TWI816847B - Latex adhesive composition, adhesive body and wetsuit - Google Patents

Abstract

The object of the present invention is to provide an adhesive composition containing polychloroprene rubber latex with good adhesive strength and flexibility. The solution of the present invention is to use a latex adhesive composition as an adhesive. The latex adhesive composition contains 2.0 to 8.0 parts by weight of a non-aqueous dispersible isocyanate compound relative to 100 parts by weight of polychloroprene rubber latex. , 7.0 parts by weight or less of a water-soluble carbodiimide compound, or 3.0 to 8.0 parts by weight of a polyether-modified allophanate polyisocyanate compound.

Description

Latex adhesive composition, adhesive body and wetsuit

The present invention relates to a latex adhesive composition containing polychloroprene rubber. More specifically, it relates to a latex that can achieve both excellent bonding strength and flexibility in bonding foams to each other or to foams and fabrics. Adhesive composition.

In the manufacture of wetsuits, jockstraps, sportswear midpads, impact absorbers, etc., various foams are used as adherends. In the past, solvent-based adhesives using polychloroprene rubber as a base were used for such bonding. However, the volatilization of organic solvents used in these adhesives can cause health problems for workers and cause fires in workplaces. Therefore, there is a growing desire for a latex-based adhesive that does not have such concerns.

On the other hand, the previous polychloroprene rubber latex had the problem of insufficient bonding strength. As a method to solve this problem, for example, in adhering to a foam, an adhesive containing polychloroprene latex as a main component and polyisocyanate as a cross-linking agent and an adhesion method thereof are known (for example, refer to Patent Document 1 ,2). However, by using polyisocyanate, the adhesive film hardens and the adhesive strength is improved. However, there is a problem of impairing the flexibility of the foam after adhesion.

As a method to solve this problem, an adhesive composition containing polychloroprene latex as a main component and a water-dispersed carbodiimide compound as a cross-linking agent for adhering to a foam and its adhesive composition are known. Next, the method (for example, refer to Patent Document 3). However, although the flexibility is good, the adhesion strength is insufficient, and particularly the toluene resistance required in the manufacturing process of the wetsuit is insufficient. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2000-104028 [Patent Document 2] Japanese Patent Application Publication No. 2003-27024 [Patent Document 3] Japanese Patent Application Publication No. 2018-168327

The problem to be solved by the invention

The present invention was made in view of this problem, and its purpose is to use conventional polychloroprene rubber latex-based adhesives for sports goods and wetsuits where sufficient bonding strength cannot be obtained or flexibility is reduced. ) provides a latex adhesive composition with good bonding strength and softness by bonding foams of materials to each other or foams and fabrics. means to solve problems

Against this background, the inventors of the present invention conducted intensive research in order to solve the above-mentioned problems and found that by mixing non-water-dispersible isocyanate or polyether-modified allophanate-type polyester with polychloroprene rubber latex, The isocyanate compound can improve the bonding strength between an adhesive composition containing polychloroprene rubber latex as a main component and a foam, and the present invention was completed.

That is, the present invention contains 2.0 to 8.0 parts by weight of a non-aqueous dispersible isocyanate compound and 7.0 parts by weight or less of a water-soluble carbodiimide compound, or 3 to 8.0 parts by weight of a chloroprene rubber latex. 8 parts by weight of a latex adhesive composition of a polyether-modified allophanate polyisocyanate compound.

Hereinafter, the present invention will be described in detail. The latex adhesive composition of the present invention contains 2.0 to 8.0 parts by weight of a non-aqueous dispersible isocyanate compound or 3.0 to 8.0 parts by weight of polyether-modified ureamethyl, based on 100 parts by weight of polychloroprene rubber latex. An acid ester type polyisocyanate compound is used as the isocyanate compound.

Various products of polychloroprene rubber latex are commercially available. There are latexes containing homopolymers of chloroprene monomers; chloroprene monomers are selected from carboxyl-containing monomers and hydroxyl-containing monomers. Latex of copolymers of more than one monomer, etc. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, fumaric acid, and maleic acid; examples of the hydroxyl group-containing monomer include hydroxyethyl acrylate, hydroxyethyl methacrylate, and methyl Hydroxypropyl acrylate, etc.

The polychloroprene latex is not particularly limited, because polychloroprene rubber hardens by crystallization at low temperatures, and is a polychloroprene rubber latex containing a copolymer with one or more monomers. Better.

The adhesive composition containing polychloroprene rubber latex as the main component of the present invention must contain a non-water-dispersible isocyanate compound or a polyether-modified carbamide methyl compound in order to achieve both sufficient adhesive strength and flexibility. Acid ester type polyisocyanate compound.

The isocyanate compound is a compound having a functional group represented by -N=C=O. Although some water-dispersed types (dispersed types) that can be water-dispersed by modification treatment etc. are used in the present invention, such is not carried out. Treatment of non-water dispersible type. The content of isocyanate group (NCO) is not particularly limited, but is usually 12 to 23%. From a balance between cost and service life, 15 to 21% is preferred. In addition, as the isocyanate compound, trimer type, allophanate type, etc. are known. In terms of flexibility, the allophanate type is superior. In the present invention, polyether-modified urea is used. Formate type polyisocyanate compound.

When a non-water-dispersible isocyanate compound is used, the adhesive strength can be improved by containing a carbodiimide compound. The carbodiimide compound is a compound having a functional group represented by -N=C=N- and can usually be synthesized by decarbonation condensation reaction of diisocyanate in the presence of a carbodiimide catalyst. The NCN content is usually about 5 to 15%, and the content with higher reactivity is preferably more than 10%. The carbodiimide compound is made into various forms such as water-soluble type, emulsified type, water-dispersed type, etc. by making a part of it hydrophilic or emulsifying using an emulsifier, etc., and there are various commercially available products. Among them, in terms of toluene resistance and softness, water-soluble ones that are soluble in water are preferred. Since emulsified and water-dispersed types impair softness, it is best not to use them.

The non-aqueous dispersible isocyanate compound used in the present invention is 2.0 to 8.0 parts by weight, preferably 3.0 to 7.0 parts by weight, and preferably 4.0 to 5.0 parts by weight based on 100 parts by weight of polychloroprene rubber. When the amount of the non-water-dispersible isocyanate compound is less than 2.0 parts by weight, the adhesion properties decrease, and when it exceeds 8.0 parts by weight, the flexibility of the adherend decreases. The water-soluble carbodiimide compound is 7.0 parts by weight or less based on 100 parts by weight of polychloroprene rubber, preferably 2.0 to 6.0 parts by weight based on 100 parts by weight of polychloroprene rubber, and more preferably 3.0~5.0 parts by weight. By setting the amount of the water-dispersed carbodiimide compound to 7.0 parts by weight or less, the adhesive properties and coating properties of the adhesive composition become good.

The polyether-modified allophanate-type polyisocyanate compound used in the present invention is preferably an allophanate body of polyether alcohol (b1) and organic diisocyanate (b2), and may optionally be included. Methoxypolyethylene glycol.

Because polyether alcohol (b1) is called a so-called polymer polyol, polyethylene polyol, polypropylene polyol, and polytetramethylene polyol are preferred. When considering the flexibility and bonding strength of the bonded body, the polyether alcohol (b1) is a so-called polymer polyol. Polytetramethylene polyol is particularly preferred. The polyether alcohol (b1) preferably has an average number of functional groups of 2 or more and a number average molecular weight of 200 to 3,000.

Examples of the organic diisocyanate (b2) include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 2,4'-diphenylmethane diisocyanate. Isocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitriphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane -4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, isophthalic diisocyanate, terephthalic diisocyanate Isocyanates, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate and other aromatic diisocyanates ;Hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysate diisocyanate , aliphatic diisocyanates such as trioxyethylene diisocyanate; xylylenedimethyl-1,4-diisocyanate, xylylenedimethyl-1,3-diisocyanate, tetramethylxylylenedimethyldiisocyanate, etc. Aromatic aliphatic diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated xylyl diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylyl diisocyanate, etc. Diisocyanate, etc. Any of these can be used individually or in mixture of 2 or more types. In the present invention, when considering the flexibility and bonding strength of the adhesive body, aliphatic diisocyanate and alicyclic diisocyanate are preferred, and hexamethylene diisocyanate is particularly preferred.

The allophanate catalyst system uses zirconium carboxylate. By using zirconium carboxylate, a substantially uncolored allophanate-modified polyisocyanate can be easily obtained without using a cocatalyst or the like. Examples of the carboxylic acid used here include saturated aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and 2-ethylhexanoic acid. Acid, saturated monocyclic carboxylic acids such as cyclohexanecarboxylic acid and cyclopentanecarboxylic acid, saturated polycyclic carboxylic acids such as bicyclo(4.4.0)decane-2-carboxylic acid, naphthenic acid and other carboxylic acids mentioned above Mixtures, unsaturated aliphatic carboxylic acids such as oleic acid, linoleic acid, linolenic acid, soybean oil fatty acids, tall oil fatty acids, and aromatic aliphatic carboxylic acids such as diphenylacetic acid , monocarboxylic acids such as aromatic carboxylic acids such as benzoic acid and phenylacetic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, pentanoic acid Diacid, adipic acid, pimelic acid, suberic acid, glutenedic acid, azelaic acid, sebacic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, 1,4-cyclohexyl di Carboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α,β-diethylsuccinic acid, Polycarboxylic acids such as maleic acid, fumaric acid, trimellitic acid, and pyromellitic acid. These carboxylic acid zirconium salts can be used alone or in any form of a mixture of two or more kinds. In the present invention, the preferred allophanate catalyst is a monocarboxylic acid zirconium salt having 10 or less carbon atoms.

Next, the specific manufacturing procedures are explained. The manufacturing process consists of the following steps. The first step is a step of reacting polyether polyol (b1) and organic diisocyanate (b2) in the presence of an allophanate catalyst. The second step is the step of adding a catalyst poison to stop the allophanate reaction. The third step: is the step of removing free organic diisocyanate.

The first step consists of urethane reaction and allophanate reaction. The specific procedure is to add the polyether polyol (b1) and the organic diisocyanate (b2) so that the isocyanate group becomes an excess to the hydroxyl group and perform a urethanation reaction at 20 to 100°C, and then proceed to 70 ~150℃ and in the presence of an allophanate catalyst, the allophanate reaction is carried out until the ethyl urethane group substantially no longer exists.

The so-called "isocyanate group to hydroxyl group is in excess" here refers to the amount of isocyanate group to hydroxyl group to be in excess when the raw material is added. The molar ratio of isocyanate group to hydroxyl group is preferably isocyanate group/hydroxyl group = 8 or more. 10~50 is particularly good.

The reaction temperature of the urethane esterification reaction is 20~120°C, preferably 50~100°C. In addition, during the urethanation reaction, a conventional so-called urethanization catalyst can be used. Specific examples include organic metal compounds such as dibutyltin dilaurate and dipyltin dilaurate, organic amines such as triethylenediamine and triethylamine, and salts thereof.

The reaction time of the urethanization reaction varies according to the presence or absence of a catalyst, the type of catalyst, and the reaction temperature. It is usually within 10 hours, preferably 1 to 5 hours.

After the urethanization reaction is completed, the allophanate reaction is performed. The allophanating reaction is performed by adding the aforementioned allophanating catalyst and adjusting the reaction temperature to 70 to 150°C, preferably 80 to 130°C. When the reaction temperature is too low, allophanate groups are less formed and the average number of functional groups of the resulting polyisocyanate decreases. When such a polyisocyanate is used as a hardener, the adhesive properties tend to become insufficient. When the reaction temperature is too high, the obtained polyisocyanate is heated unnecessarily and may cause coloring of the polyisocyanate. In addition, the average number of functional groups of polyisocyanate refers to the average number of isocyanate groups present in one molecule.

Furthermore, in the present invention, the urethanation reaction and the allophanate reaction can be performed simultaneously. At this time, the polyether polyol (b1) and the organic diisocyanate (b2) are added so that the isocyanate group becomes an excess to the hydroxyl group, and the temperature is 70 to 150° C. and the allophanate catalyst is present. The urethane esterification reaction and the allophanate esterification reaction are carried out simultaneously.

The usage amount of the allophanate catalyst varies according to its type. Relative to the total amount of the above (b1) and (b2), 0.0005 to 1 mass % is preferred, and 0.001 to 0.1 mass % is preferred. . When the amount of catalyst used is less than 0.0005% by mass, the reaction becomes slow and takes a long time, and coloring may occur due to heat exposure. On the other hand, when the amount of catalyst used exceeds 1% by mass, reaction control becomes difficult and side reactions such as dimerization reaction (isocyanate dimerization reaction) and trimerization reaction (isocyanurate reaction) may occur. situation, and when the obtained polyisocyanate is used as a hardener, problems such as loss of elasticity may occur.

The reaction time varies depending on the type and amount of catalyst added, and the reaction temperature. Generally, within 10 hours is optimal, and 1 to 5 hours is particularly optimal.

In addition, at this time, an organic solvent can be used as necessary. Examples of the organic solvent include aliphatic hydrocarbon-based organic solvents such as n-hexane and octane, alicyclic hydrocarbon-based organic solvents such as cyclohexane and methylcyclohexane, acetone, methyl ethyl ketone, and methyl ethyl ketone. Ketone-based organic solvents such as isobutyl ketone and cyclohexanone, ester-based organic solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, etc., ethylene glycol ether acetate, propylene glycol methyl ether Glycol ether ester organic solvents such as acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, etc., diethyl ether, tetrahydrofuran, dihexane, etc. Ether-based organic solvents, halogenated aliphatic hydrocarbon-based organic solvents such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, diiodomethane, and dichloroethane, and N-methylpyrrolidine Polar aprotic solvents such as ketone, dimethylformamide, dimethylacetamide, dimethyltrisoxide, hexamethylphosphonamide, etc. One type or two or more types of the aforementioned solvents can be used.

The second step is a step in which, after the allophanate reaction, a catalyst poison is added to stop the allophanate reaction. The period of adding the catalyst poison is not particularly limited as long as it is after the allophanate reaction. When performing thin film distillation in the third step of removing free organic diisocyanate, it is after the allophanate reaction. It is better to add catalyst poison after thin film distillation. This is to prevent side reactions caused by the heat during thin film distillation.

Examples of the catalyst poison include inorganic acids such as phosphoric acid and hydrochloric acid, organic acids having a sulfonic acid group, an amine sulfonic acid group, etc., their esters, and commonly known substances such as acyl halide.

The amount of catalyst poison added varies depending on the type of catalyst and the type of catalyst. An amount of 0.5 to 2 equivalents to become a catalyst is preferred, and an amount of 0.8 to 1.5 equivalents is particularly preferred. When there are too few catalyst poisons, the storage stability of the obtained polyisocyanate is easily reduced. When too much is used, the resulting polyisocyanate may be colored.

The third step is a step of removing free organic diisocyanate (b2). In the present invention, basically the product after the allophanation reaction contains free organic diisocyanate. Since this free organic diisocyanate causes odor and turbidity over time, it is preferable to remove unreacted organic diisocyanate (b2) until the free organic diisocyanate content becomes 1 mass % or less.

As a method for removing free organic diisocyanate, conventional methods such as distillation, reprecipitation, and extraction can be cited. The distillation method, especially the thin film distillation method, is preferable because it does not require the use of a solvent. In addition, the preferred conditions for thin film distillation are pressure: 0.1 kPa or less and temperature: 100 to 200°C. Particularly preferred conditions are pressure: 0.05 kPa or less and temperature: 120 to 180°C.

The adhesive composition of the present invention contains 3.0 to 8.0 parts by weight of a polyether-modified allophanate-type polyisocyanate compound based on 100 parts by weight of polychloroprene rubber. When the polyisocyanate compound content is less than 3.0 parts by weight, the physical properties of the adhesive are reduced, and when it exceeds 8.0 parts by weight, the flexibility of the adherend is reduced.

The viscosity of the adhesive composition can be determined by formulating various tackifiers such as polyalkylene oxide, polyvinyl alcohol, hydrophobized cellulose, associative nonionic surfactants and other water-soluble polymers, and by formulating carboxyl-containing polymers. The required viscosity can be adjusted to the required viscosity by using alkali-soluble thickeners, silicate compounds such as hectorite, etc. When using polyethylene oxide at this time, it is preferable that the coating property when applied by roll coat is good. The polyethylene oxide system preferably contains 0.05 to 1.0 parts by weight relative to 100 parts by weight of polychloroprene rubber latex. In addition, adhesion-imparting resins such as rosin ester, terpene phenol, petroleum resin, and cumarone resin, antioxidants, preservatives, antifreezes, film-forming aids, and plasticizers may be appropriately blended as necessary. agents, pH adjusters, etc.

The adhesive composition of the present invention can be used to adhere foams used as materials for sportswear, diving wear, etc., or foams and fabrics.

Examples of foam materials include polychloroprene rubber, styrene-butadiene rubber, ethylene-vinyl acetate copolymer, chlorinated polyethylene, and molding and foaming of mixtures thereof. made thing. In particular, polychloroprene rubber with excellent flexibility can be used as a foam for diving suits.

Fabrics include synthetic fibers such as nylon and polyester, and natural fibers such as cotton and silk, and non-woven fabrics. As a diving suit, a jersey fabric (jersey) that has a water-repellent effect can be used. Invention effect

The adhesive composition of the present invention has excellent bonding strength between foams or between foams and fabric, and the bonded body maintains excellent flexibility.

Form used to implement the invention [Example]

The present invention will be specifically described below through examples, but the present invention is not limited by these examples.

In addition, "%" in the synthesis examples and examples means "mass %", and the normal temperature peel strength and flexibility were measured and evaluated using the following methods.

>Confirmation of peeling status at room temperature> The bonded sample was cured in a constant temperature chamber at 23° C. for 1 day, and then punched using a 25 mm × 150 mm cutting machine to produce a test piece. The end of each adherend was mounted on a TENSILON type tensile testing machine, a 180° peeling test was performed at 23° C. at a tensile speed of 20 mm/min, and the peeling state was observed. The peeling state is judged as follows. (Good) Material damage (material breakage)/cohesion damage (cohesion)/interface damage (interface) (Poor)

>Determination of toluene resistance> After the bonded sample was cured in a constant temperature chamber at 23° C. for 7 days, a normal temperature peeling test using a TENSILON type tensile testing machine was performed while dropping toluene onto the sample, and the peeling state was observed. Peel strength is measured when the material is not damaged. The peeling state is judged as follows. (Good) Material damage (material breakage)/cohesion damage (cohesion)/interface damage (interface) (Poor)

>Measurement of softness> The adhered sample was cured in a constant temperature chamber at 23° C. for 7 days, and then punched using a 25 mm × 150 mm cutting machine to produce a test piece. Both ends of the test piece were mounted on a TENSILON tensile testing machine, and the tensile stress at 60% elongation at 23°C was measured at a tensile speed of 100 mm/min.

[Manufacturing of allophanate-type polyisocyanate compounds]

Synthesis example 1

In a 1L reactor equipped with a stirrer, thermometer, cooler and nitrogen inlet pipe, add 890g of hexamethylene diisocyanate and 110g of polytetramethylene glycol (product name: TERA THANE250) with a number average molecular weight of 250. The urethane reaction was performed at 90° C. for 2 hours. When the reaction product was analyzed by FT-IR, the hydroxyl groups had disappeared. Next, 0.36 g of zirconium 2-ethylhexanoate was added, and the allophanate reaction was performed at 90° C. for 3 hours. When the reaction product was analyzed by FT-IR and 13C-NMR, the ethyl urethane group had disappeared. Next, 0.1 g of phosphoric acid was added and the reaction was stopped at 50°C for 1 hour, and free hexamethylene diisocyanate was removed by thin film distillation to obtain a polyether-modified allophanate isocyanate with an isocyanate content of 16.5%. Compound (NCO-1).

Synthesis example 2

In a reactor with a capacity of 1 L equipped with a stirrer, a thermometer, a cooler and a nitrogen inlet pipe, 900 g of NCO-1 obtained in Synthesis Example 1 and 100 g of methoxypolyethylene glycol with a number average molecular weight of 400 were added to a temperature of 80 The reaction was carried out at ℃ for 4 hours to obtain a polyether-modified allophanate polyisocyanate (NCO-2) with an isocyanate content of 13.7%.

Synthesis Examples 3 and 4

The allophanate-type polyisocyanate was produced in the same manner as in Synthesis Example 2 using the raw materials shown in Table 1.

Synthesis Comparative Example 1

In a 1L reactor equipped with a stirrer, thermometer, cooler and nitrogen inlet pipe, add 950g of hexamethylene diisocyanate and 50g of 3-methyl-1,5-pentanediol, and conduct ethyl carbamate at 90°C. reaction for 2 hours. When the reaction product was analyzed by FT-IR, the hydroxyl groups had disappeared. Next, 0.36 g of zirconium 2-ethylhexanoate was added, and the allophanate reaction was performed at 90° C. for 3 hours. When the reaction product was analyzed by FT-IR and 13C-NMR, the ethyl urethane group had disappeared. Next, 0.1 g of phosphoric acid was added, the reaction was stopped at 50°C for 1 hour, and free hexamethylene diisocyanate was removed by thin film distillation to obtain a diol-modified allophanate type with an isocyanate content of 19.4%. Isocyanate compound (NCO-5).

Synthesis Comparative Examples 2 and 3 It was carried out similarly to Synthesis Example 2 and produced the diol-modified allophanate type polyisocyanate compound using the raw materials shown in Table 2.

[Table 2]

Example 1 100 parts by weight of polychloroprene rubber latex (chloroprene-methacrylic acid copolymer manufactured by TOSOH Co., Ltd., trade name: SKYPRENE GFL-890) and non-water-dispersible isocyanate compound A (TOSOH ( Co., Ltd., trade name: CORONATE C-2793, NCO16.4%) 4.0 parts by weight, water-soluble carbodiimide compound (manufactured by Nisshinbo Chemical Co., Ltd., trade name: CARBODILITE V-04, 40% active ingredient) 10.0 parts by weight (4 parts by weight in pure form), 2.5 parts by weight of associative viscosity modifier (manufactured by ADEKA Co., Ltd., trade name: ADEKANOL UH-438) and polyethylene oxide compound (manufactured by Sumitomo Seika Co., Ltd. , trade name: PEO-1, white powder), 10% aqueous solution of 1 part by weight, uniformly mixed using a homomixer (homomixer) to prepare an adhesive composition. Apply about 80 g/m ² (wet) of the adhesive composition to a sponge sheet made of chloroprene rubber, overlap the water-repellent nylon jersey fabric so that wrinkles do not occur, and place about 10 kg in an oven at 100°C. The iron plate is pressed and dried for 90 seconds.

In the peel test, the sponge material was mainly broken and the normal temperature peel strength in the toluene resistance test was high. The tensile stress of the test piece was low and the softness was good.

Example 2

An adhesive composition was produced and evaluated according to Example 1, except that the weight of the mixed non-aqueous dispersible isocyanate compound was changed to the amount shown in Table 3. In the peel test, the sponge material was mainly broken and the normal temperature peel strength in the toluene resistance test was high. The tensile stress of the test piece was low and the softness was good.

Example 3

An adhesive composition was produced and carried out according to Example 1, except that the mixed non-aqueous dispersible isocyanate compound was changed to isocyanate compound B (manufactured by TOSOH Co., Ltd., trade name: CORONATE C-2785, NCO 19.2%). Evaluation. In the peeling test, the sponge material was mainly broken and the normal temperature peeling strength and softness were both good results.

Examples 4 and 5

An adhesive composition was produced and evaluated according to Example 1, except that the weight of the mixed water-soluble carbodiimide compound was changed to the amount shown in Table 3. In the peeling test, the sponge material was mainly broken and the peeling strength and softness at normal temperature were both good results.

Example 6

An adhesive composition was produced and evaluated according to Example 1 except that the water-soluble carbodiimide compound was not mixed and the non-aqueous dispersible isocyanate B was mixed in the amount shown in Table 3. The softness is good and the subsequent peel strength is high and good.

Example 7

The adhesive set was produced according to Example 1 except that water-soluble carbodiimide was not mixed. compounds and evaluated. In the peeling test, the sponge material was mainly broken and the normal temperature peeling strength and softness were both good results.

Example 8

An adhesive composition was produced and evaluated according to Example 1, except that the weight of the mixed non-aqueous dispersible isocyanate compound was changed to the amount shown in Table 1, and a water-soluble carbodiimide was not mixed. In the peeling test, the sponge material was mainly broken and the normal temperature peeling strength and softness were both good results.

The compositions and evaluation results of the samples produced in Examples 1 to 8 are shown in Table 3.

Comparative example 1

An adhesive composition was produced and evaluated according to Example 1, except that the isocyanate compound to be mixed was changed to a water-dispersed isocyanate compound (manufactured by TOSOH Co., Ltd., trade name: CORONATE AQ-140, NCO 18.0%). The adhesion properties at room temperature are good, but the flexibility and toluene resistance are poor.

Comparative example 2

An adhesive composition was produced and evaluated according to Example 1, except that the weight of the mixed non-aqueous dispersible isocyanate compound was changed to the amount shown in Table 4. The flexibility is good, but the adhesion properties are poor.

Comparative example 3

An adhesive composition was produced and evaluated according to Example 1, except that the weight of the mixed non-aqueous dispersible isocyanate compound was changed to the amount shown in Table 4. The adhesive composition is difficult to apply and causes poor adhesion.

Comparative example 4

An adhesive composition was produced and evaluated according to Example 1, except that the weight of the mixed water-soluble carbodiimide compound was changed to the amount shown in Table 4. The adhesive composition is difficult to apply and causes poor adhesion.

Reference example

100 parts by weight of polychloroprene rubber latex (chloroprene-methacrylic acid copolymer manufactured by TOSOH Co., Ltd., trade name: SKYPRENE GFL-890) and a water-dispersed carbodiimide compound (Nisshinbo CHEMICAL (manufactured by ADEKA Co., Ltd., trade name: CARBODILITE E-05, active ingredient 40%) 4.0 parts by weight, and 2.5 parts by weight of associative viscosity modifier (manufactured by ADEKA Co., Ltd., trade name: ADEKANOL UH-438), use homogeneous The adhesive composition was uniformly mixed with a mixer, and a test was conducted under the conditions of Example 1. The adhesive properties and flexibility at room temperature are good, but the toluene resistance is poor.

Table 4 shows the compositions and evaluation results of the samples produced in Comparative Examples 1 to 5 and Reference Example.

Example 9

100 parts by weight of polychloroprene rubber latex (chloroprene-methacrylic acid copolymer manufactured by TOSOH Co., Ltd., trade name: SKYPRENE GFL-890) and 5 parts by weight of an allophanate-type isocyanate compound NCO-1 and 2.5 parts by weight of an associative viscosity modifier (manufactured by ADEKA Co., Ltd., trade name: ADEKANOL UH-438) were uniformly mixed using a homomixer to produce an adhesive composition. Apply about 50~100g/m ² (wet) of adhesive on a CR sponge sheet, overlap the water-repellent nylon jersey fabric in a manner that does not cause wrinkles, and press-dry it in an oven at 100°C for 1 minute. Dry further for 5 minutes. Table 5 shows the composition and evaluation results of the produced samples.

In the peeling test, the sponge material was mainly broken and the peeling strength at room temperature was relatively high. Furthermore, while the toluene resistance is good and the peel strength is high, the tensile stress of the test piece is low and the flexibility is good.

Examples 10 and 11

An adhesive composition was produced and evaluated in accordance with Example 9, except that the weight of the mixed allophanate isocyanate compound NCO-1 was changed to the amount shown in Table 5. In the peeling test, the main reason is that the sponge material is broken and the peeling strength is high at room temperature, and the toluene resistance is also good. Softness is also a good result.

Examples 12, 13, 14

An adhesive composition was produced and evaluated according to Example 9, except that the mixed allophanate isocyanate compound was changed to NCO-2, NCO-3, and NCO-4. In the peeling test, the main reason is that the sponge material is broken and the peeling strength is high at room temperature, and the toluene resistance is also good. Softness is also a good result.

Comparative example 6

An adhesive composition was produced and evaluated in accordance with Example 9, except that the weight of the mixed allophanate isocyanate compound NCO-1 was changed to the amount shown in Table 6. The softness is good, but in the peeling test, it peeled off at the sponge interface and the normal temperature peeling strength and toluene resistance were poor.

Comparative example 7

An adhesive composition was produced and evaluated in accordance with Example 9, except that the weight of the mixed allophanate isocyanate compound NCO-1 was changed to the amount shown in Table 6. The adhesive strength and toluene resistance are good, but the tensile stress of the adhesive is high and the flexibility is poor.

Comparative example 8

An adhesive composition was produced and evaluated according to Example 9, except that the mixed allophanate isocyanate compound was changed to NCO-5. The bonding strength and toluene resistance are good, but the bonding strength and toluene resistance are good. The adhesive has high tensile stress and poor flexibility.

Comparative Examples 9 and 10

An adhesive composition was produced and evaluated according to Example 9, except that the mixed allophanate type isocyanate compound was changed to NCO-6 and NCO-7. The adhesive strength is good, but the toluene resistance is low, and the tensile stress of the adhesive is high and the flexibility is poor.

without.

Claims (11)

A latex adhesive composition, characterized in that: it contains 2.0 to 8.0 parts by weight of a non-aqueous dispersible isocyanate compound and 7.0 or less parts by weight of a water-soluble carbodiimide relative to 100 parts by weight of polychloroprene rubber latex. compound, or containing 3.0 to 8.0 parts by weight of a polyether-modified allophanate polyisocyanate compound. For the latex adhesive composition described in item 1 of the patent application, the content of the non-aqueous dispersible isocyanate compound is 3.0 to 7.0 parts by weight. For the latex adhesive composition described in item 1 of the patent application, the content of the water-soluble carbodiimide compound is 2.0 to 6.0 parts by weight. The latex adhesive composition described in item 1 of the patent application does not contain an emulsified dispersed carbodiimide compound. The latex adhesive composition as described in item 1 of the patent application, wherein the polyether modified allophanate polyisocyanate compound is an allophanate of polyether polyol (b1) and organic diisocyanate (b2) body. The latex adhesive composition described in item 5 of the patent application, wherein the organic diisocyanate (b2) is hexamethylene diisocyanate. The latex adhesive composition as described in any one of items 1 to 6 of the patent application, which contains 0.05 to 1.0 parts by weight of polyethylene oxide relative to 100 parts by weight of polychloroprene rubber latex. The latex adhesive composition as described in any one of items 1 to 6 of the patent application, wherein the polychloroprene rubber in the polychloroprene rubber latex is chloroprene monomer, and is selected from A copolymer of one or more monomers including a carboxyl group-containing monomer and a hydroxyl group-containing monomer. An adhesive body in which foam bodies or foam bodies and fabrics are bonded to each other using the latex adhesive composition as described in any one of items 1 to 8 of the patent application. As for the adhesive body described in item 9 of the patent application, the material of the foam body is polychloroprene rubber. A wetsuit is composed of an adhesive body as described in item 9 or 10 of the patent application.