Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/04—Homopolymers or copolymers of ethene
  • C09J123/08—Copolymers of ethene
  • C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
  • C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
  • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
  • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
  • C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
  • C08L23/0853—Ethylene vinyl acetate copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
  • C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof

Definitions

• Aqueous dispersion, method for producing the same, and method for bonding molded article comprising ethylene' ⁇ -olefin copolymer
• the present invention relates to an aqueous dispersion, an adhesive composition containing the same, such as an adhesive and a primer, and a method for adhering a molded article made of an ethylene / ⁇ -olefin copolymer using the same.
• the technology of using a crosslinked foam to obtain a product having a low specific gravity, that is, light weight, and being flexible and having high mechanical strength, is used for building interior and exterior materials, interior materials, automobile parts such as door glass run, packaging materials, It is used in a wide range of fields such as daily necessities. Since foaming resin alone for light weight dangling causes a decrease in mechanical strength, this crosslinked foam suppresses a decrease in mechanical strength by bonding molecular chains by a crosslinking reaction of the resin. In addition, lightweight foaming is achieved by foaming.
• Footwear and shoe soles (mainly mittsoles) of footwear components such as sports shoes are lightweight, have low mechanical strength and rebound resilience that can suppress deformation due to long-term use and can withstand severe use conditions.
• a material having the following properties and a resin crosslinked foam is also used in such a field.
• crosslinked foams formed using an ethylene-vinyl acetate copolymer composition are widely used for shoe soles, but these crosslinked foams have a high specific gravity and a compression set.
• the shoe sole is compressed by heavy and long-term use, and the mechanical strength such as rebound resilience is lost.
• Patent Document 1 discloses an ethylene having an Asker C hardness in the range of 20 to 80, a low specific gravity, a small permanent compression set (CS), and excellent tensile strength properties, tear strength properties and rebound resilience.
• CS small permanent compression set
• organic solvent-based adhesives have been widely used as adhesive compositions for bonding various molded products such as plastic films, plastic sheets, plastic foams, fibers, synthetic leather, and metals. Have been.
• Organic solvent-based adhesives exhibit high adhesiveness even to relatively hard molded products, and are used for various applications.
• water-based adhesives have recently been developed in place of organic solvent-based adhesives because of the danger of ignition and not very favorable in terms of environmental hygiene.
• water-based primers have been required.
• Patent Document 2 discloses an aqueous emulsion composition containing a carboxyl-modified resin of a saponified ethylene'butyl acetate copolymer and a surfactant. More specifically, a carboxyl-modified resin of a saponified ethylene-vinyl acetate copolymer is emulsified in water with a surfactant, and an adhesive containing an ethylenically unsaturated monomer or a photopolymerization initiator, if necessary. Compositions are described. It is described that this adhesive composition has a high adhesive strength to a wide range of materials and can be satisfactorily adhered to a molded product or the like.
• Patent Document 3 discloses an aqueous emulsion composition in which micelles containing an ethylene'butyl acetate copolymer or a modified resin thereof, a photopolymerization initiator, and an ethylenically unsaturated monomer are dispersed in water. Is disclosed. This emulsion composition has a low surface polarity. ⁇ It can exhibit sufficient adhesion to adherends, and the emulsion stability is good, and mechanical stability and storage stability can be improved. It also discloses what it can do.
• the adhesive composition described in Patent Literature 2 and the aqueous emulsion composition described in Patent Literature 3 have high copolymer properties such as ethylene / butyl acetate copolymer.
• the molded body that has high adhesive strength exhibits high adhesive strength, for example, as described in Patent Document 1. It was difficult to develop sufficient adhesiveness for low-polarity molded products such as ethylene-a-one-year-old olefin copolymer. For this reason, an organic solvent-based adhesive is still used in the molded article of the ethylene-one-year-old olefin copolymer, and is composed of a low-polarity copolymer such as an ethylene-one-year-old olefin copolymer. There has been a demand for the development of water-based adhesives and water-based primers that exhibit high bonding strength and high strength for molded articles.
• Patent Document 1 Japanese Patent Application Laid-Open No. 2000-344924
• Patent Document 2 European Patent Publication EP1106628A1
• Patent Document 3 JP 2003-113207 A
• the present invention is intended to solve the problems associated with the prior art as described above, and is intended to reduce the strength of various molded articles, particularly copolymers having a low polarity, such as ethylene' ⁇ -olefin copolymer.
• An aqueous dispersion having high adhesive strength to the molded body, capable of exhibiting sufficient adhesive strength from the initial stage of bonding, and further having excellent storage stability and mechanical stability, and containing this aqueous dispersion It is intended to provide an adhesive composition. It is another object of the present invention to provide a method for bonding a molded article comprising an ethylene-a-olefin copolymer with high adhesive strength.
• the present inventors have conducted intensive studies to solve the above-mentioned problems, and found that an aqueous dispersion containing an ethylene' ⁇ -lean olefin copolymer and a modified ethylene'vinyl acetate copolymer is an ethylene-based dispersion.
• the aqueous dispersion according to the present invention comprises (A) an ethylene' ⁇ -olefin copolymer,
• This aqueous dispersion preferably further contains ( ⁇ ) an ethylene 'butyl acetate copolymer and (F) a non-aqueous organic solvent.
• melt flow rate (MFR (2.16)) at 190 ° C and 2.16 kg load measured in accordance with ASTM D1238 is in the range of 0.1 to 40 gZlO,
• the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (MwZMn) measured by gel permeation chromatography (GPC) is in the range of 1.5-3.0. Is preferred.
• the ethylene ' ⁇ -olefin copolymer (A) is
• Mw indicates a weight average molecular weight
• Mn indicates a number average molecular weight
• the ethylene ' ⁇ -olefin copolymer (A) is an ethylene' 1-butene copolymer.
• the modified ethylene-vinyl acetate copolymer ( ⁇ ⁇ ⁇ ⁇ ) is preferably a carboxyl-modified resin of a partially kneaded ethylene-vinyl acetate copolymer.
• the ethylenically unsaturated monomer (D) is preferably (meth) acrylate.
• the (meth) acrylate is represented by the following formula (4)
• R 1 is a hydrogen atom or a methyl group
• R 2 is a hydrocarbon group having 6 to 16 carbon atoms.
• the non-aqueous organic solvent (F) is preferably an organic solvent having a boiling point of 100 ° C or higher.
• the aqueous dispersion is prepared by adding 10 to 300 parts by weight of the modified ethylene-vinyl acetate copolymer ( ⁇ ) to 100 parts by weight of ethylene ' ⁇ -olefin copolymer (A), Bi
• the copolymer preferably contains 0 to 200 parts by weight of the copolymer ( ⁇ ).
• the method for producing an aqueous dispersion according to the present invention comprises:
• 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 aqueous dispersion described above.
• the bonding method according to the present invention includes bonding a molded body made of an ethylene ⁇ -olefin copolymer using a primer for an ethylene ⁇ -olefin copolymer made of a UV-curable aqueous emulsion composition. As a feature.
• the UV-curable aqueous emulsion composition preferably contains the aqueous dispersion.
• the bonding method according to the present invention comprises:
• a composition for a detergent comprising at least one surfactant selected from surfactants represented by the following formula: It is preferable to wash the molded body having a high ethylene- ⁇ -olefin copolymer strength by using the above, and then apply the above-mentioned UV-curable water-based emulsion composition to adhere the molded body having a strong ethylene- ⁇ -olefin copolymer strength. Better ,.
• R 3 in the above formula (5) is represented by the following formula (7)
• composition for a detergent 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 to a wide range of materials.
• a high adhesive strength can be obtained for a molded article having a strong ethylene ' ⁇ -olefin copolymer.
• this adhesive composition can ensure sufficient wettability even for an adherend, particularly an adherend having a low surface polarity, and exhibit sufficient adhesive performance. Since this aqueous dispersion is aqueous, a good sanitary environment with less danger of ignition can be obtained. Further, when the aqueous dispersion is an aqueous emulsion composition, the stability of the emulsion is good, and the mechanical stability and the storage stability can be improved.
• the aqueous dispersion according to the present invention comprises an ethylene ' ⁇ -olefin copolymer ( ⁇ ), a modified ethylene' butyl acetate copolymer ( ⁇ ), a photopolymerization initiator (C) and an ethylenically unsaturated monomer.
• This is an aqueous dispersion containing (D), and further contains an ethylene-vinyl acetate copolymer (E) and a non-aqueous organic solvent (F) as necessary.
• the ethylene ' ⁇ -olefin copolymer (A) used in the present invention is an amorphous or low-crystalline random or block copolymer obtained from ethylene and an a-lefin olefin having 3 to 20 carbon atoms. Coalescence is preferred.
• Such an ethylene- ⁇ -olefin copolymer (A) includes (i) density (23.C) force S usually 0.857-0.910 g / cm 3 , and preferably 0.860-0. was 905g / cm 3, (ii) a melt flow rate (MFR ⁇ 190 ° C, load 2. 16 kg) is normally 0. 1-40 g Zlo fraction, soft ethylene 'alpha preferably 0.
• the density is a value measured at 23 ° C. according to ASTM D1505, and the melt flow rate (MFR) is 190 according to ASTM D1238. C, measured under a load of 2.16 kg.
• the ethylene- ⁇ -olefin copolymer (A) is prepared by (iii) the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC).
• Mw / Mn force S is preferably in the range of 1.5-3.0, more preferably 1.7-2.5.
• Mw and Mn were determined by gel permeation chromatography (GPC) using a column: TSK GNHHT, a column temperature: 140 ° C., a mobile phase: orthodichlorobenzene, a flow rate: 1. OmL Zmin, and a sample concentration: 0.
• the adhesive composition containing the aqueous dispersion containing the ethylene ' ⁇ -olefin copolymer ( ⁇ ) in which MwZMn is in the above range has high adhesiveness to a molded article made of the ethylene' olefin copolymer. Show. Such an ethylene ' ⁇ -olefin copolymer ( ⁇ ) usually shows properties as an elastomer.
• the ethylene / ⁇ -branched olefin copolymer ( ⁇ ) has a melt flow rate (MFR (IO)) at 190 ° C and a load of 10 kg measured according to ASTM D1238.
• MFR (IO) melt flow rate
• MFR (2.16) melt flow rate
• MFR (2.16) melt flow rate
• Mw indicates a weight average molecular weight
• Mn indicates a number average molecular weight
• Narubutsu containing aqueous dispersion containing old Refuin copolymer (A) is an ethylene alpha -.
• Old Refin copolymer Shows high adhesion to molded products.
• the ethylene' ⁇ -branched olefin copolymer ( ⁇ ) preferably has an intensity ratio (To; ⁇ / ⁇ a) of Taj8 to ⁇ a in the (v) 13 C-NMR ⁇ vector of 0.5. Or less, more preferably 0.4 or less.
• 13 ⁇ and ⁇ in the 13 C-NMR spectrum are a-olefin forces having 3 or more carbon atoms, and are the peak intensities of CH in the induced unit.
• the To; ⁇ / ⁇ a intensity ratio can be determined by the following method.
• the measured 13 C-NMR ⁇ vector was analyzed by Lindemann Adams (Analysis Chemistry 43, pl245 (1971)), JCRandall (Review
• the ethylene'a one-year-old olefin copolymer (A) is represented by the following formula (3):
• the B value, from which the force is calculated, is preferably in the range of 0.9-1.5.
• [PE], [PO], and [POE] can be determined from the 13 C-NMR spectrum of the ethylene' ⁇ -olefin copolymer (A).
• the ⁇ value is an index indicating the distribution state of ethylene and ⁇ -olefin having 3 to 10 carbon atoms in the ethylene ′ ⁇ -olefin copolymer.
• JC Randall Mocromolecules, 15, 353 (1982 )
• J. Ray Mocromolecules, 10, 773 (1977)
• the higher the B value the shorter the block chain of ethylene or ⁇ -leufin, indicating that the distribution of ethylene and ⁇ -leufin is more uniform and the composition distribution of the copolymer rubber is narrower.
• the ⁇ value becomes smaller than 1.0, the composition distribution of the ethylene • ⁇ -olefin copolymer becomes broader, and there is a problem that handling property is deteriorated.
• the ethylene' ⁇ -olefin olefin copolymer ( ⁇ ) preferably has a crystallinity of usually 40% or less, preferably 30% or less, as measured by X-ray diffraction.
• Such an ethylene- ⁇ -olefin copolymer ( ⁇ ) is prepared by using ethylene and an ⁇ -olefin having 3 to 20 carbon atoms using a vanadium-based catalyst, a titanium-based catalyst, or a meta-aqueous catalyst. And a copolymer known in the art.
• ⁇ -olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1 otaten, 1 nonene, 1-decene, 1-decene, and 1-decene , 1-hexadecene, 1-octadecene, 1 nonadecene, 1-eicosene, 4-methyl-1-pentene, and the like.
• ⁇ -olefins having 3 to 10 carbon atoms are preferred, and propylene, 1-butene, 1-hexene and 1-otaten are particularly preferred. Also this These ⁇ -olefins can be used alone or in combination of two or more.
• Ethylene ' ⁇ -leufine copolymer ( ⁇ ) is composed of 75-95 mol% of units derived from ethylene, and 5 units derived from ⁇ -leufine having 3-20 carbon atoms. - it is desirable to contain an amount of 25 mol 0/0.
• the ethylene' ⁇ -olefin copolymer ( ⁇ ) may contain, in addition to these units, units from which other polymerizable monomer powers can be derived as long as the object of the present invention is not impaired. .
• Specific ethylene-a-one-year-old olefin copolymer (A) is an ethylene-propylene copolymer, an ethylene / 1-butene copolymer, an ethylene-propylene / 1-butene copolymer, an ethylene-propylene-propylene copolymer.
• Examples include a tylidenenorbornene copolymer, an ethylene / 1-hexene copolymer, and an ethylene / 1-otene copolymer.
• ethylene-propylene copolymer ethylene / 1-butene copolymer, ethylene-11-hexene copolymer, ethylene / 1-octene copolymer and the like are preferably used, and especially ethylene / 1-butene copolymer. Coalescence is preferably used.
• These copolymers are preferably random or block copolymers, particularly preferably random copolymers.
• the modified ethylene-vinyl acetate copolymer ( ⁇ ) used in the present invention is not particularly limited, but is preferably a carboxyl modified ethylene-butyl acetate copolymer or an ethylene-vinyl acetate copolymer.
• An isocyanate-modified product and an epoxy modified product of an ethylene'vinyl acetate copolymer are exemplified.
• a carboxyl-modified resin hereinafter abbreviated as “C HEVA” of a partially modified ethylene-butyl acetate copolymer is preferred.
• C HEVA can be manufactured, for example, based on the description in Japanese Patent Publication No. 5-26802.
• 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 and partially kneaded (approximately 10-90%) to obtain a partially saponified ethylene-butyl acetate copolymer (hereinafter referred to as “HEVA”). Abbreviated as "). Next, the HEVA is modified with an acid such as an unsaturated carboxylic acid or an acid anhydride.
• EVA ethylene-vinyl acetate copolymer
• an alkali alcoholate is added as a catalyst in the presence of a specific amount of water and partially kneaded (approximately 10-90%) to obtain a partially saponified ethylene-butyl acetate copolymer (hereinafter referred to as “HEVA”).
• HEVA partially saponified
• the modified product (B) of the ethylene / butyl acetate copolymer preferably has a hydroxyl value of 0 to 250 mg KO HZg, and more preferably has an acid value of 2 to 150 mg KOHZg.
• the adhesive performance may be deteriorated.
• Examples of the photopolymerization initiator (C) used in the present invention include polymerization initiators such as an acylphosphinoxide type, an acetophenone type, a benzoin ether type, a benzophenone type and a thioxanthone type.
• acylphosphinoxide-based polymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphinoxide (for example, Lucylin TPO manufactured by BASF), and bis (2,6-dimethoxybenzoyl).
• BAPO 2,4,6-trimethylbenzoyldiphenylphosphinoxide
• BAPO 2,4,6-trimethylbenzoyldiphenylphosphinoxide
• acetophenone-based polymerization initiator examples include diethoxyacetophenone-1-hydroxy-2-methyl-2-phenylpropane 1one (for example, Darocure-1173 manufactured by Chinoku Specialty Chemicals), benzyl Dimethyl ketal (for example, Irgacure-1 651, manufactured by Chinoku Specialty Chemicals, Lucilin BDK, manufactured by BASF), 1-hydroxy-cyclohexylphenol ketone (for example, Irgacure, manufactured by Chinoku Specialty Chemicals) 1-184), 2-Methyl-2 morpholino (4-thiomethylphenol) propane 1 on (for example, Chiroku's Specialty Chemicals, Inc., irgacure 1907), 2-benzylyl 2-dimethylmethyl 1- (4- Morpholinophyl) butanone (for example, Chiroku 'Specialty' Chemical Products Co., Ltd.) 69), and oligomers of 2-hydroxy-2-methyl-1- [4-
• benzoin ether-based polymerization initiator examples include benzoin, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
• benzophenone-based polymerization initiator examples include benzophenone, methyl O-benzoylbenzoate, 4-methylbenzophenone, 4-phenylbenzophenone, 4-benzoylphenyl, 4-methylbenzene.
• Examples of the thioxanthone-based polymerization initiator include 2 or 4 isopropyl thioxanthone, 2,4 getyl thioxanthone, and 2,4-dichloro thioxanthone.
• methylphenyldalioxy ester (Vicure-1 55 manufactured by A KZO) and 3,6-bis (2 morpholinoisobutyl) -9-butylcarbazole (Asahi Denki Co., Ltd.) A-Cure3) manufactured by Danisha, titanoseni dani, and the like can also be used.
• photopolymerization initiators can be used alone or in combination of two or more.
• Commercial products such as Koku Specialty Chemicals).
• photopolymerization accelerators such as dialkylaminobenzoic acid or a derivative thereof (4-dimethylamino) Benzoic acid, 4-dimethylaminobenzoic acid ester, etc.
• phosphine-based photopolymerization accelerators arylphosphine such as triphenylphosphine, phosphine conjugated compounds such as trialkylphosphine, etc.
• Examples of the ethylenically unsaturated monomer (D) used in the present invention include a monofunctional monomer, a difunctional monomer, and a polyfunctional monomer.
• Examples of the monofunctional monomer include:
• Heterocyclic ethylenically unsaturated compounds for example, N-butyl nitrogen-containing heterocyclic compounds such as N-methylpyrrolidone, N-vinylpyridin, and N-vinylcaprolatatam; morpholine (meth) acrylate, tetrahydrofurfuryl (meth) acrylate) Heterocyclic (meta) acrylates such as
• N-bulformamide, N-bulacetoamide Dialkylaminoethyl (meth) acrylates (eg, dimethylaminoethyl (meth) acrylate, getylaminoethyl (meth) acrylate);
• alkoxy (poly) alkylene glycol (meth) atalylates eg, methoxyethylene (meth) atalylate, methoxypolyethylene (meth) atalylate, butoxypolyethylene (meth) acrylate
• alkoxy (poly) alkylene glycol (meth) atalylates eg, methoxyethylene (meth) atalylate, methoxypolyethylene (meth) atalylate, butoxypolyethylene (meth) acrylate
• Alkylphenoxymethyl (meth) atalylates eg, norfenoxhetyl (meth) atalylate
• Phenoxy (poly) alkylene glycol (meth) atalylates eg, phenoxyshetyl (meth) atalylate, phenoxypolyethylene glycol (meth) atalylate
• Alkyl (meth) acrylates eg, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isootatyl (meth) acrylate, isodecyl (meth) acrylate, lauri
• Cycloalkyl (meth) acrylate eg, cyclohexyl (meth) acrylate
• aralkyl (meth) acrylate eg, benzyl (meth) acrylate
• (Meth) acrylates having a bridged cyclic hydrocarbon group for example, isovol (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopente-loxyalkyl (meth) acrylate, tricyclode force-loxyshetyl (Meta) atalylate, isovolmilo quichetyl (meth) atalylate);
• Hydroxyl-containing (meth) acrylates for example, 2-hydroxyethyl (meth) acrylate
• Gen-containing (meth) acrylates eg, trifluoroethyl (meta) acrylate, 2, 2, 3, 3-tetrafluoropropyl (meth) acrylate, perfluorooctylethyl ( Meta) atelylate.
• bifunctional monomer (bifunctional polymerizable diluent)
• bifunctional polymerizable diluent examples include:
• (Polyoxy) alkylene glycol di (meth) acrylates eg, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene Glycolic di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexamethylene glycol di (meth) atalylate, neopentyl glycol di (meth) atalylate, pentane diol di ( Meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) atalylate, pentaerythritol di (meth) atalylate, bisphenol ⁇ ⁇ ⁇ ⁇ alkylene oxides (ethylene oxide, propylene oxide) Di (meth) atalylate of an oxide
• Di (meth) acrylates having a bridged cyclic hydrocarbon group for example, di (meth) atalylate of tricyclodecane dimethylol, dicyclopentadiene (meth) atalylate); (Meth) acrylic acid adducts (eg, (meth) acrylic acid adducts of 2,2-bis (glycidyloxyphenyl) propane).
• Examples of the polyfunctional monomer include trimethylolpropane tri (meth) atalylate, trimethylol propane trioxy tri (meth) acrylate, pentaerythritol tri (meth) acrylate Pentaerythritol tetra (meth) atalylate, diantaerythritol hexa (meth) atalylate, tetramethylol methane tri (meth) atalylate, tetramethylol methane tetra (meth) atalylate, tris (atalyloyloxy) isocyanu , Tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (hydr Roxypropyl) isocyanurate tri (meth) atalylate, triallyl trimellitic acid, and triaryl isocyanurate.
• (meth) acrylate is preferably used.
• R 1 is a hydrogen atom or a methyl group
• R 2 is a hydrocarbon group having 6 to 16 carbon atoms.
• (Meta) acrylate 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.
• Such (meth) acrylates include, for example, 2-ethylhexyl (meth) acrylate, isootatyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomiristyl (meta) ) Athalylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isovol (meth) acrylate, and dicyclopentagen (meth) acrylate.
• 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.
• Examples of (meth) acrylates represented by the above formula (8) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. ) Phthalate, 4-hydroxybutyl (meth) acrylate, and pentaerythritol tri (meth) acrylate.
• the solubility of both the ethylene-vinyl acetate copolymer and its modified product and the photopolymerization initiator can be improved in the preparation of the oil droplet component described later.
• the dispersibility and the adhesiveness can be improved.
• other ethylenically unsaturated Adhesiveness can be adjusted, for example, improved, by using a suitable combination of monomers.
• the (meth) acrylate which has high hydrophilicity may be added later to the aqueous dispersion.
• an ethylene'vinyl acetate copolymer (E) can be used, if necessary.
• the ethylene'butyl acetate copolymer (E) used in the present invention can be produced, for example, by a known method such as a high-pressure method and an emulsification method.
• the ratio of the butyl 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 butyl acetate.
• the ratio of vinyl acetate is less than the above lower limit, the adhesiveness to a wide range of molded articles may be reduced, and if it exceeds the above upper limit, the adhesiveness to a molded article having ethylene-vinyl acetate copolymer power may be reduced.
• the melt index of the ethylene / butyl acetate copolymer (E) (at 190 ° C. under a load of 2160 g) is preferably 0.1 to 500 gZlO, more preferably 1 to 300 gZlO.
• the melt index of the ethylene / butyl acetate copolymer (E) is measured at 190 ° C. under a load of 2160 g according to ASTM D-1238.
• the ethylene'butyl acetate copolymer (E) can be used alone or in combination of two or more.
• the ethylene-vinyl acetate copolymer (E) is difficult to dissolve as an oil droplet component in the aqueous dispersion, but the ethylene-vinyl acetate copolymer (E) has a high proportion of vinyl acetate.
• the stability of the aqueous dispersion is improved.
• the non-aqueous organic solvent (F) used in the present invention has a negligibly low solubility in water.
• 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 room temperature.
• non-aqueous organic solvent examples include hydrocarbons such as aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, and halogenated hydrocarbons; alcohols; phenols; Monoters; ketones; esters and the like.
• Examples of the aliphatic hydrocarbon include hexane, heptane, octane, isooctane, nonane, and deca. And dodecane.
• aromatic hydrocarbon examples include benzene, toluene, xylene, ethylbenzene, tamene, mesitylene, cyclohexibenzene, getylbenzene, dodecylbenzene, styrene and the like.
• Examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, p-menthane, bicyclohexyl, cyclohexene, ⁇ -binene, dipentene, d— Limonene, decalin and the like.
• halogenated hydrocarbon examples include methyl chloride, dichloromethane, chloroform, and carbon tetrachloride.
• hydrocarbons those naturally produced and purified, for example, benzine, naphtha, rig mouth, gasoline, kerosene, solvent naphtha, camphor oil, turpentine oil, pine Oil and the like.
• alcohols include heptanol, octanol, 2-ethyl-1-oxanol, nonanol, decanol, dodecanol, terbineol, and the like.
• phenols examples include phenol, cresol, xylenol and the like.
• ethers include getyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, anisol, butylphenyl ether, methoxytoluene, benzylethyl ether, diphenyl ether, and furan.
• examples include tetrahydrofuran, tetrahydran pyran, and cineol.
• ketones include methyl ethyl ketone, 2-pentanone, 2-xanone, methyl isobutyl ketone, heptanone, diisobutyl ketone, isophorone, cyclohexanone, methylcyclohexanone, acetophenonone, camphor, camphor oil and the like.
• ketones include methyl ethyl ketone, 2-pentanone, 2-xanone, methyl isobutyl ketone, heptanone, diisobutyl ketone, isophorone, cyclohexanone, methylcyclohexanone, acetophenonone, camphor, camphor oil and the like.
• esters include methyl formate, methyl formate, butyl formate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, isopentyl acetate, ethyl ethyl propionate, isopentyl propionate, and the like.
• non-aqueous organic solvents can be used alone or in combination of two or more.
• a non-aqueous organic solvent having a boiling point of 100 ° C. or higher is preferably used from the viewpoint of handleability.
• Sarapiko ethylene-vinyl acetate copolymer and An alicyclic hydrocarbon is preferably used because the solubility of the modified ethylene-butyl acetate copolymer is high.
• a modified ethylene-butyl acetate copolymer ( ⁇ ⁇ ⁇ ) is 5-500 parts by weight, preferably 1 part by weight, based on 100 parts by weight of the ethylene ' ⁇ -olefin copolymer (A). Contains 0-300 parts by weight. If the content of the modified ethylene-butyl acetate copolymer ( ⁇ ) is within the above range, it is particularly high for hard-to-adhesive materials such as molded articles made of ethylene-vinyl acetate copolymer. Shown, surface polarity is low! ⁇ Sufficient adhesive strength can be achieved even from the initial stage of adhesion to the adherend.
• the adhesiveness to a molded article having a low polarity such as an ethylene ⁇ -olefin copolymer may be reduced. If it is less than the above lower limit, the adhesion to a wide range of materials as well as low-polarity materials may decrease.
• the water-based dispersion does not impair the effects of the present invention.
• Other resins such as an ethylene / butyl acetate copolymer may be contained.
• the aqueous dispersion contains 15% by weight or more of ethylene' ⁇ -olefin copolymer ( ⁇ ) based on the solid content.
• the solid content of the aqueous dispersion refers to a component remaining when water in the aqueous dispersion is removed.
• the amount of this solid content is determined by irradiating the aqueous dispersion with ultraviolet rays so as to contain the ethylenically unsaturated monomer in the aqueous dispersion, drying in an oven at 130 ° C for 10 minutes, and drying.
• UV irradiator after irradiation (Japan Storage Battery Co., Ltd., a mercury lamp format, H120N) in a 150m of JZcm 2 UV 10 times, and dried for 10 minutes in 130 ° C oven, a dry ⁇ It can be determined by measuring the weight.
• the aqueous dispersion contains 0 to 500 parts by weight, preferably 0 to 200 parts by weight of an ethylene 'butyl acetate copolymer ( ⁇ ) based on 100 parts by weight of an ethylene' ⁇ -olefin olefin copolymer (A). weight Parts, more preferably 5 to 200 parts by weight.
• ⁇ ethylene 'butyl acetate copolymer
• A ethylene' ⁇ -olefin olefin copolymer
• weight Parts more preferably 5 to 200 parts by weight.
• the ratio of the photopolymerization initiator (C) contained in the aqueous dispersion is determined by the total amount of the ethylene ' ⁇ -olefin copolymer ( ⁇ ) and the modified ethylene'vinyl acetate copolymer ( ⁇ ).
• the amount is preferably 5 to 1000 parts by weight, more preferably 10 to 500 parts by weight, based on 100 parts by weight.
• the proportion of the ethylenically unsaturated monomer (D) is preferably 50 parts by weight based on 100 parts by weight of the total amount of the ethylene ' ⁇ -olefin copolymer ( ⁇ ) and the modified ethylene-vinyl acetate copolymer ( ⁇ ).
• the amount of the non-aqueous organic solvent (F) may be an amount sufficient to dissolve the ethylene-vinyl acetate copolymer ( ⁇ ) and its modified product ( ⁇ ).
• the total amount of the ethylene ' ⁇ -olefin copolymer ( ⁇ ) and the modified ethylene'butyl acetate copolymer ( ⁇ ) is 100 parts by weight. Preferably, it is in the range of 150-1000 parts by weight.
• the aqueous dispersion according to the present invention comprises an ethylene ' ⁇ -olefin copolymer ( ⁇ ), a modified ethylene' vinyl acetate copolymer ( ⁇ ), a photopolymerization initiator (C), an ethylenic copolymer.
• the form is not particularly limited as long as it contains a saturated monomer (D), and if necessary, an ethylene-vinyl acetate copolymer ( ⁇ ) and a non-aqueous organic solvent (F).
• an aqueous emulsion composition in which micelles composed of the above components ( ⁇ ) to (F) are dispersed in water may be mentioned.
• 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.
• the above-mentioned components ( ⁇ )-(F) may be completely dissolved in water without forming micelles! / ,.
• the aqueous dispersion according to the present invention may be, depending on its purpose and use, a component that improves the adhesiveness of chlorinated polyolefin, rosin, urethane emulsion, silane coupling agent, etc .; Various additives such as an absorbent, a colorant, a whitening agent and a dye may be contained.
• the chlorinated polyolefin include chlorinated polyolefin resins and those obtained by mixing chlorinated polyolefin resins with other polymers. Examples of such chlorinated polyolefin resins include known polyolefin resins such as polyethylene, polypropylene, ethylene-polypropylene copolymer, and polybutene.
• Polyolefins such as styrene-butadiene copolymer and styrene-isoprene copolymer, or modified polyolefins obtained by introducing carboxyl groups, hydroxyl groups, acid anhydride groups, etc. into these polyolefins by a known method. And the like.
• chlorinated polyolefins may be used alone or in combination of two or more.
• the amount of the chlorinated polyolefin is appropriately selected within a range that does not impair the effects of the present invention.
• the chlorine content of the chlorinated polyolefin is not particularly limited, but is preferably from 15 to 40% by weight from the viewpoint that the adhesion to an adherend made of polyolefin can be improved.
• chlorinated polyolefins obtained by chlorinating polypropylene and Z or polyethylene, and acid anhydrides obtained by modifying the above-described chlorinated polyolefin resins with maleic anhydride or the like.
• a substance-modified chlorinated polyolefin resin is preferred.
• rosins examples include gum rosin, wood rosin, and tall oil rosin, which are thermoplastic resins containing abietic acid as a main component. More specifically, for example, modified rosins such as hydrogenated gin (dihydroabietic acid, tetrahydroabietic acid), disproportionated rosin, disproportionated hydrogenated gin, and polymerized rosin (including partially polymerized rosin) Rosin or modified rosins; alkyl esters, glycol esters, glycerin esters or pentaerythritol esters; and rosin-modified polyesters using rosin or modified rosin as part of the polyester acid.
• modified rosins such as hydrogenated gin (dihydroabietic acid, tetrahydroabietic acid), disproportionated rosin, disproportionated hydrogenated gin, and polymerized rosin (including partially polymerized rosin) Rosin or modified rosins
• a rosin-modified polyester can be obtained by reacting a glycidyl ester of rosin or 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 the rosin used is appropriately selected within a range that does not impair the effects of the present invention.
• Examples of the silane coupling agent include epoxy silane, amino silane, and vinylinolesilane. Of these, epoxy silane is preferably used. Specific epoxy silanes include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxyprovirt Liethoxysilane , polyglycidoxypropylmethyl ethoxysilane, j8- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. One of these silane coupling agents may be used alone, or two or more thereof may be used in combination. Further, the amount of the silane coupling agent to be used is appropriately selected within a range that does not impair the effects of the present invention.
• the aqueous dispersion according to the present invention can be produced, for example, by the following method.
• the ethylene butyl acetate copolymer (E) is blended with the non-aqueous organic solvent (F) according to the above, and the components (A)-(E) are mixed with the non-aqueous organic solvent (F). Dissolve or disperse in F) to prepare oil droplet components.
• a water-soluble component may be added at the time of emulsification described later.
• the mixture may be heated to 40-90 ° C, if necessary.
• the non-aqueous organic solvent (F) may be distilled off from the oil droplet component prepared here to reduce the weight.
• this oil droplet component is emulsified in water using, for example, a surfactant to obtain an aqueous dispersion.
• a surfactant for example, water
• examples of the method of emulsification include a method in which a surfactant and water are added to an oil droplet component under vigorous stirring to carry out phase inversion emulsification (forced emulsification).
• a water-soluble component may be added during this emulsification.
• components for improving the adhesiveness and various additives may be added to the oil droplet components before emulsification! /, Or may be added to the aqueous dispersion after emulsification.
• the surfactant used in the present invention is not particularly limited, and a known surfactant can be used.
• fatty acids alkyl sulfates, alkylbenzene sulfates, alkyl sulfosuccinates, polyoxyalkylene alkyl ether sulfates, polyoxyalkyl ether carboxylates, polyoxyalkylene alkyl ether phosphates, etc.
• -On surfactants alkylamine salts, quaternary ammonium
• Cationic surfactants such as -pium salts; polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl ethers, and sorbitan fatty acid esters; On-type surfactants and the like can be mentioned.
• surfactants having an oxyethylene group are preferably used.
• examples of the surfactant having an oxyethylene group include polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ethers, polyoxyethylene sorbitan fatty acid esters, other polyoxyethylene derivatives, and ethylenically unsaturated derivatives thereof.
• a polyoxyethylene surfactant such as a reactive surfactant to which a saturated group or the like has been added is exemplified.
• 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).
• the surfactant is preferably used in an amount of 3 to 50 parts by weight, more preferably 100 parts by weight based on 100 parts by weight of the oil droplet component. Preferably, it is 5 to 30 parts by weight. If the amount of the surfactant is less than the above lower limit, the dispersibility may be reduced, and if the amount exceeds the upper limit, the adhesiveness may be reduced.
• 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, preferably 100 to 3000 parts by weight per 100 parts by weight of the oil droplet component , More preferably 200 to 2000 parts by weight.
• the aqueous dispersion thus obtained is desirably prepared so as to have a solid content of usually 110 to 50% by weight, preferably 3 to 40% by weight.
• the aqueous dispersion is an aqueous emulsion composition
• the aqueous emulsion composition may be an ethylene ' ⁇ -olefin copolymer (A), a modified ethylene-vinyl acetate copolymer (B), or a photopolymerized polymer.
• Micelles containing the initiator (C), the ethylenically unsaturated monomer (D), and, if necessary, the ethylene-vinyl acetate copolymer ( ⁇ ) and the non-aqueous organic solvent (F) are dispersed in water. It is in the state of being.
• the size of the micelle is preferably 200 to 300 nm.
• the above components (A) to (F) may all be included in micelles, but may be partially dissolved in the aqueous phase.
• the component soluble in the aqueous phase include a water-soluble ethylenically unsaturated monomer such as water-soluble phthalate.
• the adhesive composition according to the present invention is a composition containing the aqueous dispersion, It is used as an agent or primer.
• the adhesive composition has high adhesive strength to a wide range of materials including low polarity materials. For example, various molded products such as plastic film, plastic sheet, plastic foam, fiber, synthetic leather, and metal can be adhered well.
• the aqueous dispersion contained in the adhesive composition contains the above-mentioned components (A) and (F)
• the polarity of the surface of a molded body such as an ethylene ⁇ -olefin copolymer is increased.
• Such an adhesive composition can be applied to the surface of a molded article by a conventionally known method, and can be used as an adhesive to adhere to another substrate.
• the adhesive composition may be applied to the surface of the molded article, used as a primer, and further applied with another conventionally known adhesive to adhere to another substrate.
• the adhesive composition may be used alone, or may be used in combination with a known adhesive or primer.
• After applying the adhesive composition preferably to be irradiated with ultraviolet rays of 50- lOOOmjZcm 2,.
• the bonding method according to the present invention is a method of bonding a molded body made of an ethylene-one-olefin copolymer using an adhesive or a primer for an ethylene- ⁇ -olefin copolymer made of a UV-curable aqueous emulsion composition.
• the UV-curable aqueous emulsion composition preferably contains the aqueous dispersion described above.
• the molded article made of the ethylene' ⁇ -olefin copolymer is molded using the ethylene' ⁇ -olefin copolymer.
• a molded article obtained by mixing a foaming agent and molding as a foam is used. What was molded as a crosslinked body by using is. Specifically, a molded article described in JP-A-2000-344924 can be mentioned.
• the UV-curable aqueous emulsion composition is applied to the surface of a molded product made of an ethylene-a-one-year-old olefin copolymer, and the formed coating film is used as an adhesive. Adhere to other materials as a layer. Further, the UV-curable water-based emulsion composition was applied to the surface of a molded article made of ethylene ' ⁇ -olefin copolymer, and the formed coating film was formed into a single layer of a primer. A known adhesive may be applied to form an adhesive layer and adhere to another material.
• Conventionally known adhesives include, for example, urethane resin-based adhesives, acrylic resin-based adhesives, ethylene 'butyl acetate copolymer' resin-based adhesives, and modified ethylene 'vinyl acetate copolymer'. Fat-based adhesives, polyolefin-based resin-based adhesives, modified polyolefin-based adhesives, synthetic rubber-based adhesives, and rosin-based resin-based adhesives. As these adhesives, any of a solvent-based adhesive and a water-based adhesive can be used, but a water-based adhesive is preferably used in view of danger of ignition and environmental hygiene.
• 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 .
• the coating amount is less than the above lower limit, the effect of the UV-curable water-based emulsion cannot be obtained, and the adhesive strength may be insufficient, and the coating amount exceeding the above upper limit is not economically preferable.
• an adherend a molded article made of an ethylene- ⁇ -olefin copolymer
• a UV-curable water-based emulsion composition is applied.
• the adhesion-inhibiting component adhered or generated during molding can be removed.
• the adhesion inhibiting component include release agents, oils and fats, dust, and the like, and these can be washed using water, warm water, a solvent, a detergent, or the like. Of these, it is preferable to use a water-based cleaning agent because the cleaning effect is high, and there is no danger of ignition or deterioration of the working environment.
• the cleaning agent used in the present invention is a cleaning agent for removing an adhesion inhibitory component used or generated at the time of molding a molded article made of an ethylene' ⁇ -olefin copolymer, and has a surfactant effect. It is a composition obtained by dispersing a detergent composition containing a surfactant contained in water as a medium.
• R 3 is an aliphatic or Z aromatic hydrocarbon group having 435 carbon atoms, and m is 5-20, preferably 6-15.
• the surfactant represented by the above formula (5) is a non-ionic surfactant.
• R 3 in the formula include a lauryl group, a cetyl group, a stearyl group, an oleyl group, a myristyl group, a phenyl group, a styrenated polyester group, and a distyrenated polyester group.
• n is 0-4, preferably 0-2)
• the surfactant represented by the above formula (6) is an aeon-based surfactant.
• R 4 in the formula is, for example, a lauryl group, a cetyl group, a stearyl group, an oleyl group, a myristyl group, a phenyl group, a styrenated phenyl group, a distyrenated phenyl group, a polyoxyethylene lauryl ether group. And a linear or branched dodecylbenzene group and an alkylnaphthalene group.
• surfactants can be used alone or in combination of two or more.
• surfactants that can be used for cleaning can be used. You may use together a sexual agent.
• examples of surfactants that can be used in combination include non-ionic surfactants such as polyoxyalkylene alkyl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters; alkyl sulfate salts; Aeon-based surfactants such as oxyethylene alkyl ether sulfate, alkylbenzene sulfonate, fatty acid salt, and naphthalenesulfonic acid formalin condensate; cations such as alkylamine salt and quaternary ammonium salt System surfactants: Zwitterionic surfactants such as alkyl betaines and alkyl amine oxides are exemplified.
• the composition for a detergent may further contain a builder, if necessary.
• a builder is a compound that does not have a detergency itself or does not have a remarkable cleaning power, but when added to a composition for a cleaning agent, significantly enhances its cleaning ability. It is intended to improve the cleaning ability of a surfactant which is a main component.
• Such builders exhibit at least one of a polyvalent metal cation trapping action, a soil dispersing action, and an alkali buffering action.
• the builder having such an action include a water-soluble inorganic compound, a water-insoluble inorganic compound, and an organic compound.
• the water-soluble inorganic compound include phosphates, silicates, carbonates, sulfates and the like.
• water-insoluble inorganic compound examples include aluminosilicate and crystalline silicate.
• organic compound examples include a carboxylate and an organic carboxylate polymer.
• alkali metal salts and amines are preferred, and sodium and / or potassium, monoethanolamine and diethanolamine are particularly preferred.
• Cloth detergents and dishwashing detergents which are mixtures of these builders and surfactants, can be used in the present invention.
• the detergent used in the present invention is obtained by dissolving or dispersing the above-mentioned composition for detergent in water.
• the concentration of the detergent composition is preferably as low as possible, but is preferably from 0.01% to 20%, more preferably from 0.1% to 10%. At a concentration of 0.01% or less, the effect of the detergent is not exhibited, and at a concentration of 20% or more, it is not economically preferable.
• the adherend (molded body) is washed with this detergent and an ethylene-vinyl acetate copolymer. This is performed by bringing the molded body into contact.
• the washing method may be a batch type or a continuous type.
• the contact time can be appropriately selected, but if the contact time is short, the effect of the cleaning agent is not exhibited, and if the washing time is long, the production efficiency is reduced. Further, by stirring the detergent during the contact between the detergent and the molded body, the cleaning effect can be improved. It is also preferable to use a combination of an ultrasonic wave and ultrasonic waves.
• the cleaning agent is brought into contact with the molded body in this way, the cleaning agent attached to the surface of the molded body is removed. If the detergent remains at a high concentration on the surface of the molded body, the adhesive strength of the UV-curable water-based emulsion decreases.
• the removal of the detergent is preferably performed using water, which is possible by a known method. In addition, by using a method of removing the detergent by centrifugal separation, the efficiency of detergent removal can be improved.
• Toluenecarbamate (tetrakispentafluorophenol) borate (18.4 mg) was added with 5 ml of toluene and dissolved to prepare a toluene solution (a) having a concentration of 0.004 mMZml.
• 1.8 ml of [dimethyl (t-butylamide) (tetramethyl- 5 -cyclopentagel) silane] titanium dichloride was dissolved in 5 ml of toluene to prepare a toluene solution (b) having a concentration of 0.000M Zml. did.
• the obtained ethylene '1-butene copolymer has a density (23 ° C) of 885 kgZm 3 , an MFR (190 ° C, 2.16 kg load) of 1.2 gZlO, an MwZMn of 2.1, and an MFR (10)
• the / MFR (2.16) was 10.0 and the B value was 1. ⁇ , ⁇ / ⁇ was 0.3.
• Non-ionic surfactant (trade name: Emulgen 90 (manufactured by Kao Corporation) 1000 parts by weight, sodium linear alkylbenzene sulfonate (trade name: Neoperex No. 6F powder (manufactured by Kao Corporation)) 200 1 part by weight, 200 parts by weight of 4A zeolite, 100 parts by weight of sodium silicate, 100 parts by weight of sodium carbonate, and 400 parts by weight of sodium sulfate are dispersed in 18 000 parts by weight of water to obtain a detergent.
• Emulgen 90 manufactured by Kao Corporation
• sodium linear alkylbenzene sulfonate trade name: Neoperex No. 6F powder (manufactured by Kao Corporation)
• the obtained sheet was filled in a press mold, and pressurized and heated under the conditions of 150 kgZcm 2 , 160 ° C, and 12 minutes, and foamed (thickness 24.5 mm, length 150 mm, width 200 mm) Got Example 1
• a polyoxyethylene alkyl ether sulfate ester-based surfactant (trade name: Emal 27C (manufactured by Kao Corporation)) was added to the oil droplet component while stirring with a high-speed mixer (rotation speed: 2000 rpm). And 810 parts by weight of ion-exchanged water and 40 parts by weight of 2-hydroxymethyl methacrylate were added to carry out forced emulsification to obtain an aqueous emulsion composition.
• the foam molded article obtained in the above Production Example was immersed in the washing liquid obtained in Preparation Example (3), and stirred for 5 minutes. Thereafter, the foamed molded body was taken out, sufficiently washed with tap water, and dried in a 55 ° C oven for 5 minutes to obtain a washed foamed molded body.
• aqueous emulsion composition prepared in the above (1) to the washed foam molded body was coated at a rate of 10gZ m 2, dried for 2 minutes in an oven at 55 ° C. Thereafter, ultraviolet irradiation of 150 mjZcm 2 was performed twice using a UV irradiator (manufactured by Nippon Battery Co., Ltd., mercury lamp type: HI20N). After the UV irradiation, two liquid urethane-based adhesives were further applied and dried.
• a UV irradiator manufactured by Nippon Battery Co., Ltd., mercury lamp type: HI20N
• the adhesive surface of a rubber sheet (200 mm x 50 mm x 3 mm molded product) is puffed, coated with a rubber primer, dried, and then coated with a two-part urethane aqueous adhesive. And dried.
• Adhesive performance A Adhesive strength 20NZcm or more
• Odor A no strong odor
• Ethylene ' ⁇ -olefin copolymer (density: 862 kgZm 3 , melt index: 1.2 g / 10 min, trade name: Tuffmer DF610 (manufactured by Mitsui Iridakusha))
• Ethylene instead of 5 parts by weight a—Olefin copolymer (density: 885 kgZm 3 , melt index: 1.2 gZl0 min, trade name: Tuffmer DF810 (manufactured by Mitsui Idakusha))
• a water-based copolymer was prepared in the same manner as in Example 1 except that 5 parts by weight was used. An emulsion composition was obtained.
• Ethylene ' ⁇ -olefin copolymer (density: 862 kgZm 3 , melt index: 1.2 g / 10 minutes, trade name: Toughmer DF610 (manufactured by Mitsui Iridakusha))
• Ethylene instead of 5 parts by weight a—Olefin copolymer (density: 870kgZm 3 , melt index: 35gZlO, trade name: TA Fumah DF7350 (Mitsui Chemicals) 5 parts by weight, instead of 40 parts by weight of turpentine oil, 20 parts by weight of turpentine (trade name: Gum turpentine N (manufactured by Yashara Chemical) and limonene (trade name: D-limonene (manufactured by Yashara Chemical))
• a water-based emulsion composition was obtained in the same manner as in Example 1 except that 20 parts by weight was used.
• Ethylene ' ⁇ -lean olefin copolymer (density: 862 kgZm 3 , melt index: 1.2 g / 10 minutes, trade name: Tuffmer DF7350 (manufactured by Mitsui Irigaku Co., Ltd.))
• Tuffmer DF7350 (manufactured by Mitsui Irigaku Co., Ltd.)
• Engage 8100 (manufactured by Dupont Welastomer Co., Ltd.)
• Ethylene ' ⁇ -lean olefin copolymer (density: 862 kgZm 3 , melt index: 1.2 g / 10 min, trade name: Tuffmer DF610 (manufactured by Mitsui Iridakusha))
• Ethylene instead of 5 parts by weight a—Olefin copolymer (density: 902 kg / m 3 , melt index: 30 g / 10 min, trade name: Engage 8402 (manufactured by Dupont Welastomer Co., Ltd.)) 2.
• a polyoxyethylene alkyl ether sulfate ester-based surfactant (trade name: Emar 27C) was added to the oil droplet component while stirring with a high-speed mixer (rotation speed: 2000 rpm).
• 30 parts by weight of polyoxyethylene alkyl ether surfactant (trade name: Emalgen A-90 (manufactured by Kao Corporation)
• 20 parts by weight, 810 parts by weight of ion-exchanged water, and 2-hydroxymethyl meta 40 parts by weight of tallylate was added to the mixture to carry out forced emulsification to obtain an aqueous emulsion composition.
• Ethylene ' ⁇ -branched olefin copolymer (density: 862 kgZm 3 , melt index: 1.2 g / 10 min, trade name: Tuffmer DF610 (manufactured by Mitsui Iridakusha)) Instead of 5 parts by weight of ethylene' a—Olefin copolymer (density: 862 kgZm 3 , melt index: 1.2 gZlO, trade name: Tuffmer DF610 (manufactured by Mitsui Chemicals, Inc.)) 2.
• Ethylene ' ⁇ -olefin copolymer (density: 862 kgZm 3 , melt index: 1.2 g / 10 min, trade name: Toughmer DF610 (manufactured by Mitsui Iridakusha))
• Toughmer DF610 manufactured by Mitsui Iridakusha
• Toughmer DF810 manufactured by Mitsui Idakusha
• Ethylene ' ⁇ -olefin copolymer (density: 862 kgZm 3 , melt index: 1.2 g / 10 min, trade name: and Tafmer DF610 (made by Mitsui Chemicals, Inc.)) 1 part by weight, the ethylene 'alpha - Orefi down copolymer (density: 885kg / m 3, Melt Index: 1.
• an ethylene' ⁇ -olefin copolymer (density: 870 kgZm 3 , melt index: lgZlO content, trade name : Engage 8100 (manufactured by Dupont Wellastomer Co., Ltd.)) 1 part by weight and ethylene ' ⁇ -refined copolymer (density: 902 kgZm 3 , melt index: 30 gZlO, product name: Engeji 8402 (Dupont Wellastomer Co., Ltd.) 1 part by weight) and 1 part by weight of ethylene ' ⁇ -olefin copolymer (density: 870 kg / m 3 , melt index: 30 g / 10 minutes, trade name: Engage 8407 (manufactured by Dupont Welastomer Co., Ltd.)) Ethylene vinyl acetate copolymer (But
• limonene (trade name: D-limonene (manufactured by Yashara Chemical Co., Ltd.)) and aromatic hydrocarbons (trade name: solvesso 150 (manufactured by ExxonMosentani))
• An aqueous emulsion composition was obtained in the same manner as in Example 8, except that 10 parts by weight) was used.
• the foam molded article obtained in the above production example was washed in the same manner as in Example 1 to obtain a washed foam molded article.
• a two-part urethane-based aqueous adhesive was applied to the surface of the washed foamed molded article, and dried.
• 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.
• a washed foamed molded article was bonded to a rubber sheet 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. Table of results
• C HEVA (hydroxyl group) was used without using ethylene ' ⁇ -olefin copolymer (density: 862 kgZm 3 , melt index: 1.2 g / 10 minutes, trade name: Tuffmer DF610 (manufactured by Mitsui Iridakusha)). Value: 0 mgKOH / g, acid value: 84 mgKOH / g, tetrahydrofuran solution (20% by weight of resin), trade name: Takemelt SD-700 (manufactured by Mitsui Takeda Chemical Co.)) was changed from 25 parts by weight to 50 parts by weight.
• a water-based emulsion composition was obtained in the same manner as in Example 2 except for the above.
• Example 1 C HEVA (hydroxyl value: OmgKOHZg, acid value: 84mgKOHZg, tetrahydrofuran solution (20% by weight of resin), trade name: Takemelt SD-700 (manufactured by Mitsui Takeda Chemical Co., Ltd.)) and ethylene.
• Example 1 was repeated except that the olefin copolymer (density: 862 kgZm 3 , melt index: 1.2 gZlO, trade name: Tuffmer DF610 (manufactured by Mitsui Iridakusha)) was changed from 5 parts by weight to 10 parts by weight. In the same manner, an aqueous emulsion composition was obtained.
• Ethylene ' ⁇ -olefin copolymer (density: 862 kgZm 3 , melt index: 1.2 g / 10 min, trade name: Tuffmer DF610 (manufactured by Mitsui Chemicals, Inc.)) Instead of 5 parts by weight, ethylene acetate butyl copolymer (Vinyl acetate content: 33%, melt index: lgZlO content, trade name: Evaflex EV170 (manufactured by Mitsui DuPont Polychemicals) 3 parts by weight and ethylene acetate vinyl copolymer (vinyl acetate content: 19%, melt index Water-based emulsion composition was obtained in the same manner as in Example 1 except that 2.5 g of ZlO and 2 parts by weight of Evaflex EV460 (manufactured by Mitsui DuPont Polychemicals) were used.
• Limonene 20 20 10 20 20 20 10 Solvesso 1 50 30 10
• Adhesive performance (after 5 minutes) A: Adhesive strength 20 NZcm or more, B: Adhesive strength 1 0 20 N / cm, C: Adhesive strength 1 Less than 0N / cm
• a low-polarity polymer such as a molded article of an ethylene-one-year-old olefin copolymer is used.

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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Dispersion Chemistry (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)
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