WO2008026429A1

WO2008026429A1 - Vulcanizable aqueous adhesive and use thereof

Info

Publication number: WO2008026429A1
Application number: PCT/JP2007/065382
Authority: WO
Inventors: Sang-Taek Oh; Jae-Hwan Chun; Kosuke Watanabe; Kenji Mochizuki
Original assignee: Denki Kagaku Kogyo Kabushiki Kaisha
Priority date: 2006-08-28
Filing date: 2007-08-06
Publication date: 2008-03-06
Also published as: JP2008050511A; CN101506322A; TW200817485A; KR20090042923A

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

Specification

Vulcanized water-based adhesive and its use

Technical field

[0001] The present invention relates to a vulcanization-type water-based adhesive that can be suitably used for vulcanization adhesion and its use.

Background art

[0002] When producing shoes by a vulcanized method such as canvas shoes, chloroprene solvent type adhesives and natural rubber latex adhesives have been used. However, the demand for development of alternative adhesives for solvent-based adhesives has been increasing year by year from the viewpoint of environmental impact and safety and health of workers, and for natural rubber latex adhesives due to the problem of latex protein allergies. Yes. (For example, refer nonpatent literature 1 and 2.).

Non-Patent Document 1: Journal of the Japan Rubber Association Vol. 78, No. 2 (2005) (p. 55; paragraph 4.2.1) Non-Patent Document 2: Adhesion Technology Vol. 21, No. 4 (2002), Volume 65 No. (page 12; 2.1.4) Disclosure of Invention

Problems to be solved by the invention

[0003] An object of the present invention is to provide a vulcanized water-based adhesive that does not use an organic solvent and that is free from protein allergy.

Means for solving the problem

[0004] As a result of diligent research to achieve the above object, the present invention has reached the present invention having the following gist.

(1) A vulcanized water-based adhesive characterized by containing black-opened latex, sulfur, and zinc oxide.

(2) The vulcanized water-based adhesive according to (1) above, wherein the solid content concentration in the black-opened latex is 40 to 70% by mass.

(3) The emulsifier and / or dispersant strength S in the black mouth plain latex is 0.5 to 10 parts by weight based on the total monomers used to obtain the black mouth plain polymer (1 ) Or the vulcanized water-based adhesive according to (2). (4) Any one of the above (1) to (3) containing 2 to 5 parts by mass of sulfur and 3 to 10 parts by mass of zinc oxide with respect to 100 parts by mass of the solid content in the black mouth plain latex The vulcanized water-based adhesive described in 1.

(5) The vulcanized water-based adhesive according to any one of the above (1) to (4) used in the production of canvas shoes.

(6) The vulcanized water-based adhesive according to any one of the above (1) to (4), which is used for vulcanizing and bonding two or more of a rubber outsole of canvas shoes, a cloth upper, and a fixing tape Agent.

(7) Two or more rubber outsole, cloth upper, and fixing tape are vulcanized using the vulcanized water-based adhesive described in (1) to (4) above. A method for producing canvas shoes characterized by bonding.

(8) The method for producing canvas shoes according to (7) above, wherein the vulcanized water-based adhesive is applied to the adhesive surface at 100 to 300 g / cm ² and heat-adhered.

(9) Apply vulcanization-type water-based adhesive, 60 ~; Dry at 100 ° C, crimp the coated surface, and vulcanize and bond at 100–150 ° C (7) or (8) The manufacturing method of the canvas shoes of description. The invention's effect

[0005] The vulcanized water-based adhesive of the present invention contains an organic solvent! /, N! /, Which is gentle to the environment and the human body, and uses synthetic rubber latex as a raw material. It is an adhesive without any. Moreover, since sufficient adhesive strength is exhibited after vulcanization, it can be suitably used as a vulcanization-type adhesive used in canvas shoes and the like. BEST MODE FOR CARRYING OUT THE INVENTION

[0006] The black mouth plain latex is obtained by emulsifying / dispersing a black mouth plain polymer in water via an emulsifier and / or a dispersant (hereinafter also referred to as an emulsifier / dispersant). The solid content concentration in the chloroprene latex is not particularly limited, but is preferably in the range of 40 to 70% by mass, more preferably 50 from the viewpoint of improving workability and stability of the chloroprene latex itself. It is good to set in the range of -60 mass%.

[0007] The black mouth plain polymer is a homopolymer obtained by polymerizing 2-chloro-1,3-butadiene (hereinafter referred to as black mouth plain), or can be copolymerized with black mouth plain and black mouth plain. Na It is a copolymer obtained by polymerizing monomers. The content of the polymer unit of black mouthprene in the copolymer is preferably 80 mol% or more, particularly 90 mol% or more.

[0008] Monomers that can be copolymerized with black mouth-prene are not particularly limited. For example, 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, butadiene, isoprene Styrene, acrylonitrile, acrylic acid or esters thereof, methacrylic acid or esters thereof, and the like, and if necessary, two or more of these may be used in combination. Among them, the copolymerizable monomer is preferably 2,3 dichloro-1,3 butadiene.

[0009] The structure of the black-opened polyene polymer is not particularly limited! /, However, the polymerization temperature, polymerization initiator, chain transfer agent, polymerization terminator, final polymerization rate, etc. are appropriately selected and controlled. By doing so, it is possible to adjust the molecular weight, molecular weight distribution, gel content, molecular terminal structure, crystallization speed, and the like.

[0010] The emulsifier / dispersant used in the production of black mouth plain latex is not particularly limited, and various types such as anion type, nonion type, cationic type and the like used for usual emulsion polymerization of black mouth plains. Can be used.

Examples of the anionic emulsifying / dispersing agent include carboxylic acid type and sulfuric acid ester type. For example, alkali metal salts of rosin acid, alkyl sulfonates having 8 to 20 carbon atoms, alkyl aryl sulfate, naphthalene sulfone. Examples include condensates of sodium acid and formaldehyde, sodium alkyldiphenyl ether disulfonate, and the like.

Nonionic emulsifying / dispersing agents include, for example, polybulal alcohol (hereinafter referred to as PVA) or a copolymer thereof (for example, a copolymer with acrylamide), polybull ether or a copolymer thereof (for example, maleic acid). ), Polybulurpyrrolidone or a copolymer thereof (for example, a copolymer with butyl acetate), a chemical modification of these (co) polymers, or a cellulose derivative (hydroxyethyl). Cellulose), polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene styrene enore enoenoate, polyoxyethylene enorephenino enoate, poly , Polyoxyethylene acetylene glycol ether, Sol Fatty acid ester and the like. Cationic emulsifying / dispersing agents include, for example, aliphatic amine salts, aliphatic quaternary ammonium salts, etc., for example, octadecinole trimethyl ammonium chloride, dodecinole trimethyl ammonium chloride, dioctyl chloride. And lauryl dimethyl ammonium chloride.

[0011] Among these emulsifiers and dispersants, the use of a rosin acid salt, which is preferably an anion type, is particularly preferable. As the rosin acid, any of wood rosin acid, gum rosin acid, tall oil rosin acid, or a disproportionated rosin acid obtained by disproportionating these can be used.

In the case of using a rosin acid salt, it is preferable to use a sulfate-based sulfonate-based anionic emulsifier and a dispersant in order to impart sufficient stability to the black mouth-prene latex.

The amount of the emulsifier / dispersant used is preferably 0.5 to 10 parts by mass and more preferably 2 to 6 parts by mass with respect to 100 parts by mass of the total monomers used to obtain the black-opened polymer.

[0012] Sulfur is not particularly limited, but powdered sulfur, precipitated sulfur, colloidal sulfur and the like generally used as a rubber vulcanizing agent are used. In consideration of dispersibility, it is preferable to use finely divided sulfur. In consideration of handling when added to the black-opened latex, sulfur is more preferably used as an aqueous dispersion. As for the method of making sulfur into an aqueous dispersion, for example, the usual methods described in Adhesion Vol. 36, No. 8 (1992), Vol. 388 (page 343; item 3) and the like can be used.

[0013] The content of sulfur is not particularly limited, but the solid content in the black mouth plain latex

! To 10 parts by mass is preferable with respect to 100 parts by mass, and more preferably 2 to 5 parts by mass. If the amount of sulfur added is set within this range, the adhesive strength after vulcanization bonding will be sufficient, and sulfur bloom will be less likely to occur.

[0014] Zinc oxide is not particularly limited, but any zinc oxide generally used as a compounding chemical for rubber can be used. Specifically, there are 1 type, 2 types, 3 types, active zinc white and the like. Zinc oxide is also preferably used as an aqueous dispersion, but the preparation method of the aqueous dispersion is the same as in the case of sulfur. Adhesion Vol. 36, No. 8 (1992) vol. 388 (page 343; Section 3) ) And the like can be used. Products marketed as aqueous dispersions of zinc oxide can also be used.

[0015] The content of zinc oxide is not particularly limited, but the solid content in the black mouth plain latex is not limited. From 10 to 10 parts by mass is more preferable, more preferably from 3 to 10 parts by mass, and particularly preferably from 3 to 7 parts by mass with respect to 100 parts by mass of the form. When the amount of zinc oxide added is set within this range, the adhesive strength after vulcanization adhesion is sufficient, and the adhesive itself is difficult to separate.

[0016] Vulcanizing water-based adhesives include tackifying resins, thickeners, metal oxides other than zinc oxide, fillers, film-forming aids, ultraviolet absorbers, and antioxidants according to the required performance. In addition, a plasticizer, a vulcanizing agent other than sulfur, a vulcanization accelerator, an antifoaming agent and the like can be optionally added.

[0017] The use of the vulcanized water-based adhesive is not particularly limited, but cement, mortar, slate, cloth, wood, synthetic rubber material, polyurethane material, polychlorinated bur material, polyolefin resin It can be suitably used when bonding various materials such as materials. In particular, it can be suitably used as a vulcanizing adhesive when producing canvas shoes.

[0018] In order to produce canvas shoes using a vulcanized water-based adhesive, the following procedure may be used.

First, a cloth upper part is made into an upper by sewing, gluing or the like. Next, the upper is bonded to the insole by a so-called lasting operation and shaped. Apply vulcanized water-based adhesive to the surfaces of the shaped fabric upper, rubber outsole and rubber fixing tape. The coating amount at this time, while securing a sufficient adhesive strength to prevent the protrusion boundary surface force also show, and preferably 100 to 300 g / cm ^2, particularly preferably set in a range of 0.99 to 250 g / cm ² Les. The material coated with these vulcanized water-based adhesives is dried at 60 to 100 ° C, preferably 70 to 90 ° C for 5 to 30 minutes. After 100-; 150. C, preferably 120-; 140. It is preferred to complete by vulcanizing with C for 0.5 to 2 hours.

Example

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but these examples do not limit the interpretation of the present invention. In the following explanation, unless otherwise specified, parts and percentages are expressed on a mass basis.

[0020] "Example 1"

[Polymerization Example 1]

Using a reactor with an internal volume of 3 liters, disproportionated rosin acid 5 in 100 parts of water in a nitrogen atmosphere Part, sodium hydroxide 0.5 part, potassium hydroxide 0.8 part, sodium salt of formaldehyde naphthalene sulfonic acid condensate 0.5 part and sodium hydrogen sulfite 0.5 part were dissolved. While stirring, 100 parts of black mouth-prene monomer and 0.14 part of n-dodecyl mercaptan were added. Polymerization was carried out under an atmosphere of nitrogen at 10 ° C. using potassium persulfate as an initiator. When the polymerization rate reached 90%, an emulsion of phenothiazine was added to terminate the polymerization. The mixture was heated under reduced pressure to remove unreacted monomers, and then concentrated to a solid content of 50% to obtain black mouth plain latex.

[0021] [Preparation of aqueous sulfur dispersion]

100 parts of powdered sulfur, 5 parts of a 20% by weight aqueous solution of sodium dodecylbenzenesulfonate, 1 part of bentonite, 10 parts of a 5% by weight aqueous sodium hydroxide solution and 184 parts of pure water were placed in a ball mill and mixed with stirring overnight to obtain 33 parts of sulfur % Aqueous dispersion was prepared.

[Preparation of vulcanized water-based adhesive]

To 200 parts (100 parts dry standard) of the black mouth plain latex obtained in Polymerization Example 1, 3 parts of aqueous dispersion of sulfur obtained above (1 part of dry standard) and aqueous dispersion of zinc oxide (manufactured by Osaki Kogyo Co., Ltd.) 2 parts (1 part dry basis) were added. Next, an talyl-based thickener (Alon A-20L manufactured by Toagosei Co., Ltd.) was added, and the viscosity was adjusted to about 3, OOOmPa's to obtain an adhesive.

[0023] [Adhesion test]

The obtained adhesive was applied to a natural rubber unvulcanized rubber sheet (20 × 120 mm) and canvas (20 × 120 mm). After drying at 90 ° C for 2 minutes, the unvulcanized rubber sheet and canvas were bonded together. The bonded adherends were vulcanized at 120 ° C for 1 hour in a vulcanizer.

The vulcanized adherend was allowed to stand at room temperature for 24 hours, and the peel strength was measured at a pulling rate of 200 mm / min.

[0024] [Examples 2 to 5]

Tests were carried out in the same manner as in Example 1 except that the amounts of the aqueous sulfur dispersion and the aqueous zinc oxide dispersion were changed as shown in Table 1.

[0025] [Comparative Example 1]

The amounts of aqueous sulfur dispersion and zinc oxide aqueous dispersion used were changed as shown in Table 1. A test was carried out in the same manner as in Example 1 except that it was changed to Comparative Examples 1 to 3.

[0026] From the comparison of Examples and Comparative Examples shown in Table 1, it can be seen that the vulcanized water-based adhesive of the present invention exhibits excellent adhesion strength.

[0027] [Table 1]

[0028] In Table 1, MF indicates that the material destruction of the rubber sheet has been confirmed, mf indicates that material destruction has occurred on a part of the rubber sheet, and AC indicates that interface peeling or cohesive failure of the adhesive surface has been confirmed. It represents that.

Industrial applicability

[0029] The vulcanized water-based adhesive obtained by the present invention does not contain an organic solvent and exhibits sufficient adhesive strength while suppressing the risk of protein allergy due to natural rubber latex. It can be suitably used as a vulcanized adhesive for canvas shoes and the like. It should be noted that the Japanese Patent Application No. 2006-230000 filed on August 28, 2006, the entire contents of the description, claims, drawings, and abstract described herein are incorporated herein by reference. It is incorporated as a document disclosure.

Claims

The scope of the claims

[1] A vulcanized water-based adhesive containing black-opened latex, sulfur, and zinc oxide.

[2] The vulcanized water-based adhesive according to claim 1, wherein the solid content concentration in the black-opened latex is 40 to 70% by mass.

[3] The emulsifier and / or dispersant in the black mouth plain latex is contained in an amount of 0.5 to 10 parts by weight based on all monomers used for obtaining the black mouth plain polymer. The vulcanizable water-based adhesive described in 1.

[4] The vulcanization according to any one of claims 1 to 3, comprising 2 to 5 parts by mass of sulfur and 3 to 7 parts by mass of zinc oxide with respect to 100 parts by mass of the solid content in the black-opened latex. Type water-based adhesive

Yes

[5] The vulcanized water-based adhesive according to any one of claims 1 to 4, which is used for producing canvas shoes.

6. The vulcanized water-based adhesive according to any one of claims 1 to 4, which is used for vulcanizing and bonding two or more of a rubber outsole of canvas shoes, a cloth upper, and a fixing tape.

[7] A rubber outsole using the vulcanized water-based adhesive according to any one of claims 1 to 4.

A method for producing canvas shoes, comprising vulcanizing and bonding two or more of a cloth upper, a cloth upper, and a fixing tape.

8. The method for producing canvas shoes according to claim 7, wherein the vulcanized water-based adhesive is applied to the adhesive surface at an application amount of 100 to 300 g / cm ² and heat-adhered.

[9] Apply vulcanized water-based adhesive, 60 ~; dry at 100 ° C, crimp the applied surface, 100 ~ 150

The method for producing canvas shoes according to claim 7 or 8, wherein the vulcanization adhesion is performed at ° C.