JP4507234B2 - Adhesion method for ethylene-vinyl acetate copolymer resin molding and cleaning composition - Google Patents

Description

  The present invention relates to a method for adhering a resin molded product based on an ethylene-vinyl acetate copolymer, and more particularly to an adhesion method for adhering an ethylene-vinyl acetate copolymer resin molded product using an aqueous adhesive.

  Conventionally, taking advantage of its excellent physical properties, molded articles of ethylene-vinyl acetate copolymer have been used for various applications including shoes, toys and daily necessities. Organic solvent-based adhesives are widely used in the bonding process for manufacturing products by combining the molded products with the same kind of resin or other materials.

  This organic solvent-based adhesive has high adhesiveness even for relatively hard molded products, and is used for various applications. On the other hand, however, water-based adhesives have recently been developed in place of such organic solvent-based adhesives from the viewpoint of safety and environmental hygiene.

  As such an adhesive, for example, an adhesive composition composed of an aqueous emulsion containing an ethylene-vinyl acetate copolymer is known. For example, in European Patent Publication EP 1106628A1 (Patent Document 1), an ethylene-vinyl acetate copolymer is known. A water-based emulsion composition containing a carboxyl-modified resin of a polymer saponified product and a surfactant has been proposed. If this composition is used as an adhesive composition, it has high adhesive strength for a wide range of materials and is molded. Even if it is a product etc., it is described that it can adhere | attach well.

  JP-A-7-62265 (Patent Document 2) discloses that an organic solvent containing a chlorinated polyolefin, an olefinically unsaturated monomer and / or a film-forming polymer is dispersed in water by a surfactant. It is described that the coating composition comprising the aqueous dispersion obtained as described above is effective as an adhesive film for coating a plastic substrate such as polypropylene.

Furthermore, JP-A-2001-220474 (Patent Document 3) discloses an aqueous emulsion composition containing a carboxyl-modified resin of a saponified ethylene-vinyl acetate copolymer and a surfactant for a wide range of materials. In addition, it is described that even a molded article made of an ethylene-vinyl acetate copolymer or the like can be bonded well with high adhesive strength.
European Patent Publication EP 1106628A1 JP-A-7-62265 JP 2001-220474 A

  The aqueous emulsion composition described in Patent Document 1, the coating composition comprising the aqueous dispersion described in Patent Document 2, and the aqueous emulsion composition described in Patent Document 3 are polypropylene and ethylene-vinyl acetate. Effective for adhesion of copolymers and the like. However, since components that inhibit adhesion, such as a release agent used at the time of molding, usually remain on the surface of such a molded product, such a release agent or the like is removed at the time of adhesion. Therefore, it has been difficult to develop sufficient adhesion performance unless the degreasing treatment is performed using an organic solvent.

  The adhesive composition has been converted from an organic solvent system to an aqueous system. However, an organic solvent must still be used for degreasing, and further improvements are desired in terms of safety and environmental hygiene. It was rare.

  The present invention has been made in view of such circumstances. The purpose of the present invention is to bond without using an organic solvent in terms of safety and environmental hygiene when bonding a molded body of an ethylene-vinyl acetate copolymer. It is to provide a method.

As a result of intensive studies to solve the above problems, the present inventors have found that a surfactant having a specific structure is effective as a cleaning composition for cleaning an ethylene-vinyl acetate copolymer molded product. The headline and the present invention were completed. That is, the present invention provides the following (1) to (5).
(1) The method for adhering an ethylene-vinyl acetate copolymer resin molding according to the present invention is as follows:
When adhering an ethylene-vinyl acetate copolymer resin molding,
Surfactant represented by general formula (1):

Wherein R ¹ is an aliphatic and / or aromatic hydrocarbon having 4 to 35 carbon atoms, and n is 1 to 50
Integer)
And a surfactant represented by the general formula (2) or (3):
R ² —SO ₃ —Na (2)
R ² —SO ₄ —Na (3)
(Wherein R ² is an aliphatic and / or aromatic hydrocarbon having 4 to 25 carbon atoms)
After cleaning with a cleaning composition containing
It is characterized by applying and bonding an adhesive.
(2) R ^{1 in the} general formula (1) is represented by the general formula (4):

(Where n is an integer from 1 to 5)
It is preferable that it is a styrenated phenyl group represented by these.
(3) It is preferable that a cleaning composition contains a builder with surfactant represented by said formula (1)-(3).
(4) As the adhesive, micelles containing ethylene-vinyl acetate copolymer, modified ethylene-vinyl acetate copolymer, photopolymerization initiator, ethylenically unsaturated monomer, and non-aqueous organic solvent are dispersed in water. The weight ratio of the ethylene-vinyl acetate copolymer and the modified ethylene-vinyl acetate copolymer resin is preferably 95: 5 to 5:95.
(5) It is desirable to perform ultraviolet irradiation after applying the adhesive (4).

  The method for adhering an ethylene-vinyl acetate copolymer resin molding of the present invention is suitable as an adhesive method for an ethylene-vinyl acetate copolymer resin molding widely used in various applications including shoes, toys and daily necessities. Further, since an organic solvent is not used for the bonding process, it is possible to provide a bonding process that is highly safe and can provide a good sanitary environment.

Hereinafter, the adhesion method of the ethylene-vinyl acetate copolymer resin molding of the present invention will be described in more detail.
(Cleaning composition)
The detergent composition used in the present invention is a detergent for removing an adhesion-inhibiting component that is used or produced when molding an ethylene-vinyl acetate copolymer molded article, and has a surface active effect. It contains an agent.

Surfactant In the detergent composition used in the present invention,
Surfactant represented by general formula (1):

Wherein R ¹ is an aliphatic and / or aromatic hydrocarbon having 4 to 35 carbon atoms, and n is 1 to 50
Integer)
And a surfactant represented by the general formula (2) or (3):
R ² —SO ₃ —Na (2)
R ² —SO ₄ —Na (3)
(Wherein R ² is an aliphatic and / or aromatic hydrocarbon having 4 to 25 carbon atoms)
including.

That is, a cleaning composition comprising at least one nonionic surfactant represented by the general formula (1) and an anionic surfactant represented by the general formula (2) or (3) is used. . Two or more types of nonionic surfactants and anionic surfactants can be mixed and used. In the case of anionic surfactants, the surfactants represented by formulas (2) and (3) May be used in combination.

Examples of the hydrocarbon group R ¹ of the nonionic surfactant of the formula (1) include lauryl group, cetyl group, stearyl group, oleyl group, myristyl group, phenyl group, styrenated phenyl group, and distyrenated phenyl group. It is done.

In this, the R ¹ of formula (1), the general formula (4):

(Where n is an integer from 1 to 5)
And a polymer thereof are preferred.

As the hydrocarbon group R ² of the anionic surfactants (sulfonates) of the formulas (2) and (3), lauryl group, cetyl group, stearyl group, oleyl group, myristyl group, phenyl group, styrenated phenyl group A distyrenated phenyl group, a polyoxyethylene lauryl ether group, a dodecylbenzene group (straight chain), a dodecylbenzene group (branched) alkylnaphthalene group, and the like.

  Specific examples of the surfactant represented by the formula (2) include sodium dodecylbenzenesulfonate, sodium laurylbenzenesulfonate, sodium cetylbenzenesulfonate, and sodium stearylbenzenesulfonate.

  Specific examples of the surfactant represented by the formula (3) include sodium dodecyl sulfate, sodium lauryl sulfate, sodium cetyl sulfate, and sodium stearyl sulfate.

  Preferably, it is desirable to use a nonionic surfactant represented by the formula (1) and an anionic surfactant (sulfonate) represented by the formula (2) in combination.

  In the present invention, the amount ratio of the nonionic surfactant represented by the formula (1) and the anionic surfactant represented by the formula (2) or (3) is represented by the formula (1): (formula (2 ) Or (3)) in a weight ratio of 100: 3 to 100: 50, preferably 100: 5 to 100: 40.

  Moreover, you may use together the surfactant which can be used for washing | cleaning in the range which does not inhibit the effect of this invention.

Examples of surfactants that may be used in combination include nonionic surfactants such as polyoxyalkylene alkyl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and alkyl sulfate salts (other than the above formulas). Anionic surfactants such as polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates (other than the above formula), fatty acid salts, naphthalene sulfonic acid formalin condensate salts, alkylamine salts, quaternary Examples include cationic surfactants such as ammonium salts, and zwitterionic surfactants such as alkylbetaines and alkylamine oxides. The compounding amount of these surfactants that may be used in combination is 50% by weight or less, preferably 30% by weight or less, based on the total amount of the surfactants represented by the formulas (1) to (3). That's fine.

Builder The builder can be used as the cleaning agent in the bonding method of the present invention, if necessary. A builder has no detergency by itself or is not so significant, but it improves the detergency significantly when incorporated in a detergent composition, and is a surfactant that is a major component of the detergent. This improves the cleaning ability. The action has at least one action of capturing a polyvalent metal cation, dispersing dirt, and alkali buffering, and examples thereof include water-soluble inorganic compounds, water-insoluble inorganic compounds, and organic compounds. .

  Examples of water-soluble inorganic compounds include phosphates, silicates, carbonates, sulfates, and the like, and examples of water-insoluble inorganic compounds include aluminosilicates and crystalline silicates. Examples of the organic compound include carboxylate and organic carboxylate polymer. In these builder salts, alkali metal salts and amines are preferable as the counter ion, and sodium and / or potassium, monoethanolamine, and diethanolamine are particularly preferable.

  In the present invention, it is also possible to use a laundry detergent, dishwashing detergent, or the like, which is a mixture of these builder and surfactant.

The blending amount of the builder is based on the total amount of the surfactants represented by the formulas (1) to (3).
It is desirable to be in the range of 10 to 200% by weight, preferably 30 to 150% by weight, and if it is in such a range, the effect of blending the builder is sufficiently expressed.

  In the present invention, a detergent obtained by dispersing or dissolving the detergent composition containing the surfactant and the builder in water, methanol, ethanol or the like is used. Among these, it is desirable to use water.

The smaller the total concentration of surfactant and builder in the detergent used, the better, but 0.01% to 20% by weight, preferably 0.1% to 10% by weight is preferred. If it exists in this range, it is economical and the effect as a washing | cleaning agent is fully expressed. (Washing)
In this invention, it wash | cleans by making the said cleaning agent and an ethylene-vinyl acetate copolymer molded object contact. The cleaning method may be a batch method or a continuous method.

The contact time can be arbitrarily selected. When the contact time is short, the effect of the cleaning agent is not exhibited, and when the cleaning time is long, the production efficiency is lowered. The cleaning effect is increased by stirring during the contact time between the cleaning agent and the ethylene-vinyl acetate copolymer molding. Moreover, you may use an ultrasonic wave etc. together as needed.

By such cleaning, the mold release agent and the like can be removed. Moreover, since the organic solvent is not used in such a degreasing process, it is excellent in terms of safety and environmental hygiene.
(Removal of cleaning agent)
After washing the ethylene-vinyl acetate copolymer molding, the cleaning agent is removed. This is because if the cleaning composition remains at a high concentration on the surface of the ethylene-vinyl acetate copolymer molded body, the subsequent adhesive strength decreases. As a method for removing the cleaning composition, it can be removed by a known method, but a method using water is preferred. In addition, it is preferable to use a method of removing the cleaning agent by centrifugation in order to improve the efficiency of removing the cleaning agent.
(Adhesion)
In this invention, after wash | cleaning an ethylene-vinyl acetate copolymer molded object using the said cleaning composition, an unnecessary cleaning agent is removed, and it adhere | attaches after apply | coating an adhesive agent.

Adhesive As the adhesive in the present invention, an existing adhesive can be used, but a primer such as a solvent-based primer, a solvent-free primer, or an aqueous primer can be used. Among these, an aqueous primer can be preferably used from the viewpoint of the risk of ignition and environmental sanitation.

  Examples of adhesives include urethane resin adhesives, acrylic resin adhesives, ethylene-vinyl acetate copolymer resin adhesives, modified ethylene-vinyl acetate copolymer resin adhesives, polyolefin resin adhesives, Examples thereof include a modified polyolefin adhesive, a synthetic rubber adhesive, and a rosin resin adhesive. Among them, an ethylene-vinyl acetate copolymer resin-based adhesive having a good compatibility with the molded article of ethylene-vinyl acetate copolymer resin washed with the detergent composition, modified ethylene-vinyl acetate copolymer resin A system adhesive is preferably used.

  These adhesives may be used alone or in combination. Furthermore, you may use it, laminating | stacking in multiple layers, and you may apply | coat an adhesive agent, after apply | coating an adhesive agent as a primer to the surface which contact | connects an ethylene-vinyl acetate copolymer resin molding.

Specific examples of the adhesive used in the present invention include ethylene-vinyl acetate copolymer, modified ethylene-vinyl acetate copolymer, photopolymerization initiator, ethylenically unsaturated monomer, and non-aqueous organic solvent. An aqueous emulsion composition in which micelles are dispersed in water,
A water-based emulsion composition characterized in that the ratio of the ethylene-vinyl acetate copolymer and the modified ethylene-vinyl acetate copolymer is 95: 5 to 5:95 by weight.

  Hereinafter, each component which comprises the water-system emulsion composition used as an adhesive agent is demonstrated.

(Ethylene-vinyl acetate copolymer)
The ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA) used in the present invention can be produced by a known method such as a high pressure method or an emulsification method. As a ratio of the raw material composition, the vinyl acetate content is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. If the vinyl acetate content is lower than that, the heat resistance may be lowered, and if it is higher than that, the heat resistance may be lowered. The melt index (g / 10 min (190 ° C., 2160 g): based on ASTM D-1238, the same shall apply hereinafter) is preferably 0.1 to 500, and more preferably 1 to 300.

  Furthermore, EVA may be used alone, or two or more types of EVA may be used in combination. EVA having a low vinyl acetate content is difficult to dissolve as an oil droplet component of the emulsion, but the stability of the emulsion is improved by using it together with EVA having a high vinyl acetate content.

(Modified product of ethylene-vinyl acetate copolymer)
The modified ethylene-vinyl acetate copolymer used in the present invention is not particularly limited. For example, a partially saponified carboxyl-modified resin of ethylene-vinyl acetate copolymer (hereinafter abbreviated as C-HEVA). Is preferably used. C-HEVA is prepared by, for example, first dissolving EVA in an organic solvent and adding a lower alcohol to the solution, as described in, for example, Japanese Patent Publication No. 5-26802. Partial saponification of an ethylene-vinyl acetate copolymer (hereinafter abbreviated as HEVA) by adding an alkali alcoholate as a catalyst in the presence of a specific amount of water to effect partial saponification (degree of saponification of about 10 to 90%). And the HEVA can be obtained by modification with an acid such as an unsaturated carboxylic acid or an acid anhydride. The carboxyl-modified resin of the partially saponified ethylene-vinyl acetate copolymer thus obtained preferably has a hydroxyl value of 0 to 250 mgKOH / g and an acid value of 2 to 150 mgKOH / g. When the hydroxyl value and the acid value are out of the above ranges, the adhesive performance may be deteriorated.
(Photopolymerization initiator)
Examples of the photopolymerization initiator used in the present invention include polymerization initiators such as acylphosphine oxide, acetophenone, benzoin ether, benzophenone, and thioxanthone.

  Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (for example, Lucillin TPO manufactured by BASF), bis (2,6-dimethoxybenzoyl) -2,4,4. -Trimethylpentylphosphine oxide (BAPO), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) n-butylphosphine oxide and the like.

Examples of the acetophenone photopolymerization initiator include diethoxyacetophenone-2-hydroxy-2-methyl-1-phenylpropan-1-one (for example, Darocur 1173 manufactured by Ciba Specialty Chemicals), benzyldimethyl ketal ( For example, Ciba Specialty Chemicals, Irgacure 651, BASF, Lucillin BDK, etc.), 1-hydroxy-cyclohexyl phenyl ketone (for example, Ciba Specialty Chemicals, Irgacure 184), 2-methyl- 2-morpholino (4-thiomethylphenyl) propan-1-one (for example, Irgacure 907 manufactured by Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone ( For example, Ciba Specialty Chemicals, Irgacure 369), 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer (eg, Lamberti, Esacure KIP), etc. Is mentioned.

  Examples of the benzoin ether photopolymerization initiator include benzoin, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone photopolymerization initiator include benzophenone, methyl O-benzoylbenzoate, 4-methylbenzophenone, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 2,4,6-trimethylbenzophenone, (4-benzoylbenzyl) trimethylammonium chloride and the like.

  Examples of the thioxanthone photopolymerization initiator include 2- or 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and the like.

  In addition, methylphenylglyoxyester (manufactured by AKZO, BYCURE 55), 3,6-bis (2-morpholinoisobutyl) -9-butylcarbazole (manufactured by Asahi Denka Co., Ltd., A-Cure3), titanocene compounds, etc. Can be mentioned.

  Moreover, these photoinitiators may be used independently and may be used together 2 or more types. Specific examples thereof include Irgacure 1700 (bis (2,6-dimethoxybenzoyl) -2,4-4-trimethylpentylphosphine oxide / 2-hydroxy-2-methylphenylpropan-1-one as a commercial product). = 25/75%), Irgacure 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide / 1-hydroxycyclohexyl-phenylketone = 25/75%) Specialty Chemicals).

  In order to accelerate the photopolymerization reaction by the photopolymerization initiator, various sensitizers and photopolymerization accelerators such as dialkylaminobenzoic acid or derivatives thereof (for example, 4-dimethylaminobenzoic acid, for example) , 4-dimethylaminobenzoate, etc.), phosphine-based photopolymerization accelerators (arylphosphine compounds such as triphenylphosphine, phosphine compounds such as trialkylphosphine), and the like may be blended together with the photopolymerization initiator.

(Ethylenically unsaturated monomer)
Examples of the ethylenically unsaturated monomer used in the present invention include monofunctional monomers, bifunctional monomers, and polyfunctional monomers.

Monofunctional monomers (monofunctional polymerizable diluents) include, for example, heterocyclic ethylenically unsaturated compounds (for example, N-vinyl-nitrogen such as N-methylpyrrolidone, N-vinylpyridine, N-vinylcaprolactam) Heterocyclic compounds such as heterocyclic (meth) acrylates such as morpholine (meth) acrylate and tetrahydrofurfuryl (meth) acrylate), N-vinylformamide, N-vinylacetamide, dialkylaminoethyl (meth) acrylate (eg Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (
Meth) acrylate), N, N′-dimethylacrylamide, alkoxy (poly) alkylene glycol (meth) acrylate (for example, methoxyethylene (meth) acrylate, methoxypolyethylene (meth) acrylate, butoxypolyethylene (meth) acrylate, etc.), Alkylphenoxymethyl (meth) acrylate (eg, nonylphenoxyethyl (meth) acrylate), phenoxy (poly) alkylene glycol (meth) acrylate (eg, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, etc.), Alkyl (meth) acrylates (eg, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) ) Acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, etc.), cycloalkyl (meth) acrylate (eg, cyclohexyl (meth) acrylate), aralkyl (meth) acrylate (eg, benzyl (meth) acrylate) , (Meth) acrylates having a bridged cyclic hydrocarbon group (for example, isobornyl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyalkyl (meth) acrylate, tricyclodecanyloxyethyl (meth)) Acrylate, isobornyloxyethyl (meth) acrylate, etc.), hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl) Pyr (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, 3-acryloyloxyglycerin mono (meth) acrylate, 2-hydroxy Butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) Acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, etc.), poly ε-caprolactone mono (meth) acrylate, glycidyl (meth) acrylate, mono [2- (meth) acrylo Ruoxyethyl] acid phosphate, halogen-containing (meth) acrylate (for example, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, etc.)) It is done.

  Examples of the bifunctional monomer (difunctional polymerizable diluent) include 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate di (meth) acrylate, (polyoxy) alkylene Glycol di (meth) acrylate (for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1 , 4-butanediol di (meth) acrylate, 1,6-hexamethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylol The Pandi (meth) acrylate, pentaerythritol di (meth) acrylate, di (meth) acrylate of bisphenol A alkylene oxide (ethylene oxide, propylene oxide) adduct (for example, 2,2-bis (2-hydroxyethoxyphenyl) propane Di (meth) acrylates), di (meth) acrylates with bridged cyclic hydrocarbon groups (eg di (meth) acrylates of tricyclodecane dimethylol, dicyclopentadiene di (meth) acrylates) bifunctional (Meth) acrylic acid adducts of curable epoxy resins (for example, (meth) acrylic acid adducts of 2,2-bis (glycidyloxyphenyl) propane) and the like.

Examples of the polyfunctional monomer (polyfunctional polymerizable diluent) include trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth). ) Acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, tris (acryloyloxy) isocyanurate, tris (2-hydroxyethyl) isocyanurate tri ( And (meth) acrylate, tris (hydroxypropyl) isocyanurate tri (meth) acrylate, triallyl trimellitic acid, triallyl isocyanurate, and the like.

  These ethylenically unsaturated monomers may be used alone or in combination of two or more. Of these ethylenically unsaturated monomers, (meth) acrylate is preferable.

  As such (meth) acrylate, the ester portion of (meth) acrylate ((meth) acrylic acid ester) is a hydrocarbon group having 6 to 16 carbon atoms (for example, aliphatic hydrocarbon group, alicyclic hydrocarbon). (Meth) acrylate having a group, an araliphatic hydrocarbon group, an aromatic hydrocarbon group, etc.) is preferably used, and more specifically, for example, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate , Isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadiene (meth) acrylate, and the like.

  Moreover, (meth) acrylate which has a hydroxyl group as an ester part and a C2-C5 hydrocarbon group with such a (meth) acrylate which has a C6-C16 hydrocarbon group as an ester part. It is preferable to use (meth) acrylate having a hydroxyl group and a C2-C5 hydrocarbon group as the ester moiety, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Examples include meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like.

  By using such a (meth) acrylate, in the preparation of oil droplet components described later, the solubility and dispersibility of both the ethylene-vinyl acetate copolymer and its modified resin and photopolymerization initiator are further improved. The adhesiveness can be improved, and the adhesiveness can be adjusted by appropriately combining other (ethyl) unsaturated monomers with such (meth) acrylate.

  If a hydrophilic (meth) acrylate such as the hydroxyl group-containing (meth) acrylate is added to the obtained emulsion composition, the formation of micelles that are well dispersed in water may be impaired.

(Non-aqueous organic solvent)
As the non-aqueous organic solvent, a solvent whose solubility in water is negligibly small is desirable. For example, a solvent having a solubility in water of 5% by weight or less, preferably 3% by weight or less and having fluidity at room temperature. That's fine.

Examples thereof include hydrocarbons such as aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, phenols, ethers, ketones, esters, and the like. Examples of the aliphatic hydrocarbon include hexane, heptane, octane, isooctane, nonane, decane, dodecane, and the like. Examples of the aromatic hydrocarbon include benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, cyclohexylbenzene, diethylbenzene, dodecylbenzene, styrene, and the like. Examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, p-menthane, bicyclohexyl, cyclohexene, α-pinene, dipentene, d-limonene, decalin and the like. Examples of the halogenated hydrocarbon include methyl chloride, dichloromethane, chloroform, carbon tetrachloride and the like. In addition, benzine, naphtha, ligroin, gasoline, kerosene, solvent naphtha, camphor oil, turpentine oil, pine oil, and the like can be mentioned as a mixture that is naturally produced and purified. Examples of alcohols include heptanol, octanol, 2-ethyl-1-hexanol, nonanol, decanol, dodecanol, and terpineol. Examples of phenols include phenol, cresol, xylenol, and the like. Examples of ethers include diethyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, anisole, butyl phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, and furan. Tetrahydrofuran, tetrahydropyran, cineol and the like can be mentioned. Examples of the ketones include methyl ethyl ketone, 2-pentanone, 2-hexanone, methyl isobutyl ketone, heptanone, diisobutyl ketone, isophorone, cyclohexanone, methylcyclohexanone, acetophenone, camphor, and camphor oil. Examples of the esters include methyl formate, methyl formate, butyl formate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, isopentyl acetate, ethyl propionate, isopentyl propionate, and the like.

  Furthermore, the non-aqueous organic solvent may be used alone, or two or more kinds of non-aqueous organic solvents may be used in combination.

  Among these non-aqueous organic solvents, a non-aqueous organic solvent having a boiling point of 100 ° C. or higher is preferable from the viewpoint of handling. Moreover, since the solubility of the ethylene-vinyl acetate copolymer and the modified ethylene-vinyl acetate copolymer is high, an alicyclic hydrocarbon is preferably used.

(Oil droplet component)
The water-based emulsion composition used in the present invention includes an ethylene-vinyl acetate copolymer, a modified ethylene-vinyl acetate copolymer, a photopolymerization initiator, an ethylenically unsaturated monomer, a non-aqueous organic solvent (these oils Micelles that contain droplet components) are dispersed in water.

The ratio of the ethylene-vinyl acetate copolymer and the modified ethylene-vinyl acetate copolymer is 95: 5 to 5:95 by weight. Within this range, it has high adhesive strength for a wide range of materials such as molded products, and sufficient wettability is ensured even for adherends with low surface polarity. Furthermore, an aqueous emulsion composition having good emulsion stability and excellent mechanical stability and storage stability can be obtained. If the blending ratio of the ethylene-vinyl acetate copolymer and the modified ethylene-vinyl acetate copolymer is higher than this, the solubility and dispersibility with respect to the ethylenically unsaturated monomer will decrease, and the stability of the emulsion will decrease. As a result, the adhesiveness is lowered, and if it is less, the adhesiveness may be lowered. The ethylene-vinyl acetate copolymer is changed to 100 parts by weight of the modified ethylene-vinyl acetate copolymer. In contrast, it is preferably contained in an amount of 30 to 200 parts by weight. If it is within this range, it can be suitably used as an adhesive because of its particularly high adhesive strength to molded products. The blending ratio of ethylene-vinyl acetate copolymer, modified product, photopolymerization initiator and ethylenically unsaturated monomer is The ethylene-vinyl acetate copolymer is 3 to 60 parts by weight, more preferably 5 to 40 parts by weight, and the ethylene-vinyl acetate copolymer is 3 to 60 parts by weight based on 100 parts by weight of the ethylenically unsaturated monomer. It is preferable that the amount is 5 to 40 parts by weight, 1 to 80 parts by weight, and further 5 to 60 parts by weight of the photopolymerization initiator. Further, the amount of the non-aqueous organic solvent may be an amount necessary for dissolving the ethylene-vinyl acetate copolymer and the modified product, but in order to make the next reaction proceed smoothly, (ethylene-vinyl acetate) The total amount of the copolymer and the modified product is preferably in the range of 150 to 500 parts by weight per 100 parts by weight.

(Preparation of aqueous emulsion composition)
In order to obtain the aqueous emulsion composition used in the present invention, first, at least an ethylene-vinyl acetate copolymer, a modified product, a photopolymerization initiator and an ethylenically unsaturated monomer are blended in a non-aqueous organic solvent. The oil droplet component is prepared by dissolving or dispersing.

  The oil droplet component is prepared by, for example, blending an ethylenic unsaturated monomer with an ethylene-vinyl acetate copolymer and a modified product thereof, a photopolymerization initiator, and a non-aqueous organic solvent, and stirring and mixing appropriately. , Dissolved or dispersed. In addition, in such stirring and mixing, you may heat to 40-90 degreeC as needed, for example. In addition, the non-aqueous organic solvent added in that case may be distilled off or reduced if it is not necessary as an aqueous emulsion composition.

  The aqueous emulsion composition used in the present invention can be obtained by emulsifying the oil droplet component thus prepared in water with a surfactant.

  In order to emulsify the oil droplet component in water with a surfactant, for example, a surfactant and water may be added to the oil droplet component under strong stirring to perform phase inversion emulsification (forced emulsification).

  The surfactant used in the present invention is not particularly limited, and a known surfactant can be used. For example, fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfate salt, alkylsulfosuccinate, polyoxyalkylene Anionic surfactants such as alkyl ether sulfates, polyoxyalkyl ether carboxylates, polyoxyalkylene alkyl ether phosphates, for example, cationic surfactants such as alkylamine salts, quaternary ammonium salts, etc. And nonionic surfactants such as polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, and sorbitan fatty acid ester.

  In the present invention, a surfactant having an oxyethylene group is preferably used. Examples of such a surfactant having an oxyethylene group include polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, Examples thereof include oxyethylene sorbitan fatty acid esters, other polyoxyethylene derivatives, and polyoxyethylene-based surfactants such as reactive surfactants obtained by adding an ethylenically unsaturated group thereto.

  Such surfactants may be used alone or in combination of two or more. Further, the amount of the surfactant used is not particularly limited as long as the oil droplet component can be emulsified (forced emulsification). For example, 3 to 50 parts by weight with respect to 100 parts by weight of the oil droplet component, and further 5 It is preferable that it is -30 weight part. When the amount of the surfactant used is less than that, the dispersibility may be lowered, and when it is more than that, the adhesion may be lowered.

  Further, the amount of water is not particularly limited as long as the oil droplet component can be emulsified (forced emulsification). For example, the amount of water is 100 to 3000 parts by weight with respect to 100 parts by weight of the oil droplet component, and further 200 to 2000. It is preferable that it is a weight part.

  In addition, it is desirable that the aqueous emulsion composition thus obtained is finally prepared with a solid content of 3 to 50% by weight, preferably 5 to 40% by weight.

  The aqueous emulsion composition thus obtained contains an ethylene-vinyl acetate copolymer, an ethylene-vinyl acetate copolymer modified product, a photopolymerization initiator, an ethylenically unsaturated monomer, and a non-aqueous organic solvent. Micelles are dispersed in water.

  In addition, the aqueous emulsion composition obtained in this manner has components and components that improve adhesiveness such as chlorinated polyolefins, logistics, and silane coupling agents depending on the purpose and application, for example, an antioxidant, A conversion agent such as an ultraviolet absorber, a colorant, a brightening agent, and a dye may be appropriately added to the droplet component before emulsification or the emulsion composition after emulsification.

  Examples of the chlorinated polyolefin include those obtained by mixing the chlorinated polyolefin resin alone or by mixing the chlorinated polyolefin resin with other polymers. Such chlorinated polyolefin resin is not particularly limited, for example, polyolefins such as polyethylene, polypropylene, ethylene-polypropylene-diene copolymer, polybutene, styrene-butadiene copolymer, styrene-isoprene copolymer, Examples thereof include chlorinated polyolefin resins obtained by chlorinating modified polyolefins in which carboxyl groups, hydroxyl groups, acid anhydride groups and the like are introduced into these polyolefins by a known method.

  These chlorinated polyolefins may be used alone or in combination of two or more. The amount of chlorinated polyolefin used is appropriately selected. Preferably, a polyolefin resin obtained by chlorinating polypropylene and / or polyethylene and an acid anhydride-modified chlorinated polyolefin resin obtained by modifying the above-described chlorinated polyolefin resin with maleic anhydride or the like can be used. In addition, the chlorine content of these chlorinated polyolefins is not particularly limited, but when it is 15 to 40% by weight, the adhesion to the adherend made of polyolefin can be improved.

  Examples of rosins include gum rosin, wood rosin, tall oil rosin and the like, which are thermoplastic resins mainly composed of abietic acid. More specifically, for example, modified rosins such as hydrogenated rosin (dihydroabietic acid, tetrahydroabietic acid), disproportionated rosin, disproportionated hydrogenated rosin, polymerized rosin (including partially polymerized rosin), such as And alkyl esters, glycol esters, glycerin esters, pentaerythritol esters of rosin or modified rosins, such as rosin or a rosin modified polyester using modified rosin as part of the acid of the polyester. The rosin-modified polyester can also be obtained by a reaction between rosin or a glycidyl ester of the modified rosin and a compound having gallic acid. These rosins may be used alone or in combination of two or more. The amount of rosin used is appropriately selected.

  Examples of the silane coupling agent include epoxy silane, amino silane, and vinyl silane. Epoxy silane is preferably used. Examples of such epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. These silane coupling agents may be used alone or in combination of two or more. Moreover, the usage-amount of a silane coupling agent is selected suitably.

  The aqueous emulsion composition thus obtained can be suitably used as an adhesive composition, that is, a primer or an adhesive, and has a high adhesive strength for a wide range of materials. For example, a plastic film Various molded products such as plastic sheets, plastic foams, fibers, synthetic leather, and metals can be bonded well.

  In particular, in such an adhesive composition, the resulting aqueous emulsion composition comprises an ethylene-vinyl acetate copolymer, a modified resin of an ethylene-vinyl acetate copolymer, a photopolymerization initiator, an ethylenically unsaturated monomer, Since it is encapsulated in micelles in a state dissolved or dispersed in a solvent, sufficient wettability is ensured even for adherends, especially adherends with low surface polarity, and sufficient adhesion performance is ensured. In addition, the emulsion can have good stability, and mechanical stability and storage stability can be improved.

  Moreover, since such an adhesive composition is water-based, there is little danger of ignition and a favorable sanitary environment can be ensured. Furthermore, it is excellent in initial adhesive strength and water resistance, and can be used effectively in various applications.

In addition, in order to adhere using the adhesive composition as described above, for example, it may be applied to the adherend to be adhered by a known method, and the method of use is not limited. It may be used as a primer used as a pretreatment or may be used as an adhesive. Moreover, it may be used so that it may mix | blend with a primer and an adhesive agent. In addition, after application | coating, it is preferable to irradiate the ultraviolet-ray of 50-1000mJ / cm < ² >, for example.

  If such an aqueous emulsion is used, since an organic solvent is not used in both the degreasing step and the bonding step, an adhesion process that is highly safe and can provide a good sanitary environment can be provided.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following, parts and% used in the examples are based on weight unless otherwise specified.

Example 1
Nonionic surfactant (trade name: Emulgen A90 (manufactured by Kao Corporation)) 1000 parts by weight, linear alkylbenzene sulfonate sodium (trade name: Neoperex No. 6F powder (manufactured by Kao Corporation)) 200 parts by weight, 4A zeolite A cleaning composition comprising 200 parts by weight, 100 parts by weight of sodium silicate, 100 parts by weight of sodium carbonate, and 400 parts by weight of sodium sulfate was dispersed in 18000 parts by weight of water to obtain a cleaning liquid. A foamed molded product (manufactured by Eclipse Polymer Co., Ltd.) of an ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA) having a size of 300 mm × 100 mm × 10 mm is put into this cleaning agent dispersion, and stirred for 5 minutes with a magnetic stirrer. , Washed. After washing, the EVA foam was taken out, thoroughly washed with tap water, and dried in an oven at 55 ° C. for 5 minutes to obtain a washed ethylene-vinyl acetate copolymer molded body.

As a primer, EVA (vinyl acetate content: 19%, melt index: 2.5,
Product name: EVAFLEX EV460 (manufactured by Mitsui DuPont Polychemical Co., Ltd.) 3 parts by weight, EVA (vinyl acetate content: 33%, melt index: 1, product name: EVAFLEX EV170 (manufactured by Mitsui DuPont Polychemical Co., Ltd.), 3 parts by weight HEVA (hydroxyl value: 0 mg KOH / g, acid value: 84 mg KOH / g, tetrahydrofuran solution (resin content: 20% by weight), trade name: Takemelt SD-700 (manufactured by Mitsui Takeda Chemicals)) and 1-hydroxy-cyclohexyl -Phenyl ketone (photopolymerization initiator, trade name: Irgacure 184 (manufactured by Ciba Specialty Chemicals)), 5 parts by weight of 4-methylbenzophenone, 20 parts by weight of isobornyl methacrylate, 20 parts by weight of cyclohexyl methacrylate 2-hydroxymethyl methacrylate And 30 parts by weight of turpentine, 10 parts by weight of turpentine, and 10 parts by weight of limonene were dissolved by heating to 60 ° C. with stirring, and tetrahydrofuran was removed under reduced pressure to prepare oil droplet components. Stir oil droplet components with a high-speed mixer (rotation speed:
2,000 rpm), 25 parts by weight of polyoxyethylene alkyl ether sulfate ester surfactant (trade name: EMAL 27C (manufactured by Kao Corporation) and 860 parts by weight of ion-exchanged water are added to forcibly emulsify the primer ( The primer A thus obtained was applied to a washed EVA foam, dried in an oven at 55 ° C. for 3 minutes, and irradiated with 300 mJ / cm ² of ultraviolet rays using an ultraviolet irradiation device. Irradiated.

  On the other hand, a rubber primer was applied to the buffed rubber and dried at room temperature for 5 minutes.

  After drying, a two-component polyurethane-based water-based adhesive is applied to the primer-treated EVA foam molding and primer-coated rubber, dried in an oven at 55 ° C. for 8 minutes, and then clamped at a pressure of 0.4 MPa. Gluing was performed. The adhesive strength was measured by a 180 degree peel test in accordance with JIS K 6854 for the adhesive strength after 5 minutes after bonding and the adhesive strength after standing at room temperature for 1 day. The results are shown in Table 1.

Example 2
In Example 1, instead of 200 parts by weight of linear alkylbenzene sulfonate sodium (trade name: Neoperex No. 6F powder (manufactured by Kao Corporation)) as a detergent composition, linear sodium alkylbenzene sulfonate (trade name: Neo) Adhesion was carried out in the same manner except that 100 parts by weight of PELEX No. 6F powder (manufactured by Kao Corporation) and 100 parts by weight of polyoxyethylene alkyl ether sulfate (trade name: EMAL 270J (manufactured by Kao Corporation)) were used. A test was conducted.

Example 3
Instead of the detergent composition of Example 1, 1000 parts by weight of nonionic surfactant (trade name: Emulgen A90 (manufactured by Kao)), 1000 parts by weight of detergent for clothing (trade name: Attack (manufactured by Kao)) The adhesion test was conducted in the same manner except that was used.

Example 4
EVA of the primer of Example 1 (vinyl acetate content: 19%, melt index: 2.
5. Product name: 3 parts by weight of Evaflex EV460 (Mitsui DuPont Polychemical Co., Ltd.), EVA (vinyl acetate content: 33%, melt index: 1, Product name: Evaflex EV170 (Mitsui DuPont Polychemical Co., Ltd.) of 3 weights Instead of 20 parts by weight of C-HEVA (hydroxyl value: 0 mg KOH / g, acid value: 84 mg KOH / g, tetrahydrofuran solution (resin content: 20% by weight), trade name: Takemelt SD-700 (manufactured by Mitsui Takeda Chemicals)) In addition, EVA (vinyl acetate content: 28%, melt index: 15, product name: EVAFLEX EV250 (manufactured by Mitsui DuPont Polychemical)), C-HEVA (hydroxyl value: 0 mgKOH / g, acid value: 84 mgKOH / g, tetrahydrofuran solution (resin content 20% by weight), trade name: Takemelt S -700 (manufactured by Mitsui Takeda Chemicals, Inc.)) other than prepared (primer B) primers with 25 parts by weight, were subjected to adhesion test in the same blending and operation as in Example 1.

Example 5
An adhesion test was conducted in the same composition and operation as in Example 1 except that the concentration of the cleaning liquid in Example 1 was halved (that is, the amount of the detergent composition was halved).

Example 6
Adhesiveness in the same composition and operation as in Example 1 except that the concentration of the cleaning liquid in Example 1 was 1/5 (that is, the amount of the cleaning composition was 1/5) and the cleaning time was 10 minutes. A test was conducted.

Comparative Example 1
An adhesion test was conducted in the same manner as in Example 1 except that the cleaning operation was performed using 20000 parts by weight of water not containing the cleaning agent in place of the cleaning composition of Example 1.

Comparative Example 2
An adhesive test was conducted in the same composition and operation as in Example 1, except that 2000 parts by weight of sodium lauryl sulfate (trade name: EMAL 0 (manufactured by Kao Corporation)) was used instead of the detergent composition in Example 1. went.

Comparative Example 3
Nonionic surfactant (trade name: Emulgen A90 (manufactured by Kao Corporation)) 1000 parts by weight of the cleaning liquid of Example 1, linear alkylbenzene sulfonate sodium (trade name: Neoperex No. 6F powder (manufactured by Kao Corporation)) 200 Instead of obtaining a cleaning liquid by dispersing a detergent composition comprising 200 parts by weight of 4A zeolite, 100 parts by weight of sodium silicate, 100 parts by weight of sodium silicate, 100 parts by weight of sodium carbonate, and 400 parts by weight of sodium sulfate in 18000 parts by weight of water. 200 parts by weight of linear sodium alkylbenzene sulfonate (trade name: Neoperex No. 6F powder (manufactured by Kao)) 200 parts by weight of 4A zeolite, 100 parts by weight of sodium silicate, 100 parts by weight of sodium carbonate, 400 parts of sodium sulfate 19000 parts by weight of a detergent composition consisting of parts by weight Distributed to, in addition to the washing solution was subjected to adhesion test in the same blending and operation as in Example 1.

Comparative Example 4
Example 1 except that instead of the washed EVA foam molded body of Example 1, an EVA foam molded body (manufactured by Eclipse Polymer Co., Ltd.) was washed with methyl ethyl ketone and dried at room temperature for 5 minutes. An adhesion test was conducted with the same formulation and operation.

  Those with EVA or rubber material failure were labeled (material failure) after the adhesive strength.

Claims (4)

When bonding an ethylene-vinyl acetate copolymer resin molding, the surfactant represented by the general formula (1):
(Wherein R ¹ is an aliphatic and / or aromatic hydrocarbon having 4 to 35 carbon atoms, n is an integer of 1 to 50) and a surfactant represented by the general formula (2) or (3):
R ² —SO ₃ —Na (2)
R ² —SO ₄ —Na (3)
(Wherein, R ² is from 4 to 25 carbon atoms in the aliphatic and / or aromatic hydrocarbons) in the following washing with detergent composition comprising,
Micelle containing ethylene-vinyl acetate copolymer, carboxyl-modified resin of partially saponified ethylene-vinyl acetate copolymer , photopolymerization initiator, (meth) acrylate monomer , non-aqueous organic solvent is dispersed in water. An aqueous emulsion composition, wherein the ratio of the carboxyl-modified resin of the ethylene-vinyl acetate copolymer and the partially saponified ethylene-vinyl acetate copolymer is 95: 5 to 5:95 by weight. A method for adhering a molded article of ethylene-vinyl acetate copolymer resin, characterized in that an adhesive is applied and adhered. R ^{1 in the} general formula (1) is the general formula (4):
(Where n is an integer from 1 to 5)
The method for bonding an ethylene-vinyl acetate copolymer resin molded product according to claim 1, wherein the styrenated phenyl group is represented by:   The adhesion of the ethylene-vinyl acetate copolymer resin molding according to claim 1 or 2, wherein the cleaning composition contains a builder together with the surfactant represented by the above formulas (1) to (3). Method.   2. The method for adhering an ethylene-vinyl acetate copolymer resin molding according to claim 1, wherein ultraviolet irradiation is performed after applying the adhesive.