts (solid content) of each latex whose pH was adjusted, 1.0 part of Aron T-40 (manufactured by Toagosei Co., Ltd .: low molecular weight sodium polyacrylate) and 400 parts of heavy calcium carbonate were added as dispersants, respectively. 1.0 part of Aron A-20P (manufactured by Toagosei Co., Ltd .: high molecular weight sodium polyacrylate) was added as a thickener, and the solid content concentration was 75% by weight with ion-exchanged water.
To obtain a carpet backing adhesive composition having a viscosity of 17,000 to 20000 centipoise (BM type rotational viscometer, 12 rpm, # 4 rotor, 20 ° C.).

The adhesive composition thus obtained was uniformly applied to the back surface of a tufted carpet greige machine having a polypropylene split yarn as a base cloth and 6 nylon with a pile of 1/8 inch gauge at an apparent weight of 1200 g / m ² . , 7 ounces / square yard of jute woven backing, 12
Drying at 0 ° C. for 20 minutes gave a jute backed carpet.

Using these carpets, the adhesive strength was measured according to JIS 10211. Next, after immersing the carpet prepared in the same manner in ion exchange water at 20 ° C. for 1 hour,
The adhesive strength was measured according to JIS10211. Also, 10 cm
A test piece with a size of 10 cm was prepared, and the test piece was placed in a glass bottle capable of being sealed and allowed to stand at 50 ° C. for 1 hour, and then the stopper was removed to determine the degree of odor. ◯: Almost no odor Δ: Slight odor ×: Odor is shown in Table 5.

[0073]

[Table 4]

[0074]

[Table 5]

Polymerization Example 3 of Copolymer Latex In a 20 liter autoclave, 100 parts of water, 0.8 part of sodium dodecylbenzenesulfonate, 0.3 part of sodium hydrogen carbonate, 0.9 part of potassium persulfate and the first stage monomer shown in Table 6 were used. Charge a mixture, a chain transfer agent, and a cyclic unsaturated hydrocarbon having one unsaturated bond in the ring at 65 ° C.
A second stage polymerization was carried out. When the conversion in the first stage reached 80%, the monomer mixture in the second stage, the chain transfer agent and the unsaturated hydrocarbon were continuously added for 8 hours to carry out the second stage polymerization. Then, in order to complete the polymerization, the reaction was continued for another 3 hours to complete the polymerization. The polymerization conversion rates were all 98% or more. The obtained copolymer latex was adjusted to pH 8 with sodium hydroxide, and then unreacted monomers and unsaturated hydrocarbons remaining as unreacted products were removed by steam distillation to obtain copolymer latexes 23 to 29. Obtained.

Preparation of adhesive composition for rock fiber base material Copolymer latex 23 to 29 100 parts (solid content) each
, 2 parts of zinc white, 1 part of zinc dibutyldithiocarbamate and 1 part of antigen S (styrenated phenol: manufactured by Sumitomo Chemical Co., Ltd.) are added, 0.3 part of carboxymethyl cellulose is added as a thickener, and solidified with ion exchange water. The content was adjusted to 48.0% by weight, and the viscosity was 1000 to 1300 centipoise (BM type rotational viscometer, 60 rpm, # 3 rotor, 20
An adhesive composition for rock fiber base material of (° C.) was prepared.

These adhesive compositions were adjusted to a solid content of 40.0% by weight with ion-exchanged water, and were 100 mm long, 100 mm wide,
About 2 g of the palm-rock fiber having a thickness of 20 mm and a weight of 3.0 g was spray-coated on the surface and dried at 80 ° C. for 10 minutes.
Further, the back surface was similarly spray-coated and dried at 80 ° C. for 10 minutes. Then, heat at 130 ℃ for 15 minutes,
A lock test piece was prepared by promoting crosslinking.

Using these test pieces, tests of adhesive strength and water resistant adhesive strength were conducted. The results are shown in Table 6.

Adhesive strength: Measured with an Instron tensile tester.

Adhesion strength after immersion: Each lock test piece was at 20 ° C.
After being immersed in the ion-exchanged water, the measurement was performed with an Instron tensile tester.

[0081]

[Table 6]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location D06M 15/693 D21H 21/14 19/56

Claims (6)

[Claims] 1. Emulsion polymerization of an aliphatic conjugated diene monomer and another monomer copolymerizable therewith in the presence of a cyclic unsaturated hydrocarbon having one unsaturated bond in the ring. A method for producing a copolymer latex, comprising: 2. An aliphatic conjugated diene-based monomer 10 to 80% by weight, an ethylenically unsaturated carboxylic acid monomer 0.5 to 10% by weight, and another monomer 10 to 89.5 copolymerizable therewith.
The method for producing a copolymer latex according to claim 1, which comprises using a monomer mixture consisting of wt%. 3. An adhesive composition containing the copolymer latex obtained by the production method according to claim 1. 4. A paper coating composition comprising a copolymer latex obtained by the production method according to claim 1. 5. An adhesive composition for carpet backing, which comprises the copolymer latex obtained by the production method according to claim 1. 6. An adhesive composition for a rock fiber base material, which comprises a copolymer latex obtained by the production method according to claim 1.