JP4609788B2 - Aqueous dispersion, method for producing the same, and method for bonding molded article comprising ethylene / α-olefin copolymer - Google Patents

Description

  The present invention relates to an aqueous dispersion, an adhesive composition containing the aqueous dispersion, an adhesive, a primer, and the like, and a method for adhering a molded article made of an ethylene / α-olefin copolymer using the same.

  Low specific gravity, that is, lightweight, flexible, and technology that uses cross-linked foam to obtain high mechanical strength products is a wide range of fields such as automotive interior and exterior materials, interior materials and door glass runs, packaging materials, daily necessities, etc. It is used in. If the resin is simply foamed for weight reduction, the mechanical strength is reduced. In this crosslinked foam, the mechanical strength is reduced by bonding molecular chains by the resin crosslinking reaction, and foaming Lighter weight has been achieved.

  Footwear and parts for footwear such as sports shoes (mainly midsole) are lightweight, materials that have mechanical strength and rebound resilience that can resist deformation due to long-term use and can withstand harsh usage conditions. Resin crosslinked foams are also used in such fields.

  For example, a cross-linked foam molded using an ethylene / vinyl acetate copolymer composition is widely used for shoe soles, but this cross-linked foam has a high specific gravity and a large compression set. There is a problem that the shoe sole is compressed due to its heavy use for a long time and mechanical strength such as rebound resilience is lost.

  Patent Document 1 discloses an ethylene / α-olefin having an Asker C hardness in the range of 20 to 80, a low specific gravity, a small permanent compression strain (CS), and excellent tensile strength characteristics, tear strength characteristics, and rebound resilience. Copolymer uncrosslinked foams and crosslinked foams are disclosed.

  However, the molded body made of this ethylene / α-olefin copolymer cross-linked foam has excellent physical properties, but has a small polarity due to the structure of the resin that constitutes it. When products such as shoes are manufactured in combination, adhesion failure or the like may occur.

  On the other hand, organic solvent adhesives have been widely used as adhesive compositions for adhering various molded products such as plastic films, plastic sheets, plastic foams, fibers, synthetic leather, and metals.

  Organic solvent-based adhesives have high adhesiveness even to relatively hard molded products, and are used in various applications. However, since it is not very preferable in terms of the risk of ignition and environmental hygiene, in recent years, water-based adhesives have been developed in place of organic solvent-based adhesives. Water-based primers have been demanded.

As an aqueous adhesive, an adhesive composition comprising an aqueous emulsion containing an ethylene / vinyl acetate copolymer is known. For example, Patent Document 2 discloses an aqueous emulsion composition containing a carboxyl-modified resin of a saponified ethylene / vinyl acetate copolymer and a surfactant. More specifically, an ethylene / vinyl acetate copolymer saponified carboxyl-modified resin is emulsified in water with a surfactant and, if necessary, an adhesive composition containing an ethylenically unsaturated monomer and a photopolymerization initiator. Things are listed. It is described that this adhesive composition has a high adhesive strength with respect to a wide range of materials and can be bonded well even to a molded product.

  Patent Document 3 discloses an aqueous emulsion composition in which micelles containing an ethylene / vinyl acetate copolymer or a modified resin thereof, a photopolymerization initiator, and an ethylenically unsaturated monomer are dispersed in water. . The emulsion composition can exhibit sufficient adhesion performance to adherends with low surface polarity, and the emulsion has good stability and can improve mechanical stability and storage stability. Is also disclosed.

However, the adhesive composition described in Patent Document 2 and the water-based emulsion composition described in Patent Document 3 have high adhesion with respect to a molded body made of a highly polar copolymer such as an ethylene / vinyl acetate copolymer. Although it shows strength, for example, it is difficult to develop sufficient adhesiveness for a molded article having low polarity such as an ethylene / α-olefin copolymer described in Patent Document 1. For this reason, organic solvent-based adhesives are still used for molded products of ethylene / α-olefin copolymers, and molded products made of low polarity copolymers such as ethylene / α-olefin copolymers. There has been a demand for the development of water-based adhesives and water-based primers that exhibit high adhesive strength.
JP 2000-344924 A European Patent Publication EP 1106628A1 JP 2003-113207 A

  The present invention is intended to solve the problems associated with the prior art as described above, and various molded products, particularly molded products made of low polarity copolymers such as ethylene / α-olefin copolymers. An aqueous dispersion that has high adhesive strength, can exhibit sufficient adhesive strength from the initial stage of adhesion, and is excellent in storage stability and mechanical stability, and an adhesive composition containing the aqueous dispersion It is an issue to provide. Another object of the present invention is to provide a method for bonding a molded body made of an ethylene / α-olefin copolymer with high adhesive strength.

  The present inventor has intensively studied to solve the above problems, and an aqueous dispersion containing an ethylene / α-olefin copolymer and a modified ethylene / vinyl acetate copolymer has been obtained. It has been found that it has a high adhesive strength with respect to a molded body made of a polymer, and the present invention has been completed.

  That is, the aqueous dispersion according to the present invention comprises (A) an ethylene / α-olefin copolymer, (B) a modified ethylene / vinyl acetate copolymer, (C) a photopolymerization initiator and (D) an ethylenic polymer. It is characterized by containing an unsaturated monomer. This aqueous dispersion preferably further contains (E) an ethylene / vinyl acetate copolymer and (F) a non-aqueous organic solvent.

The ethylene / α-olefin copolymer (A) is:
(I) a copolymer obtained from ethylene and an α-olefin having 3 to 20 carbon atoms,
(Ii) the density (23 ° C.) measured according to ASTM D1505 is in the range of 0.857 to 0.910 g / cm ³ ;
(Iii) The melt flow rate (MFR (2.16)) at 190 ° C. and a load of 2.16 kg, measured according to ASTM D1238, is in the range of 0.1 to 40 g / 10 minutes,
(Iv) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 1.5 to 3.0. Is preferred.

The ethylene / α-olefin copolymer (A) is:
(Iv) The melt flow rate (MFR (10)) at 190 ° C. and 10 kg load and the melt flow rate (MFR (2.16)) at 190 ° C. and 2.16 kg load, measured according to ASTM D1238. The ratio (MFR (10) / MFR (2.16)) satisfies the relationship of the following formulas (1) and (2),
MFR (10) / MFR (2.16) ≧ 6.0 (1)
Mw / Mn + 5.0 ≦ MFR (10) / MFR (2.16) (2)
(In the formula, Mw represents a weight average molecular weight, and Mn represents a number average molecular weight.)
(V) The intensity ratio of Tαβ to Tαα (Tαβ / Tαα) in the ¹³ C-NMR spectrum is 0.5 or less,
(Vi) The following formula (3)
B = [POE] / (2 [PE] [PO]) (3)
(Wherein [PE] is the molar fraction of structural units derived from ethylene in the copolymer, [PO] is the molar fraction of structural units derived from α-olefin in the copolymer, [POE] ] Is the ratio of the number of ethylene / α-olefin chains to the total number of dyad chains in the copolymer)
It is preferable that the B value calculated from is in the range of 0.9 to 1.5.

  The ethylene / α-olefin copolymer (A) is preferably an ethylene / 1-butene copolymer.

  The modified ethylene-vinyl acetate copolymer (B) is preferably a carboxyl-modified resin of a partially saponified ethylene-vinyl acetate copolymer.

  The ethylenically unsaturated monomer (D) is preferably (meth) acrylate.

The (meth) acrylate has the following formula (4)
CHR ¹ = CHCOOR ² (4)
(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrocarbon group having 6 to 16 carbon atoms.)
It is preferable to contain at least (meth) acrylate represented by.

  The non-aqueous organic solvent (F) is preferably an organic solvent having a boiling point of 100 ° C. or higher.

  The aqueous dispersion comprises 10 to 300 parts by weight of a modified ethylene / vinyl acetate copolymer (B), 100 parts by weight of ethylene / α-olefin copolymer (A), ethylene / vinyl acetate copolymer It is preferable to contain 0 to 200 parts by weight of the union (E).

The method for producing an aqueous dispersion according to the present invention includes:
At least (A) an ethylene / α-olefin copolymer, (B) a modified ethylene / vinyl acetate copolymer, (C) a photopolymerization initiator and (D) an ethylenically unsaturated monomer (F) a non-aqueous system Prepare oil droplet components by dissolving or dispersing in organic solvent,
The oil droplet component is dispersed in water using a surfactant (G).

  The adhesive composition according to the present invention is characterized by containing the above-mentioned aqueous dispersion.

The bonding method according to the present invention is characterized in that a molded body made of an ethylene / α-olefin copolymer is bonded using a primer for an ethylene / α-olefin copolymer made of a UV curable aqueous emulsion composition. .

  The UV curable aqueous emulsion composition preferably contains the aqueous dispersion.

The bonding method according to the present invention includes:
Following formula (5)

Wherein R ³ is an aliphatic and / or aromatic hydrocarbon group having 4 to 35 carbon atoms, and m is 5 to 20
Is)
And the following formula (6)
R ⁴ —SO ₃ —Na (6)
(Wherein R ⁴ is an aliphatic and / or aromatic hydrocarbon group having 4 to 25 carbon atoms)
After cleaning the molded body made of an ethylene / α-olefin copolymer using a cleaning composition containing at least one surfactant selected from the surfactants represented by formula (1), the UV curable aqueous system It is preferable to apply an emulsion composition and adhere a molded body made of an ethylene / α-olefin copolymer.

R ³ in the formula (5) represents the following formula (7)

(Where n is 0 to 4)
It is preferable that it is a styrenated phenyl group represented by these.

  The cleaning composition preferably further contains a builder.

  The aqueous dispersion of the present invention can be suitably used as an adhesive composition such as a primer or an adhesive, and has high adhesive strength for a wide range of materials. In particular, a high adhesive strength can be obtained for a molded body made of an ethylene / α-olefin copolymer. Moreover, with this adhesive composition, sufficient wettability can be secured even for an adherend, particularly an adherend having a low surface polarity, and sufficient adhesive performance can be exhibited. Since this aqueous dispersion is aqueous, there is little risk of ignition and a good sanitary environment can be obtained. Furthermore, when this aqueous dispersion is an aqueous emulsion composition, the stability of the emulsion is good, and the mechanical stability and storage stability can be improved.

<Aqueous dispersion>
The aqueous dispersion according to the present invention comprises an ethylene / α-olefin copolymer (A), a modified ethylene / vinyl acetate copolymer (B), a photopolymerization initiator (C), and an ethylenically unsaturated monomer (D ), And further contains an ethylene / vinyl acetate copolymer (E) and a non-aqueous organic solvent (F) as necessary.

  First, components (A) to (F) used in the present invention will be described.

(A) Ethylene / α-olefin copolymer:
The ethylene / α-olefin copolymer (A) used in the present invention is preferably an amorphous or low crystalline random or block copolymer obtained from ethylene and an α-olefin having 3 to 20 carbon atoms. . As such an ethylene / α-olefin copolymer (A), (i) density (23 ° C.) is usually 0.857 to 0.910 g / cm ³ , preferably 0.8.
A 60~0.905g / cm ^3, (ii) a melt flow rate (MFR, 190 ° C., load of 2.16 kg) is usually 0.1 to 40 g / 10 min, preferably 0.5 to 20 g / 10 min Some soft ethylene / α-olefin copolymers are desirable. The density is a value measured at 23 ° C. according to ASTM D1505, and the melt flow rate (MFR) is a value measured at 190 ° C. under a load of 2.16 kg according to ASTM D1238.

This ethylene / α-olefin copolymer (A) has a ratio (Mw / Mn) of (iii) weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC). Preferably it is 1.5-3.0, More preferably, it exists in the range of 1.7-2.5. Mw and Mn were measured by gel permeation chromatography (GPC), column: TSK GNHHT, column temperature: 140 ° C., mobile phase: orthodichlorobenzene, flow rate: 1.0 mL / min, sample concentration: 0.1 weight %, Injection amount: a value measured under conditions of 400 μL and converted by polystyrene. The adhesive composition containing the aqueous dispersion containing the ethylene / α-olefin copolymer (A) having Mw / Mn in the above range is higher than the molded product made of the ethylene / α-olefin copolymer. Shows adhesion. Such an ethylene / α-olefin copolymer (A) usually exhibits properties as an elastomer.

In addition, the ethylene / α-olefin copolymer (A) was measured according to (iv) ASTM D1238 at 190 ° C. under a 10 kg load (MFR (10)) and 190 ° C. under 2.16 kg. The ratio (MFR (10) / MFR (2.16)) to the melt flow rate (MFR (2.16)) under load is the following formula (1)
MFR (10) / MFR (2.16) ≧ 6.0 (1)
Preferably the following formula (1) ′
7.0 ≦ MFR (10) / MFR (2.16) ≦ 15.0 (1) ′
And the following formula (2)
Mw / Mn + 5.0 ≦ MFR (10) / MFR (2.16) (2)
(In the formula, Mw represents a weight average molecular weight, and Mn represents a number average molecular weight.)
It is preferable to satisfy the relationship. An adhesive composition containing an aqueous dispersion containing an ethylene / α-olefin copolymer (A) in which MFR (10) / MFR (2.16) satisfies the above relational formula is obtained by using an ethylene / α-olefin copolymer. High adhesion to a molded body made of coalescence.

In the ethylene / α-olefin copolymer (A), (v) the intensity ratio of Tαβ to Tαα (Tαβ / Tαα) in the ¹³ C-NMR spectrum is preferably 0.5 or less, more preferably 0.4 or less. . In the ¹³ C-NMR spectrum, Tαα and Tαβ are the peak intensities of CH ₂ in units derived from α-olefins having 3 or more carbon atoms,
As shown below, it means two types of CH ₂ having different positions relative to the tertiary carbon.

The Tαβ / Tαα intensity ratio can be determined by the following method. The ¹³ C-NMR spectrum of the ethylene / α-olefin copolymer (A) is measured using a ¹³ C-NMR measuring apparatus (for example, JEOL-GX270 manufactured by JEOL Ltd.). Using a mixed solution of hexachlorobutadiene / d ⁶ -benzene = 2/1 (volume ratio) adjusted to a sample concentration of 5% by weight, 67.8 MHz, 25 ° C., d ⁶ -benzene (128 ppm) standard Measure under the following conditions. The measured ¹³ C-NMR spectrum is analyzed according to the proposal of Lindeman Adams (Analysis Chemistry 43, p1245 (1971)), JCRandall (Review Macromolecular Chemistry Physics, C29, 201 (1989)), and the Tαβ / Tαα intensity ratio is obtained.

The ethylene / α-olefin copolymer (A) has the following formula (3):
B = [POE] / (2 [PE] [PO]) (3)
(Wherein [PE] is the molar fraction of structural units derived from ethylene in the copolymer, [PO] is the molar fraction of structural units derived from α-olefin in the copolymer, [POE] ] Is the ratio of the number of ethylene / α-olefin chains to the total number of dyad chains in the copolymer)
It is preferable that the B value calculated from is in the range of 0.9 to 1.5. [PE], [PO] and [POE] can be determined from the ¹³ C-NMR spectrum of the ethylene / α-olefin copolymer (A).

This B value is an index representing the distribution state of ethylene and an α-olefin having 3 to 10 carbon atoms in the ethylene / α-olefin copolymer. JCRandall (Macromolecules, 15, 353 (1982)), J. It can be obtained based on the report of Ray (Macromolecules, 10, 773 (1977)). The larger the B value, the shorter the block chain of ethylene or α-olefin, the more uniform the distribution of ethylene and α-olefin, and the narrower the composition distribution of the copolymer rubber. In addition, there exists a problem that the composition distribution of an ethylene / α-olefin copolymer becomes wider as the B value becomes smaller than 1.0, and the handleability deteriorates.

  The ethylene / α-olefin copolymer (A) preferably has a crystallinity measured by an X-ray diffraction method of usually 40% or less, preferably 30% or less.

  Such an ethylene / α-olefin copolymer (A) is obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms using a vanadium catalyst, a titanium catalyst or a metallocene catalyst. It can be produced by a known method.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene. 1-hexadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 4-methyl-1-pentene and the like. Of these, 3 to 1 carbon atoms
An α-olefin of 0 is preferable, and propylene, 1-butene, 1-hexene and 1-octene are particularly preferable. Moreover, these alpha olefins can be used individually by 1 type or in combination of 2 or more types.

  The ethylene / α-olefin copolymer (A) is an amount of 75 to 95 mol% of units derived from ethylene and 5 to 25 mol% of units derived from an α-olefin having 3 to 20 carbon atoms. It is desirable to contain. In addition to these units, the ethylene / α-olefin copolymer (A) may contain units derived from other polymerizable monomers as long as the object of the present invention is not impaired.

  Specific ethylene / α-olefin copolymers (A) include ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / propylene / 1-butene copolymers, ethylene / propylene / ethylidene norbornene copolymers. Examples thereof include a polymer, an ethylene / 1-hexene copolymer, and an ethylene / 1-octene copolymer. Of these, ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / 1-hexene copolymers, ethylene / 1-octene copolymers and the like are preferably used. A polymer is preferably used. These copolymers are random or block copolymers, and are particularly preferably random copolymers.

(B) Modified ethylene / vinyl acetate copolymer:
The modified ethylene-vinyl acetate copolymer (B) used in the present invention is not particularly limited, but is preferably a carboxyl-modified ethylene-vinyl acetate copolymer or an isocyanate of ethylene-vinyl acetate copolymer. Examples thereof include a modified narate and an epoxy-modified ethylene / vinyl acetate copolymer. Among these, a carboxyl-modified resin (hereinafter abbreviated as “C-HEVA”) of a partially saponified product of an ethylene / vinyl acetate copolymer is preferable. C-HEVA can be manufactured based on the description of Japanese Patent Publication No. 5-26802, for example. First, an ethylene / vinyl acetate copolymer (hereinafter abbreviated as “EVA”) is dissolved in an organic solvent, and a lower alcohol is added to the solution. Thereafter, an alkali alcoholate is added as a catalyst in the presence of a specific amount of water to partially saponify the saponification degree (about 10 to 90%), thereby partially saponifying the ethylene / vinyl acetate copolymer (hereinafter referred to as “HEVA”). Is abbreviated as “). Next, the HEVA is modified with an acid such as an unsaturated carboxylic acid or an acid anhydride.

  The modified product (B) of the ethylene / vinyl acetate copolymer 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 adhesion performance may be deteriorated.

(C) Photopolymerization initiator:
Examples of the photopolymerization initiator (C) used in the present invention include polymerization initiators such as acylphosphine oxide, acetophenone, benzoin ether, benzophenone, and thioxanthone.

  Examples of the acylphosphine oxide polymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (for example, Lucylin TPO manufactured by BASF), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine. Examples thereof include oxide (BAPO), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and bis (2,4,6-trimethylbenzoyl) n-butylphosphine oxide.

As the acetophenone polymerization initiator, diethoxyacetophenone-2-hydroxy-
2-methyl-1-phenylpropan-1-one (for example, Darocur 1173 manufactured by Ciba Specialty Chemicals), benzyldimethyl ketal (for example, Irgacure 651 manufactured by Ciba Specialty Chemicals, Lucillin BDK manufactured by BASF), 1-hydroxy-cyclohexyl phenyl ketone (for example, Irgacure 184 manufactured by Ciba Specialty Chemicals), 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (for example, Ciba Specialty Chemicals) Irgacure 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone (for example, Irgacure 369 manufactured by Ciba Specialty Chemicals), 2-hydroxy-2-methyl -1- [4- (1-methylvinyl) phenyl] propanone oligomer (e.g., Ranberuchi Co. Esakyua KIP), and the like.

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

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

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

  In the present invention, in addition to the above-described photopolymerization initiator, methylphenylglyoxyester (Vicure 55 manufactured by AKZO) or 3,6-bis (2-morpholinoisobutyl) -9-butylcarbazole (A-Cure3 manufactured by Asahi Denka Co., Ltd.) ), Titanocene compounds and the like can also be used.

  These photopolymerization initiators can be used alone or in combination of two or more. As a combination of two or more, for example, Irgacure 1700 (bis (2,6-dimethoxybenzoyl) -2,4-4-trimethylpentylphosphine oxide / 2-hydroxy-2-methylphenylpropan-1-one = 25 / 75%), Irgacure 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide / 1-hydroxycyclohexyl-phenylketone = 25/75%) (both are Ciba Specialty) Commercial products such as Chemicals).

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

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

As a monofunctional monomer (monofunctional polymerizable diluent), for example,
Heterocyclic ethylenically unsaturated compounds (for example, N-vinyl-nitrogen-containing heterocyclic compounds such as N-methylpyrrolidone, N-vinylpyridine, N-vinylcaprolactam; morpholine (meth) acrylate, tetrahydrofurfuryl (meth) acrylate Heterocyclic (meth) acrylates such as;
N-vinylformamide, N-vinylacetamide;
Dialkylaminoethyl (meth) acrylate (eg, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate);
N, N′-dimethylacrylamide; alkoxy (poly) alkylene glycol (meth) acrylate (eg, methoxyethylene (meth) acrylate, methoxypolyethylene (meth) acrylate, butoxypolyethylene (meth) acrylate);
Alkylphenoxymethyl (meth) acrylate (eg, nonylphenoxyethyl (meth) acrylate);
Phenoxy (poly) alkylene glycol (meth) acrylate (eg, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate);
Alkyl (meth) acrylates (for example, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl ( (Meth) acrylate);
Cycloalkyl (meth) acrylate (eg, cyclohexyl (meth) acrylate);
Aralkyl (meth) acrylate (eg, benzyl (meth) acrylate);
(Meth) acrylate having a bridged cyclic hydrocarbon group (for example, isobornyl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyalkyl (meth) acrylate, tricyclodecanyloxyethyl (meth) acrylate) , Isobornyloxyethyl (meth) acrylate);
Hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (Meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, 3-acryloyloxyglycerin mono (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Pentanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, poly B propylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate);
Poly [epsilon] -caprolactone mono (meth) acrylate; glycidyl (meth) acrylate; mono [2- (meth) acryloyloxyethyl] acid phosphate;
Halogen-containing (meth) acrylates (for example, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, perfluorooctylethyl (meth) acrylate) may be mentioned.

As a bifunctional monomer (bifunctional polymerizable diluent), for example,
Di (meth) acrylate of 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate;
(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, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, alkylene oxide of bisphenol A (ethylene oxide, B pyrene oxide) adduct di (meth) acrylate (
For example, 2,2-bis (2-hydroxyethoxyphenyl) propane di (meth) acrylate);
Di (meth) acrylates having bridged cyclic hydrocarbon groups (eg, di (meth) acrylate of tricyclodecane dimethylol, dicyclopentadiene di (meth) acrylate);
And (meth) acrylic acid adducts of bifunctional epoxy resins (for example, (meth) acrylic acid adducts of 2,2-bis (glycidyloxyphenyl) propane).

  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 ( Examples include (meth) acrylate, tris (hydroxypropyl) isocyanurate tri (meth) acrylate, triallyl trimellitic acid, and triallyl isocyanurate.

  These ethylenically unsaturated monomers can be used singly or in combination of two or more.

Of the ethylenically unsaturated monomers, (meth) acrylate is preferably used. As the (meth) acrylate, the following formula (4)
CHR ¹ = CHCOOR ² (4)
(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrocarbon group having 6 to 16 carbon atoms.)
(Meth) acrylate containing is preferably used. The hydrocarbon group having 6 to 16 carbon atoms includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an araliphatic hydrocarbon group, an aromatic hydrocarbon group, and the like. Examples of such (meth) acrylates include 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, and cyclohexyl (meth) acrylate. , Benzyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentadiene (meth) acrylate.

In addition, the R ² described above has a (meth) acrylate having a hydrocarbon group having 6 to 16 carbon atoms, together with the following formula (8):
CHR ¹ = CHCOOR ^{2 '} (8)
(In the formula, R ¹ is a hydrogen atom or a methyl group, R ^{2 ′} has a hydroxyl group, and has 2 to 2 carbon atoms.
And a group having 5 hydrocarbon groups. )
It is preferable to use together (meth) acrylate represented by these.

  Examples of the (meth) acrylate represented by the above formula (8) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( And (meth) acrylate and pentaerythritol tri (meth) acrylate. By using the (meth) acrylate represented by the above formula (8), in the preparation of the oil droplet component described later, the solubility of both the ethylene / vinyl acetate copolymer and its modified product and the photopolymerization initiator and It is possible to improve dispersibility and further improve adhesiveness. Moreover, adhesiveness can be adjusted, for example, improved by using other ethylenically unsaturated monomers in combination with such (meth) acrylate as appropriate.

  In addition, among the (meth) acrylates represented by the above formula (8), (meth) acrylate having high hydrophilicity may be added afterwards to the aqueous dispersion.

(E) Ethylene / vinyl acetate copolymer:
In the present invention, an ethylene / vinyl acetate copolymer (E) can be used as necessary. The ethylene / vinyl acetate copolymer (E) used in the present invention can be produced, for example, by a known method such as a high pressure method or an emulsification method. The proportion of vinyl acetate used at this time is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, based on the total amount of ethylene and vinyl acetate. When the ratio of vinyl acetate is less than the above lower limit, the adhesiveness to a wide range of molded articles may be lowered, and when the upper limit is exceeded, the adhesiveness to a molded article made of an ethylene / vinyl acetate copolymer may be lowered.

  The melt index (190 ° C., 2160 g load) of the ethylene / vinyl acetate copolymer (E) is preferably 0.1 to 500 g / 10 minutes, more preferably 1 to 300 g / 10 minutes. In the present invention, the melt index of the ethylene / vinyl acetate copolymer (E) is measured under the conditions of 190 ° C. and 2160 g load in accordance with ASTM D-1238.

  The ethylene / vinyl acetate copolymer (E) can be used alone or in combination of two or more. Ethylene / vinyl acetate copolymer (E) with a small proportion of vinyl acetate is difficult to dissolve as an oil droplet component in an aqueous dispersion, but should be used in combination with an ethylene / vinyl acetate copolymer (E) with a large proportion of vinyl acetate. This improves the stability of the aqueous dispersion.

(F) Non-aqueous organic solvent:
The non-aqueous organic solvent (F) used in the present invention is desirably such that its solubility in water is negligible. For example, the solubility in water is usually 5% by weight or less, preferably 3% by weight or less. The non-aqueous organic solvent (F) is a solvent having fluidity at normal temperature.

  Examples of such non-aqueous organic solvents (F) include hydrocarbons such as aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, and halogenated hydrocarbons; alcohols; phenols; ethers; An ester or the like.

  Examples of the aliphatic hydrocarbon include hexane, heptane, octane, isooctane, nonane, decane, and dodecane.

  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.

  Examples of such a mixture of hydrocarbons include naturally produced and refined products such as benzine, naphtha, ligroin, gasoline, kerosene, solvent naphtha, camphor oil, turpentine oil, and pine oil.

  Examples of alcohols include heptanol, octanol, 2-ethyl-1-hexanol, nonanol, decanol, dodecanol, and terpineol.

  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 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.

  These non-aqueous organic solvents can be used alone or in combination of two or more. Of these non-aqueous organic solvents, a non-aqueous organic solvent having a boiling point of 100 ° C. or higher is preferably used from the viewpoint of handleability. Furthermore, since the solubility of the ethylene / vinyl acetate copolymer and the modified ethylene / vinyl acetate copolymer is high, alicyclic hydrocarbons are preferably used.

<Aqueous dispersion>
The aqueous dispersion according to the present invention comprises 5 to 500 parts by weight, preferably 10 to 10 parts by weight of the modified ethylene / vinyl acetate copolymer (B) with respect to 100 parts by weight of the ethylene / α-olefin copolymer (A). Contains ~ 300 parts by weight. When the content of the modified body (B) of the ethylene / vinyl acetate copolymer is in the above range, it exhibits a high adhesive strength particularly for difficult-to-adhere materials such as a molded body made of ethylene / vinyl acetate copolymer, Adhesive strength sufficient from the initial stage of adhesion can be expressed even on an adherend having a low surface polarity. If the content of the modified body (B) of the ethylene / vinyl acetate copolymer exceeds the above upper limit, the adhesiveness to a molded body made of a material having low polarity such as an ethylene / α-olefin copolymer may be lowered. If the amount is less than the above lower limit, adhesion to a wide range of materials as well as low polarity materials may be lowered.

In addition to the ethylene / α-olefin copolymer (A) and the modified ethylene / vinyl acetate copolymer (B), the aqueous dispersion contains ethylene / vinyl acetate as long as the effects of the present invention are not impaired. Other resins such as a copolymer may be contained. In this case, the aqueous dispersion preferably contains 15% by weight or more of the ethylene / α-olefin copolymer (A) based on the solid content. In the present specification, the solid content of the aqueous dispersion is a component remaining when water in the aqueous dispersion is removed. In the present invention, the amount of the solid content is such that the aqueous dispersion contains an ethylenically unsaturated monomer, and then the aqueous dispersion is irradiated with ultraviolet rays and then dried in an oven at 130 ° C. for 10 minutes. It can be determined by measuring the weight. Specifically, an aluminum evaporating dish having a diameter of 70 mmφ is exposed to the same size as the inner diameter of the evaporating dish, and 0.5 g of an aqueous dispersion is precisely weighed on this. Then, after irradiating UV rays of 150 mJ / cm ² 10 times with a UV irradiator (Nihon Battery Co., Ltd., mercury lamp type, H120N), drying in an oven at 130 ° C. for 10 minutes, weight after drying Can be determined by measuring.

Further, the aqueous dispersion may be 0 to 500 parts by weight, preferably 0 to 200 parts by weight of the ethylene / vinyl acetate copolymer (E) with respect to 100 parts by weight of the ethylene / α-olefin copolymer (A). More preferably, it contains 5 to 200 parts by weight. When the content of the ethylene / vinyl acetate copolymer (E) is within the above range, it exhibits high adhesive strength for a wide range of materials and sufficient wettability for adherends with low surface polarity. It is possible to secure sufficient adhesive strength from the initial stage of adhesion. Furthermore, the stability of the aqueous dispersion is good, and an aqueous dispersion excellent in mechanical stability and storage stability can be obtained.

  The proportion of the photopolymerization initiator (C) contained in the aqueous dispersion is 100 parts by weight in total of the ethylene / α-olefin copolymer (A) and the modified ethylene / vinyl acetate copolymer (B). On the other hand, it is preferably 5-1000 parts by weight, more preferably 10-500 parts by weight. The ratio of the ethylenically unsaturated monomer (D) is preferably 50 with respect to 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (A) and the modified ethylene / vinyl acetate copolymer (B). -5000 parts by weight, more preferably 100-2000 parts by weight. The amount of the non-aqueous organic solvent (F) may be an amount sufficient to dissolve the ethylene / vinyl acetate copolymer (E) and its modified body (B). From the viewpoint of the handleability of the aqueous dispersion in the adhesion method described later, the total amount of the ethylene / α-olefin copolymer (A) and the modified ethylene / vinyl acetate copolymer (B) is 100 parts by weight. In the range of 150 to 1000 parts by weight.

  The aqueous dispersion according to the present invention comprises an ethylene / α-olefin copolymer (A), a modified ethylene / vinyl acetate copolymer (B), a photopolymerization initiator (C), an ethylenically unsaturated monomer (D As long as it contains an ethylene / vinyl acetate copolymer (E) and a non-aqueous organic solvent (F) as required, its form is not particularly limited. For example, an aqueous emulsion composition in which micelles composed of the above components (A) to (F) are dispersed in water can be mentioned. Further, although it is an aqueous emulsion composition, a part of the components (A) to (F), for example, a water-soluble component of the ethylenically unsaturated monomer (D) may be dissolved in the aqueous phase. Furthermore, the above-mentioned components (A) to (F) may be all dissolved in water without forming micelles.

  The aqueous dispersion according to the present invention is a component that improves adhesiveness such as chlorinated polyolefin, rosin, urethane emulsion, silane coupling agent, etc., depending on its purpose and application; antioxidant, ultraviolet absorber, colorant Further, various additives such as a brightening agent and a dye may be contained.

  Examples of the chlorinated polyolefin include those obtained by mixing a chlorinated polyolefin resin and a chlorinated polyolefin resin with other polymers. Examples of such chlorinated polyolefin resins include known polyolefin resins, for example, polyolefins such as polyethylene, polypropylene, ethylene-polypropylene-diene copolymer, polybutene, styrene-butadiene copolymer, and styrene-isoprene copolymer. Examples thereof include 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 within a range not impairing the effects of the present invention. The chlorine content of the chlorinated polyolefin is not particularly limited, but is preferably 15 to 40% by weight from the viewpoint of improving the adhesion with an adherend made of polyolefin.

  Among such chlorinated polyolefins, chlorinated polyolefin resins obtained by chlorinating polypropylene and / or polyethylene, acid anhydride-modified chlorinated polyolefin resins obtained by modifying the above-exemplified chlorinated polyolefin resins with maleic anhydride, etc. Is preferred.

  Examples of rosins include gum rosin, wood rosin and tall oil rosin, 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); Alternatively, alkyl esters, glycol esters, glycerin esters, or pentaerythritol esters of modified rosins; rosin-modified polyesters using rosin or modified rosin as part of the polyester acid may be mentioned. The rosin-modified polyester can be obtained by reacting rosin or a glycidyl ester of a modified rosin with a compound having a carboxyl group. These rosins may be used alone or in combination of two or more. The amount of rosins used is appropriately selected within a range not impairing the effects of the present invention.

  Examples of the silane coupling agent include epoxy silane, amino silane, and vinyl silane. Of these, epoxysilane is preferably used. Specific epoxy silanes include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyl. Examples include trimethoxysilane. 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 suitably selected in the range which does not impair the effect of this invention.

<Method for producing aqueous dispersion>
The aqueous dispersion according to the present invention can be produced, for example, by the following method.

First, ethylene / α-olefin copolymer (A), modified ethylene / vinyl acetate copolymer (B), photopolymerization initiator (C), ethylenically unsaturated monomer (D), and as required By blending the ethylene / vinyl acetate copolymer (E) in the non-aqueous organic solvent (F) and mixing with appropriate stirring, the above components (A) to (E) are added to the non-aqueous organic solvent (F). An oil droplet component is prepared by dissolving or dispersing. At this time, among the components (A) to (E), a water-soluble component may be added during emulsification described later. During the stirring and mixing, the mixed solution may be heated to 40 to 90 ° C. as necessary. Moreover, when a non-aqueous organic solvent (F) is unnecessary in an aqueous dispersion, the non-aqueous organic solvent (F) may be distilled off from the oil droplet component prepared here to reduce the amount.

  Next, an aqueous dispersion is obtained by emulsifying the oil droplet component in water using, for example, a surfactant. Examples of the emulsification method include a method in which a surfactant and water are added to the oil droplet component under strong agitation to cause phase inversion emulsification (forced emulsification). Moreover, you may add a water-soluble component in the case of this emulsification among the said components (A)-(E).

  When using the component and various additives which improve adhesiveness, you may add to the oil droplet component before emulsification, and may add to the aqueous dispersion after emulsification.

  The surfactant used in the present invention is not particularly limited, and a known surfactant can be used. For example, anionic surface activity such as fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfate salt, alkyl sulfosuccinate, polyoxyalkylene alkyl ether sulfate ester, polyoxyalkyl ether carboxylate, polyoxyalkylene alkyl ether phosphate Agents; Cationic surfactants such as alkylamine salts and quaternary ammonium salts; Nonionic surfactants such as polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers and sorbitan fatty acid esters.

  Of these, surfactants having an oxyethylene group are preferably used. Examples of the surfactant having an oxyethylene group include polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, other polyoxyethylene derivatives, and ethylenically unsaturated groups. And polyoxyethylene-based surfactants such as reactive surfactants to which are added.

  The surfactants may be used alone or in combination of two or more. The amount of the surfactant used is not particularly limited as long as the oil droplet component can be emulsified (forced emulsification). For example, it is preferably 3 to 50 parts by weight, more preferably 100 parts by weight of the oil droplet component. Is 5 to 30 parts by weight. When the amount of the surfactant used is less than the above lower limit, the dispersibility may be lowered, and when it exceeds the upper limit, the adhesiveness may be lowered.

  The amount of water to be added is not particularly limited as long as the oil droplet component can be emulsified (forced emulsification). For example, the amount of water is preferably 100 to 3000 parts by weight, more preferably 200 to 100 parts by weight of the oil droplet component. -2000 parts by weight.

  The aqueous dispersion thus obtained is desirably prepared so that its solid content is usually 1 to 50% by weight, preferably 3 to 40% by weight.

  When the aqueous dispersion is an aqueous emulsion composition, the aqueous emulsion composition comprises an ethylene / α-olefin copolymer (A), a modified ethylene / vinyl acetate copolymer (B), and a photopolymerization initiator (C). , An ethylenically unsaturated monomer (D), and an ethylene / vinyl acetate copolymer (E) and a non-aqueous organic solvent (F) as required are micelles dispersed in water. The size of the micelle is preferably 200 to 300 nm in diameter. In addition, although all the said components (A)-(F) may be included in the micelle, a part may be melt | dissolving in the water phase. Examples of the component dissolved in the aqueous phase include water-soluble ethylenically unsaturated monomers such as water-soluble acrylates.

<Adhesive composition>
The adhesive composition according to the present invention is a composition containing the above-mentioned aqueous dispersion and is used as an adhesive or a primer. This adhesive composition has high adhesive strength for a wide range of materials including low polarity materials. For example, various molded products such as plastic films, plastic sheets, plastic foams, fibers, synthetic leather, and metals can be favorably bonded. In particular, since the aqueous dispersion contained therein contains the components (A) to (F) described above, the adhesive composition has a surface polarity such as a molded body made of an ethylene / α-olefin copolymer. Ensuring sufficient wettability even on low adherends, allowing sufficient adhesive performance to be exhibited, and the stability of the aqueous dispersion is excellent, with excellent mechanical stability and storage stability Yes. Moreover, it is excellent in initial adhesive strength and water resistance, and can be used effectively in various applications. Furthermore, since this adhesive composition is water-based, there is little risk of ignition and a good sanitary environment can be ensured.

Such an adhesive composition can be applied to the surface of a molded body by a conventionally known method, and can be adhered to another substrate as an adhesive. Alternatively, the adhesive composition may be applied to the surface of the molded body to use it as a primer, and another conventionally known adhesive may be applied to adhere to another substrate. The adhesive composition may be used alone or in combination with a known adhesive or primer. Usually, after applying the adhesive composition, it is preferable to irradiate with 50 to 1000 mJ / cm ² of ultraviolet rays.

<Adhesion method>
The adhesion method according to the present invention comprises an ethylene / α-comprising UV-curable aqueous emulsion composition.
This is a method of adhering a molded body made of an ethylene / α-olefin copolymer using an olefin copolymer adhesive or a primer. The UV curable aqueous emulsion composition preferably contains the above-described aqueous dispersion. The molded body made of an ethylene / α-olefin copolymer is molded using an ethylene / α-olefin copolymer, and is, for example, a crosslinking agent that is molded as a foam by mixing a foaming agent. What was shape | molded as a crosslinked body using is mentioned. Specifically, a molded article described in JP 2000-344924 A can be mentioned.

  In the bonding method according to the present invention, the UV curable aqueous emulsion composition is applied to the surface of a molded body made of an ethylene / α-olefin copolymer, and the formed coating film is bonded to another material as an adhesive layer. To do. In addition, the UV curable aqueous emulsion composition is applied to the surface of a molded body made of an ethylene / α-olefin copolymer, the formed coating film is used as a primer layer, and a conventionally known adhesive is further applied thereon. Then, an adhesive layer can be formed and bonded to other materials.

  Conventionally known adhesives include, for example, urethane resin adhesives, acrylic resin adhesives, ethylene / vinyl acetate copolymer resin adhesives, modified ethylene / vinyl acetate copolymer resin adhesives, and polyolefin resin adhesives. Examples thereof include an adhesive, a modified polyolefin adhesive, a synthetic rubber adhesive, and a rosin resin adhesive. As these adhesives, both solvent-based and water-based adhesives can be used, but water-based adhesives are preferably used in view of the danger of ignition and environmental hygiene.

As a coating method of the UV curable aqueous emulsion composition, a known method such as brush coating, spray coating, or dipping can be used. The coating amount of the UV curable aqueous emulsion composition is preferably 0.1 to 100 g / m ² , more preferably 0.5 to 50 g / m ² . If the coating amount is less than the above lower limit, the effect of the UV curable aqueous emulsion may not be obtained and the adhesive strength may be insufficient. An coating amount exceeding the above upper limit is economically undesirable.

(Cleaning method)
In the bonding method according to the present invention, it is preferable to apply the UV curable aqueous emulsion composition after cleaning the surface of the adherend (molded body made of an ethylene / α-olefin copolymer) as necessary. By this washing operation, the adhesion-inhibiting component attached or generated at the time of molding can be removed. Examples of the adhesion inhibiting component include release agents, oils and fats, dusts, and the like, which can be cleaned using water, warm water, solvents, cleaning agents, and the like. Among these, it is preferable to use an aqueous cleaning agent because it has a high cleaning effect and does not deteriorate the danger of ignition or the working environment.

  The cleaning agent used in the present invention is a cleaning agent for removing an adhesion-inhibiting component used or generated at the time of molding a molded body made of an ethylene / α-olefin copolymer, and has a surfactant effect. A composition for a cleaning agent containing is dispersed in water as a medium.

  Specifically, the following formula (5)

Wherein R ³ is an aliphatic and / or aromatic hydrocarbon group having 4 to 35 carbon atoms, and m is 5 to 20
, Preferably 6-15)
And the following formula (6)
R ⁴ —SO ₃ —Na (6)
(Wherein R ⁴ is an aliphatic and / or aromatic hydrocarbon group having 4 to 25 carbon atoms)
The composition for cleaning agents containing the at least 1 sort (s) of surfactant selected from surfactant represented by these.

The surfactant represented by the above formula (5) is a nonionic surfactant. Examples of R ³ in the formula include lauryl group, cetyl group, stearyl group, oleyl group, myristyl group, phenyl group, styrenated phenyl group, and distyrenated phenyl group. Of these, the following formula (7)

(Wherein n is 0 to 4, preferably 0 to 2)
And a polymer thereof are preferred.

The surfactant represented by the above formula (6) is an anionic surfactant. As R ⁴ in the formula, for example, lauryl group, cetyl group, stearyl group, oleyl group, myristyl group, phenyl group, styrenated phenyl group, distyrenated phenyl group, polyoxyethylene lauryl ether group, linear or branched And dodecylbenzene group and alkylnaphthalene group.

  These surfactants can be used alone or in combination of two or more. 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 can be used in combination include nonionic surfactants such as polyoxyalkylene alkyl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters; alkyl sulfate salts, polyoxyethylene alkyl ethers Anionic surfactants such as sulfate ester salts, alkylbenzene sulfonates, fatty acid salts, naphthalene sulfonic acid formalin condensate salts; cationic surfactants such as alkylamine salts and quaternary ammonium salts; alkylbetaines, alkylamine oxides Zwitterionic surfactants such as

(builder)
The said composition for cleaning agents can contain a builder further as needed. The builder itself has no detergency or, if at all, does not have a significant detergency, but when it is incorporated into a detergent composition, it significantly improves its detergency, especially as a major component of the detergent. It improves the cleaning ability of a certain surfactant. Such a builder exhibits at least one of a multivalent metal cation scavenging action, a soil dispersing action, and an alkali buffering action. Examples of the builder having such an action include water-soluble inorganic compounds, water-insoluble inorganic compounds, and organic compounds. Examples of the water-soluble inorganic compound include phosphate, silicate, carbonate, sulfate and the like. Examples of water-insoluble inorganic compounds include aluminosilicates and crystalline silicates. Examples of the organic compound include carboxylate and organic carboxylate polymer. The counter ions in these builder salts are preferably alkali metal salts and amines, particularly sodium and / or potassium, monoethanolamine, and diethanolamine. A laundry detergent, dishwashing detergent, and the like, which are a mixture of these builder and surfactant, can be used in the present invention.

  The cleaning agent used in the present invention is obtained by dissolving or dispersing the cleaning composition in water. The concentration of the cleaning composition is preferably as low as possible, but is preferably 0.01% to 20%, more preferably 0.1% to 10%. When the concentration is 0.01% or less, the effect of the cleaning agent is not exhibited, and when the concentration is 20% or more, it is economically undesirable.

  The adherend (molded product) is washed by bringing the molded product made of ethylene-vinyl acetate copolymer into contact with this cleaning agent. The cleaning method may be batch or continuous. The contact time can be selected as appropriate. However, if the contact time is short, the effect of the cleaning agent is not exhibited. If the cleaning time is long, the production efficiency is lowered. Further, the cleaning effect can be improved by stirring the cleaning agent during the contact between the cleaning agent and the molded body. Further, it is also preferable to use ultrasonic waves or the like together.

  Thus, after making a cleaning agent and a molded object contact, the cleaning agent adhering to the surface of a molded object is removed. When the cleaning agent remains at a high concentration on the surface of the molded body, the adhesive strength of the UV curable aqueous emulsion is lowered. The cleaning agent can be removed by a known method, but it is preferably removed using water. Moreover, the efficiency of cleaning agent removal can be improved by using together the method of removing a cleaning agent by centrifugation.

<Example>
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. Further, “parts” and “%” used in the following Examples and Comparative Examples represent “parts by weight” and “% by weight” unless otherwise specified.

<Preparation example>
(1) Preparation of catalyst solution To 18.4 mg of triphenylcarbenium (tetrakispentafluorophenyl) borate was added 5 ml of toluene and dissolved to prepare a toluene solution (a) having a concentration of 0.004 mM / ml. Further, ⁵ ml of toluene was added to and dissolved in 1.8 mg of [dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride, and a toluene solution (b) having a concentration of 0.001 mM / ml. Was prepared.

Next, 4.24 ml of toluene for dilution is added to 0.38 ml of the toluene solution (a) and 0.38 ml of the toluene solution (b), and triphenylcarbenium (tetrakispentafluorophenyl) borate is reduced to 0 in terms of boron atoms. 5 ml of a catalyst solution having 0.002 mM / L and [dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride of 0.0005 mM / L in terms of titanium atoms was prepared.

(2) Preparation of ethylene / 1-butene copolymer 750 ml of heptane was introduced at 23 ° C. into a SUS autoclave with a stirring blade having a capacity of 1.5 liters sufficiently purged with nitrogen. To this autoclave, 10 g of 1-butene and 120 ml of hydrogen were introduced while rotating a stirring blade and cooling with ice. Next, the autoclave was heated to 100 ° C. and further pressurized with ethylene so that the total pressure was 6 KG. When the internal pressure of the autoclave reached 6KG, 1.0 ml of a 1.0 mM / ml hexane solution of triisobutylaluminum (TIBA) was injected with nitrogen.

Subsequently, 5 ml of the catalyst solution prepared in (1) above was pressed into the autoclave with nitrogen to initiate polymerization. Thereafter, the temperature of the autoclave was adjusted to an internal temperature of 100 ° C. for 5 minutes, and ethylene was directly supplied so that the pressure was 6 KG. Five minutes after the start of polymerization, 5 ml of methanol was introduced into the autoclave by a pump to stop the polymerization, and then the autoclave was depressurized to atmospheric pressure. 3 liters of methanol was poured into the reaction solution with stirring. The resulting polymer containing the solvent was dried at 130 ° C. for 13 hours at 600 torr to obtain 10 g of ethylene / butene copolymer. The obtained ethylene / 1-butene copolymer had a density (23 ° C.) of 885 kg / m ³ , MFR (190 ° C., 2.16 kg load) of 1.2 g / 10 min, Mw
/ Mn was 2.1, MFR (10) / MFR (2.16) was 10.0, B value was 1.0, and Tαβ / Tαα was 0.3.

(3) Preparation of detergent Nonionic surfactant (trade name: Emulgen A90 (manufactured by Kao Corporation)) 1000 parts by weight, sodium alkylbenzene sulfonate (trade name: Neoperex No. 6F powder (Kao Corporation) ))) 200 parts by weight, 4A zeolite 200 parts by weight, sodium silicate 100 parts by weight, sodium carbonate 100 parts by weight, sodium sulfate 400 parts by weight dispersed in 18000 parts by weight of water, A cleaning agent was obtained.

<Production example>
100 parts by weight of the ethylene / 1-butene copolymer obtained in Preparation Example (2), 0.5 parts by weight of dicumyl peroxide (DCP), triallyl isocyanurate (TAIC) (trade name: M-60 (TAIC (Content 60% by weight) (manufactured by Nippon Kasei Chemical Co., Ltd.)) 0.35 parts by weight (TAIC conversion), 7 parts by weight of azodicarbonamide and 10 parts by weight of talc were mixed at a roll surface temperature of 100 ° C. for 10 minutes. After kneading with a roll, it was formed into a sheet.

Next, the obtained sheet was filled into a press die, and 150 kg / cm ² , 160 ° C., 12
A foamed molded article (thickness: 24.5 mm, length: 150 mm, width: 200 mm) was obtained by applying pressure and heating under the condition of minutes.

(1) Preparation of aqueous dispersion (aqueous emulsion composition) Ethylene / α-olefin copolymer (density: 862 kg / m ³ , melt index:
1.2 g / 10 minutes, trade name: Toughmer DF610 (manufactured by Mitsui Chemicals)) 5 parts by weight, C—H
25 parts by weight of EVA (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 Chemical Company)), and 1-hydroxy- 5 parts by weight of cyclohexyl-phenyl ketone (photopolymerization initiator, trade name: Irgacure 184 (manufactured by Ciba Specialty Chemicals)), 5 parts by weight of 4-methylbenzophenone, 40 parts by weight of isobornyl methacrylate, turpentine oil (Product name: 40 parts by weight of gum turpentine N (manufactured by Yasuhara Chemical Co., Ltd.) was charged into a reaction vessel and dissolved by stirring up to 60 ° C. Then, tetrahydrofuran was removed under reduced pressure to remove oil droplets. Ingredients were prepared.

  While stirring this oil droplet component with a high-speed mixer (rotation speed: 2000 rpm), 50 parts by weight of polyoxyethylene alkyl ether sulfate ester surfactant (trade name: EMAL 27C (manufactured by Kao Corporation) and ions 810 parts by weight of exchange water and 40 parts by weight of 2-hydroxymethyl methacrylate were added and forced emulsification was performed to obtain an aqueous emulsion composition.

  The obtained emulsion was visually observed immediately after production (initial) and stored at 40 ° C. for 7 days, and evaluated according to the following criteria.

A: Uniformly dispersed and stable emulsion B: Phase separation or precipitation occurs (2) Adhesion of molded product The foamed molded product obtained in the above production example is immersed in the cleaning liquid obtained in Preparation Example (3), Stir for 5 minutes. Thereafter, the foamed molded product was taken out, sufficiently washed with tap water, and dried in an oven at 55 ° C. for 5 minutes to obtain a washed foamed molded product.

The aqueous emulsion composition prepared in the above (1) was applied to the washed foamed molded article at a rate of 10 g / m ² and dried in an oven at 55 ° C. for 2 minutes. Thereafter, UV rays of 150 mJ / cm ² were applied with a UV irradiator (made by Nippon Battery Co., Ltd., mercury lamp type: HI20N).
Irradiated once. After UV irradiation, a two-component urethane-based aqueous adhesive was further applied and dried.

  On the other hand, the adhesive surface of a rubber sheet (200 mm × 50 mm × 3 mm sheet-like molded product) was buffed, applied with a primer for rubber, dried, and then applied with a two-component urethane aqueous adhesive and dried.

The foamed molded body coated with the adhesive and the rubber sheet were bonded to each other on the surfaces coated with the adhesive, and pressed with a pressure of 0.4 MPa. After 5 minutes, 10 minutes, 30 minutes and 1 day after the completion of pressing, the adhesive strength was measured by a 180 degree peel test in accordance with JIS K6854. The adhesion performance after 5 minutes of adhesion was evaluated in the following three stages. However, actual measurement values are shown in parentheses. In addition, “sf” was written after the adhesive strength value on a molded body or rubber sheet in which material destruction was observed.

Adhesive performance A: Adhesive strength of 20 N / cm or more
B: Adhesive strength 10-20 N / cm
C: Adhesive strength less than 10 N / cm Moreover, generation | occurrence | production of the odor during the said operation | work was confirmed and it evaluated on the following reference | standard. The results are shown in Table 1.

Odor A: No strong odor
B: Strong odor generated

Ethylene / α-olefin copolymer (density: 862 kg / m ³ , melt index:
1.2 g / 10 min, trade name: Tuffmer DF610 (manufactured by Mitsui Chemicals) 5 parts by weight, ethylene / α-olefin copolymer (density: 885 kg / m ³ , melt index: 1.2 g / 10 min, A water-based emulsion composition was obtained in the same manner as in Example 1 except that 5 parts by weight of Tuffmer DF810 (manufactured by Mitsui Chemicals) was used.

  Using this aqueous emulsion composition, the washed foamed molded product and the rubber sheet were bonded in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 1.

Ethylene / α-olefin copolymer (density: 862 kg / m ³ , melt index:
1.2 g / 10 min, trade name: Tuffmer DF610 (manufactured by Mitsui Chemicals)) 5 parts by weight of ethylene / α-olefin copolymer (density: 870 kg / m ³ , melt index: 3
5 g / 10 min, 5 parts by weight of Tuffmer DF7350 (Mitsui Chemicals) are used, and instead of 40 parts by weight of turpentine oil, 20 parts by weight of turpentine oil (trade name: gum turpentine N (manufactured by Yasuhara Chemical)) and limonene (trade name) : An aqueous emulsion composition was obtained in the same manner as in Example 1 except that 20 parts by weight of D limonene (manufactured by Yasuhara Chemical Co., Ltd.) was used.

  Using this aqueous emulsion composition, the washed foamed molded product and the rubber sheet were bonded in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 1.

Ethylene / α-olefin copolymer (density: 862 kg / m ³ , melt index:
1.2 g / 10 min, trade name: Tuffmer DF7350 (manufactured by Mitsui Chemicals)) 5 parts by weight of ethylene / α-olefin copolymer (density: 870 kg / m ³ , melt index:
An aqueous emulsion composition was obtained in the same manner as in Example 3 except that 5 parts by weight of 1 g / 10 minutes, trade name: Engage 8100 (manufactured by DuPont Dow Elastomer Co., Ltd.) was used.

  Using this aqueous emulsion composition, the washed foamed molded product and the rubber sheet were bonded in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 1.

Ethylene / α-olefin copolymer (density: 862 kg / m ³ , melt index:
1.2 g / 10 min, trade name: Toughmer DF610 (manufactured by Mitsui Chemicals)) 5 parts by weight of ethylene / α-olefin copolymer (density: 902 kg / m ³ , melt index: 3
0 g / 10 min, trade name: Engage 8402 (manufactured by DuPont Dow Elastomer)) and ethylene / α-olefin copolymer (density: 870 kg / m ³ , melt index: 30 g / 10 min, trade name) : Engage 8407 (manufactured by DuPont Dow Elastomer Co., Ltd.) 2.5 parts by weight, instead of isoformyl methacrylate 40 parts by weight, isobornyl methacrylate 20 parts by weight and cyclohexyl methacrylate 20 parts by weight, turpentine oil 40 parts by weight Except for using 10 parts by weight of limonene (trade name: D limonene (manufactured by Yasuhara Chemical Co.)) and 30 parts by weight of aromatic hydrocarbon (trade name: Solvesso 150 (manufactured by ExxonMobil Chemical Co.)) An oil droplet component was prepared in the same manner as in Example 1.

  While stirring this oil droplet component with a high-speed mixer (rotation speed: 2000 rpm), 30 parts by weight of polyoxyethylene alkyl ether sulfate ester surfactant (trade name: EMAL 27C (Kao Corporation)) and polyoxyethylene 20 parts by weight of an alkyl ether surfactant (trade name: Emulgen A-90 (manufactured by Kao Corporation)), 810 parts by weight of ion-exchanged water and 40 parts by weight of 2-hydroxymethyl methacrylate are added to perform forced emulsification. An aqueous emulsion composition was obtained.

  Using this aqueous emulsion composition, the washed foamed molded product and the rubber sheet were bonded in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 1.

Ethylene / α-olefin copolymer (density: 862 kg / m ³ , melt index:
1.2 g / 10 min, trade name: Tuffmer DF610 (Mitsui Chemicals Co., Ltd.) 5 parts by weight, ethylene / α-olefin copolymer (density: 862 kg / m ³ , melt index: 1.2 g / 10 min) , Trade name: Toughmer DF610 (manufactured by Mitsui Chemicals)) and 2.5 parts by weight of ethylene / α-olefin copolymer (density: 870 kg / m ³ , melt index: 35 g / 1)
0 min, using 2.5 parts by weight of Tuffmer DF7350 (Mitsui Chemicals) and 20 parts by weight of limonene (trade name: D limonene (manufactured by Yasuhara Chemical)) instead of 40 parts by weight of turpentine oil and isoparaffin type A water-based emulsion composition was obtained in the same manner as in Example 1 except that 20 parts by weight of hydrocarbon oil (trade name: IP solvent (manufactured by Idemitsu Petrochemical Co., Ltd.)) was used.

  Using this aqueous emulsion composition, the washed foamed molded product and the rubber sheet were bonded in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 1.

Ethylene / α-olefin copolymer (density: 862 kg / m ³ , melt index:
1.2 g / 10 min, trade name: TAFMER DF610 (manufactured by Mitsui Chemicals) 2.5 parts by weight of ethylene / α-olefin copolymer (density: 885 kg / m ³ , melt index: 1.2 g / An aqueous emulsion composition was obtained in the same manner as in Example 6 except that 2.5 parts by weight of 10 min, trade name: TAFMER DF810 (manufactured by Mitsui Chemicals) was used.

  Using this aqueous emulsion composition, the washed foamed molded product and the rubber sheet were bonded in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 1.

Ethylene / α-olefin copolymer (density: 862 kg / m ³ , melt index:
1.2 g / 10 min, 1 part by weight of Tuffmer DF610 (manufactured by Mitsui Chemicals), ethylene / α-olefin copolymer (density: 885 kg / m ³ , melt index: 1.2 g / 10 min, product) Name: Tuffmer DF810 (manufactured by Mitsui Chemicals) 2 parts by weight, ethylene / α-olefin copolymer (density: 870 kg / m ³ , melt index: 35 g / 10 min, trade name: Toughmer DF7350 (manufactured by Mitsui Chemicals) )) 1 part by weight, 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 Takei Chemical Co., Ltd.)) 20 parts by weight and 1-hydroxy-cyclohexyl-phenyl ketone (photopolymerization initiator, trade name: Irgacure 184 (Ciba Speci 5 parts by weight, 5 parts by weight of 4-methylbenzophenone, 40 parts by weight of isobornyl methacrylate, 20 parts by weight of limonene (trade name: D limonene (manufactured by Yashara Chemicals)), and isoparaffin type 20 parts by weight of hydrocarbon oil (trade name: IP solvent (manufactured by Idemitsu Petrochemical Co., Ltd.)) and ethylene-vinyl acetate copolymer (vinyl acetate content: 33%, melt index: 1 g / 10 min, trade name: EVAFLEX) EV170 (manufactured by Mitsui DuPont Polychemical Co., Ltd.) and ethylene-vinyl acetate copolymer (vinyl acetate content: 19%, melt index: 2.5 g / 10 min, trade name: EVAFLEX EV460 (Mitsui DuPont Polychemical) 1 part by weight) was charged into the reaction vessel and then heated to 60 ° C. with stirring to dissolve. After, under reduced pressure, to prepare an oil droplet components to remove tetrahydrofuran.

  While stirring this oil droplet component with a high-speed mixer (rotation speed: 2000 rpm), 30 parts by weight of polyoxyethylene alkyl ether sulfate ester surfactant (trade name: EMAL 27C (manufactured by Kao Corporation) and poly Oxyethylene alkyl ether surfactant (trade name: Emulgen A-90 (manufactured by Kao Corporation)), 20 parts by weight, 810 parts by weight of ion-exchanged water, and 40 parts by weight of 2-hydroxymethyl methacrylate were added to forcibly emulsify. To obtain an aqueous emulsion composition.

  Using this aqueous emulsion composition, the washed foamed molded product and the rubber sheet were bonded in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 1.

Instead of the three types of ethylene / α-olefin copolymers used in Example 8, an ethylene / α-olefin copolymer (density: 870 kg / m ³ , melt index: 1 g / 10 min, trade name: Engage 8100 1 part by weight and ethylene / α-olefin copolymer (density: 902 kg / m ³ , melt index: 30 g / 1)
0 minutes, 1 part by weight of trade name: Engage 8402 (manufactured by DuPont Dow Elastomer) and ethylene / α-olefin copolymer (density: 870 kg / m ³⁾ , melt index: 30 g
/ 10 min, trade name: Engage 8407 (manufactured by DuPont Dow Elastomer Co., Ltd.) 1 part by weight, ethylene-vinyl acetate copolymer (vinyl acetate content: 33%, melt index: 1 g / 10 min, trade name: Evaflex EV170 (Mitsui DuPont Polychemical Co., Ltd.) was changed from 1 part by weight to 2 parts by weight. Instead of 20 parts by weight of limonene, 10 parts by weight of limonene (trade name: D limonene (manufactured by Yasuhara Chemical)) and aromatic carbonization An aqueous emulsion composition was obtained in the same manner as in Example 8, except that 10 parts by weight of hydrogen (trade name: Solvesso 150 (manufactured by ExxonMobil Chemical)) was used.

  Using this aqueous emulsion composition, the washed foamed molded product and the rubber sheet were bonded in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 1.

<Comparative Example 1>
The foamed molded product obtained in the above production example was washed in the same manner as in Example 1 to obtain a washed foamed molded product. A two-component urethane-based water-based adhesive was applied to the surface of the washed foamed molding and dried.

  The rubber sheet coated with an adhesive in the same manner as in Example 1 and the foamed molded article coated with the adhesive were bonded in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 2.

<Comparative Example 2>
An oil droplet component was prepared in the same manner as in Example 1 except that 890 parts by weight of toluene was used instead of 40 parts by weight of turpentine oil.

  The washed foamed molded article and the rubber sheet were bonded together in the same manner as in Example 1 except that this oil droplet component was used instead of the aqueous emulsion composition, and the adhesive strength was measured. The results are shown in Table 2.

  In addition, the odor of the solvent was strong during drying and UV irradiation, and the working environment deteriorated.

<Comparative Example 3>
Ethylene / α-olefin copolymer (density: 862 kg / m ³ , melt index:
1.2 g / 10 min, product name: TAFMER DF610 (manufactured by Mitsui Chemicals)), C-H
EVA (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 Chemical Co., Ltd.)) from 25 to 50 parts by weight A water-based emulsion composition was obtained in the same manner as in Example 2 except for the change.

  Using this aqueous emulsion composition, the washed foamed molded product and the rubber sheet were bonded in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 2.

<Comparative example 4>
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 Chemical Co., Ltd.))) α-olefin copolymer (density: 862 kg / m ³
, Melt index: 1.2 g / 10 min, trade name: Tafmer DF610 (manufactured by Mitsui Chemicals) was changed from 5 parts by weight to 10 parts by weight, and an aqueous emulsion composition was obtained in the same manner as in Example 1. It was.

  Using this aqueous emulsion composition, the washed foamed molded product and the rubber sheet were bonded in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 2.

<Comparative Example 5>
Ethylene / α-olefin copolymer (density: 862 kg / m ³ , melt index:
1.2 g / 10 min, trade name: Tuffmer DF610 (manufactured by Mitsui Chemicals)) instead of 5 parts by weight ethylene-vinyl acetate copolymer (vinyl acetate content: 33%, melt index: 1 g / 10 min, trade name : 3 parts by weight of Evaflex EV170 (manufactured by Mitsui DuPont Polychemical Co., Ltd.) and ethylene-vinyl acetate copolymer (vinyl acetate content: 19%, melt index: 2.
An aqueous emulsion composition was obtained in the same manner as in Example 1 except that 5 parts by weight and 2 parts by weight of Evaflex EV460 (manufactured by Mitsui DuPont Polychemical Co., Ltd.) were used.

  Using this aqueous emulsion composition, the washed foamed molded product and the rubber sheet were bonded in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 2.

<Comparative Example 6>
Except that the foamed molded product was used without washing, the foamed molded product and the rubber sheet were bonded in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 2.

  According to the present invention, a molded body having a low polarity such as a molded body made of an ethylene / α-olefin copolymer can be bonded with high adhesive strength, and plastic film, plastic sheet, plastic foam, fiber, synthetic leather, metal Various molded products such as can be satisfactorily bonded. For example, it can be suitably used for automobile interior parts such as interior / exterior materials, interior materials, door glass runs, cross-linked foams such as packaging materials and daily necessities, and particularly footwear parts such as shoe soles such as footwear and sports shoes.

Claims (13)

(A) ethylene / α-olefin copolymer, (B) modified ethylene / vinyl acetate copolymer which is a carboxyl-modified resin of partially saponified ethylene / vinyl acetate copolymer, (C) photopolymerization initiator And (D) the ethylenically unsaturated monomer includes (meth) acrylate represented by the following formula (4) and (meth) acrylate represented by the following formula (8) ,
Containing 5 to 500 parts by weight of the modified body (B) with respect to 100 parts by weight of the copolymer (A);
5 to 1000 parts by weight of photopolymerization initiator (C) with respect to a total of 100 parts by weight of the copolymer (A) and the modified body (B), and
The monomer (D) is included in an amount of 50 to 5000 parts by weight with respect to a total of 100 parts by weight of the copolymer (A) and the modified body (B).
An aqueous dispersion characterized by that.
CHR ¹ = CHCOOR ² (4)
(Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrocarbon group having 6 to 16 carbon atoms).
CHR ¹ = CHCOOR ² (8)
(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a group having a hydroxyl group and a hydrocarbon group having 2 to 5 carbon atoms). (E) an ethylene / vinyl acetate copolymer and (F) a non-aqueous organic solvent ,
2. The aqueous dispersion according to claim 1 , wherein 0 to 500 parts by weight of the copolymer (E) is contained with respect to 100 parts by weight of the copolymer (A) . The ethylene / α-olefin copolymer (A) is:
(I) a copolymer obtained from ethylene and an α-olefin having 3 to 20 carbon atoms,
(Ii) the density (23 ° C.) measured according to ASTM D1505 is in the range of 0.857 to 0.910 g / cm ³ ;
(Iii) The melt flow rate (MFR (2.16)) at 190 ° C. and a load of 2.16 kg, measured according to ASTM D1238, is in the range of 0.1 to 40 g / 10 minutes,
(Iv) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 1.5 to 3.0. The aqueous dispersion according to claim 1 or 2, wherein: The ethylene / α-olefin copolymer (A) is:
(V ) Melt flow rate (MFR (10)) at 190 ° C. and 10 kg load and melt flow rate (MFR (2.16)) at 190 ° C. and 2.16 kg load, measured according to ASTM D1238 The ratio (MFR (10) / MFR (2.16)) satisfies the relationship of the following formulas (1) and (2),
MFR (10) / MFR (2.16) ≧ 6.0 (1)
Mw / Mn + 5.0 ≦ MFR (10) / MFR (2.16) (2)
(In the formula, Mw represents a weight average molecular weight, and Mn represents a number average molecular weight.)
(V i ) The intensity ratio of Tαβ to Tαα in the ¹³ C-NMR spectrum (Tαβ / Tαα) is 0.5 or less,
(Vi i ) The following formula (3)
B = [POE] / (2 [PE] [PO]) (3)
(Wherein [PE] is the molar fraction of structural units derived from ethylene in the copolymer, [PO] is the molar fraction of structural units derived from α-olefin in the copolymer, [POE] Is a ratio of the number of ethylene / α-olefin chains to the total number of dyad chains in the copolymer), and the B value is in the range of 0.9 to 1.5. Item 4. The aqueous dispersion according to any one of Items 1 to 3. The aqueous dispersion according to any one of claims 1 to 4, wherein the ethylene / α-olefin copolymer (A) is an ethylene / 1-butene copolymer. The aqueous dispersion according to claim 2 , wherein the non-aqueous organic solvent (F) is an organic solvent having a boiling point of 100 ° C or higher. 10 to 300 parts by weight of the modified ethylene / vinyl acetate copolymer (B) and 0 to 0 parts of the ethylene / vinyl acetate copolymer (E) with respect to 100 parts by weight of the ethylene / α-olefin copolymer (A). The aqueous dispersion according to claim 2 , which comprises ˜200 parts by weight. At least (A) ethylene / α-olefin copolymer, (B) modified ethylene / vinyl acetate copolymer that is a carboxyl-modified resin of partially saponified ethylene / vinyl acetate copolymer, (C) photopolymerization As the initiator and (D) the ethylenically unsaturated monomer , the (meth) acrylate represented by the following formula (4) and the (meth) acrylate represented by the following formula (8) are used as the copolymer (A) 100. The photopolymerization initiator (C) is added to 5 to 500 parts by weight of the modified body (B) with respect to parts by weight, and to 100 parts by weight of the total of the copolymer (A) and the modified body (B). 5 to 1000 parts by weight, and 50 to 5000 parts by weight of the monomer (D) with respect to a total of 100 parts by weight of the copolymer (A) and the modified body (B). (F) In a non-aqueous organic solvent Prepare oil droplet components by dissolving or dispersing ,
A method for producing an aqueous dispersion, wherein the oil droplet component is dispersed in water using a surfactant (G).
CHR ¹ = CHCOOR ² (4)
(Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrocarbon group having 6 to 16 carbon atoms).
CHR ¹ = CHCOOR ² (8)
(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a group having a hydroxyl group and a hydrocarbon group having 2 to 5 carbon atoms). An adhesive composition comprising the aqueous dispersion according to any one of claims 1 to 7 . From an ethylene / α-olefin copolymer using a primer for an ethylene / α-olefin copolymer comprising a UV curable aqueous emulsion composition containing the aqueous dispersion according to claim 1. A bonding method characterized in that a molded body is bonded. Following formula (5)

(Wherein R ³ is an aliphatic or aromatic hydrocarbon group , R ^{3 has} a carbon number in the range of 4 to 35, and m is 5 to 20)
And the following formula (6)
R ⁴ —SO ₃ —Na (6)
(Wherein, R ⁴ is an aliphatic or aromatic hydrocarbon radical der is, and the carbon number of R ⁴ is area by near 4 to 25)
After cleaning the molded body made of an ethylene / α-olefin copolymer using a cleaning composition containing at least one surfactant selected from the surfactants represented by formula (1), the UV curable aqueous system The adhesion method according to claim 10 , wherein an emulsion composition is applied to adhere a molded body made of an ethylene / α-olefin copolymer. R ³ in the formula (5) is the following formula (7)

(Wherein, n is 0-3)
It is a styrenated phenyl group represented by these. The adhesion method of Claim 11 characterized by the above-mentioned. The bonding method according to claim 11 or 12 , wherein the cleaning composition further contains a builder.