WO2003037980A1

WO2003037980A1 - Polychloroprene latex composition, water-base primer and adhesive bonding process

Info

Publication number: WO2003037980A1
Application number: PCT/JP2002/011463
Authority: WO
Inventors: Kosuke Watanabe; Kenji Mochizuki
Original assignee: Denki Kagaku Kogyo Kabushiki Kaisha
Priority date: 2001-11-02
Filing date: 2002-11-01
Publication date: 2003-05-08
Also published as: TWI275610B; KR100880136B1; CN100339426C; TW200300155A; CN1582315A; KR20040062562A

Abstract

The invention provides a water-base primer capable of giving a bond strength equivalent to that of organic solvent type primers or adhesives of the prior art, specifically, a polychloroprene latex composition which comprises as the essential components polychloroprene and sodium orthosilicate in a state dispersed or dissolved in water and further contains polyethyleneimine and a tackifier resin. Adhesive bonding of adherends is conducted by using a water-base primer containing the latex composition.

Description

Description Polypropylene mouth-based latex composition, water-based primer, and bonding method

INDUSTRIAL APPLICABILITY The present invention exhibits good adhesive strength to adherends such as rubber, elastomers, synthetic resins, etc., and is useful as a main component of aqueous adhesives and primers used for bonding these adherends. To provide a latex composition. Background art

Conventionally, solvent-based primers and adhesives have been mainly used as a method for bonding hardly adherent adherends such as rubber, elastomers, and synthetic resins. However, in the case of solvent-based systems, organic solvents such as toluene, ethyl acetate, and methyl ethyl ketone are used in large amounts, which is unfavorable in terms of worker health and safety and the environment.

For this reason, the demand for water-based adhesives and primers has been increasing year by year, and for example, there are some methods such as Japanese Patent Application Laid-Open No. 2001-646416 and Japanese Patent Application Laid-open No. 2001-266756. A proposal has been made. However, at the time of practical use, the current situation was that the adhesive strength was still insufficient.

In view of the current situation, the present invention provides a water-based primer or a polychloroprene-based latex composition suitable as a main component of a water-based primer or a water-based adhesive that provides an adhesive strength comparable to that of a conventionally used solvent-based primer or adhesive. The purpose is to provide. Disclosure of the invention

The present inventors have conducted intensive studies to achieve the above object, and as a result, a polychloroprene latex composition containing polychloroprene and sodium orthosilicate as essential components and dispersing or dissolving them in water is a rubber, The inventors have found that excellent adhesion strength is provided to adherends such as elastomers and synthetic resins, and have completed the present invention.

That is, the present invention has the following gist. 1

(1) A polychloroprene-based latex composition comprising, as essential components, polychloroprene and sodium orthosilicate, which are dispersed or dissolved in water.

(2) The polychloroprene-based latex composition according to the above (1), wherein the solid content concentration in the polyclonal-prene-based latex is 40 to 70% by weight.

(3) The polycycloprene-based latex composition according to (1) or (2), wherein the content of sodium orthosilicate is 0.1 to 30 parts by weight per 100 parts by weight of polychloroprene (solid content).

(4) The polychloroprene latex composition according to any of (1) to (3) above, wherein the polyethyleneimine is contained in an amount of 0.1 to 5 parts by weight per 100 parts by weight of polychloroprene (solid content). object.

(5) The polychloroprene-based latex composition according to any one of the above (1) to (4), wherein the tackifier resin is contained in an amount of 1 to 80 parts by weight per 100 parts by weight of polychloroprene (solid content).

(6) The polychloroprene latex composition according to any one of the above (1) to (5), wherein the thickener is contained in an amount of 0.01 to 10 parts by weight per 100 parts by weight of polychloroprene (solid content). object.

(7) An aqueous primer mainly comprising the polychlorinated propylene-based latex composition according to any one of the above (1) to (6).

(8) A bonding method for bonding an adherend using the aqueous primer according to (7). BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the contents of the present invention will be described in detail. The polychloroprene as referred to in the present invention is a homopolymer of 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene) or a copolymer of chloroprene and a monomer copolymerizable with chloroprene. It is a copolymer. The term "copolymer" as used herein also includes a graft copolymer obtained by subjecting another monomer to the polymerization in the presence of polychloroprene.

Preferred monomers copolymerizable with the above-mentioned black-mouthed platen are, for example, 2,3-dichloro-1,3-butadiene, 1,3-butadiene, 1,3-butadiene, Styrene, isoprene, styrene, acrylonitrile, acrylic acid or its esters, methacrylic acid or its esters, and the like. If necessary, two or more kinds may be used.

The method of polymerizing black-mouthed polyprene to obtain polycloth-prene is not particularly limited, but a method based on emulsion polymerization is general and simple. In order to obtain the polychloroprene latex of the present invention, it is necessary to disperse the polyclone prene in water, but when the polychloroprene is obtained by an emulsion polymerization method, the obtained polychloroprene latex is used as it is. be able to.

The emulsifier and the dispersant or emulsifier used in the emulsion polymerization method of the polychloroprene latex are not particularly limited, and various anion types, nonionic types, and cationic types commonly used for black color prene latex can be used.

Examples of the anion type emulsifier include a carboxylic acid type, a sulfonic acid type, a sulfate ester type, and the like. Examples thereof include alkali metal salts of rosin acid, alkyl sulfonates having 8 to 20 carbon atoms, alkyl aryl sulfates, and naphthenates. Examples include condensates of sodium phosphorus sulfonate and formaldehyde. Specific examples of the nonionic type include polyvinyl alcohol or a copolymer thereof (for example, a copolymer with acrylamide), polyvinyl ether or a copolymer thereof (for example, a copolymer with maleic acid), polypinylpyrrolidone or The copolymer (for example, a copolymer with vinyl acetate), or those obtained by chemically modifying these (co) polymers, or a cellulose-based derivative (hydroxyethyl cellulose) can be used. . Specific examples of the cationic type include an aliphatic amine salt and an aliphatic quaternary ammonium salt, and examples include o-chloride, dilauryl dimethyl ammonium chloride and the like.

The emulsifier and / or Z or dispersant in the polybutene-based latex are used at the time of polymerization of the soda. And preferably 0.5 to 20 parts by mass. If the amount is less than 0.5 part by mass, the emulsifying power is not sufficient, and if it exceeds 20 parts by mass, there is a disadvantage that the water-resistant adhesive strength is reduced.

Weight in the case of obtaining the polychloroprene-based latex in the present invention by polymerization. The combination temperature is not particularly limited, but the polymerization temperature is preferably 0 to 50 ° C in order to smoothly carry out the polymerization reaction. As the polymerization initiator, a persulfate such as potassium persulfate, an organic peroxide such as tert-butyl hydroperoxide, and the like are preferably used, but are not limited thereto.

A chain transfer agent is used as needed for the polymerization of black-mouthed plain, but the type thereof is not particularly limited, and those usually used for emulsion polymerization of black-mouthed plain can be used. For example, known chain transfer agents such as long-chain alkyl mercaptans such as n-dodecyl mercaptan and tert-dodecyl mercaptan, diisopropylxanthogen disulfide, and jordform can be used. Polymerization terminator (polymerization inhibitor) for polychloroprene mp is not particularly limited, and for example, 2,6-tert-butyl-4-methylphenol, phenothiazine, hydroxyamine and the like can be used.

The final polymerization rate of polyclonal polyprene is not particularly limited and can be arbitrarily adjusted. Unreacted monomers are removed by a demonomer operation, but the method is not particularly limited.

The polychloroprene-based latex of the present invention can control the solid content concentration to a necessary concentration by concentrating or diluting the polychloroprene latex obtained by polymerization by adding water or the like. Examples of the method for concentration include concentration under reduced pressure, but are not particularly limited.

The properties of the polychloroprene-based latex in the present invention are not particularly limited, but the polymerization temperature, polymerization initiator, chain transfer agent, polymerization terminator, final polymerization rate, demonomerization, concentration conditions, etc. are appropriately selected. By controlling the concentration, it is possible to adjust the solid concentration, the molecular weight of the toluene-soluble portion, the toluene-insoluble content (gel content), and the like. From the viewpoint of the balance between the initial adhesive strength and the normal adhesive strength, it is preferable to adjust the gel content of the chloroprene (co) polymer in the polychloroprene latex to preferably 3 to 60% by weight. . The gel content is determined as follows. The polychloroprene-based latex sample is freeze-dried and weighed accurately to obtain A. Dissolve in toluene (adjusted to 0.6%), use a centrifuge, and add 200 mesh wire mesh Separate the gel using. After air-drying the gel, dry it at 100 ° C for 1 hour, and weigh it accurately. Using the above A and B, calculate the gel content by the following formula.

Gel content (%) = B / AX 100

Sodium Kei acid is represented by the general formula Na ₂ 〇 _{· n S i 0 2 · mH} 2 0, the mole ratio of Na ₂ O and S I_〇 _2, i.e. sodium Orusokei acid by a factor n, sodium meta Kei acid, Kei Sodium silicate No. 1, sodium silicate No. 2, sodium silicate No. 3, sodium silicate No. 4, etc., and in the present invention, sodium orthosilicate is particularly used. The use of sodium orthosilicate has an excellent effect in terms of adhesive strength as compared with other sodium silicates, as will be shown in Examples described later.

In the present invention, the content of sodium orthosilicate in the polycloth-prene latex is not particularly limited. However, from the viewpoint of adhesive strength, 0.1 to 30 parts by weight per 100 parts by weight (solid content) of polychloroprene is preferable, and more preferably:! ~ 15 parts by weight.

The polychloroprene-based latex composition of the present invention exhibits sufficient adhesive strength as it is, but the effect can be further enhanced by including polyethyleneimine. The content of polyethyleneimine is preferably 0.1 to 5 parts by weight (solid content), and particularly preferably 0.5 to 3 parts by weight, based on 100 parts by weight (solid content) of the polyclonal prene-based latex. Is preferred.

Polyethyleneimine used in the present invention is a polymer having the following general formula, and the synthesis method is not particularly limited. In general, it can be synthesized by ring-opening polymerization of ethyleneimine. In the following general formula, X and y are selected so that the average molecular weight of the polymer is preferably at least 1,000, particularly preferably at least 10,000.

H.

H ₂ N-(CH ₂ -CH ₂ -N) _x- (CH ₂ -CH ₂ — N) _y-

I

CH ₂ -CH ₂ -N < In addition, by adding a tackifying resin to the polychloroprene latex composition of the present invention, properties such as initial adhesive strength, water resistant adhesive strength, and adhesive holding time can be more practically balanced. can do.

The type of tackifier resin to be added to the water-based adhesive is not particularly limited. In order to obtain a sufficient initial adhesive strength, a resin having a softening point temperature of 50 to 160 ° C is preferable. Specifically, a rosin resin, polymerized rosin resin, alpha-pinene resins, Pinen resins, terpene phenol resin, (: ₅ fraction petroleum resin, Ji ₉ fraction petroleum resin, C ₅ ZC ₉ fraction petroleum Resins, DCPD petroleum resins, alkylphenol resins, xylene resins, coumarone resins, coumarone-indene resins, etc. Among them, rosin resins are preferred.

The amount of the tackifying resin is preferably 1 to 80 parts by weight (solid content), particularly preferably 5 to 50 parts by weight, based on 100 parts by weight (solid content) of the polychloroprene latex. It is suitable. The method of compounding the tackifier resin is not particularly limited, but it is preferable to add it as an aqueous emulsion in order to uniformly disperse the resin in the latex. The aqueous emulsion of the tackifying resin is produced by emulsifying a solution dissolved in an organic solvent such as toluene in water using an emulsifier, dispersing the mixture in water, heating the organic solvent under reduced pressure, and removing the fine particles. There is a method of pulverizing the emulsion into milk and dispersing the emulsion, but the former which can produce a finer emulsion is preferable.

The solids concentration of the polychloroprene latex composition of the present invention is not particularly limited, but is preferably 70% by weight or less in order not to impair the stability of the emulsified system. Further, when the polyprene latex composition of the present invention is used as an aqueous adhesive, it is preferably 40 to 70% by weight, and when it is used as an aqueous primer, it is preferably It is preferable that the solid content is adjusted to 10 to 40% by weight for use. Such adjustment of the solid content can be arbitrarily performed by dilution with pure water or concentration by removing water. In addition, the solid concentration of the polychloroprene-based latex in the present invention is determined as follows. Weigh only the aluminum pan and call it A. Weigh the aluminum dish containing 2 ml of the latex sample and call it B. Aluminum dish with latex sample 1 After drying in an atmosphere of 10 ° C for 2 hours, weigh and set to C. The solid content (% by weight) is calculated by the following equation.

Solids concentration (%) = [(C-A) / (B-A)] X 100

In addition to the above, the polychloroprene latex composition according to the present invention may further comprise a thickener, a metal oxide, a filler, a film-forming aid, an ultraviolet absorber, an antioxidant, and a plasticizer according to the required performance. , A vulcanizing agent, a vulcanization accelerator, an antifoaming agent and the like can be arbitrarily added.

The polychloroprene-based latex composition of the present invention can be adjusted to any viscosity by adding a thickener. Specific thickeners include polyvinyl alcohol (PVA), sodium polyacrylate, water-soluble polyurethane, associative polyurethane-based emulsion, alkali-swellable acrylic-based emulsion, potassium oxymethyl cellulose (CMC), methyl cellulose (MC), Examples include hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), polyvinyl alcohol, and synthetic smectite.

The amount of the thickener to be added is preferably 0.01 to 10 parts by mass (in terms of solids) with respect to 100 parts by mass (in terms of solids) of polychlorinated propylene latex. By blending in this range, it is possible to control the viscosity of the polychloroprene latex composition without adversely affecting the adhesive properties.

The material such as rubber, elastomer, and synthetic resin to which the polychloroprene-based latex composition of the present invention is applied is not particularly limited. Specifically, butadiene rubber (BR), chloroprene rubber (CR), natural rubber (NR), isoprene rubber (IR), styrene butadiene rubber (SBR), butyl rubber (IIR), norpolene rubber (NOR), nitrile rubber (NBR), hydrogenated nitrile rubber (H NBR), brominated butyl rubber (BIIR), chlorinated butyl rubber (CIIR), acrylonitrile-isoprene copolymer (NIR), vulcanization of ethylene-propylene-gen rubber (EPDM), etc. Rubber, styrene-butadiene-styrene block copolymer (SBS), elastomers such as polyester, urethane, and olefin, pinyl chloride resin (PVC), ethylene-vinyl acetate copolymer (EVA), 1, 2 Polybutadiene (RB), polyolefin resin, styrene resin, acrylonitrile Examples thereof include a tri-butadiene-styrene copolymer (ABS).

The composition, cross-link density, shape, etc., of these materials are not particularly limited, and foams can be applied. It can be used in any field, such as grips for sports equipment, shoe soles, and building materials.

Example

Hereinafter, the effects of the present invention will be described in detail with reference to Examples and Comparative Examples, but these Examples do not limit the present invention. In the following description, parts and% are expressed on a weight basis unless otherwise specified.

[Synthesis example 1]

100 parts of water, 5 parts of disproportionated rosin acid, 0.6 parts of sodium hydroxide, 0.7 parts of potassium hydroxide, and 0.7 parts of formaldehydedonaphthalenesulfonic acid in a 3 liter reactor under a nitrogen stream After charging 0.3 parts of sodium salt of the condensate and 0.3 parts of sodium bisulfite, after dissolution, 100 parts of chloroprene monomer and 0.114 parts of n-dodecylmercaptan were added with stirring. Was. Polymerization was performed at 10 ° C. under a nitrogen atmosphere using potassium persulfate as an initiator. When the conversion reached 90%, an emulsion of phenothiazine was added to stop the polymerization. The unreacted monomers were removed under reduced pressure to obtain polyclonal prene latex. Further, water was evaporated under reduced pressure to concentrate the solution, and the solid content was adjusted to 50% by mass.

[Example 1]

100 parts of the polychloroprene latex obtained in Synthesis Example 1 was used as a tackifier resin, and terpene phenol / fat emulsion (solids concentration: 53%) (Yumanor E_100 Z Arakawa) was used as a tackifier resin. 50 parts of Sodium Orthosilicate (manufactured by Asahi Denka Kogyo Co., Ltd.) having a solid content of 30% were added. Further, pure water was added to adjust the solid content of the whole formulation to 20% to obtain an aqueous primer.

Also, 100 parts of the polychloroprene latex obtained in Synthesis Example 1 was used as a tackifying resin in a terbenephenol resin emulsion (solids concentration: 53%) (Yumanol E-100 / Arakawa Chemical Industry Co., Ltd.). 50 parts) and 2.0 parts of sodium polyacrylate aqueous thickener (Aron A—20 L / Toagosei Co., Ltd.) 10 parts of aluminum hydroxide powder (NO, Igilite H-42 MZ manufactured by Showa Denko KK) as an agent, 2 parts of a zinc oxide dispersion having a solid content of 50% as an acid acceptor, and water dispersion as a curing agent An isocyanate compound (Takenate WD-730 / Mitsui Takeda Chemical Co., Ltd.) was mixed in 2 parts to obtain an aqueous adhesive.

Two pieces of vulcanized styrene-butadiene rubber (vulcanized SBR, size of glue margin is 2 Omm wide x 7 Omm long) after puffing (surface polishing) the adhesive surface and removing swarf by acetone washing Each surface was lightly wiped with a gauze impregnated with the aqueous primer obtained in Example 1, and dried at 60 ° C. for 10 minutes. A water-based adhesive was applied thereon with a brush of ²⁰⁰ g (wet) / m ² , dried in an atmosphere of 60 ° C. for 6 minutes, laminated, and pressed with a hand roller. The test pieces obtained by this method were evaluated as follows.

[Initial adhesion evaluation test]

Ten minutes after the pressure bonding, the T-peel strength was measured at a tensile speed of 20 O mmZmin using a tensile tester.

[Normal adhesion evaluation test]

One day after the pressure bonding, T-peel strength was measured at a tensile speed of 20 OmmZmin using a tensile tester.

[Example 2]

With the primer prepared in Example 1, before adding pure water, 3.3 parts of polyethyleneimine (epomin Ρ—100 (solid content: 30%) 製 manufactured by Nippon Shokubai Co., Ltd.) was further added. Thereafter, a test was conducted in the same manner as in Example 1 except that the solid content was adjusted to 20% with pure water, and the test was performed as Example 2.

[Comparative Example 1]

A test was performed in the same manner as in Example 1 except that the aqueous primer was not used, and the result was set as Comparative Example 1.

[Comparative Example 2]

A test was conducted in the same manner as in Example 1 except that sodium orthosilicate was not used, and Comparative Example 2 was obtained.

[Comparative Examples 3 to 5] The tests were carried out in the same manner as in Example 1 except that other kinds of sodium silicate were used instead of sodium orthosilicate, and Comparative Examples 3 to 5 were obtained.

[Comparative Example 6]

A test was conducted in the same manner as in Example 1 except that a solvent-based primer was used instead of the water-based primer, and Comparative Example 6 was performed. Here, the solvent-based primer was prepared as follows.

Using a reactor with an internal volume of 3 liters, under a nitrogen stream, 120 parts of water, 4 parts of disproportionated rosin acid, 0.8 parts of sodium hydroxide, sodium salt of condensed formaldehyde naphthylene sulfonic acid 0 After charging 5 parts and 0.3 parts of sodium bisulfite, and dissolving, 100 parts of chloroprene monomer and 0.25 parts of n-dodecylmercaptan were added with stirring. Polymerization was performed at 10 ° C. under a nitrogen atmosphere using potassium persulfate as an initiator. When the conversion reached 70%, an emulsion of phenothiazine was added to stop the polymerization. After removing unreacted monomers under reduced pressure, polish by a conventional freeze-drying method.

100 g of the obtained polychlorinated chip was placed in a reactor having an internal volume of 1 liter, and 600 g of toluene was added thereto and dissolved with stirring. After dissolution, 50 g of methyl methacrylate was added, and graft polymerization was performed at 85 ° C for 5 hours using benzoyl peroxide as an initiator. The polymerization reaction was stopped by adding a solution of 2,6-di-t-butyl-4-methylphenol in toluene, and further diluted with toluene to adjust the solid concentration to 5%. did.

table 1

1) Addition of each additive in 100 parts by mass of polychloroprene-prene latex

2) Addic acid sodium silicate sodium orthosilicate / Asahi Denka Kogyo Co., Ltd.

3) Sodium silicate Sodium silicate No. 1 / Asahi Denka Kogyo Co., Ltd.

4) Adeca sodium silicate Sodium silicate No.2 manufactured by Asahi Denka Kogyo Co., Ltd.

5) Sodium silicate Sodium silicate No.3 manufactured by Asahi Denka Kogyo Co., Ltd.

6) Epomin P-100 / Nippon Shokubai Co., Ltd.

7) Tamanor E-100

Industrial applicability

The polychloroprene latex composition of the present invention exhibits good adhesive strength and can be suitably used as a main component of an aqueous primer.

Claims

The scope of the claims

1. A polychloroprene-based latex composition comprising, as essential components, polychloroprene and sodium orthosilicate, which are dispersed or dissolved in water.

2. The polychloroprene-based latex composition according to claim 1, wherein the solid content concentration in the polychloroprene-based latex is from 40 to 70% by weight.

3. The polychloroprene-based latex composition according to claim 1, wherein the content of sodium orthosilicate is 0.1 to 30 parts by weight per 100 parts by weight of polychloroprene (solid content).

4. The polychloroprene-based latex composition according to any one of claims 1 to 3, wherein the polyethyleneimine is contained in an amount of 0.1 to 5 parts by weight per 100 parts by weight of polychloroprene (solid content).

5. The polychloroprene-based latex composition according to any one of claims 1 to 4, wherein the tackifier resin is contained in an amount of 1 to 80 parts by weight per 100 parts by weight of polychloroprene (solid content).

6. The polychlorinated mouth-based latex according to any one of claims 1 to 5, wherein the thickener is contained in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the polyclonal mouth plane (solid content). Composition.

7. An aqueous primer comprising the polychlorinated propylene-based latex composition according to any one of claims 1 to 6 as a main component.

8 · A bonding method for bonding an adherend using the aqueous primer according to claim 7.