TW200817485A - Vulcanizable aqueous adhesive and the use thereof - Google Patents

Abstract

A vulcanizable aqueous adhesive which does not contain any organic solvent and is free from anxieties about protein allergy, specifically a vulcanizable aqueous adhesive containing a chloroprene polymer latex, sulfur, and zinc oxide. It is preferable that the adhesive contain 2 to 5 parts by mass of sulfur and 3 to 10 parts by mass of zinc oxide per 100 parts by mass of the solid matter of the chloroprene polymer latex. The adhesive is useful in the production of canvas shoes for vulcanization-bonding an outsole, a fabric upper and a foxing tape.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vulcanization type aqueous adhesive which can be suitably used for vulcanization adhesion and uses thereof. [Prior Art] When a shoe is manufactured by a vulcanized (v u 1 c a n i z e ) method, a chloroprene solvent-based adhesive or a natural rubber latex adhesive is used. However, with regard to solvent-based adhesives, the demand for the development of alternative adhesives is increasing year by year in terms of environmental impact or safety of workers, and about natural rubber latex adhesives, which are allergic to latex proteins. (For example, refer to Non-Patent Document 1, 2). Non-Patent Document 1: Japanese Rubber Association, Vol. 78, No. 2 (2005) (55 pages; 4·2·1) Non-Patent Document 2: Adhesive Technology Vol. 21, Ν〇·4 (2002) 6 No. 5 (1 2 pages; 2 · 1 _ 4 items) [Disclosure of the Invention] [Problems to be Solved by the Invention] The present invention provides a vulcanization type which does not use an organic solvent and which is free from protein allergy. Water-based adhesive. [Means for Solving the Problems] -5 - 200817485 In order to achieve the above object, the present invention has been made in an effort to achieve the present invention. (1) A vulcanized aqueous adhesive characterized by a chloroprene rubber latex, sulfur, and zinc oxide. (2) The vulcanized aqueous adhesive according to the above (1), wherein the solid content of the chloroprene rubber latex is 40 to 70% by mass. (3) The vulcanized aqueous adhesive according to (1) or (2) above, wherein the emulsifier and/or dispersant contained in the chloroprene rubber latex is a total of the total used for obtaining the chloroprene polymer. Body, for 〇·5~1 〇 by mass. (4) The vulcanized aqueous adhesive according to any one of the above (1) to (3), which contains 2 to 5 parts by mass of sulfur relative to 1% by mass of the solid content of the chloroprene rubber latex. And 3 to 10 parts by mass of zinc oxide. (5) The vulcanized aqueous adhesive according to any one of the above (1) to (4), which is used for the manufacture of a canvas shoe. (6) The vulcanized aqueous adhesive according to any one of the above (1) to (4), which is used for a rubber sole, a cloth upper, and a side strip for vulcanizing and affixing two or more canvas shoes. (7) A method for producing a canvas shoe in which two or more rubber soles, a cloth upper, and a side strip are vulcanized and adhered by using the vulcanized aqueous adhesive according to any one of the above (1) to (4). (8) The method for producing a canvas shoe according to the above (7), wherein the adhesive surface is coated with a vulcanized aqueous adhesive of 100 to 300 g/cm 2 and heat-adhered. (9) The method for producing a canvas shoe according to the above (7) or (8), wherein the vulcanized aqueous adhesive is applied and dried at 60 to 100 ° C, and the pressure-coated surface is -6-200817485 to 1 0 0~ 1 50 °c vulcanization adhesion. [Effect of the invention] The vulcanized aqueous adhesive of the present invention is not harmful to the environment or the human body because it is not contained, and because it is a synthetic rubber compound, it has no adhesive which is allergic to protein. Further, since it exhibits sufficient adhesive strength, it can be suitably used as a vulcanized aqueous adhesive for canvas. [The best mode for carrying out the invention] The chloroprene rubber latex is an emulsified/dispersed chloroprene water by means of an emulsifier and/or dispersion, also called an emulsifier/dispersant. The concentration of the solid content in the chloroprene rubber latex is not limited, but it is preferably in the range of 40 to 70% by mass, and preferably 50% in terms of workability or improvement of the chloroprene rubber latex itself. . The chloroprene polymer is a polymer obtained by polymerizing 2-chloro-1,3-butadiene as a chloroprene or a copolymer obtained by polymerizing a monomer copolymerized with chlorobutyldichlorobutadiene. The polymerization unit content of the olefin in the copolymer is preferably 80% by mole or more, and more preferably the above. As the monomer copolymerizable with chloroprene, although it is not particularly, it may, for example, be 2,3-chloro-1,3-butane, 1-chloro-: ene, butadiene, isoprene , styrene, acrylonitrile, acrylic solvent, milk as the original agent for vulcanized shoes (the following polymers are particularly limited to the stability of ~60 quality 以下 (hereinafter the olefin and can be mixed with chloroprene = 9 〇 Mo Ear % is limited, 1,3 - butyl = acid or its _ 200817485 class, methacrylic acid or its esters, etc., if necessary, can also use these two types or more. Among them, as a copolymerizable single amount 2,3-dichloro-1,3-butadiene is preferred. The structure of the chloroprene polymer is not particularly limited, but the polymerization temperature, polymerization initiator, and chain shift are appropriately selected. The agent, the polymerization stopper, the final polymerization rate, etc., can adjust the molecular weight, the molecular weight distribution, the gel content, the molecular end structure, the crystallization rate, etc. The emulsifier/dispersant used in the manufacture of the chloroprene rubber latex, In particular, those used in the emulsion polymerization of chloroprene can be used. Examples of the anionic, nonionic, cationic, etc. Examples of the anionic emulsifier/dispersant include a carboxylic acid type and a sulfate type, and examples thereof include an alkali metal salt of rosin acid and a carbon number of 8 to 20 alkyl sulfonates, alkyl aryl sulfates, condensates of sodium naphthalene sulfonate and formaldehyde, sodium alkyl diphenyl ether disulfonate, etc. as a nonionic emulsifier / dispersant For example, polyvinyl alcohol (hereinafter PVA) or a copolymer thereof (for example, a copolymer with acrylamide), a polyvinyl ether or a copolymer thereof (for example, a copolymer with maleic acid), polyvinylpyrrolidone or the like a copolymer (for example, a copolymer with vinyl acetate), or a (co)polymer chemical modification, or a cellulose derivative (hydroxyethyl cellulose), a polyethylene oxide alkyl ether, a polyepoxy Ethyl alkyl aryl ether, polyethylene oxide styryl phenyl ether, polyethylene oxide alkyl phenyl ether, polyoxyalkylene alkyl ether, polyethylene oxide monoacetylene glycol ether, sorbus A sugar alcohol anhydride fatty acid ester, etc. As a cationic emulsifier/dispersant, such as an aliphatic Salt, -8-200817485 Aliphatic 4-grade ammonium salt, for example, octadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, dilauryldimethylammonium chloride, etc. In the case of an emulsifier or a dispersant, an anionic type is preferred, and a rosin acid salt is preferably used. As the rosin acid, wood rosin acid, lip abietic acid, tall oil rosin acid, or disproportionation of such disproportionation may be used. When any of rosin acids is used as a rosin acid salt, it is preferable to use a sulfate-based or sulfonate-based anionic emulsifier or dispersant in order to impart sufficient stability to the chloroprene rubber latex. The amount of the dispersant used is preferably from 0.5 to 10 parts by mass, more preferably from 2 to 6 parts by mass, per part by mass of the total monomer used to obtain the chloroprene polymer. Although sulfur is not particularly limited, powder sulfur, precipitated sulfur, colloidal sulfur, or the like which is generally used as a vulcanizing agent for rubber can be used. When considering dispersibility, it is preferable to use fine powder of sulfur. Considering the treatment added to the chloroprene rubber latex, the sulfur is preferably used as the aqueous dispersion. As a method of making sulfur into an aqueous dispersion, for example, a usual method described in Adhesive Vol. 36, No. 8 (1992), Vol. 38 (343 pages; 3) can be used. The content of sulfur is not particularly limited, but is preferably 1 to 5 parts by mass, more preferably 2 to 5 parts by mass, per 1 part by mass of the solid content of the chloroprene rubber latex. When the amount of addition of sulfur is set to be in this range, the viscosity of the adhesive after vulcanization is sufficient, and sulfur bleeding is less likely to occur. The zinc oxide is not particularly limited, and any zinc oxide generally used as a compounding agent for rubber can be used. Specifically, there are one, two, three kinds of -9-200817485, active zinc oxide, and the like. It is preferable to use zinc oxide as an aqueous dispersion, and the method of preparing an aqueous dispersion can be used in the same manner as sulfur.

The usual method described in Vol. 36, No. 8 (1992), 388 (343 pages; 3 items). Further, as the aqueous dispersion of zinc oxide, a commercially available product can also be used. The content of the zinc oxide is not particularly limited, but it is preferably 1 to 1 part by mass, more preferably 3 to 10 parts by mass, based on the solid content of the chloroprene rubber latex. More preferably 3 to 7 parts by mass. When the addition amount of zinc oxide is set in this range, the adhesion strength after vulcanization adhesion is sufficient, and the adhesive itself is not easily separated. Vulcanized water-based adhesives can be blended with required properties, and can be optionally added with tackifying resins, tackifiers, metal oxides other than zinc oxide, chelating agents, film-forming aids, UV absorbers, antioxidants, plasticizers, sulfur Other than vulcanizing agents, vulcanization accelerators, defoamers, etc. The use of the vulcanized water-based adhesive is not particularly limited, and can be suitably used for adhering cement, concrete, slate, cloth, synthetic rubber material, polyamine-ethyl acetate material, polychlorinated silicon material, and poly When the key is used for various materials such as tobacco materials. It is especially suitable for vulcanized adhesives used in the manufacture of canvas shoes. The vulcanized type water-based adhesive can be manufactured as follows. First, the upper is made into a shoe upper by sewing or uppering the upper member. Then, 'Lasting' work to bond the upper to the midsole, and the whole shape. The vulcanized water-based adhesive is applied to the adhesive surfaces of the integrated cloth upper, the rubber sole, and the rubber side strip. The coating amount at this time is to ensure sufficient adhesion -10- 200817485 strength, and to prevent oozing out of the boundary surface, the setting range is preferably 100 to 300 g/cm 2 , and more preferably 1 50 0 to 2 5 0 g / c m 2 . Apply the materials of these vulcanization type aqueous adhesives at 60 to 100 ° C, 70 to 9 (TC is preferred, dry for 5 to 30 minutes, and bond the coated surfaces to each other, and press them fully. 1 〜 150 ° C, preferably 120 to 140 ° C, preferably 0.5 to 2 hours after the end of the curing. [Embodiment] EXAMPLES Hereinafter, the present invention will be more specifically described by way of Examples and Comparative Examples, but these The examples are not intended to limit the present inventors. In addition, in the following description, unless otherwise, parts and % indicate the mass basis. "Examples" [Polymer Example 1] A reactor having an internal volume of 3 liters was used in a nitrogen atmosphere. , dissolving 5 parts of disproportionated rosin acid, 0.5 parts of sodium hydroxide, 0.8 parts of potassium hydroxide, 份·5 parts of sodium salt of formaldehyde-naphthalenesulfonic acid condensate, 0.5 parts of sodium hydrogen sulfite in 1 0 0 parts of water. Add 10 parts of chloroprene monomer and 〇. 14 parts of n-dodecyl mercaptan under stirring. Under nitrogen atmosphere, at 1 ° C, with persulfate When potassium is used as a starter and polymerization is carried out, when the polymerization rate reaches 90%, the emulsion of phenothiazine is added to stop the polymerization. Heat, remove unreacted monomer, and then concentrate the solid content to 50% to obtain a chloroprene rubber latex. -11 - 200817485 [Preparation of sulfur-containing aqueous dispersion] Put 1 part of powdered sulfur, 5 parts 20% by mass aqueous solution of sodium dodecylbenzenesulfonate, 1 part of bentonite, 10 parts by weight of 5% by mass aqueous sodium hydroxide solution, and 184 parts of pure water in a ball mill, and stirred and mixed for a whole day. Preparation of 33% by mass of the sulfur-containing aqueous dispersion. [Preparation of vulcanized aqueous adhesive] In 20 parts of the chloroprene rubber latex obtained in Polymerization Example 1 (dry basis 100 parts), 3 parts obtained above were added. An aqueous sulfur-containing dispersion (1 part by dry basis) and 2 parts of an aqueous zinc oxide dispersion (AZ-SW manufactured by Osaki Industries Co., Ltd., containing 50% by mass of zinc oxide) (1 part by dry basis). A tackifier (aron A -2 0L manufactured by Toagosei Co., Ltd.), which has a viscosity of about 3,000 mPa*s as an adhesive. [Adhesive test] The adhesive obtained by coating is applied to an unvulcanized rubber sheet (20 x 120 mm) made of natural rubber and On canvas (20x120mm). After drying at 90 °C for 2 minutes, The unvulcanized rubber sheets and the canvas were adhered to each other, and the coating system adhered to each other was vulcanized at 120 ° C for 1 hour in a vulcanization kettle. The vulcanized coating system was allowed to stand at room temperature for 24 hours, and the peeling strength at a pulling speed of 200 mm/min was measured. [Examples 2 to 5] Tests were carried out in the same manner as in Example 1 except that the amount of the sulfur-containing aqueous dispersion and the aqueous zinc oxide dispersion were changed so that the amount of -12-200817485 was as shown in Table 1. [Comparative Example] Tests were carried out in the same manner as in Example 1 except that the amounts of the sulfur-containing aqueous dispersion and the aqueous zinc oxide dispersion were changed as shown in Table 1, and Comparative Examples 1 to 3 were used. From the comparison of the examples and comparative examples shown in Table 1, the sulfurized aqueous adhesive of the present invention was judged to exhibit excellent adhesion strength. [Table 1]

EXAMPLES Comparative Example 1 2 3 4 5 1 2 3 Prescription (dry basis) Latex [parts] 100 100 100 100 100 100 100 100 Sulfur [parts] 1 1 2 2 3 雠3 - Zinc oxide [Parts] 1 2 1 3 5 - - 3 Adhesives Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount Adhesive strength Peel strength [N/mm] 2.21 2.06 2.21 3.43 4.41 0.44 1.23 1.27 State mf mf mf MF MF AC AC AC Table 1 shows, MF confirmation The rubber sheet material was broken, and the mf system confirmed that some of the rubber sheet material was broken, and the AC system confirmed the interface peeling or cohesive failure of the adhesive surface. [Industrial Applicability] The vulcanized aqueous adhesive obtained by the present invention does not contain an organic solvent -13-200817485, and also suppresses a sufficient adhesive strength due to natural rubber rubber, and can be used as an aqueous adhesive. Also, quote here 2006! The entire contents of the application and invention summary described in the application No. 2006-230000, the same. • The risk of protein allergy in milk and the use of sulfur for canvas shoes, etc. The Japanese patent specification, the scope of patent application, and the disclosure of FIG.

Claims (1)

200817485 X. Application for Patent Park 1 · A vulcanized water-based adhesive characterized by containing chloroprene rubber latex, sulfur and zinc oxide. 2. The vulcanized type aqueous adhesive according to the first aspect of the invention, wherein the solid content of the chloroprene rubber latex is from 40 to 70% by mass. 3. The vulcanized aqueous adhesive according to claim 1 or 2, wherein the emulsifier and/or dispersant contained in the chloroprene rubber latex is used relative to the chloroprene polymer. The total monomer is 〇. 5~ 1 〇 by mass. The vulcanized type aqueous adhesive according to any one of the items 1 to 3, wherein the solid content in the chloroprene rubber latex of 100 parts by mass is 2 to 5 parts by mass. Sulfur, and 3 to 7 parts by mass of zinc oxide. The vulcanized type aqueous adhesive according to any one of claims 1 to 4, which is used for the manufacture of a canvas shoe. 6. The vulcanized water-based adhesive according to any one of claims 1 to 4, which is used for a rubber sole, a cloth upper, and a side strip for vulcanizing and adhering two or more canvas shoes. band. A method for producing a canvas shoe, characterized in that the vulcanized type aqueous adhesive according to any one of claims 1 to 4 is used, vulcanized and adhered to two or more rubber soles, a cloth upper, and Side strips. 8. The method for producing a canvas shoe according to claim 7, wherein the vulcanized type aqueous adhesive is applied to the adhesive surface at a coating amount of 100 to 3 〇〇g/cm 2 and heat-adhered. 15-200817485 9. The method for manufacturing a canvas shoe according to claim 7 or 8, wherein the vulcanized type aqueous adhesive is coated with 60 to 10 (TC dry, pressure-coated coated surface, 1 〇) 〇~1 50 °C vulcanization adhesion. -16- 200817485 Seven designated representative map: (1) The representative representative of the case is: (2), the representative symbol of the representative figure is a simple description: no eight, if the case In the chemical formula, please reveal the chemical formula that best shows the characteristics of the invention: none