WO2015194611A1 - 水性エマルション並びに塗膜、硬化物及び積層体 - Google Patents
水性エマルション並びに塗膜、硬化物及び積層体 Download PDFInfo
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- WO2015194611A1 WO2015194611A1 PCT/JP2015/067537 JP2015067537W WO2015194611A1 WO 2015194611 A1 WO2015194611 A1 WO 2015194611A1 JP 2015067537 W JP2015067537 W JP 2015067537W WO 2015194611 A1 WO2015194611 A1 WO 2015194611A1
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/022—Emulsions, e.g. oil in water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/02—Rubber derivatives containing halogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D115/00—Coating compositions based on rubber derivatives
- C09D115/02—Rubber derivatives containing halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
Definitions
- the present invention relates to an aqueous emulsion, a coating film, a cured product, and a laminate.
- Patent Document 1 describes an aqueous emulsion containing an acid-modified chlorinated polyolefin that can be used as an adhesive. However, such an aqueous emulsion could not adhere to adherends or adherends with sufficient strength.
- the present invention includes the following inventions.
- [3] containing water as the dispersion medium The aqueous emulsion according to [1] or [2], comprising a mixture of the chlorinated rubber and the compound having a polymerizable group as a dispersoid.
- a cured product according to [19], one or more adhesive layers, and a second substrate are laminated in this order on the first substrate made of an olefin polymer. Laminated body.
- the cured product according to [19] On the first substrate made of an ethylene / vinyl acetate copolymer, the cured product according to [19], one or more adhesive layers thereon, and a second substrate A laminated body laminated in this order.
- adherends or adherends can be bonded to each other with sufficient strength.
- the aqueous emulsion of the present invention mainly contains a chlorinated rubber and a compound having a polymerizable group.
- the aqueous emulsion usually contains water as a dispersion medium.
- the aqueous emulsion of the present invention is useful as an aqueous adhesive.
- Chlorinated rubber is a chlorinated rubber having a chlorine atom content of 45% by mass or more. One type of chlorinated rubber may be used, or two or more types may be combined.
- the chlorinated rubber may or may not have a melting point, but preferably has a melting point. Melting
- the chlorine atom content of the chlorinated rubber is preferably 45 to 90% by mass, more preferably 55 to 90% by mass, and further preferably 60 to 80% by mass.
- the chlorinated rubber one having no carboxy group and carboxylic anhydride structure can be used.
- a chlorinated rubber is used in the aqueous emulsion of the present invention, particularly when the aqueous emulsion is used as an aqueous adhesive, the concern about a decrease in water resistance of the aqueous adhesive is extremely small and effective.
- a carboxylic acid anhydride such as maleic anhydride which is not acid-modified.
- the chlorinated rubber is not particularly limited as long as it is a chlorinated natural rubber or synthetic rubber, and specifically, chlorinated natural rubber, chlorinated butadiene rubber, chlorinated butyl rubber, chlorinated isoprene rubber, butadiene / halogen. Cyclic conjugated diene adduct, chlorinated butadiene styrene copolymer, brominated poly (2,3-dichloro-1,3-butadiene) and ⁇ -haloacrylonitrile-co-2,3-dichloro-1,3-butadiene A copolymer etc. are mentioned. A copolymer or rubber containing a hydrocarbon group having 4 or more carbon atoms as a raw material is preferable. More preferred are chlorinated natural rubber, chlorinated isoprene rubber and chlorinated butadiene rubber.
- a method of chlorinating natural rubber or synthetic rubber a conventionally known method can be adopted.
- the aggregated and solidified natural rubber or synthetic rubber may be dissolved in an organic solvent and then chlorinated, or the aggregated and solidified natural rubber or synthetic rubber may be dissolved in an organic solvent and then emulsified and dispersed to volatilize the solvent. It can also be chlorinated in a wet state.
- natural rubber when chlorinated, it can be chlorinated by blowing chlorine gas into latex natural rubber.
- polyisoprene, a surfactant, and an acid such as hydrochloric acid, sulfuric acid, or nitric acid are added to water and emulsified, and then uniformly chlorinated polyisoprene can be obtained by blowing chlorine gas.
- the chlorinated rubber has a polystyrene-equivalent weight average molecular weight of usually 1000 or more, preferably 3000 or more, more preferably 5000 or more, and further preferably 10,000 or more. Moreover, it is 400000 or less normally, Preferably it is 200000 or less.
- the weight average molecular weight in terms of polystyrene can be measured by gel permeation chromatography (GPC). By setting it as such a range, when the aqueous emulsion of the present invention is used as an aqueous adhesive, sufficient adhesive strength can be secured, and an excessive increase in viscosity can be suppressed to adhere to an adherend. Sufficient sex can be secured.
- chlorinated rubber examples include commercially available products and those manufactured according to any known method.
- Commercially available products include Supercron (registered trademark) CR-10, CR-20 (Nippon Paper Industries Co., Ltd.), Pergut S-5, Pergut S-10, Pergut S-20, Pergut S-40, Pergut S-90 Pergut S-130, Pergut S-170 (Bayer MaterialScience), Alloprene (registered trademark) R10, R20, R40 (manufactured by ICI UK) and the like.
- Supercron registered trademark
- CR-10 Registered trademark
- CR-20 Nippon Paper Industries Co., Ltd.
- Pergut S-5 Pergut S-10
- Pergut S-20 Pergut S-40
- Pergut S-90 Pergut S-130 Pergut S-170
- Alloprene registered trademark
- R10, R20, R40 manufactured by ICI UK
- the compound having a polymerizable group includes, for example, a vinyl group, an allyl group, a propenyl group, a vinylidene group, a vinylene group (meth) acryl group, a (meth) acryloyl group, a vinyl ether group, a vinyl benzyl ether group as the polymerizable group.
- Examples of the compound having a polymerizable group include a compound having an ethylenically unsaturated double bond, an epoxy compound, an oxetane compound, and a glycidyl ether compound. These compounds may be used alone or in combination of two or more.
- a compound having at least one ethylenically unsaturated double bond is preferable.
- the compound having an ethylenically unsaturated double bond preferably has 1 to 10 ethylenically unsaturated double bonds, more preferably 1 to 6, still more preferably 1 to 3, and still more preferably 1 to Have two.
- Compounds having one ethylenically unsaturated double bond include heterocyclic ethylenically unsaturated compounds (for example, N-vinyl-nitrogen-containing heterocycles such as N-methylpyrrolidone, N-vinylpyridine and N-vinylcaprolactam).
- heterocyclic ethylenically unsaturated compounds for example, N-vinyl-nitrogen-containing heterocycles such as N-methylpyrrolidone, N-vinylpyridine and N-vinylcaprolactam.
- heterocyclic (meth) acrylate such as morpholine (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and glycidyl (meth) acrylate), N-vinylformamide, N-vinylacetamide, dialkylaminoethyl (meth) acrylate ( For example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate), N, N′-dimethylacrylamide, alkoxy (poly) alkylene glycol (meth) acrylate (for example, methoxyethylene (meth) acrylate, Ethoxy-diethylene glycol (meth) acrylate, methoxypolyethylene (meth) acrylate, butoxypolyethylene (meth) acrylate, etc.), phenoxyalkyl (meth) acrylate (for example, 2-phenoxyethyl (meth) acrylate,
- Examples of the compound having two ethylenically unsaturated double bonds include 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, polyethylene glycol -Propylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate Rate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-
- Examples of the compound having three or more ethylenically unsaturated double bonds include trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, tris (acryloyloxy) Isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate tri (meth) Examples include acrylate,
- the compound having one or more ethylenically unsaturated double bonds is preferably a compound having 5 to 25 carbon atoms, more preferably a compound having 6 to 18 carbon atoms, and further preferably 8 to 16 carbon atoms. It is a compound of this.
- epoxy compound examples include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2 -Epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, bisphenol A diglycidyl ether, Neopentyl glycol diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether Tellurium, brominated bisphenol A diglycidyl ether,
- an aromatic epoxide and an alicyclic epoxide are preferable and an alicyclic epoxide is more preferable from a viewpoint of being excellent in a cure rate.
- oxetane compounds include 2-hydroxymethyl-2-methyloxetane, 2-hydroxymethyl-2-ethyloxetane, 2-hydroxymethyl-2-propyloxetane, 2-hydroxymethyl-2-butyloxetane, and 1,4-bis And [(3-ethyl-3-oxetanylmethoxy) methyl] benzene.
- glycidyl ether compound examples include 1,4-butanediol glycidyl ether, 1,6-hexanediol glycidyl ether, cyclohexanedimethanol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerin polyglycidyl ether, diethylene glycol diglycidyl ether, and the like.
- the compound having a polymerizable group may be solid at 23 ° C., but is preferably a compound that is liquid at atmospheric pressure.
- Liquids include solutions, emulsions, suspensions, colloids and the like. Due to these properties, a uniform aqueous emulsion can be obtained.
- the compound having a polymerizable group contained in the aqueous emulsion of the present invention is usually 50 to 10,000 parts by weight, preferably 100 to 10,000 parts by weight, more preferably 200 to 10,000 parts by weight per 100 parts by weight of chlorinated rubber.
- the amount is 5000 parts by mass, and more preferably 400 to 5000 parts by mass.
- the aqueous emulsion of the present invention may contain a polymerization inhibitor. Any polymerization inhibitor may be used as long as it delays or stops the radical reaction.
- Polymerization inhibitors include hydroquinone, methylhydroquinone, hydroquinone monoester, N-nitrosodiphenylamine, phenothiazine, 4-t-butylcatechol, N-phenylnaphthylamine, 2,6-di-t-butyl-p-methylphenol 2,5-di-t-butylhydroquinone, 1,4-benzoquinone, 2,6-di-t-butyl-1,4-benzoquinone, methyl-p-benzoquinone, 2,5-diphenyl-p-benzoquinone, Examples include 4-methoxyphenol, chloranil, pyrogallol, 2-oxydiphenylamine, phenothiazine and the like.
- polymerization inhibitors include Kinopower QS-10, Kinopower QS-20, Kinopower QS-30, Kinopower QS-40, Kinopower QS-W10 (manufactured by Kawasaki Kasei Kogyo Co., Ltd.), Metoquinone Flakes, Nonflex Alba, MH, TBH, PBQ, tolquinone, TBQ (manufactured by Seiko Chemical Co., Ltd.) and the like can be mentioned.
- the polymerization inhibitor also has an aspect of maintaining a high storage stability of the composition and ensuring the curability. Therefore, in consideration of such actions and the like, the addition amount of the polymerization inhibitor is preferably 0 with respect to 100 parts by mass of the total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. 0.005 to 0.4 parts by mass, more preferably 0.01 to 0.3 parts by mass, still more preferably 0.02 to 0.2 parts by mass, and particularly preferably 0.035 to 0.2 parts by mass.
- the polymerization inhibitor is preferably dissolved in the compound having a polymerizable group.
- water contained in the aqueous emulsion of the present invention tap water or deionized water is usually used.
- the water contained in the aqueous emulsion is not particularly limited as long as it is an amount that allows the chlorinated rubber and the compound having a polymerizable group to exist as a uniform dispersion medium.
- additives can be added in addition to the chlorinated rubber and the compound having a polymerizable group.
- Additives include surfactants, photopolymerization initiators, light stabilizers, UV curable oligomers, fluorescent brighteners, leveling agents, basic compounds, organic solvents, crosslinking agents, photosensitizers, other resins, Phenol stabilizer, phosphite stabilizer, amine stabilizer, amide stabilizer, anti-aging agent, weathering stabilizer, antiseptic, anti-settling agent, antioxidant, thermal stabilizer, thixotropic agent, thickening Agent, antifoaming agent, viscosity modifier, weathering agent, pigment dispersant, antistatic agent, lubricant, nucleating agent, flame retardant, oil agent, dye, curing agent; transition metal compounds such as titanium oxide (rutile type) and zinc oxide Pigments such as carbon black; glass fibers, carbon fibers, potassium titanate fibers
- additives and the like may constitute a dispersoid of the aqueous emulsion.
- at least a part of the chlorinated rubber may be dissolved in the dispersoid.
- that at least a part of the chlorinated rubber is dissolved in the dispersoid means that at least a part of the chlorinated rubber is dissolved in at least one component among the components forming the dispersoid.
- the aqueous emulsion of the present invention is filtered with a filter having a pore size of 0.50 ⁇ m, it is sufficient that at least a part of the chlorinated rubber is contained in the filtrate.
- the chlorinated rubber contained in the filtrate is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 30% by mass or more, relative to 100 parts by mass of the chlorinated rubber contained in the aqueous emulsion before filtration. More preferably, it is 70 mass% or more. Filtration with a filter is preferably performed after heating to a temperature equal to or higher than the melting point of the compound having a polymerizable group contained in the aqueous emulsion.
- the chlorinated rubber contains other resins
- the part may be dissolved in a compound having a polymerizable group or a dispersoid. Filtration with a filter is preferably performed after heating to a temperature equal to or higher than the melting point of the compound having a polymerizable group contained in the aqueous emulsion.
- all the additives may be mixed with the dispersoid in an aqueous
- the surfactant preferably acts as an emulsifier.
- examples of the surfactant include cationic, anionic, amphoteric and nonionic surfactants, and preferred are anionic and nonionic surfactants.
- Surfactants may be used alone or in combination of two or more.
- Anionic surfactants include fatty acid sodium such as sodium palmitate, sodium ether carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, amino acid condensate of higher fatty acid such as sodium lauroyl sarcosine, sodium N-lauroyl glutamate, Alkyl sulfonates, higher fatty acid ester sulfonates such as lauric acid ester sulfonates, dialkyl sulfosuccinates such as dioctyl sulfosuccinate, higher fatty acid amide sulfonates such as oleic acid amide sulfonic acid, sodium dodecylbenzene sulfonate Alkyl aryl sulfonates such as diisopropyl naphthalene sulfonate, formalin condensates of alkyl aryl sulfonates, pentadecane-2-sulfate, etc.
- polyoxyethylene alkyl phosphate such as dipolyoxyethylene dodecyl ether phosphate, lignin sulfonate, polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate, polyoxyethylene nonylpropenyl Ammonium phenyl ether sulfate, bis (polyoxyethylene polycyclic phenyl ether) bismethacrylate sulfate, alkyl allyl succinate sulfonate sodium salt, polyoxyalkylene alkenyl ether ammonium sulfate, 2-sodium sulfoethyl methacrylate, alkoxy polyethylene glycol maleate , Higher alcohol sulfates, higher carboxylates, alkylbenzene sulfonates, polyoxygens Lenalkyl sulfate salt, polyoxyethylene alkylphenyl ether sulfate salt and vinyl sulf
- Cationic surfactants include alkylamine hydrochlorides such as dodecylamine hydrochloride, alkyl quaternary ammonium salts such as alkyldimethylbenzylammonium salts, alkylisoquinolinium salts, dialkylmorpholinium salts, benzethonium chloride, Alkylvinylpyridinium salts, alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt, alkylpyridium salts such as cetylpyridium salt and decylpyridium salt, oxyalkylenetrialkylammonium salt, dioxyalkylenedialkylammonium salt, allyltri Examples thereof include alkylammonium salts, diallyldialkylammonium salts, and polydiallyldimethylammonium chloride.
- alkylamine hydrochlorides such as dodecylamine hydrochloride
- Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene lanolin alcohol, polyoxyethylene alkylphenol formalin condensate, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glyceryl mono fatty acid.
- Ester polyoxypropylene glycol monofatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene castor oil derivative, polyoxyethylene fatty acid ester, higher fatty acid glycerin ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene polyoxypropylene Block polymer, polyoxyethylene fatty acid amide, alkylolamide, polyoxye Alkylene alkyl amines, and polyoxyethylene alkanediol, alkoxy polyethylene glycol methacrylate, and the like.
- amphoteric surfactants include N-laurylalanine, N, N, N-trimethylaminopropionic acid, N, N, N-trihydroxyethylaminopropionic acid, N-hexyl-N, N-dimethylaminoacetic acid, Examples thereof include 1- (2-carboxyethyl) pyrimidinium betaine, lecithin, lauryl betaine, and lauryl dimethylamine oxide.
- surfactants include EMAL 0, EMAL 10G, EMAL 2F paste, EMAL 20C, EMAL E-27C, EMAL 270J, EMAL E-27C, Neoperex GS, Neoperex G-15, Neoperex G-25 , Neoperex G-65, Latemul PD-104, Perex OT-P, Perex TR, Perex SS-L, Perex SS-H, Demol N, Demol EP, Emulgen 102KG, Emulgen 104P, Emulgen 105, Emulgen 106, Emulgen 108 Emulgen 404, Emulgen 130K, Emulgen 147, Emulgen LS-106, Emulgen LS-110, Emulgen A-60, Emulgen 109P, Emulgen 350, Latemul PD-420, Rheodor 430V , Emanon 1112, Emanon CH-25, Amit 102, Acetamine 86, Coatamine 24P, Amhitor 24B, Neoperex
- the aqueous emulsion of the present invention preferably contains a surfactant.
- a surfactant When a surfactant is included, the content of the surfactant is good to form an aqueous emulsion, the adhesiveness of the aqueous emulsion is good, but it has a mass part of chlorinated rubber and a polymerizable group. Preferably, it is 30 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less with respect to 100 parts by mass of the total of the compounds.
- the lower limit of the amount of surfactant is preferably at least 1 part by mass.
- a photopolymerization initiator is a compound that generates an active species by the action of light, a photo radical generator that generates an active radical by the action of light, a photo acid generator that generates an acid by the action of light, and the action of light. Examples include photobase generators that generate bases.
- photo radical generator examples include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, sulfonic acid derivatives, onium salts (such as iodonium salts and sulfonium salts), and carboxylic acid esters.
- benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
- benzophenone compounds examples include benzophenone, 4-methylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone.
- alkylphenone compound examples include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane.
- acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
- triazine compounds examples include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2 -(5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3 , 5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,
- Examples include sulfonic acid derivatives, onium salts (such as iodonium salts and sulfonium salts), carboxylic acid esters, and the like described later.
- a commercially available thing can be used as a photoradical generator.
- Commercially available photoradical generators include Irgacure (registered trademark) 907, 184, 651, 819, 250, 2959, 127, 754 and 369 (BASF Japan Co., Ltd.), Seikol (registered trademark) BZ, Z And BEE (Seiko Chemical Co., Ltd.), Kayacure (registered trademark) BP100 (Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adekaoptomer SP-152 and SP-170 (( ADEKA), TAZ-A and TAZ-PP (Nihon Shibel Hegner Co., Ltd.), TAZ-104 (Sanwa Chemical Co., Ltd.), Darocur (registered trademark) 1173 and MBF (BASF Japan Co., Ltd.) It is done.
- photo radical generators may be used alone or in combination.
- Specific examples of the combination include Irgacure (registered trademark) 500 (1-hydroxy-cyclohexyl-phenyl-ketone / benzophenone: 50/50%), Irgacure (registered trademark) 1700 (bis (2,6-dimethoxybenzoyl) -2 , 4,4-trimethylpentylphosphine oxide / 2-hydroxy-2-methylphenylpropan-1-one: 25/75%) and Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethylpentylphosphine oxide / 1-hydroxycyclohexyl-phenylketone: 25/75%) (BASF Japan Ltd.).
- photoacid generator examples include sulfonic acid derivatives, onium salts, carboxylic acid esters, and the like.
- sulfonic acid derivatives examples include disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidesulfonates such as trifluoromethylsulfonate derivatives, benzoinsulfonates, 1-oxy-2-hydroxy-3 Mention may be made of sulfonates of propyl alcohol, pyrogallol trisulfonates, benzyl sulfonates.
- onium salts include tetrafluoroborate (BF 4 ⁇ ), hexafluorophosphate (PF 6 ⁇ ), hexafluoroantimonate (SbF 6 ⁇ ), hexafluoroarsenate (AsF 6 ⁇ ), hexachloroantimonate (SbC 16).
- Tetraphenylborate Tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate, perchlorate ion (ClO 4 ⁇ ), trifluoromethanesulfonate ion (CF 3 SO 3 ⁇ ), fluorosulfone acid ion (FSO 3-), toluenesulfonic acid ion, trinitrobenzene sulfonic acid anion, the use of sulfonium salts or iodonium salts having an anion such as trinitrotoluene sulfonate anion Kill.
- sulfonium salt examples include triphenylsulfonium hexafluoroacylate, triphenylsulfonium hexafluoroborate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorobenzyl) borate, methyldiphenylsulfonium tetrafluoroborate, methyldiphenylsulfonium.
- iodonium salt examples include (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluoroantimonate, [4- (2- Hydroxy-n-tetradecyloxy) phenyl] phenyliodonium trifluorosulfonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluorophosphate, [4- (2-hydroxy-n-tetrade Siloxy) phenyl] phenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium
- aromatic diazonium salts can be used, for example, p-methoxybenzenediazonium, hexafluoroantimonate, and the like.
- onium salts include Sun Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI-L160, SI-L110.
- SI-L147 manufactured by Sanshin Chemical Industry Co., Ltd.
- UVI-6950, UVI-6970, UVI-6974, UVI-6990 manufactured by Union Carbide
- Adekaoptomer SP-150, SP- 151, SP-170, SP-171, SP-172 Adekaoptomer SP-150, SP- 151, SP-170, SP-171, SP-172 (Asahi Denka Kogyo Co., Ltd.), Irgacure 261, Irgacure 250 (Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI-2439 CI-2064 (Nippon Soda Co., Ltd.), CD-1010, CD-10 1, CD-1012 (above, manufactured by Sartomer), DS
- Examples of the photobase generator include acyclic acyloxyimino compounds, acyclic carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, Examples include sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, ⁇ -lactone ring derivative compounds, amine imide compounds, and phthalimide derivative compounds. These can be used alone or in combination of two or more.
- the aqueous emulsion of the present invention contains a photopolymerization initiator, the content thereof is stable with respect to 100 parts by mass of the total of the parts by mass of the chlorinated rubber and the compound having a polymerizable group, From the viewpoint of reactivity and odor, it is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less.
- Light stabilizer examples include an ultraviolet absorber and a hindered amine light stabilizer.
- a light stabilizer may be used independently and may be used in combination of 2 or more type.
- UV absorber examples include salicylic acids (eg, phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, etc.), benzophenones (eg, oxalic acid 2,4-dihydroxybenzophenone, 2-hydroxy -4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'- Dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, etc.), benzotriazoles (for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5) '-Ter -Butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-buty
- hindered amine light stabilizers include ester group-containing piperidines (for example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4 -Acryloyloxy-2,2,6,6-tetramethylpiperidine, etc.), ether group-containing piperidines (for example, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2 , 6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, etc.), amide group-containing piperidines (for example, 4- (phenylcarbamoyloxy) -2,2,6,6 -Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-1,6-di As well as high molecular weight piperidine polycondensates (for example, dimethyl)
- the content thereof is preferably 15 parts by mass or less with respect to 100 parts by mass of the total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. More preferably, it is 10 mass parts or less, More preferably, it is 5 mass parts or less.
- UV curable oligomer examples include urethane acrylate oligomer, epoxy acrylate oligomer, and polyester acrylate oligomer.
- the ultraviolet curable oligomers may be used alone or in combination.
- a commercially available urethane acrylate oligomer can be used.
- Examples of commercially available urethane acrylate oligomers include CN929, CN965, CN968, CN981A75, CN985B88, CN991, CN970AH75, CN975, CN992, CN994 and CN9165 (Sartomer), U-4HA and U-6HA (manufactured by Shin-Nakamura Chemical Co., Ltd.) AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
- a commercially available epoxy acrylate oligomer can be used.
- Examples of commercially available epoxy acrylate oligomers include CN116, CN120B60, CN120M50, CN131B, CN132, CN137, CN152, and CN2102E (manufactured by Sartomer).
- polyester acrylate oligomer A commercially available polyester acrylate oligomer can be used.
- polyester acrylate oligomers include CN292, CN2259, CN2262, CN2270, CN2271E, CN2272, CN2273, CN2276, CN2279, CN2285, CN2298, CN2300, CN2301, CN2302, CN2303, and CN2304. These polyester acrylate oligomers may be used alone or in combination.
- the content is preferably 20 parts by mass with respect to 100 parts by mass of the total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. Part or less, more preferably 15 parts by weight or less, still more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less.
- fluorescent brighteners examples include dialkylaminocoumarin, bisdimethylaminostilbene, bismethylaminostilbene, 4-alkoxy-1,8-naphthalenedicarboxylic acid-N-alkylimide, bisbenzoxazolylethylene, 1,4-bis (2-Benzoxazolyl) naphthalene, dialkylstilbene and the like.
- optical brighteners include Kayahor 3BS Liq. Kayahor TAC Liq. Kyaphor HBC Liq. , Kayalight B, Kyaphor AS 150, Kyaphor CR 200, Kyaphor JB Liq., Mikawhite ATN conc.
- the aqueous emulsion of the present invention contains a fluorescent brightening agent
- the content thereof is preferably 5 with respect to 100 parts by mass of the total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. It is no more than 3 parts by mass, more preferably no more than 3 parts by mass, and even more preferably no more than 1 part by mass.
- ⁇ Leveling agent> As a leveling agent, polyflow no. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, polyflow no. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), BYK300, BYK306, BYK310, BYK320, BYK330, BYK346, BYK349, BYK-333, BYK-345, BYK-347, BYK-348, BYK-378 (manufactured by BYK Japan) KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (manufactured by AGC Seimi Chemical Co., Ltd.), Footgent 222F, footage 251, FTX-218 (manufactured by Neos), EFTOP EF-351, EFTOP
- the content thereof is preferably 20 parts by mass or less with respect to 100 parts by mass of the total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. More preferably, it is 10 mass parts or less, More preferably, it is 5 mass parts or less.
- ⁇ Base compound> As a basic compound, ammonia, an organic amine compound, a metal hydroxide, etc. are mentioned, for example. Preferably, it is ammonia or an organic amine compound.
- organic amine compounds include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3- Examples include diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine. N, N-dimethylethanolamine is preferable.
- the metal hydroxide include lithium hydroxide, potassium hydroxide and sodium hydroxide. Basic compounds are readily available from the market.
- the content thereof is preferably 20 parts by mass with respect to 100 parts by mass of the total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. Part or less, more preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less.
- Organic solvents include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol, and n-propanol.
- Alcohols such as isopropyl alcohol and n-butanol; glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol; methyl cellosolve, cellosolve, butyl cellosolve, dioxane, MTBE (methyl tertiary butyl ether) and butyl carbitol Cellosolve solvents; diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether and 3-methyl And glycol solvents such as xyl-3-methyl-1-butanol; and glycol ester solvents such as ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate), diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate. It is done. These may be used alone or in combination.
- the content thereof is 100 parts by mass with respect to 100 parts by mass of the mass part of the chlorinated rubber and the compound having a polymerizable group, from the viewpoint of odor, Preferably it is 100 mass parts or less, More preferably, it is 50 mass parts or less, More preferably, it is 30 mass parts or less, More preferably, it is 10 mass parts or less.
- Crosslinking agent By including a crosslinking agent, there exists a tendency for adhesiveness, the water resistance of a contact bonding layer, and the solvent resistance of a contact bonding layer to improve more.
- the crosslinking agent include epoxy compounds, polyisocyanate compounds, oxazoline compounds, aziridine compounds, carbodiimide compounds, active methylol compounds, active alkoxymethyl compounds, metal chelates, hydrazide compounds, and hydrazine compounds.
- Preferred are aliphatic polyisocyanate compounds, carbodiimide compounds, oxazoline group-containing compounds, hydrazide compounds, and hydrazine compounds. Of these, aqueous (water-soluble or water-dispersible) ones are more preferable.
- These crosslinking agents may be used alone or in combination.
- polyisocyanate compound examples include hexamethylene diisocyanate (HDI), 4,4′-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), and oligomers or polymers thereof.
- HDI hexamethylene diisocyanate
- MDI 4,4′-diphenylmethane diisocyanate
- TDI tolylene diisocyanate
- oligomers or polymers thereof examples include oligomers or polymers thereof.
- Sumidur registered trademark
- N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547, 44V10, 44V20 made by Sumika Bayer Urethane And E 21-1
- Death Module registered trademark
- carbodiimide-based crosslinking agents include Nisshinbo Chemical Co., Ltd .: Carbodilite (SV-02, V-02, V-02-L, V-04, E-01, E-02), etc. Can be mentioned.
- hydrazide compound crosslinking agents include: Otsuka Chemical Co., Ltd .: ADH (adipic acid dihydrazide), SDH (sebacic acid dihydrazide), DDH (dodecanediohydrazide), IDH (isophthalic acid dihydrazide), SAH. (Salicylic acid hydrazide) and the like.
- hydrazine compound crosslinking agent examples include Otsuka Chemical Co., Ltd .: hydrazine monohydrochloride, hydrazine dihydrochloride, hydrazine monohydrobromide, hydrazine carbonate, and the like.
- the content thereof is preferably 30 parts by mass with respect to 100 parts by mass of the total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. It is below, More preferably, it is 15 mass parts or less, More preferably, it is 10 mass parts or less, More preferably, it is 5 mass parts or less.
- the photosensitizer can be appropriately selected according to the wavelength to be enhanced.
- the effective excitation wavelength range is usually 450 nm or less, preferably in the range of 250 to 380 nm.
- Examples of the photosensitizer include triethanolamine, triisopropanolamine, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminoethylbenzoate, and isoacyl 4-dimethylaminobenzoate. .
- the content thereof is preferably 15 with respect to 100 parts by mass of the total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. It is not more than part by mass, more preferably not more than 10 parts by mass, and still more preferably not more than 5 parts by mass.
- the aqueous emulsion of the present invention may contain other resins as long as the intended properties are not impaired.
- resins include ethylene-vinyl ester resins, styrene-maleic acid resins, resins having structural units derived from ⁇ -olefins having 2 to 20 carbon atoms, chlorinated products and modified products thereof, (meth) acrylic resins, polystyrene , Polyvinyl acetate, polyurethane, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic ester copolymer resin, vinyl chloride-vinylidene chloride copolymer resin, chloride Vinylidene- (meth) acrylic acid ester copolymer resin, vinylidene chloride-acrylonitrile copolymer resin, chlorinated resin having a structural unit derived from ⁇ -olefin having 2 to 20 carbon atoms, ethylene-vinyl ester resin, polyurea, acrylonitrile Butadiene s
- the ethylene-vinyl ester resin is a copolymer containing a polymer composed of ethylene units and vinyl ester units.
- vinyl ester units include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl esters of tertiary carboxylic acids having 8 to 10 carbon atoms, and so-called vinyl versatates (for example, trade name: Veova (registered trademark) manufactured by Shell Chemical Co., Ltd.). And alkyl acid vinyl esters such as 10).
- vinyl ester units vinyl acetate is preferred.
- the copolymer is an ethylene-vinyl acetate copolymer (hereinafter sometimes abbreviated as “EVA”).
- ethylene-vinyl acetate copolymers have various vinyl acetate contents and shapes (films, blocks, fibers, foams), although the properties differ depending on the vinyl acetate content and the like.
- the ethylene-vinyl acetate copolymer may contain a polymer such as polyolefin.
- Preferred polyolefins include ethylene-octene copolymers, ethylene-butene copolymers, polypropylene and polyethylene.
- the ethylene-vinyl ester resin may contain monomer units copolymerizable therewith.
- the monomer unit include vinyl halides such as vinyl chloride, monomers having a small amount of a functional group such as an amide group, and (meth) acrylic acid esters.
- the ethylene-vinyl ester resin copolymer include VINNOL E15 / 45, E15 / 45M, E15 / 48A, H15 / 42, H15 / 50, H11 / 59, H14 / 36, H40 / 50, H40 / 55, H40 / 60, H30 / 48M (Wacker Chemie AG) and the like.
- the ethylene-vinyl ester resin and the copolymer thereof may be in the form of an emulsion.
- Such an emulsion may be produced by emulsion polymerization of monomers constituting the ethylene units and vinyl ester units, or commercially available ones may be used.
- Examples of the emulsion of the ethylene-vinyl ester resin copolymer include Sumikaflex (registered trademark) 201HQ, 303HQ, 355HQ, 400HQ, 401HQ, 408HQ, 410HQ, 450HQ, 455HQ, 456HQ, 460HQ, 465HQ, 467HQ, 7400HQ, 470HQ.
- Examples of the styrene-maleic acid resin include ARASTOR 700 and 703S (manufactured by Arakawa Chemical Industries, Ltd., SMA (registered trademark) 1000, SMA (registered trademark) 2000, SMA (registered trademark) 3000 (Cray Valley's).
- Examples of the emulsion of styrene-maleic acid resin include VE-1122 (Starlight PMC Co., Ltd.).
- Examples of the ⁇ -olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and vinylcyclohexane. Preferably, they are ethylene and propylene.
- Examples of the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms include polyethylene (PE), high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), and linear low density. Homopolymers such as polyethylene, ultra high molecular weight polyethylene and polypropylene (PP), isotactic (isotactic) polypropylene, syndiotactic polypropylene and atactic polypropylene, ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene ⁇ -olefin copolymers such as a 1-butene copolymer, an ethylene-1-octene copolymer and an ethylene-1-hexene copolymer, and an ⁇ -olefin having 2 to 20 carbon atoms and the ⁇ -olefin Copolymers of monomers copolymerizable with olefins It is below.
- the copolymer of an ⁇ -olefin having 2 to 20 carbon atoms and a monomer copolymerizable with the ⁇ -olefin may contain one type of each monomer or two or more types. It may be a thing.
- the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms may be any of a homopolymer, a random copolymer, a block copolymer, and a graft copolymer. Further, it may be reduced in molecular weight or high molecular weight by peroxide or the like.
- the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is modified with an ⁇ , ⁇ -unsaturated carboxylic acid or the like. Modified products.
- the modification rate of the modified product modified with ⁇ , ⁇ -unsaturated carboxylic acid or the like is usually 0.1 to 10% by mass, preferably 0.2 to 0.2% with respect to 100% by mass of the copolymer before modification. 5% by mass, more preferably 0.2 to 4% by mass.
- Examples of ⁇ , ⁇ -unsaturated carboxylic acids include ⁇ , ⁇ -unsaturated carboxylic acids (maleic acid, itaconic acid, citraconic acid, etc.), ⁇ , ⁇ -unsaturated carboxylic acid esters (methyl maleate, methyl itaconate) ), ⁇ , ⁇ -unsaturated carboxylic anhydrides (maleic anhydride, itaconic anhydride, citraconic anhydride, etc.).
- a modified product obtained by combining these ⁇ , ⁇ -unsaturated carboxylic acids may also be used. These may be carboxylic anhydrides, carboxylic acids formed by hydrolysis, or a mixture thereof.
- Such a modified product includes a resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms or a copolymer of an ⁇ -olefin having 2 to 20 carbon atoms and a monomer copolymerizable with the ⁇ -olefin.
- the modification rate of the chlorinated resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is such that the chlorine atom content is preferably 5 to 80 with respect to 100% by mass of the copolymer before modification. % By mass, more preferably 40 to 75% by mass. More preferably, it is 55 to 70% by mass.
- Chlorination of a resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is performed by dissolving or dispersing the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms in a solvent. It can be obtained by chlorinating a resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms by a method of blowing chlorine gas or the like.
- Monomers copolymerizable with ⁇ -olefins having 2 to 20 carbon atoms include ⁇ , ⁇ -unsaturated carboxylic acids and anhydrides, metal salts of ⁇ , ⁇ -unsaturated carboxylic acids, ⁇ , ⁇ -unsaturated carboxylic acids, and the like.
- Examples include acid esters, vinyl esters, vinyl ester saponified products, cyclic olefins, vinyl aromatic compounds, polyene compounds (dienes and the like), (meth) acrylonitrile, vinyl halides, amides and vinylidene halides. These may be used alone or in combination for copolymerization.
- ⁇ , ⁇ -unsaturated carboxylic acid and its anhydride include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, monomethyl maleate, monoethyl maleate, maleic Examples include acid half esters, maleic acid half amides, itaconic acid half esters, itaconic acid half amides, and the like. Of these, acrylic acid, methacrylic acid, maleic acid and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.
- Examples of the metal salt of ⁇ , ⁇ -unsaturated carboxylic acid include salts of monovalent metals such as lithium, sodium and potassium, and salts of polyvalent metals such as magnesium, calcium and zinc. Specifically, the sodium salt and magnesium salt of (meth) acrylic acid are mentioned.
- ⁇ , ⁇ -unsaturated carboxylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl acrylate, maleic acid Examples include esterified products of dimethyl and methacrylic acid and alcohol. Of these, methyl (meth) acrylate and ethyl (meth) acrylate are preferred.
- vinyl esters examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate and vinyl versatate. Of these, vinyl acetate is preferred.
- vinyl ester saponified product examples include vinyl alcohol obtained by saponifying vinyl ester with a basic compound or the like.
- cyclic olefin examples include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2 -Dihydrodicyclopentadiene, 5-chloronorbornene, cyclopentene, cyclohexene, cycloheptene, vinylcyclohexane and the like.
- vinyl aromatic compounds include styrene, ⁇ -methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, and vinylnaphthalene.
- styrene ⁇ -methylstyrene, p-methylstyrene, vinylxylene
- monochlorostyrene dichlorostyrene
- monobromostyrene dibromostyrene
- fluorostyrene p-tert-butylstyrene
- ethylstyrene ethylstyrene
- vinylnaphthalene vinylnaphthalene
- polyene compound examples include linear or branched aliphatic conjugated polyene compounds, alicyclic conjugated polyene compounds, aliphatic non-conjugated polyene compounds, alicyclic non-conjugated polyene compounds, and aromatic non-conjugated polyene compounds. . These may have a substituent such as an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group.
- Aliphatic conjugated polyene compounds include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2-methyl- Examples include 1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-octadiene, and 2,3-dimethyl-1,3-decadiene.
- Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclohexadiene, 2-chloro-1, Examples include 3-butadiene, 2-chloro-1,3-pentadiene and 2-chloro-1,3-cyclohexadiene.
- Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,9-decadiene, 3,3-dimethyl-1,4-hexadiene, 5-ethyl-1 , 4-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1 4, 4-decadiene, 6-methyl-1,6-undecadiene, 4-ethylidene-12-methyl-1,11-pentadecadien, and the like.
- Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexane, vinylcyclohexene, 5-vinyl-2-norbornene, 1,4-divinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane, and methyltetrahydroindene.
- aromatic non-conjugated polyene compound examples include divinylbenzene and vinylisopropenylbenzene.
- Examples of the copolymer having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms include ethylene-unsaturated carboxylic acid copolymers such as ethylene-acrylic acid copolymer and ethylene-methacrylic acid copolymer, and the ethylene -Ionomer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene / methyl methacrylate copolymer, wherein some or all of the carboxyl groups of the unsaturated carboxylic acid copolymer are neutralized with the above metals.
- ethylene-unsaturated carboxylic acid copolymers such as ethylene-acrylic acid copolymer and ethylene-methacrylic acid copolymer
- the ethylene -Ionomer ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene / methyl methacrylate copolymer,
- Polymer ethylene-isobutyl acrylate copolymer, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-n-butyl acrylate copolymer, ethylene-isobutyl acrylate-methacrylic acid copolymer, ethylene-acrylic Ethylene-unsaturated carboxylic acid esters such as n-butyl-methacrylic acid copolymer Ionomer in which part or all of the sum carboxylic acid copolymer and a carboxyl group is neutralized with the metal, ethylene - ethylene such as vinyl acetate copolymer - vinyl ester copolymer and the like.
- Examples of the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms and modified products thereof include Mersen (registered trademark) H H-6410M, H-6051, H-6960, H-6820, and H-6822X.
- the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms and a modified product thereof may be in the form of an emulsion.
- Such an emulsion may be produced by emulsifying a resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms and a modified product thereof, or a commercially available product may be used.
- Examples of emulsions of resins having structural units derived from ⁇ -olefins having 2 to 20 carbon atoms and modified products thereof include Arrow Base (registered trademark) SA-1200, SB-1200, SE-1200, SB-1010 (Unitika).
- Examples of the resin having a structural unit derived from a chlorinated ⁇ -olefin having 2 to 20 carbon atoms include Eraslene (registered trademark) 401A and 303B (Showa Denko KK), Harden (registered trademark) CY-9122P, CY- 9124P, HM-21P, M-28P, F-2P, F-6P, F-69, 13-LP, 13-LLP, 14-LWP, 14-WL-P, 15-LP, 15-LLP, 16- LP, DX-526P, DX-530P and BS-40 (Toyobo Co., Ltd.), and Supercron (registered trademark) 803L, 803MW, 814HS, 390S, HE-305, HE-505, HE-510, HE- 515, HE-910, HE-915, HE-1070, HE-1200, HP-205, HP-215 and HP-620 (Nippon Paper Chemical Co., Ltd.
- the resin having a structural unit derived from a chlorinated ⁇ -olefin having 2 to 20 carbon atoms may be in the form of an emulsion.
- Such an emulsion may be produced by emulsifying a chlorinated resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms, or a commercially available product may be used.
- Examples of emulsions of resins having structural units derived from chlorinated ⁇ -olefins having 2 to 20 carbon atoms include, for example, HARDLEN® EW-5303, EH-801, EW-5504, EZ-1000 and EZ- 2000 (Toyobo Co., Ltd.), Supercron (registered trademark) E-604, E-480T and E-415 (Nippon Paper Chemical Co., Ltd.).
- Polyurethane is a polymer composed of urethane bonds, and is usually obtained by reaction of alcohol (—OH) and isocyanate (—NCO).
- the urethane foam includes a polyurethane foamed by a volatile solvent such as carbon dioxide or freon produced by a reaction between an isocyanate and water.
- a commercially available polyurethane can be used. Examples thereof include Nipponran (registered trademark) 3110, 3116, 3016, 3113, 3124, 3126, 3230 (Nippon Polyurethane Industry Co., Ltd.).
- Examples of commercially available water-soluble urethanes include DISPAROL (registered trademark) U-42, U-53, U-54, U-56, KA-8484, KA-8484, KA-8755, KA-8756, and KA-.
- DISPAROL registered trademark
- Polyvinyl chloride is obtained by a method such as suspension polymerization or bulk polymerization of vinyl chloride.
- the polyvinyl chloride include hard polyvinyl chloride, semi-rigid polyvinyl chloride, and soft polyvinyl chloride. Preferably, it is soft polyvinyl chloride.
- the polyvinyl chloride include Kanevinyl S-400, PSH-180, PSL-180 (Kaneka).
- Examples of the polyvinyl chloride emulsion include Vinibrand 701, 700, and 711 (Nisshin Chemical Industry Co., Ltd.).
- Chlorinated polyvinyl chloride is obtained by chlorinating a polyvinyl chloride resin by a chlorination method such as a gas phase or a liquid phase.
- the polyvinyl chloride resin include a vinyl chloride homopolymer and a vinyl chloride copolymer.
- Examples of the monomer constituting the vinyl chloride copolymer together with vinyl chloride include ethylene, propylene, alkyl vinyl ether, vinylidene chloride, vinyl acetate, acrylic acid ester, maleic acid ester, and the like.
- Examples of the chlorinated polyvinyl chloride include Sekisui PVC-HA (Sekisui Chemical Co., Ltd.).
- polyvinylidene chloride examples include Saran X05253-16 (manufactured by Dow Chemical Company), Saran Wrap (registered trademark) resin (manufactured by Asahi Kasei Corporation), and the like.
- polyvinylidene chloride emulsion examples include Diofan 193D, A736, A036, A050, A063, B204, A115 (manufactured by Solvay).
- Examples of the vinyl chloride-vinylidene chloride copolymer resin include IXAN SGA-1 (manufactured by Solvay).
- vinylidene chloride- (meth) acrylic acid ester copolymer resin examples include IXAN PVS-109, 801, 815, Diofan A586, A602, A610 (manufactured by Solvay).
- the chloroprene-based resin is obtained by polymerizing chloroprene synthesized by dehydrochlorination of dichlorobutene obtained by chlorination of butadiene, or copolymerizing with other monomers.
- Such other monomers include isoprene, butadiene, dichlorobutadiene, styrene, acrylonitrile, acrylic acid esters, methacrylic acid esters, acrylic acid, methacrylic acid, itaconic acid and the like.
- the acid-modified chloroprene resin is obtained by graft copolymerizing the above chloroprene resin with at least one selected from ⁇ , ⁇ -unsaturated carboxylic acids and anhydrides thereof.
- ⁇ , ⁇ -unsaturated carboxylic acids and acid anhydrides thereof include those exemplified as modified products of resins having structural units derived from ⁇ -olefins having 2 to 20 carbon atoms.
- chloroprene resin and acid-modified chloroprene resin examples include Skyprene (registered trademark) G-42, G-40S, G-55, G-40, S-1, G-40T, B-30S, and Y-31. (Tosoh Corp.), Showprene (registered trademark) W, AF, WHV, WXJ, WB (Showa Denko), and Denkachloroprene (registered trademark) A-30, A-70, A-90, A- 91, M-130L, DCR-11 (Electrochemical Industry Co., Ltd.) and the like.
- Examples of emulsions of chloroprene resin and acid-modified chloroprene resin include Skyprene (registered trademark) GFL-820, GFL-890, GFL-280, LA-502, LA-660, SL-360, SL-390 and SL-590. (Tosoh Corporation), Shoprene (registered trademark) 115, 571, 572, 650, 671A, 750, SD78 and SD77S (Showa Denko Co., Ltd.), and Denkachloroprene (registered trademark) LA-50 and LC-501 ( Electrochemical Industry Co., Ltd.)).
- chlorinated butyl rubber examples include Enjay Butyl® HT10-66 (manufactured by Enjay Chemical), JSR® CHLOROBUTYL® 1066 (manufactured by JSR), and HT1066 (manufactured by ExxonMobil).
- brominated butyl rubber examples include JSR BROMOBUTYL552255, 2244 (manufactured by JSR), Exxon bromobutyl 2255 (ExxonMobil Chemical).
- modified rubber examples include a chlorinated or brominated modified copolymer of a copolymer of isomonoolefin and paramethylstyrene, and a commercially available product is Expro 50 (manufactured by Exxon).
- styrene block copolymer examples include a block copolymer composed of a diene block and a styrene block.
- SB styrene-butadiene block copolymer
- SBS styrene-butadiene-styrene block copolymer
- SIS styrene-isoprene-styrene block copolymer
- styrene-butadiene-butylene-styrene copolymer examples include a block copolymer composed of a diene block and a styrene block.
- SB styrene-butadiene block copolymer
- SBS styrene-butadiene-styrene block copolymer
- SIS styrene-isoprene-styrene block copolymer
- Examples thereof include a polymer (SBBS) or a hydrogenated product of these block copolymers, a styrene / isobutylene-styrene triblock copolymer (SIBS), and a styrene-isobutylene diblock copolymer (SIB).
- a hydrogenated product is a block copolymer in which all of the styrene block and the diene block are hydrogenated, or a block copolymer in which only the diene block is hydrogenated or a part of the styrene block and the diene block. It may be a partially hydrogenated product such as a hydrogenated block copolymer.
- Other resins may include water-soluble resins such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, and hydroxyethyl cellulose in order to further improve the stability of the aqueous emulsion.
- an adhesive resin or a resin having a function as a tackifier may be contained.
- resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and hydrogenated resins thereof.
- resins include resins, other petroleum resins, coumarone resins, and indene resins.
- rosin polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarized rosin and their glycerin ester, pentaerythritol ester, methyl ester, triethylene glycol ester, phenol modified product and ester thereof Rosins such as fluorides; terpene polymers, terpene phenols, ⁇ -pinene polymers, aromatic modified terpene polymers, ⁇ -pinene polymers, terpene hydrogenated resins and other terpene resins; C 5 petroleum fractions A petroleum resin obtained by polymerizing a petroleum fraction, a petroleum resin obtained by polymerizing a petroleum fraction having 9 carbon atoms and a hydrogenated resin thereof; a petroleum resin such as a maleic acid-modified product and a fumaric acid-modified product, chlorinated paraffin, and the like.
- Terpene resins include YS Resin PX, PXN, YS Polyster, Mighty Ace, YS Resin TO, TR and Clearon P, M, K (Yasuhara Chemical Co., Ltd.), Tamanol 803L, 901 (Arakawa Chemical Industries, Ltd.) and And Teltac 80 (Nippon Terpene Chemical Co., Ltd.).
- Examples of the terpene resin emulsion include Tamanol E-200NT and E100 (Arakawa Chemical Industries, Ltd.).
- chlorinated paraffin examples include Empara (registered trademark) 70, 50, AR-500 (Ajinomoto Fine Techno Co., Ltd.), Toyoparax (registered trademark) 250, 265, 270, 150, A50 (Tosoh Corp.), and the like. It is done.
- the aqueous emulsion of the present invention may contain other resins as long as the properties thereof are not impaired, and the content thereof is a total of 100 parts by mass of the chlorinated rubber and the compound having a polymerizable group. Preferably it is 100 mass parts or less with respect to a mass part, More preferably, it is 50 mass parts or less, More preferably, it is 30 mass parts or less, More preferably, it is 20 mass parts or less.
- resins may be mixed with the aqueous emulsion of the present invention in the form of an emulsion, or may be emulsified with a compound having a chlorinated rubber and a polymerizable group to form an aqueous emulsion.
- Thickeners can be used to adjust the viscosity of the aqueous emulsion.
- Adecanol registered trademark
- UH-140S UH-420, UH-438, UH-450VF, UH-462, UH-472, UH-526, UH-530, UH-540, UH-541VF, UH-550, UH-752 and H-756VF
- SN thickener 920, 922, 924, 926, 929-S, A-801, A-806, A-812, A-813, A-818, 621N, 636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636, and 4050 (San Nopco).
- the aqueous emulsion of the present invention preferably contains a chlorinated rubber and a compound having a polymerizable group as a mixture.
- a mixture is a state in which a chlorinated rubber and a compound having a polymerizable group are mixed, a state in which the chlorinated rubber is dispersed or swollen in a compound having a polymerizable group, and at least a part of the chlorinated rubber is a polymerizable group.
- dissolves in the compound which has this is included.
- That at least a part of the chlorinated rubber is dissolved in the compound having a polymerizable group means that when the mixture of the chlorinated rubber and the compound having a polymerizable group is filtered with a filter having a pore diameter of about 0.50 ⁇ m, the filtrate It is sufficient that at least a part of the chlorinated rubber is contained therein.
- the chlorinated rubber contained in the filtrate is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 30% by mass or more, relative to 100 parts by mass of the chlorinated rubber contained in the aqueous emulsion before filtration. More preferably, it is 70 mass% or more. Filtration with a filter is preferably performed after heating to a temperature equal to or higher than the melting point of the compound having a polymerizable group contained in the aqueous emulsion.
- Examples of a method of using a mixture of a chlorinated rubber and a compound having a polymerizable group include a method of mixing a chlorinated rubber and a compound having a polymerizable group using a mixer.
- the mixing temperature is usually 25 to 100 ° C.
- the mixing time is preferably as short as possible.
- Examples of the mixer include a Banbury mixer, a Henschel mixer, and a homomixer.
- the mixture of the chlorinated rubber and the compound having a polymerizable group is preferably contained as a dispersoid.
- dispersoid means particles dispersed in water.
- the dispersoid may be a solid at 23 ° C. and atmospheric pressure, but is preferably a liquid.
- the dispersoid is liquid as long as at least one of the components constituting the dispersoid has fluidity, and the dispersoid may contain a solid component or an insoluble component.
- the dispersoid is a liquid and has fluidity, the fluidity may be high or low. This is because the stability of the aqueous emulsion tends to improve when the fluidity is low, and the adhesiveness tends to improve when the fluidity is high.
- the total content of the mass part of the chlorinated rubber and the mass part of the compound having a polymerizable group is preferably 0.1 relative to the total mass of the chlorinated rubber, the compound having a polymerizable group and water. It is ⁇ 70% by mass, more preferably 1 to 70% by mass, and further preferably 2% to 60% by mass. Adhesiveness becomes favorable by setting it as the said range. In particular, when the content is 30% by mass or more, the stability of the aqueous emulsion becomes good. Therefore, it is more preferably 30% by mass to 60% by mass, further preferably 40% by mass to 60% by mass, and still more preferably 45% by mass to 60% by mass.
- the dispersoid in the aqueous emulsion has a volume-based median diameter of preferably 10 ⁇ m or less, more preferably 0.01 to 5 ⁇ m, still more preferably 0.01 to 2 ⁇ m, and even more preferably 0.01. ⁇ 1 ⁇ m.
- the volume-based median diameter is a particle diameter corresponding to a cumulative particle diameter distribution value of 50% on a volume basis, and means a median diameter measured on a volume basis unless otherwise specified.
- the average particle size of the dispersoid can be measured with a laser diffraction particle size measuring device LA-950V2 manufactured by HORIBA Corporation.
- the aqueous emulsion of the present invention can be produced by a known method.
- it can be produced by a post-emulsification method (for example, forced emulsification method, self-emulsification method, phase inversion emulsification method, etc.) in which a chlorinated rubber and a compound having a polymerizable group are dispersed in a dispersion medium such as water.
- a post-emulsification method for example, forced emulsification method, self-emulsification method, phase inversion emulsification method, etc.
- a chlorinated rubber and a compound having a polymerizable group are added to a reactor (optional additives may be added), and after mixing, water and / or a solvent are added, and optionally a surfactant.
- a method of emulsifying by adding an additive such as a photopolymerization initiator and then stirring while heating can be mentioned.
- Examples of the reactor include a container equipped with a heating device and a stirrer capable of applying a force such as a shearing force to the contents.
- a sealed container or a pressure vessel is preferable.
- a common agitator can be used.
- Examples of such a reactor include a pressure-resistant autoclave with a stirrer. Stirring may be performed at normal pressure or reduced pressure. The rotation speed of the stirrer is usually 50 to 20000 rpm.
- the mixing temperature and the heating and stirring temperature are usually 10 to 90 ° C., preferably 15 to 80 ° C., more preferably 15 to 60 ° C., and usually 25 to 100 ° C.
- Mixing and / or heating and stirring may be performed using a mixer such as a Banbury mixer, a Henschel mixer, and a homomixer in addition to the above-described stirrer.
- additives such as a photopolymerization initiator, a crosslinking agent, an organic solvent, a basic compound, a thickener, and a leveling agent may be added before adding water and / or a solvent, and water and / or a solvent may be added. You may add after adding, and may add after emulsification.
- the light stabilizer, ultraviolet curable oligomer, fluorescent whitening agent, photosensitizer, and other resins are preferably added before adding water and / or solvent.
- An aqueous emulsion having a large particle size may be obtained by pre-emulsifying in advance, and an aqueous emulsion having a small particle size may be obtained by performing high-pressure shearing using an apparatus such as a high-pressure homogenizer or a high-pressure homojetter.
- the obtained aqueous emulsion contains an organic solvent
- the removal of the organic solvent is usually performed by distilling off under reduced pressure.
- the surfactant when a surfactant is used, the surfactant may be separated and removed from the obtained aqueous emulsion. Separation and removal of the surfactant can be performed by, for example, a centrifugal separator, a filtration filter having an average pore size smaller than the average particle size of the aqueous emulsion, or an ultrafiltration membrane. However, the separation and removal of the surfactant may only reduce the amount of the surfactant. Furthermore, it is preferable to cool the obtained aqueous emulsion. By cooling, an aqueous emulsion composed of a fine dispersoid can be obtained. It is preferable that the cooling be performed slowly, for example, by leaving it at room temperature instead of rapid cooling. Thereby, a fine and homogeneous aqueous emulsion can be obtained without aggregation of resin or the like during the cooling process.
- the aqueous emulsion of the present invention is useful as a composition constituting an aqueous adhesive or the like. Moreover, you may use as a composition for forming in a to-be-adhered body as a coating film or a coating film by an aqueous emulsion.
- a water-based adhesive, a coating film, a coating film, and the like are usually used as a dried product or a cured product. In particular, the water-based adhesive effectively exhibits its function in the form of a coating film formed from an aqueous emulsion or a cured product thereof.
- These may be composite materials composed of a plurality of components. Further, it may be a kneaded molded product of an inorganic filler such as talc, silica or activated carbon, carbon fiber and the like and a plastic material.
- an inorganic filler such as talc, silica or activated carbon, carbon fiber and the like
- plastic material such as talc, silica or activated carbon, carbon fiber and the like
- adhesives between cellulose materials and plastic materials polyvinyl chloride, ethylene-vinyl acetate copolymers, cotton-containing fibers, nylon resins, olefin polymers, polyurethanes, rubbers, styrene butadiene rubbers and other styrene block copolymers. It can be suitably used for adhesion of polymers and synthetic leather.
- the shape of these materials include various types such as a film, a sheet, or a block, and preferably a film and a sheet.
- the olefin polymer is a resin obtained by polymerizing an olefin, and examples thereof include homopolymers and copolymers having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms.
- an olefin polymer what was illustrated by said other resin is mentioned.
- the resin constituting the adherend include those exemplified above for the other resins.
- the cotton-containing fibers may be 100% cotton fibers, or may be blended fibers of cotton and other natural fibers and / or chemical fibers.
- Other natural fibers include wool, silk and hemp.
- Chemical fibers include synthetic fibers (for example, polyamide fibers such as polyester and nylon), semi-synthetic fibers (cellulose fibers such as acetate, protein fibers such as promix), and regenerated fibers (rayon, cupra, polynosic, etc.) Cellulosic fibers) and inorganic fibers (carbon fibers, glass fibers) and the like.
- Examples of the shape of the cotton-containing fiber include woven fabric, knitted fabric, nonwoven fabric, knitted fabric, felt, film, and block shape.
- Nylon resin is a so-called polyamide resin, which is a polymer composed of amide bonds. Specific examples include nylon 6, nylon 6,6, nylon 4,6, nylon 11, and nylon 12.
- the nylon resin may have any shape such as a film, a block, a fiber, or a foam.
- natural rubber thermoplastic rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber and the like are mainly used as the rubber.
- these diene rubbers may be used alone or in combination of two or more.
- reinforcing agents such as clay, carbon black or silica, silane coupling agents, anti-aging agents, softeners, zinc white, stearic acid, vulcanization accelerators, vulcanizing agents, sulfur, etc. are appropriately blended. May be.
- Synthetic leather includes both synthetic leather and artificial leather in the narrow sense.
- it may be a synthetic leather obtained by applying a synthetic resin to a natural or synthetic fabric, or may be an artificial leather obtained by impregnating a synthetic resin into a fabric (usually a nonwoven fabric) such as a microfiber, such as a microfiber.
- Artificial leather obtained by impregnating a fabric (usually a nonwoven fabric) with a synthetic resin and further applying the synthetic resin may be used.
- these synthetic resins include polyurethane resins, polyamide resins, and polyamino acid resins. A polyurethane resin is preferable.
- the aqueous emulsion of the present invention is effective for bonding materials (hereinafter sometimes referred to as adherends) such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing and shoes.
- adherends such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing and shoes.
- adherends such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing and shoes.
- adherends such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing and shoes.
- adherends such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing and shoes.
- adherends such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing and shoes.
- adherends such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials,
- an aqueous emulsion is applied to the surface of the first substrate, optionally the second substrate.
- Any known coating method can be used for coating. For example, gravure roll coating, reverse roll coating, bar coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brushing and spatula coating can be used.
- the obtained coating film may be dried or heat-treated, and then irradiated with electromagnetic waves.
- the coating film can be formed by drying or heat treatment to remove water or the solvent.
- the heating temperature include about 30 to 150 ° C, preferably about 40 to 80 ° C.
- the heating time is about 1 second to 1 hour, preferably about 5 seconds to 30 minutes, and more preferably about 5 seconds to 10 minutes.
- the first substrate may be further treated by leaving (natural drying) or using a normal hot air circulation oven, an infrared heater, electromagnetic waves such as ultraviolet rays, and the like.
- the heating temperature and time in the preliminary drying can be appropriately adjusted according to the characteristics of the substrate, the composition of the aqueous emulsion to be used, and the like. For example, the same conditions as mentioned above can be mentioned.
- Application and drying of the aqueous emulsion may be performed only once or may be performed twice or more.
- the same method may be combined, or different methods may be combined.
- examples of the light source include a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, an arc lamp, and a laser.
- a metal halide lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, and a low pressure mercury lamp are mentioned.
- the irradiation amount is usually 5 mW / cm 2 to 2000 mW / cm 2 as a peak illuminance, preferably 10 mW / cm 2 to 2000 mW / cm 2, and the integrated irradiation amount is usually 20 to 3000 mJ / cm 2, preferably 100 to 2500 mJ / cm 2. is there.
- the surface of the first substrate may be subjected to a primer treatment.
- the primer treatment include blast treatment, chemical treatment, degreasing treatment, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and anchor layer formation treatment.
- the coating film after drying it is preferable that 95% by mass or more of water contained in the aqueous emulsion is removed. Adhesiveness is securable by setting it as this range.
- the thickness of the coating film after drying is such that the thickness after drying is about 0.01 to 300 ⁇ m, preferably about 0.01 to 200 ⁇ m, more preferably about 0.01 to 50 ⁇ m. .
- an adhesive is applied to at least one of the first substrate and the second substrate to which the aqueous emulsion is applied, and is heat-dried.
- These coating and heat drying treatments may be performed only once on at least one of the first base material and the second base material. However, one or more times of application and heat drying of the adhesive may be performed on both. .
- the adhesive application method, application thickness, heat treatment method, temperature, time, and other conditions can be changed as appropriate. The same conditions as the application and drying of the aqueous emulsion described above may be selected, or different conditions may be selected.
- the adhesive layer may not be the same adhesive for the first substrate and the second substrate, Considering the adhesiveness of both, it is preferable to use the same adhesive.
- the water-based emulsion used above may be sufficient as an adhesive agent, and a commercially available adhesive agent may be sufficient as it.
- the thickness of the adhesive layer can be appropriately adjusted depending on the composition of the adhesive used, the material and form of the substrate, and the like. For example, the thickness after drying is about 0.01 to 300 ⁇ m, preferably about 0.01 to 200 ⁇ m.
- the surface of the second substrate may be subjected to a primer treatment.
- the primer treatment can be appropriately selected from the above.
- a mechanical operation or a manual method may be used as a method of bonding the surfaces of the first base material and the second base material to which the aqueous emulsion and / or adhesive is applied.
- heat, pressure or both may be applied.
- the heat load may be performed using the above-described normal hot air circulation type oven, infrared heater, microwave oven, or the like.
- a pressure in the case of applying a pressure about 100 g / cm ⁇ 2 > or more is mentioned, and less than the pressure which the shape of a 1st base material and a 2nd base material deform
- the time is, for example, about 1 second to 10 days.
- the first base material and the second base material are the same as the adherend described above.
- the first base material is preferably an equipment made of an olefin polymer or an ethylene / vinyl acetate copolymer
- the second base material is polyvinyl chloride, synthetic leather, rubber, cotton-containing fiber, and polyolefin base.
- a substrate selected from the group consisting of polymers is preferred.
- the adhesive layer can be obtained, for example, by removing water, solvent, etc. from polyurethane, rubber adhesive, acrylic adhesive, epoxy adhesive, etc. by performing heat drying, electromagnetic wave treatment, or the like.
- Examples of the polyurethane include the same ones as described above.
- Examples of rubber adhesives include natural rubber, chloroprene rubber, styrene-butadiene copolymer rubber (SBR), isobutylene rubber, butyl rubber, styrene-isoprene-styrene block copolymer rubber (SIS), and styrene-butadiene-styrene block copolymer.
- Examples thereof include polymer rubber (SBS), butadiene-acrylonitrile copolymer rubber (NBR), and butadiene rubber (BR). These may be used alone or in combination of two or more.
- an adhesion-imparting resin such as a rosin resin, a terpene resin, or a petroleum resin may be mixed.
- the acrylic adhesive include a copolymer of an acrylic ester and / or a methacrylic ester as an adhesive component, a functional group monomer component copolymerizable therewith, and an aggregating component.
- This copolymer may be crosslinked with an isocyanate crosslinking agent, a chelate crosslinking agent, an epoxy crosslinking agent, or the like.
- acrylic esters examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, Preferred examples include n-octyl acrylate and n-lauryl acrylate.
- Methacrylic acid esters include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, Preferred examples include n-octyl methacrylate and n-lauryl methacrylate.
- Examples of the functional group monomer component copolymerizable with acrylic acid ester and / or methacrylic acid ester include ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid; acrylic Acrylic acid or hydroxyalkyl ester of methacrylic acid such as hydroxyethyl acid, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-butoxy N-substituted or unsubstituted acrylamide such as methyl acrylamide and N-butoxy methacrylamide; glycidyl ester of acrylic acid or methacrylic acid such as glycidyl methacrylate and glycidyl methacrylate; Preferable examples include acrylonitrile.
- the epoxy adhesive is a compound having an average of one or more epoxy groups per molecule used as a component of a normal epoxy resin adhesive.
- useful epoxy resins include epoxy resins obtained from bisphenol A and epichlorohydrin, polyglycidyl ethers obtained from bisphenol F and epichlorohydrin, hydrogenated bisphenol A and epichlorohydrin, and the like.
- oxazolidone-modified epoxy resins, novolac type epoxy resins, polyfunctional phenol type epoxy resins, various halogenated epoxy resins, glycidyl ester type epoxy resins, polyglycol type epoxy resins, cycloaliphatic epoxy resins, and the like can also be used. . These epoxy resins can be used alone or in admixture of two or more.
- Polyurethane, rubber adhesives, acrylic adhesives, and epoxy adhesives may be in the form of adhesives such as water-based, solvent-based, and hot melt.
- the adhesive which comprises an adhesive bond layer may contain resin other than the adhesive agent mentioned above, and an additive.
- the resin that may be contained in the adhesive layer include polyolefin resin, polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polytetrafluoroethylene (PTFE),
- PVC polyvinyl chloride
- PS polystyrene
- PVAc polyvinyl acetate
- PTFE polytetrafluoroethylene
- ABS resin acrylonitrile butadiene styrene resin
- AS resin acrylonitrile butadiene styrene resin
- modified polymers and modified products may be used alone or in combination of two or more.
- Such resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and Examples thereof include hydrogenated resins, other petroleum resins, coumarone resins, indene resins and polyurethane resins.
- Additives that may be contained in the adhesive layer include surfactants, photopolymerization initiators, light stabilizers, UV curable oligomers, fluorescent whitening agents, leveling agents, basic compounds, organic solvents, crosslinking agents, Photosensitizer, other resins, phenol stabilizer, phosphite stabilizer, amine stabilizer, amide stabilizer, anti-aging agent, weathering stabilizer, anti-settling agent, antioxidant, heat stabilizer, Antiseptic, thixotropic agent, thickener, antifoaming agent, viscosity modifier, weathering agent, pigment dispersant, antistatic agent, lubricant, nucleating agent, flame retardant, oil agent, dye, curing agent; titanium oxide (rutile type) ) And transition metal compounds such as zinc oxide; pigments such as carbon black; glass fibers, carbon fibers, potassium titanate fibers, wollastonite, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate, clay, kaolin
- the coating film of the aqueous emulsion, the dried product of the coating film, and the cured product thereof preferably have a shear viscosity of less than 200 Pa ⁇ s. In this range, the adhesiveness tends to improve.
- the shear viscosity was measured with a rotary rheometer using a cone plate (angle 2 °) with a shear rate of 1 s-1 and a measurement temperature of 25 ° C. (when the melting point of the compound having a polymerizable group is higher than 25 ° C. Can be measured at a temperature 10 ° C. higher than the melting point of the compound having a polymerizable group.
- the dry product of the aqueous emulsion preferably excludes 95% by mass or more of the mass of water contained in the aqueous emulsion. Thereby, the influence of water on the shear viscosity can be suppressed, and a desired shear viscosity can be obtained.
- aqueous emulsion of the present invention examples will be described in detail below. Unless otherwise indicated, the part and% in an example mean a mass reference
- the chlorine content of the chlorinated rubber and the polymer is a value measured by a flask combustion-ion chromatography method.
- the component concentration of the aqueous emulsion is the mass of the total content of the mass part of the chlorinated rubber and the mass part of the compound having a polymerizable group, with respect to the mass of the total mass of the chlorinated rubber, the compound having a polymerizable group, and water. It is a value obtained by calculating the concentration (mass%).
- the median diameter of the dispersoid is a value measured with a laser diffraction particle diameter measuring apparatus LA-950V2 manufactured by HORIBA Corporation. Unless otherwise specified, it is a median diameter value (unit: ⁇ m) measured on a volume basis.
- the standing stability was evaluated by allowing the obtained aqueous emulsion to stand at room temperature for 1 week and observing the aqueous emulsion. When phase separation was not visually confirmed in the aqueous emulsion, it was judged that the standing stability was good. ⁇ : No change ⁇ : Phase separation was confirmed visually
- Chlorinated rubber 1 Pergut S20 (Bayer, chlorine content of 58.8% by mass or more)
- Chlorinated rubber 2 Pergut S40 (Bayer, chlorine content of 65.5% by mass or more)
- Chlorinated rubber 3 Pergut S10 (Bayer, chlorine content 64.1% by mass or more)
- Chlorinated rubber 4 Pergut S5 (Bayer, chlorine content 61.2% by mass or more)
- Polymer 1 Showrene W (Showa Denko KK, chloroprene rubber, chlorine content 37.8% by mass)
- Polymer 2 Showrene AF (Showa Denko KK, chloroprene rubber, chlorine content 38.1% by mass)
- Polymer 3 VINNOL E15 / 45 (Wacker Chemie AG, vinyl chloride / vinyl acetate copolymer resin)
- Resin aqueous dispersion 1 Arrow Base SD (Unitika Ltd., modified polyolefin resin aqueous dispersion, solid content 25%)
- Resin aqueous dispersion 2 Showrene SD77S (Showa Denko KK, chloroprene rubber, solid content 55%)
- Resin aqueous dispersion 3 Aurolen AE-202 (Nippon Paper Industries, modified polyolefin resin aqueous dispersion, solid content 30%)
- Resin aqueous dispersion 4 Aquatex HA-1100 (Chuo Rika Kogyo Co., Ltd., ethylene / vinyl acetate copolymer resin, solid content 45%)
- Resin aqueous dispersion 5 Vinyblan 700 (Nissin Chemical Industry Co., Ltd., vinyl chloride resin aqueous dispersion, solid content 30%)
- Resin aqueous dispersion 6 Diofan TM A063 (Solvay Specialty Polymers Japan, vinyl
- Compound having polymerizable group 1 dodecyl methacrylate (containing 970 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
- Compound 2 having polymerizable group: 1,6-hexanediol dimethacrylate (containing 60 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
- Compound 3 having a polymerizable group: stearyl methacrylate (containing 200 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
- Compound 4 having a polymerizable group: 2-ethylhexyl methacrylate (containing 25 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
- Compound 5 having a polymerizable group: cyclohexyl methacrylate (containing 50 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
- Compound 6 having a polymerizable group: 2-ethylhexyl
- Photopolymerization initiator 1 2-hydroxy-2-methylpropiophenone (Tokyo Chemical Industry Co., Ltd.)
- Photopolymerization initiator 2 1-hydroxycyclohexyl phenyl ketone (Tokyo Chemical Industry Co., Ltd.)
- Photopolymerization initiator 3 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine (Tokyo Chemical Industry Co., Ltd.)
- Surfactant 1 Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.)
- Surfactant 2 LATEMUL E-1000A (30% aqueous solution, Kao Corporation)
- Surfactant 3 Neugen EA-177 (Daiichi Kogyo Seiyaku Co., Ltd.)
- Surfactant 4 DKS NL-180 (Daiichi Kogyo Seiyaku Co., Ltd.)
- Surfactant 5 Kuraray Poval 217 (Kuraray Co., Ltd.)
- Surfactant 6 Kuraray Poval 205 (Kuraray Co., Ltd.)
- Surfactant 7 Adeka Pluronic F108 (ADEKA)
- Surfactant 8 Emulgen 102KG (Kao Corporation)
- Surfactant 9 Emulgen 109P (Kao Corporation)
- Surfactant 10 Emulgen 150 (Kao Corporation)
- Basic compound 1 N, N-dimethylethanolamine (Tokyo Chemical Industry Co., Ltd.)
- Light stabilizer 1 TINUVIN 1130 (BASF)
- Light stabilizer 2 TINUVIN 123 (BASF)
- UV curable oligomer 1 AH-600 (Kyoeisha Chemical Company)
- UV curable oligomer 2 UA-306H (Kyoeisha Chemical Co., Ltd.)
- Optical brightener 1 1,4-bis (2-benzoxazolyl) naphthalene (Tokyo Chemical Industry Co., Ltd.)
- Fluorescent whitening agent 2 Kyaphor SN (Nippon Kayaku Co., Ltd.)
- Fluorescent whitening agent 3 Nikkafluor OB (Nippon Chemical Industry Co., Ltd.)
- Organic solvent 1 Toluene (Wako Pure Chemical Industries, reagent special grade)
- Organic solvent 2 2-butanone (Wako Pure Chemical Industries, reagent special grade)
- Organic solvent 3 2-propanol (Wako Pure Chemical Industries, reagent special grade)
- Leveling agent 1 BYK-349 (Big Chemie Japan)
- Crosslinking agent adipic acid dihydrazide (Tokyo Chemical Industry Co., Ltd.) In each table, these components are expressed in parts by mass.
- ⁇ Production Example 1> In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)) and a compound having a polymerizable group, dodecyl methacrylate (Tokyo Chemical Industry Co., Ltd.) ) 60 parts and 30 parts of 1,6-hexanediol dimethacrylate (Tokyo Chemical Industry Co., Ltd.), 190 parts of tetrahydrofuran (Hayashi Junyaku Co., Ltd., reagent grade) were added and dissolved by stirring at 60 ° C.
- chlorinated rubber 1 Pergut S20 (Bayer)
- dodecyl methacrylate Tokyo Chemical Industry Co., Ltd.
- 60 parts and 30 parts of 1,6-hexanediol dimethacrylate Tokyo Chemical Industry Co., Ltd.
- Surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.)) (3 parts) was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an ion-exchange aqueous solution of Surfactant 1.
- the obtained aqueous emulsion was put into an eggplant flask, distilled off under reduced pressure with an evaporator, and filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-1).
- the obtained aqueous emulsion (E-1) had a nonvolatile content concentration of 45%.
- Each added component is listed in Table 1-1.
- aqueous emulsion (E) was prepared in the same manner as in Production Example 1 except that 90 parts of dodecyl methacrylate was used instead of the compound having a polymerizable group used in Production Example 1, and 5 parts of Aqualon KH-10 was used instead of the surfactant. -2) was obtained. The resulting aqueous emulsion (E-2) had a non-volatile content of 47%. Each added component is listed in Table 1-1.
- a trahydrofuran solution of the chlorinated rubber 1 and the compound having a polymerizable group was prepared.
- Surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.), 5 parts, was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an ion-exchange aqueous solution of Surfactant 1.
- the obtained mixture was stirred at 16000 rpm for 2 minutes to obtain a milky white aqueous emulsion.
- the obtained aqueous emulsion was put into an eggplant flask, distilled off under reduced pressure with an evaporator, and filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-3).
- the resulting aqueous emulsion (E-3) had a nonvolatile content concentration of 43%.
- Each added component is listed in Table 1-1.
- Surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.), 3 parts, was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an ion-exchange aqueous solution of Surfactant 1.
- an ion exchange aqueous solution of surfactant 1 and 2 parts of N, N-dimethylethanolamine as basic compound 1 (Tokyo Chemical Industry Co., Ltd.) was added and stirred to mix.
- TK Robotics manufactured by PRIMIX Co., Ltd.
- MARKII stirrer homomixer
- the obtained mixture was stirred at 16000 rpm for 2 minutes to obtain a milky white aqueous emulsion.
- a high pressure homogenizer manufactured by SMT Co., Ltd.
- LAB1000 high pressure homogenizer
- the aqueous emulsion obtained by performing the treatment once at 800 bar was filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-4).
- E-4 aqueous emulsion
- ⁇ Production Example 15> In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)), as a compound having a polymerizable group, dodecyl methacrylate (Tokyo Chemical Industry Co., Ltd.) 60 parts and 30 parts of 1,6-hexanediol dimethacrylate (Tokyo Chemical Industry Co., Ltd.) were charged, dissolved by stirring at 60 ° C., and cooled to room temperature.
- chlorinated rubber 1 Pergut S20 (Bayer)
- dodecyl methacrylate Tokyo Chemical Industry Co., Ltd.
- 60 parts and 30 parts of 1,6-hexanediol dimethacrylate Tokyo Chemical Industry Co., Ltd.
- Surfactant 2 (Latemul (registered trademark) E-1000A (30% aqueous solution, Kao)) 5 parts is added to 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. Was prepared. At room temperature, an ion exchange aqueous solution of surfactant 2 is added to a mixture of chlorinated rubber 1 and a compound having a polymerizable group, and further 2 parts of N, N-dimethylethanolamine (Tokyo) as basic compound 1 Kasei Kogyo) was added and mixed by stirring. To this, 1 part of photopolymerization initiator 1 (2-hydroxy-2-methylpropiophenone (Tokyo Kasei Kogyo Co., Ltd.)) was added and mixed by stirring.
- photopolymerization initiator 1 (2-hydroxy-2-methylpropiophenone (Tokyo Kasei Kogyo Co., Ltd.) was added and mixed by stirring.
- TK Robotics manufactured by PRIMIX Co., Ltd.
- MARKII stirrer homomixer
- the obtained mixture was stirred at 16000 rpm for 2 minutes to obtain a milky white aqueous emulsion.
- a high pressure homogenizer manufactured by SMT Co., Ltd.
- LAB1000 high pressure homogenizer
- the aqueous emulsion obtained by performing the treatment once at 800 bar was filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-15).
- E-15 aqueous emulsion
- Surfactant 2 (Latemul (registered trademark) E-1000A (30% aqueous solution, Kao)) 5 parts is added to 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. Was prepared. At room temperature, 2 parts of N, N-dimethylethanolamine (Tokyo Chemical Industry Co., Ltd.) as a basic compound 1 in an ion exchange aqueous solution of a surfactant 2 in a mixture of chlorinated rubber 1, a compound having a polymerizable group and toluene. ) was added and stirred to mix.
- N, N-dimethylethanolamine Tokyo Chemical Industry Co., Ltd.
- Surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.), 3 parts, was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an ion-exchange aqueous solution of Surfactant 1.
- 2 parts of N, N-dimethylethanolamine (Tokyo Kasei Kogyo Co., Ltd.) as the basic compound 1 is added to the mixture of the chlorinated rubber 1 and the compound having a polymerizable group in an ion exchange aqueous solution of the surfactant 1. Added and mixed with stirring.
- TK Robotics manufactured by PRIMIX Co., Ltd.
- MARKII stirrer homomixer
- aqueous emulsion (S-1) was obtained in the same manner as in Production Example 11 except that Polymer 1 (Shoprene W (Showa Denko)) was used as the chlorinated rubber 1 used in Production Example 11.
- ⁇ Production Example 150> In a separable flask reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)), polymer 3 (VINNOL E15 / 45 (Wacker Chemie AG)) 1 As a compound having a polymerizable group, 60 parts of dodecyl methacrylate (Tokyo Kasei Kogyo Co., Ltd.) and 30 parts of 1,6-hexanediol dimethacrylate (Tokyo Kasei Kogyo Co., Ltd.) are charged and dissolved by stirring at 60 ° C. Cooled to room temperature.
- dodecyl methacrylate Tokyo Kasei Kogyo Co., Ltd.
- 1,6-hexanediol dimethacrylate Tokyo Kasei Kogyo Co., Ltd.
- Surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.), 3 parts, was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an ion-exchange aqueous solution of Surfactant 1.
- an ion exchange aqueous solution of surfactant 1 and 2 parts of N, N-dimethylethanolamine as basic compound 1 (Tokyo Chemical Industry Co., Ltd.) was added and stirred to mix.
- TK Robotics manufactured by PRIMIX Co., Ltd.
- MARKII stirrer homomixer
- the obtained mixture was stirred at 16000 rpm for 2 minutes to obtain a milky white aqueous emulsion.
- the aqueous emulsion obtained by performing the treatment once at 800 bar using a high-pressure homogenizer manufactured by SMT Co., Ltd.
- LAB1000 was filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-70).
- E-70 aqueous emulsion
- ⁇ Production Examples 151 to 157> Three-one motor is mixed with water emulsion, resin aqueous dispersion, photopolymerization initiator, leveling agent 1 (BYK (registered trademark) -349, Big Chemie Japan Co., Ltd.) and ion-exchanged water in the parts by mass shown in Table 2-10.
- the aqueous adhesives (F81) to (F87) containing the aqueous emulsion obtained in the production example were obtained.
- the water-based adhesive (F1) is applied to M-EVA (ethylene-vinyl acetate copolymer foam), which is the first substrate, using a brush (coating amount: weight after drying: about 3 g / m 2) And dried at 70 ° C. for 5 minutes, and M-EVA (A) was obtained by irradiating ultraviolet rays with a conveyor-type UV irradiation device (Eye Grandage ECS-4011GX, manufactured by Eye Graphics Co., Ltd.).
- a conveyor-type UV irradiation device Eye Grandage ECS-4011GX, manufactured by Eye Graphics Co., Ltd.
- the obtained laminate (1) was allowed to stand at room temperature for 24 hours, and then, using a tensile tester (manufactured by Shimadzu Corporation, Autograph), a peeling speed of 50 mm / min, a peeling angle of 180 degrees, at room temperature, The adhesion between M-EVA and soft polyvinyl chloride in the laminate was evaluated by measuring peel strength. The results are shown in Table 3-1. ⁇ : Peel strength 55 N / inch or more. X: Peel strength less than 55 N / inch.
- the laminates (1) to (81) generally exhibited a sufficiently high peel strength of 55 N / inch or more.
- ⁇ Evaluation Example 82> The water-based adhesive (F1) was applied to M-EVA (ethylene-vinyl acetate copolymer foam) using a brush (coating amount: weight about 3 g / m 2 after drying), and 5 ° C. at 70 ° C. After drying for a minute, M-EVA (A) was obtained by irradiating ultraviolet rays with a conveyor-type UV irradiation device (Eye Grandage ECS-4011GX, manufactured by Eye Graphics Co., Ltd.).
- a conveyor-type UV irradiation device Eye Grandage ECS-4011GX, manufactured by Eye Graphics Co., Ltd.
- An aqueous emulsion (E200) was applied to the obtained cotton canvas (A) and M-EVA (A) using a brush (coating amount: weight after drying of about 50 g / m 2 ), and the oven was kept at 70 ° C. for 5 minutes. Dried. Thereafter, the coated surfaces of the obtained cotton canvas (A) and M-EVA (A) of the aqueous emulsion (E200) were bonded together, pressure bonded by hand, and further pressure bonded at 3 MPa for 20 seconds by a press. As a result, a laminate (82) was obtained in which a cotton canvas, an adhesive layer made of E200, an adhesive layer irradiated with ultraviolet rays, and M-EVA were laminated in this order.
- An aqueous emulsion (E200) was applied to the obtained rubber base material (A) and M-EVA (A) using a brush (application amount: weight after drying of about 50 g / m 2 ), and at 70 ° C. for 5 minutes. Oven dried. Thereafter, the coated surfaces of the obtained rubber base material (A) and M-EVA (A) of the aqueous emulsion (E200) were bonded together, pressure-bonded by hand, and further pressure-bonded by pressing at 3 MPa for 20 seconds. As a result, a laminate (83) was obtained in which a rubber substrate (A), an adhesive layer made of E200, an adhesive layer irradiated with ultraviolet rays, and M-EVA were laminated in this order.
- ⁇ Evaluation Example 84> The water-based adhesive (F1) was applied to M-EVA (ethylene-vinyl acetate copolymer foam) using a brush (coating amount: weight about 3 g / m 2 after drying), and 5 ° C. at 70 ° C. After drying for a minute, M-EVA (A) was obtained by irradiating ultraviolet rays with a conveyor-type UV irradiation device (Eye Grandage ECS-4011GX, manufactured by Eye Graphics Co., Ltd.).
- a conveyor-type UV irradiation device Eye Grandage ECS-4011GX, manufactured by Eye Graphics Co., Ltd.
- the obtained laminates (82) to (84) were allowed to stand at room temperature for 24 hours, and thereafter, using a tensile tester (manufactured by Shimadzu Corp., Autograph), a peeling rate of 50 mm / min, a peeling angle of 180 degrees, At room temperature, the adhesion between M-EVA and cotton canvas, rubber substrate or synthetic leather in the laminate was evaluated by measuring peel strength. The results are shown in Table 3-11. ⁇ : Peel strength 55 N / inch or more. X: Peel strength less than 55 N / inch.
- the membrane filter 2 and the precipitate attached to the membrane filter 2 were dried under reduced pressure (10 hPa) for 24 hours at 22 ° C., and the precipitate attached to the membrane filter 2 was dissolved in THF.
- GPC measurement of the obtained THF solution and IR measurement of the substance obtained by drying the THF solution were performed.
- chlorinated rubber 1 was detected.
- the mass of the chlorinated rubber 1 contained in the aqueous emulsion after filtration was calculated from the GPC measurement result, and was 96 mass. %Met.
- ⁇ Evaluation Example 88> The shear viscosity of the composition obtained by drying the aqueous emulsion of Production Example 28 at 70 ° C. for 30 minutes was measured at 56 ° C. and a shear rate of 1 s ⁇ 1 with a rotary rheometer using a cone plate (angle 2 °). did. The shear viscosity was 12 Pa ⁇ s.
- the obtained laminate was allowed to stand at room temperature for 24 hours, and then, using a tensile tester (manufactured by Shimadzu Corp., Autograph), the peel rate was 50 mm / min, the peel angle was 180 degrees, and the room temperature was The adhesion between the first substrate and soft polyvinyl chloride was evaluated by measuring peel strength. The results are shown in Table 3-12. ⁇ : Peel strength 55 N / inch or more. X: Peel strength less than 55 N / inch.
- SBBS Foam obtained by polymerizing with styrene-butadiene-butylene-styrene block copolymer (SBBS)
- Laminates (99) to (135) were obtained in the same manner as in Evaluation Example 1 except that the aqueous adhesive (F1) in Evaluation Example 1 was changed to any of the aqueous adhesives (F88) to (F124). .
- the adhesion of the laminate was evaluated. The results are shown in Table 3-14. ⁇ : Peel strength 55 N / inch or more. X: Peel strength less than 55 N / inch.
- Comparative laminates (1) to (3) were obtained in the same manner as in Evaluation Example 1 except that the aqueous adhesive (F1) in Evaluation Example 1 was changed to any of the aqueous adhesives (H1) to (H3). It was. In the same manner as in Evaluation Example 1, the adhesion of the laminate was evaluated. The results are shown in Table 3-15.
- Comparative laminates (1)-(3) generally exhibited low peel strengths of less than 55 N / inch.
- the aqueous emulsion of the present invention can be usefully used as an adhesive or a coating film in order to adhere adherends to each other or with sufficient strength.
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Abstract
Description
〔1〕塩素原子含有量が45質量%以上である塩素化ゴムと、1種以上の重合性基を有する化合物と、水を含む水性エマルション。
〔2〕前記塩素化ゴム100質量部に対する、前記重合性基を有する化合物の含有量が50~10000質量部である〔1〕に記載の水性エマルション。
〔3〕水を前記分散媒として含み、
前記塩素化ゴムと前記重合性基を有する化合物との混合物を分散質として含む〔1〕又は〔2〕に記載の水性エマルション。
〔4〕前記分散質が液体状である〔1〕~〔3〕のいずれかに記載の水性エマルション。
〔5〕前記塩素化ゴムの少なくとも一部が前記分散質に溶解している〔1〕~〔4〕のいずれかに記載の水性エマルション。
〔6〕前記塩素化ゴムの少なくとも一部が前記重合性基を有する化合物に溶解した溶液を、分散質として含む〔1〕~〔5〕のいずれかに記載の水性エマルション。
〔7〕前記重合性基を有する化合物が23℃大気圧下にて液体である〔1〕~〔6〕のいずれかに記載の水性エマルション。
〔8〕前記重合性基を有する化合物が、エチレン性不飽和二重結合を有する化合物である〔1〕~〔7〕のいずれかに記載の水性エマルション。
〔9〕さらに、界面活性剤を含む〔1〕~〔8〕のいずれかに記載の水性エマルション。
〔10〕さらに、光重合開始剤を含む〔1〕~〔9〕のいずれかに記載の水性エマルション。
〔11〕さらに、光安定剤を含む〔1〕~〔10〕のいずれかに記載の水性エマルション。
〔12〕さらに、紫外線硬化性オリゴマーを含む〔1〕~〔11〕のいずれかに記載の水性エマルション。
〔13〕さらに、蛍光増白剤を含む〔1〕~〔12〕のいずれかに記載の水性エマルション。
〔14〕さらに、レベリング剤を含む〔1〕~〔13〕のいずれかに記載の水性エマルション。
〔15〕前記分散質の体積基準のメジアン径が10μm以下である〔3〕~〔14〕のいずれかに記載の水性エマルション。
〔16〕前記塩素化ゴムがカルボキシ基及びカルボン酸無水物構造を有さない〔1〕~〔15〕のいずれかに記載の水性エマルション。
〔17〕前記塩素化ゴムの質量部と前記重合性基を有する化合物の質量部との合計量が、前記塩素化ゴムと前記重合性基を有する化合物と水の質量部の合計量に対して、0.1質量%~70質量%である〔1〕~〔16〕のいずれかに記載の水性エマルション。
〔18〕上述したいずれかの水性エマルションによって形成される塗布膜。
〔19〕〔18〕に記載の塗布膜の硬化物。
〔20〕オレフィン系重合体からなる第1の基材の上に、〔19〕に記載の硬化物と、さらにその上に一層以上の接着剤層と、第2の基材とがこの順に積層された積層体。
〔21〕エチレン・酢酸ビニル共重合体からなる第1の基材の上に、〔19〕に記載の硬化物と、さらにその上に一層以上の接着剤層と、第2の基材とがこの順に積層された積層体。
〔22〕前記接着剤層と前記第2の基材とが〔19〕に記載の硬化物を介して積層されている〔20〕又は〔21〕に記載の積層体。
<塩素化ゴム>
塩素化ゴムは、塩素原子含有量が45質量%以上である塩素化ゴムである。塩素化ゴムは、1種でもよいし、2種以上を組み合わせてもよい。
例えば、水に、ポリイソプレンと、界面活性剤と、塩酸、硫酸又は硝酸等の酸とを加え、乳化した後、塩素ガスを吹き込むことで均一に塩素化したポリイソプレンを得ることができる。
このような範囲とすることにより、本発明の水性エマルションを水性接着剤として用いた際に十分な接着強度を確保することができるとともに、粘度の過度の上昇を抑制して、被着体に対する接着性を十分に確保することができる。
重合性基を有する化合物は、例えば、重合性基として、ビニル基、アリル基、プロぺニル基、ビニリデン基、ビニレン基(メタ)アクリル基、(メタ)アクリロイル基、ビニルエーテル基、ビニルベンジルエーテル基、(メタ)アクリルオキシ基、(メタ)アリルアミド基、スチリルオキシ基、スチリルアミド基、イソシアネート基、チオイソシアネート基、カルボキシル基、アルコール性又はフェノール性水酸基、シラノール基、脂環式エポキシ基、エポキシ基、グリシジル基、オキセタン基のような環状エーテル基を等の開環重合性基を含む。これらの基は、1種のみ又は2種以上含有していてもよいし、1つのみ又は2つ以上含有していてもよい。
重合性基を有する化合物としては、例えば、エチレン性不飽和二重結合を有する化合物、エポキシ化合物、オキセタン化合物、グリシジルエーテル化合物等が挙げられる。これらの化合物は、単独で用いてもよく、2種以上の組み合わせて用いてもよい。
重合性基を有する化合物としては、なかでも、エチレン性不飽和二重結合を1個以上有する化合物が好ましい。
本発明の水性エマルションが含有する水は、通常、水道水又は脱イオン水が用いられる。水性エマルション中に含まれる水は、特に限定されず、塩素化ゴムと重合性基を有する化合物とを均一な分散媒として存在させることができる量であればよい。
本発明の水性エマルションは、上述した塩素化ゴム及び重合性基を有する化合物に加え、種々の添加剤を添加することができる。添加剤としては、界面活性剤、光重合開始剤、光安定剤、紫外線硬化性オリゴマー、蛍光増白剤、レベリング剤、塩基性化合物、有機溶剤、架橋剤、光増感剤、その他の樹脂、フェノール系安定剤、フォスファイト系安定剤、アミン系安定剤、アミド系安定剤、老化防止剤、耐候安定剤、防腐剤、沈降防止剤、酸化防止剤、熱安定剤、揺変剤、増粘剤、消泡剤、粘度調整剤、耐候剤、顔料分散剤、帯電防止剤、滑剤、核剤、難燃剤、油剤、染料、硬化剤;酸化チタン(ルチル型)及び酸化亜鉛等の遷移金属化合物;カーボンブラック等の顔料;ガラス繊維、炭素繊維、チタン酸カリウム繊維、ウオラストナイト、炭酸カルシウム、硫酸カルシウム、タルク、ガラスフレーク、硫酸バリウム、クレー、カオリン、微粉末シリカ、マイカ、珪酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、酸化アルミニウム、酸化マグネシウム、アルミナ及びセライト等の無機又は有機の充填剤等が挙げられる。
フィルターでの濾過は、水性エマルションに含まれる重合性基を有する化合物の融点以上に加熱してから行うことが好ましい。
フィルターでの濾過は、水性エマルションに含まれる重合性基を有する化合物の融点以上に加熱してから行うことが好ましい。
界面活性剤は、乳化剤として作用するものが好ましい。界面活性剤としては、カチオン性、アニオン性、両性及びノニオン性の界面活性剤が挙げられ、好ましくは、アニオン性及びノニオン性の界面活性剤である。界面活性剤は、単独で用いてもよく、2種以上を組み合わせても用いてもよい。
光重合開始剤とは、光の作用により活性種を生じる化合物であり、光の作用により活性ラジカルを発生する光ラジカル発生剤、光の作用により酸を発生する光酸発生剤及び光の作用により塩基を発生する光塩基発生剤が挙げられる。
これら光ラジカル発生剤は、単独で使用してもよく、組み合わせて使用してもよい。
組み合わせの具体例としては、イルガキュア(登録商標)500(1-ヒドロキシ-シクロヘキシル-フェニル-ケトン/ベンゾフェノン:50/50%)、イルガキュア(登録商標)1700(ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチルペンチルホスフィンオキシド/2-ヒドロキシ-2-メチルフェニルプロパン-1-オン:25/75%)及びイルガキュア(登録商標)1800(ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチルペンチルホスフィンオキシド/1-ヒドロキシシクロヘキシル-フェニルケトン:25/75%)(BASFジャパン(株))等が挙げられる。
光安定剤としては、紫外線吸収剤及びヒンダードアミン系光安定剤が挙げられる。光安定剤は単独で用いてもよく、2種以上を組み合わせて用いてもよい。
紫外線硬化性オリゴマーとしては、ウレタンアクリレートオリゴマー、エポキシアクリレートオリゴマー及びポリエステルアクリレートオリゴマー等が挙げられる。紫外線硬化性オリゴマーは、単独で使用してもよく、組み合わせて使用してもよい。
蛍光増白剤としては、ジアルキルアミノクマリン、ビスジメチルアミノスチルベン、ビスメチルアミノスチルベン、4-アルコキシ-1、8-ナフタレンジカルボン酸-N-アルキルイミド、ビスベンズオキサゾリルエチレン、1,4-ビス(2-ベンゾオキサゾリル)ナフタレン、ジアルキルスチルベン等が挙げられる。市販の蛍光増白剤としては、Kayahor 3BS Liq.、Kayahor TAC Liq.、Kayaphor HBC Liq.、Kayalight B、Kayaphor AS 150、Kayaphor CR 200、Kayaphor JB Liq.、Mikawhite ATN conc.(日本化薬社製)、TINOPAL OB、TINOPAL NFW Liqid(BASF社製)、Hakkol P、Hakkol PHD、Hakkol RF、Hakkol PSR、Hakkol PSR-B、Hakkol CHP-B、Hakkol PY-2000、Hakkol PYB-D、Hakkol BE conc、Hakkol SG conc 150、Hakkol TH-100、Hakkol S-100、Hakkol RX-1、Hakkol OW-11、Hakkol OW-10extra、Hakkol KIP H/C、Hakkol SF、Hakkol JC、及び、Hakkol PMS H/C(昭和化学工業社製)、Nikkafluor SB conc、Nikkafluor KB、Nikkafluor OB、Nikkabright CX H/C(日本化学工業所社製)等が挙げられる。蛍光増白剤は、単独で使用してもよく、組み合わせて使用してもよい。
レベリング剤としては、ポリフローNo.45、ポリフローKL-245、ポリフローNo.75、ポリフローNo.90、ポリフローNo.95(共栄社化学工業社製)、BYK300、BYK306、BYK310、BYK320、BYK330、BYK346、BYK349、BYK-333、BYK-345、BYK-347、BYK-348、BYK-378(ビックケミー・ジャパン社製)、KP-341、KP-358、KP-368、KF-96-50CS、KF-50-100CS(信越化学工業社製)、サーフロンSC-101、サーフロンKH-40(AGCセイミケミカル社製)、フタージェント222F、フタージェント251、FTX-218(ネオス社製)、EFTOP EF-351、EFTOP EF-352、EFTOP EF-601、EFTOP EF-801、EFTOP EF-802(三菱マテリアル社製)、メガファックF-171、メガファックF-177、メガファックF-475、メガファックF-556、メガファックR-30(DIC社製)、アデカコールW-193、アデカコールW-287、アデカコールW-288、アデカコールW-304(ADEKA社製)、SNウェット366、ノプコ38-C、SNディスパーサンド5468、SNディスパーサンド5034、SNディスパーサンド5027、SNディスパーサンド5040、SNディスパーサンド5020(サンノプコ社)フルオロアルキルベンゼンスルホン酸塩、フルオルアルキルカルボン酸塩、フルオロアルキルポリオキシエチレンエーテル、フルオロアルキルアンモニウムヨージド、フルオロアルキルベタイン、フルオロアルキルスルホン酸塩、ジグリセリンテトラキス(フルオロアルキルポリオキシエチレンエーテル)、フルオロアルキルトリメチルアンモニウム塩、フルオロアルキルアミノスルホン酸塩、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレントリデシルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンラウレート、ポリオキシエチレンオレレート、ポリオキシエチレンステアレート、ポリオキシエチレンラウリルアミン、ソルビタンラウレート、ソルビタンパルミテート、ソルビタンステアレート、ソルビタンオレエート、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタンラウレート、ポリオキシエチレンソルビタンパルミテート、ポリオキシエチレンソルビタンステアレート、ポリオキシエチレンソルビタンオレエート、ポリオキシエチレンナフチルエーテル、アルキルベンゼンスルホン酸塩、又はアルキルジフェニルエーテルジスルホン酸塩等が挙げられる。
塩基性化合物としては、例えば、アンモニア、有機アミン化合物及び金属水酸化物等が挙げられる。好ましくは、アンモニア又は有機アミン化合物である。
金属水酸化物としては、水酸化リチウム、水酸化カリウム及び水酸化ナトリウム等が挙げられる。
塩基性化合物は市場から容易に入手できる。
有機溶剤としては、トルエン及びキシレン等の芳香族炭化水素;ヘキサン等の脂肪族炭化水素;酢酸エチル及び酢酸ブチル等のエステル;メチルエチルケトン及びメチルイソブチルケトン等のケトン;メタノ-ル、エタノール、n-プロパノール、イソプロピルアルコール及びn-ブタノール等のアルコール;エチレングリコール、ジエチレングリコール、トリエチレングリコール及びプロピレングリコール等のグリコール系溶媒;メチルセロソルブ、セロソルブ、ブチルセロソルブ、ジオキサン、MTBE(メチルターシャリーブチルエーテル)及びブチルカルビトール等のセルソルブ系溶媒;ジエチレングリコールモノメチルエーテル、トリエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル及び3-メトキシ-3-メチル-1-ブタノール等のグリコール系溶媒及び;エチレングリコールモノメチルエーテルアセテート、PMA(プロピレングリコールモノメチルエーテルアセテート)、ジエチレングリコールモノブチルエーテルアセテート及びジエチレングリコールモノエチルエーテルアセテート等のグリコールエステル系溶媒等が挙げられる。これらは単独で用いてもよく、組み合わせて用いてもよい。
架橋剤を含むことにより、接着性、接着層の耐水性及び接着層の耐溶剤性がより向上する傾向がある。
架橋剤としては、エポキシ化合物、ポリイソシアナート化合物、オキサゾリン化合物、アジリジン化合物、カルボジイミド化合物、活性メチロール化合物、活性アルコキシメチル化合物、金属キレート、ヒドラジド化合物、ヒドラジン化合物等が挙げられる。
好ましくは脂肪族ポリイソシアナート化合物、カルボジイミド化合物、オキサゾリン基含有化合物、ヒドラジド化合物、ヒドラジン化合物である。中でも水性(水溶性もしくは水分散性)のものがさらに好ましい。これらの架橋剤は単独で使用してもよく、組み合わせて使用してもよい。
具体的には、住化バイエルウレタン製のスミジュール(登録商標)N3200、N3300、N3400、N3600、N3900、S-304、S-305、XP-2655、XP-2487、XP-2547、44V10、44V20及びE 21-1、住友バイエルウレタン社製のデスモジュール(登録商標)N3100、N3300、N3400、N3600、N3900、S-304、S-305、XP-2655、XP-2487、XP-2547及びDA-L、E14及びE 22、住友バイエルウレタン社製のバイヒジュール(登録商標)304及びXP2655、BASF社製のバソナート(BASONAT(登録商標))PLR8878及びHW-100、武田薬品工業社製のタケネート(登録商標)WD720、WD725及びWD730、旭化成工業社製のデュラネート(登録商標)WB40-100、WB40-80D及びWX-1741等が挙げられる。
光増感剤は、増強したい波長に応じて適宜選定することができる。有効励起波長域は、通常、450nm以下のものであり、好ましくは250~380nmの範囲のものである。光増感剤としては、トリエタノールアミン、トリイソプロパノールアミン、4,4-ジエチルアミノベンゾフェノン、2-ジメチルアミノエチル安息香酸、4-ジメチルアミノエチル安息香酸エチル及び4-ジメチルアミノ安息香酸イソアシル等が挙げられる。
<その他の樹脂>
本発明の水性エマルションは、意図する特性を損なわない範囲でその他の樹脂を含有してもよい。
その他の樹脂としては、エチレン-ビニルエステル樹脂、スチレン-マレイン酸樹脂、炭素数2~20のα-オレフィン由来の構造単位を有する樹脂ならびにその塩素化物及び変性物、(メタ)アクリル系樹脂、ポリスチレン、ポリ酢酸ビニル、ポリウレタン、ポリ塩化ビニル、塩素化ポリ塩化ビニル、ポリ塩化ビニリデン、塩化ビニル-酢酸ビニル共重合樹脂、塩化ビニル-アクリル酸エステル共重合樹脂、塩化ビニル-塩化ビニリデン共重合樹脂、塩化ビニリデン-(メタ)アクリル酸エステル共重合樹脂、塩化ビニリデン-アクリロニトリル共重合樹脂、塩素化された炭素数2~20のα-オレフィン由来の構造単位を有する樹脂、エチレン-ビニルエステル樹脂、ポリウレア、アクリロニトリルブタジエンスチレン樹脂、クロロプレン系樹脂、酸変性クロロプレン樹脂、ブチルゴム、塩素化ブチルゴム、臭素化ブチルゴム、変性ゴム、スチレン-(メタ)アクリル酸樹脂、合成ゴム、天然ゴム、スチレン-ブタジエン樹脂、ブタジエン樹脂、ポリ(メタ)アクリロニトリル樹脂、(メタ)アクリルアミド樹脂、ポリエステル樹脂、変性ナイロン樹脂、エポキシ樹脂、スチレン系ブロック共重合体及びこれらのオリゴマー体等が挙げられる。上記のうち、塩素原子を含有するゴムは、塩素原子含有量が45質量%未満のゴムであることが好ましい。これらは、固体(例えば、樹脂粉末)の形態であってもよいし、エマルションの形態であってもよい。
エチレン-ビニルエステル樹脂共重合体としては、VINNOL E15/45、E15/45M、E15/48A、H15/42、H15/50、H11/59、H14/36、H40/50、H40/55、H40/60、H30/48M(Wacker Chemie AG社)等が挙げられる。
エチレン-ビニルエステル樹脂及びその共重合体は、エマルションの形態であってもよい。このようなエマルションは、前記エチレン単位及びビニルエステル単位を構成する単量体を乳化重合することによって製造してもよいし、市販のものを用いてもよい。エチレン-ビニルエステル樹脂共重合体のエマルションとしては、例えば、スミカフレックス(登録商標)201HQ、303HQ、355HQ、400HQ、401HQ、408HQ、410HQ、450HQ、455HQ、456HQ、460HQ、465HQ、467HQ、7400HQ、470HQ、478HQ、510HQ、520HQ、710、752、755、SDX-5100、801HQ、808HQ、830、850HQ、900HL及び3950(以上、住友化学(株)製)、バンフレックスOM-4000及びOM-4200(以上、(株)クラレ製)、ポリゾール(登録商標)EVA AD-2、AD-3、AD-4、AD-5、AD-51、AD-56、AD-59及びP-900(以上、昭和高分子(株)製)、デンカEVAテックス(登録商標)#20、#30、#40M、#60、#81及び#82(以上、電気化学工業(株)製)等が挙げられる。
α,β-不飽和カルボン酸の金属塩としては、リチウム、ナトリウム、カリウム等の1価金属の塩、マグネシウム、カルシウム、亜鉛等の多価金属の塩が挙げられる。具体的には、(メタ)アクリル酸のナトリウム塩及びマグネシウム塩が挙げられる。
α,β-不飽和カルボン酸エステルとしては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、グリシジル(メタ)アクリレート、2-ヒドロキシエチルアクリレート、マレイン酸ジメチル及びメタクリル酸とアルコールとのエステル化物等が挙げられる。なかでも、メチル(メタ)アクリレート及びエチル(メタ)アクリレートが好ましい。
ビニルエステル鹸化物としては、ビニルエステルを塩基性化合物等でケン化して得られるビニルアルコール等が挙げられる。
炭素数2~20のα-オレフィン由来の構造単位を有する樹脂及びその変性物は、エマルションの形態であってもよい。このようなエマルションは、炭素数2~20のα-オレフィン由来の構造単位を有する樹脂及びその変性物を乳化することによって製造してもよいし、市販のものを用いてもよい。炭素数2~20のα-オレフィン由来の構造単位を有する樹脂及びその変性物のエマルションとしては、例えば、アローベース(登録商標)SA-1200、SB-1200、SE-1200、SB-1010(ユニチカ(株))、アプトロック(登録商標)BW-5550(三菱化学(株))、アウローレン(登録商標)AE-202、AE-301(日本製紙(株))、アクアテックス(登録商標)EC-1200、EC-1700、AC-3100、MC-4400、HA-1100、909(中央理化工業(株))等が挙げられる。
塩素化された炭素数2~20のα-オレフィン由来の構造単位を有する樹脂は、エマルションの形態であってもよい。このようなエマルションは、塩素化された炭素数2~20のα-オレフィン由来の構造単位を有する樹脂を乳化することによって製造してもよいし、市販のものを用いてもよい。塩素化された炭素数2~20のα-オレフィン由来の構造単位を有する樹脂のエマルションとしては、例えば、ハードレン(登録商標)EW-5303、EH-801、EW-5504、EZ-1000及びEZ-2000(東洋紡(株))、スーパークロン(登録商標)E-604、E-480T及びE-415(日本製紙ケミカル(株))等が挙げられる。
ポリウレタンは、市販のものを用いることができる。例えば、ニッポラン(登録商標)3110、3116、3016、3113、3124、3126、3230(日本ポリウレタン工業(株))等が挙げられる。市販の水溶性ウレタンとしては、例えば、ディスパコール(登録商標)U-42、U-53、U-54、U-56、KA-8481、KA-8584、KA-8755、KA-8756及びKA-8766(住友バイエルウレタン(株))、ハイドラン(登録商標)HW-111、HW-311、HW-333、HW-350、HW-337、HW-374、AP-20、AP-60LM及びAP-80(DIC(株))、ユープレン(登録商標)UXA-306、UXA-307、パーマリンUA-150、パーマリンUA-200、パーマリンUA-300、パーマリンUA-310及びユーコートUWS-145(三洋化成工業(株))、スーパーフレックス(登録商標)107M、110、126、130、150、160、210、300、361、370、410、420、460、500M、700、750、820及び860(第一工業製薬(株))、並びにアデカボンタイター(登録商標)HUX-401、HUX-420A、HUX-380、HUX-561、HUX-210、HUX-822、HUX-895及びHUX-830((株)ADEKA)等が挙げられる。
ポリ塩化ビニルとしては、硬質ポリ塩化ビニル、半硬質ポリ塩化ビニル、軟質ポリ塩化ビニル等が挙げられる。好ましくは、軟質ポリ塩化ビニルである。
ポリ塩化ビニルは、例えば、カネビニールS-400、PSH-180、PSL-180(株)カネカ)等が挙げられる。ポリ塩化ビニルのエマルションとしては、例えば、ビニブラン701、700、711(日信化学工業(株))等が挙げられる。
その他の樹脂は市場から容易に入手することができる。
本発明の水性エマルションは、その特性を損なわない限り、その他の樹脂を含んでいてもよく、その含有量は、塩素化ゴムの質量部と重合性基を有する化合物の質量部とを合計した100質量部に対して、好ましくは100質量部以下であり、より好ましくは50質量部以下であり、さらに好ましくは30質量部以下であり、より一層好ましくは20質量部以下である。その他の樹脂は、エマルションの状態で本発明の水性エマルションと混合してもよいし、塩素化ゴム及び重合性基を有する化合物と共に乳化して水性エマルションとしてもよい。
増粘剤は、水性エマルションの粘性調整のために使用することができる。増粘剤としてはアデカノール(登録商標)UH-140S、UH-420、UH-438、UH-450VF、UH-462,UH-472、UH-526、UH-530、UH-540、UH-541VF、UH-550、UH-752及びH-756VF((株)ADEKA)、並びに、SNシックナー920、922,924,926,929-S、A-801、A-806、A-812、A-813、A-818、621N、636、601、603、612、613、615、618、621N、630、634、636及び4050(サンノプコ(株))等が挙げられる。
本発明の水性エマルションでは、塩素化ゴムと重合性基を有する化合物とが混合物として含有されていることが好ましい。混合物とは、塩素化ゴムと重合性基を有する化合物が混合された状態、塩素化ゴムが重合性基を有する化合物に分散又は膨潤している状態、塩素化ゴムの少なくとも一部が重合性基を有する化合物に溶解している状態を包含する。
フィルターでの濾過は、水性エマルションに含まれる重合性基を有する化合物の融点以上に加熱してから行うことが好ましい。
分散質が液体であるとは、分散質を構成する成分のうち少なくとも1以上の成分が流動性を有していればよく、分散質に固体成分又は不溶成分が含まれていてもよい。
分散質が液体であって、流動性を有する場合には、流動性が高くても、低くてもよい。流動性が低い場合には水性エマルションの安定性が向上する傾向にあり、流動性が高い場合には接着性が向上する傾向にあるからである。
体積基準のメジアン径とは、体積基準で積算粒子径分布の値が50%に相当する粒子径であり、特に断りがない限り、体積基準で測定したメジアン径を意味する。
分散質の平均粒子径は、HORIBA製作所製、レーザー回折粒子径測定装置LA-950V2で測定することができる。
本発明の水性エマルションは、公知の方法で製造することができる。例えば、塩素化ゴムと重合性基を有する化合物とを水等の分散媒に分散させる後乳化法(例えば、強制乳化法、自己乳化法、転相乳化法等)で製造することができる。
混合及び/又は加熱攪拌は、上述した攪拌機の他、バンバリーミキサー、ヘンシェルミキサー及び、ホモミキサー等の混合機を用いて行ってもよい。
予めプレ乳化を行って粒子径の大きい水性エマルションを得、高圧ホモジナイザー又は高圧ホモジェッター等の装置で高圧せん断を行って粒子径の小さい水性エマルションを得てもよい。
さらに、得られた水性エマルションは、冷却することが好ましい。冷却により、微細な分散質からなる水性エマルションを得ることができる。冷却は、急冷ではなく、常温に放置する等して緩やかに行うのが好適である。これにより、冷却過程で樹脂等が凝集することなく、微細で均質な水性エマルションを得ることができる。
本発明の水性エマルションは、上述したように、水系接着剤等を構成する組成物として有用である。また、被着体に、水性エマルションによる塗布膜又は被覆膜等として形成するための組成物して使用してもよい。水系接着剤、塗布膜及び被覆膜等は、通常、乾燥物又は硬化物として用いられる。特に、水系接着剤は、水性エマルションによる塗布膜又はこの硬化物の形態でその機能を有効に発揮する。
なかでも、セルロース系材料とプラスチック材料との接着、ポリ塩化ビニル、エチレン-酢酸ビニル共重合体、綿含有繊維、ナイロン樹脂、オレフィン系重合体、ポリウレタン、ゴム、スチレンブタジエンゴム等のスチレン系ブロック共重合体及び合成皮革等の接着に好適に使用することができる。これら材料の形状は、フィルム、シート又はブロック状等の種々のものが挙げられるが、好ましくは、フィルム及びシート状のものである。
また、上記被着体を構成する樹脂は、上記その他の樹脂で例示したものが挙げられる。
綿含有繊維の形状としては、織物、編物、不織布、メリヤス、フェルト、フィルム又はブロック状等が挙げられる。
塗布は、公知の塗布方法のいずれをも利用することができる。例えば、グラビアロールコーティング、リバースロールコーティング、バーコーティング、ワイヤーバーコーティング、リップコーティング、エアナイフコーティング、カーテンフローコーティング、スプレーコーティング、浸漬コーティング、はけ塗り及びへら塗り等の方法を利用することができる。
加熱温度としては、30~150℃程度が挙げられ、好ましくは40~80℃程度である。
加熱時間は、1秒~1時間程度が挙げられ、好ましくは5秒~30分間程度であり、より好ましくは5秒~10分間程度である。
加熱乾燥処理の前後に、さらに、放置(自然乾燥)あるいは通常の熱風循環型のオーブン、赤外線ヒーター、紫外線等の電磁波等を使用して第1の基材の処理を行なってもよい。この場合の予備乾燥での加熱温度及び時間は、基材の特性、使用する水性エマルションの組成等に応じて適宜調整することができる。例えば、上記と同様の条件が挙げられる。
接着剤の塗布方法、塗布厚み、加熱処理の方法、温度及び時間等の条件等は、適宜変更することができる。上述した水性エマルションの塗布、乾燥等と同じ条件を選択してもよいし、異なる条件を選択してもよい。
接着剤層の厚みは、用いる接着剤の組成、基材の材料及び形態等によって適宜調整することができる。例えば、乾燥処理後の厚みが0.01~300μm程度となるような厚みが挙げられ、好ましくは0.01~200μm程度である。
貼り合せの際、熱、圧力又はその双方を負荷しながら行なってもよい。熱を負荷する場合には、第1の基材及び第2の基材並びに接着剤層が変質しない温度範囲とすることが必要であり、好ましくは120℃程度以下、より好ましくは100℃程度以下である。熱の負荷は、上述した通常の熱風循環型のオーブン、赤外線ヒーター、電子レンジ等を用いて行なってもよい。圧力を負荷する場合の圧力としては、100g/cm2程度以上が挙げられ、第1の基材及び第2の基材の形状が変形する圧力未満が挙げられる。熱及び/又は圧力を負荷する場合、その時間は、例えば、1秒~10日間程度が挙げられる。
ゴム系接着剤としては、例えば、天然ゴム、クロロプレンゴム、スチレン-ブタジエン共重合ゴム(SBR)、イソブチレンゴム、ブチルゴム、スチレン-イソプレン-スチレンブロック共重合ゴム(SIS)、スチレン-ブタジエン-スチレンブロック共重合ゴム(SBS)、ブタジエン-アクリロニトリル共重合ゴム(NBR)、ブタジエンゴム(BR)等が挙げられる。これらは、1種単独で、又は、2種以上を併用してもよい。また、これらゴム成分に加えて、ロジン樹脂、テルペン樹脂、石油樹脂等の接着付与樹脂を混合してもよい。
アクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸n-ブチル、アクリル酸イソブチル、アクリル酸n-アミル、アクリル酸イソアミル、アクリル酸n-ヘキシル、アクリル酸2-エチルヘキシル、アクリル酸n-オクチル、アクリル酸n-ラウリル等を好ましく例示することができる。メタクリル酸エステルとしては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸イソプロピル、メタクリル酸n-ブチル、メタクリル酸イソブチル、メタクリル酸n-アミル、メタクリル酸イソアミル、メタクリル酸n-ヘキシル、メタクリル酸2-エチルヘキシル、メタクリル酸n-オクチル、メタクリル酸n-ラウリル等を好ましく例示することができる。
接着剤層に含有してもよい樹脂としては、例えば、ポリオレフィン系樹脂、ポリ塩化ビニル(PVC)、ポリ塩化ビニリデン、ポリスチレン(PS)、ポリ酢酸ビニル(PVAc)、ポリテトラフルオロエチレン(PTFE)、アクリロニトリルブタジエンスチレン樹脂(ABS樹脂)、AS樹脂等のポリマー及び共重合体並びに変性ポリマー及び変性物等の種々のものが挙げられる。これらは単独で又は2種以上をブレンドしてもよい。
また、粘着樹脂又は粘着付与剤としての機能を発揮する樹脂を使用してもよい。
このような樹脂としては、例えば、ロジン類、テルペン系樹脂、炭素数5の石油留分を重合した石油系樹脂及びこの水素添加樹脂、炭素数9の石油留分を重合した石油系樹脂及びこの水素添加樹脂、その他の石油系樹脂、クマロン樹脂並びにインデン樹脂、ポリウレタン樹脂等が挙げられる。
接着剤層に含有してもよい添加剤としては、界面活性剤、光重合開始剤、光安定剤、紫外線硬化性オリゴマー、蛍光増白剤、レベリング剤、塩基性化合物、有機溶剤、架橋剤、光増感剤、その他の樹脂、フェノール系安定剤、フォスファイト系安定剤、アミン系安定剤、アミド系安定剤、老化防止剤、耐候安定剤、沈降防止剤、酸化防止剤、熱安定剤、防腐剤、揺変剤、増粘剤、消泡剤、粘度調整剤、耐候剤、顔料分散剤、帯電防止剤、滑剤、核剤、難燃剤、油剤、染料、硬化剤;酸化チタン(ルチル型)及び酸化亜鉛などの遷移金属化合物;カーボンブラック等の顔料;ガラス繊維、炭素繊維、チタン酸カリウム繊維、ウオラストナイト、炭酸カルシウム、硫酸カルシウム、タルク、ガラスフレーク、硫酸バリウム、クレー、カオリン、微粉末シリカ、マイカ、珪酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、酸化アルミニウム、酸化マグネシウム、アルミナ及びセライトなどの無機又は有機の充填剤等が挙げられる。
水性エマルションの乾燥物は、水性エマルションに含まれる水の質量のうち、95質量%以上を除くことが好ましい。これにより、せん断粘度に与える水の影響を抑え、所望のせん断粘度を得ることができる。
塩素化ゴム及び重合体の塩素含有量は、フラスコ燃焼-イオンクロマトグラフ法により測定した値である。
水性エマルションの成分濃度は、塩素化ゴムの質量部と重合性基を有する化合物の質量部とを合計した含有量の、塩素化ゴムと重合性基を有する化合物と水とを合計した質量に対する質量濃度(質量%)を計算した値である。
分散質のメジアン径は、HORIBA製作所製、レーザー回折粒子径測定装置LA-950V2で測定した値である。特に断りがない限りは体積基準で測定したメジアン径の値(単位:μm)である。
○:変化なし
×:相分離を目視で確認した
塩素化ゴム1:ペルグートS20(Bayer社、塩素含有率58.8質量%以上)
塩素化ゴム2:ペルグートS40(Bayer社、塩素含有率65.5質量%以上)
塩素化ゴム3:ペルグートS10(Bayer社、塩素含有率64.1質量%以上)
塩素化ゴム4:ペルグート S5(Bayer社、塩素含有率61.2質量%以上)
重合体2:ショウプレンAF(昭和電工社、クロロプレンゴム、塩素含有率38.1質量%)
重合体3:VINNOL E15/45(Wacker Chemie AG社、塩化ビニル・酢酸ビニル共重合樹脂)
樹脂水性分散体2:ショウプレンSD77S (昭和電工社、クロロプレンゴム、固形分55%)
樹脂水性分散体3:アウローレンAE-202 (日本製紙社、変性ポリオレフィン樹脂水性分散体、固形分30%)
樹脂水性分散体4:アクアテックス HA-1100 (中央理化工業社、エチレン・酢酸ビニル共重合樹脂、固形分45%)
樹脂水性分散体5:ビニブラン700 (日信化学工業社、塩化ビニル樹脂水性分散体、固形分30%)
樹脂水性分散体6:DiofanTM A063 (ソルベイスペシャルティポリマーズジャパン社、塩化ビニリデン樹脂水性分散体、固形分55%)
重合性基を有する化合物2:1,6-ヘキサンジオールジメタクリラート(4-メトキシフェノール60ppm含有、東京化成工業社)
重合性基を有する化合物3:メタクリル酸ステアリル(4-メトキシフェノール200ppm含有、東京化成工業社)
重合性基を有する化合物4:メタクリル酸2-エチルヘキシル(4-メトキシフェノール25ppm含有、東京化成工業社)
重合性基を有する化合物5:メタクリル酸シクロヘキシル(4-メトキシフェノール50ppm含有、東京化成工業社)
重合性基を有する化合物6:アクリル酸2-エチルヘキシル(4-メトキシフェノール100ppm含有、東京化成工業社)
重合性基を有する化合物7:ジアセトンアクリルアミド(4-メトキシフェノール100ppm含有、東京化成工業社)
重合性基を有する化合物8:ネオペンチルグリコールジグリシジルエーテル(東京化成工業社)
重合性基を有する化合物9:ブレンマーVA(4-メトキシフェノール200ppm含有、日油社)
重合性基を有する化合物11:1,6-ヘキサンジオールジアクリレート(4-メトキシフェノール100ppm含有、東京化成工業社)
重合性基を有する化合物12:アクリル酸シクロヘキシル(4-メトキシフェノール100ppm含有、東京化成工業社)
重合性基を有する化合物13:ポリエチレングリコールジメタクリレート(4-メトキシフェノール200ppm含有、東京化成工業社)
重合性基を有する化合物14:SR489(4-メトキシフェノール170ppm含有、アルケマ社)
重合性基を有する化合物15:SR340(4-メトキシフェノール200ppm、1,4-ベンゼンジオール200ppm含有、アルケマ社)
重合性基を有する化合物16:CN131(4-メトキシフェノール800ppm、アルケマ社)
重合性基を有する化合物17:NKエステル DCP(4-メトキシフェノール200ppm含有、新中村化学社)
重合性基を有する化合物18:NKエステル A-200(4-メトキシフェノール100ppm含有、新中村化学社)
光重合開始剤2:1-ヒドロキシシクロヘキシルフェニルケトン(東京化成工業社)
光重合開始剤3:2-[2-(5-メチルフラン-2-イル)ビニル]-4,6-ビス(トリクロロメチル)-1,3,5-トリアジン(東京化成工業社)
界面活性剤2:ラテムル E-1000A(30%水溶液、花王(株))
界面活性剤3:ノイゲン EA-177(第一工業製薬(株))
界面活性剤4:DKS NL-180(第一工業製薬(株))
界面活性剤5:クラレポバール 217((株)クラレ)
界面活性剤6:クラレポバール 205((株)クラレ)
界面活性剤7:アデカプルロニック F108((株)ADEKA)
界面活性剤8:エマルゲン102KG(花王(株))
界面活性剤9:エマルゲン109P(花王(株))
界面活性剤10:エマルゲン150(花王(株))
光安定剤1:TINUVIN 1130(BASF社)
光安定剤2:TINUVIN 123(BASF社)
紫外線硬化性オリゴマー1:AH-600(共栄社化学社)
紫外線硬化性オリゴマー2:UA-306H(共栄社化学社)
蛍光増白剤2:Kayaphor SN(日本化薬(株))
蛍光増白剤3:Nikkafluor OB((株)日本化学工業所社)
有機溶剤2:2-ブタノン(和光純薬工業社、試薬特級)
有機溶剤3:2-プロパノール(和光純薬工業社、試薬特級)
レベリング剤1:BYK-349(ビックケミー・ジャパン社)
架橋剤:アジピン酸ジヒドラジド(東京化成工業社)
各表において、これらの成分は質量部で表す。
攪拌機、温度計、還流冷却管を備えたセパラブルフラスコ反応容器に、塩素化ゴム1(ペルグートS20(Bayer社))を10部、重合性基を有する化合物として、メタクリル酸ドデシル(東京化成工業社)60部及び1,6-ヘキサンジオールジメタクリレート(東京化成工業社)30部を仕込み、さらに、テトラヒドロフラン(林純薬、試薬特級)190部仕込んで60℃にて攪拌して溶解し、室温に冷却し、塩素化ゴム1と重合性基を有する化合物とのトラヒドロフラン溶液を調製した。
界面活性剤1(アクアロンKH-10(第一工業製薬社))3部をイオン交換水100部に入れ、60℃で撹拌して溶解し、界面活性剤1のイオン交換水溶液を調製した。
室温にて、塩素化ゴム1と重合性基を有する化合物とのテトラヒドロフラン溶液に、界面活性剤1のイオン交換水溶液、塩基性化合物1としてN,N-ジメチルエタノールアミン2部(東京化成工業社)を仕込んで撹拌して混合した。次いで、攪拌機ホモミキサーMARKIIを取り付けたTKロボミクス((株)PRIMIX製)を準備した。得られた混合物を16000rpmで2分間攪拌して乳白色の水性エマルションを得た。得られた水性エマルションをナスフラスコに投入し、エバポレーターにて減圧留去を行い、200メッシュナイロン網にて濾過し、水性エマルション(E-1)を得た。得られた水性エマルション(E-1)の不揮発分濃度は45%であった。添加した各成分を表1-1に記載する。
製造例1で使用した重合性基を有する化合物に代えてメタクリル酸ドデシルを90部、界面活性剤に代えてアクアロンKH-10を5部使用した以外は製造例1と同様にして水性エマルション(E-2)を得た。得られた水性エマルション(E-2)の不揮発分濃度は47%であった。添加した各成分を表1-1に記載する。
攪拌機、温度計、還流冷却管を備えたセパラブルフラスコ反応容器に、塩素化ゴム1(ペルグートS20(Bayer社))10部、重合性基を有する化合物として、メタクリル酸ドデシル(東京化成工業社)45部及び1,6-ヘキサンジオールジメタクリレート(東京化成工業社)45部を仕込み、さらに、テトラヒドロフラン(林純薬、試薬特級)190部仕込んで60℃にて攪拌して溶解し、室温に冷却し、塩素化ゴム1と重合性基を有する化合物とのトラヒドロフラン溶液を調製した。
界面活性剤1(アクアロンKH-10(第一工業製薬社)5部をイオン交換水100部に入れ、60℃で撹拌して溶解し、界面活性剤1のイオン交換水溶液を調製した。
室温にて、塩素化ゴム1と重合性基を有する化合物とのテトラヒドロフラン溶液に、界面活性剤1のイオン交換水溶液、塩基性化合物1としてN,N-ジメチルエタノールアミン2部(東京化成工業社)を添加し、撹拌して混合した。さらに、光重合開始剤1(2-ヒドロキシ-2-メチルプロピオフェノン(東京化成工業社))5部を添加し、撹拌して混合した。次いで、攪拌機ホモミキサーMARKIIを取り付けたTKロボミクス((株)PRIMIX製)を準備した。得られた混合物を16000rpmで2分間攪拌して乳白色の水性エマルションを得た。得られた水性エマルションをナスフラスコに投入し、エバポレーターにて減圧留去を行い、200メッシュナイロン網にて濾過し、水性エマルション(E-3)を得た。得られた水性エマルション(E-3)の不揮発分濃度は43%であった。添加した各成分を表1-1に記載する。
攪拌機、温度計、還流冷却管を備えたセパラブルフラスコ反応容器に、塩素化ゴム1(ペルグートS20(Bayer社))10部、重合性基を有する化合物として、メタクリル酸ドデシル(東京化成工業社)60部及び1,6-ヘキサンジオールジメタクリレート(東京化成工業社)30部を仕込み、60℃にて攪拌して溶解し室温に冷却した。
界面活性剤1(アクアロンKH-10(第一工業製薬社)3部をイオン交換水100部に入れ、60℃で撹拌して溶解し、界面活性剤1のイオン交換水溶液を調製した。
室温にて、塩素化ゴム1と重合性基を有する化合物との混合液に、界面活性剤1のイオン交換水溶液、塩基性化合物1としてN,N-ジメチルエタノールアミン2部(東京化成工業社)を添加し、撹拌して混合した。次いで、攪拌機ホモミキサーMARKIIを取り付けたTKロボミクス((株)PRIMIX製)を準備した。得られた混合物を16000rpmで2分間攪拌して乳白色の水性エマルションを得た。次いで、高圧ホモジナイザー((株)エスエムテー製)LAB1000を用い、800barにて1回処理を行って得られた水性エマルションを200メッシュナイロン網にて濾過し、水性エマルション(E-4)を得た。添加した各成分を表1-2に記載する。
表1-2及び表1-3に示す質量部の塩素化ゴム、重合性基を有する化合物、界面活性剤、塩基性化合物1及びイオン交換水を使用して、製造例4と同様にして水性エマルション(E-5)~(E-14)を得た。
攪拌機、温度計、還流冷却管を備えたセパラブルフラスコ反応容器に、塩素化ゴム1(ペルグートS20(Bayer社))10部、重合性基を有する化合物として、メタクリル酸ドデシル(東京化成工業社)60部及び1,6-ヘキサンジオールジメタクリレート(東京化成工業社)30部を仕込み、60℃にて攪拌して溶解し室温に冷却した。
界面活性剤2(ラテムル(登録商標)E-1000A(30%水溶液、花王社))5部をイオン交換水100部に入れ、60℃で撹拌して溶解し、界面活性剤2のイオン交換水溶液を調製した。
室温にて、塩素化ゴム1と重合性基を有する化合物の混合液に、界面活性剤2のイオン交換水溶液を投入し、さらに、塩基性化合物1としてN,N-ジメチルエタノールアミン2部(東京化成工業社)を添加し、撹拌して混合した。これに、光重合開始剤1(2-ヒドロキシ-2-メチルプロピオフェノン(東京化成工業社))1部を添加し、撹拌して混合した。次いで、攪拌機ホモミキサーMARKIIを取り付けたTKロボミクス((株)PRIMIX製)を準備した。得られた混合物を16000rpmで2分間攪拌して乳白色の水性エマルションを得た。次いで、高圧ホモジナイザー((株)エスエムテー製)LAB1000を用い、800barにて1回処理を行って得られた水性エマルションを200メッシュナイロン網にて濾過し、水性エマルション(E-15)を得た。添加した各成分を表1-4に記載する。
表1-4に示す質量部の塩素化ゴム、重合性基を有する化合物、界面活性剤、塩基性化合物1、光重合開始剤及びイオン交換水を使用して、製造例15と同様にして水性エマルション(E-16)~(E-20)を得た。
表1-5~表1-8に示す質量部の塩素化ゴム分、重合性基を有する化合物、界面活性剤、塩基性化合物1及びイオン交換水を使用して、製造例4と同様にして水性エマルション(E-21)~(E-50)を得た。
表1-9及び表1-10に示す質量部の光安定剤、紫外線硬化性オリゴマー又は蛍光増白剤1を塩素化ゴム1と同時に添加し、表1-9及び表1-10に示す質量部の塩素化ゴム、重合性基を有する化合物、界面活性剤、塩基性化合物1、レベリング剤1及びイオン交換水を添加したこと以外は、製造例4と同様にして水性エマルション(E-51)~(E60)を得た。添加した各成分を表1-9及び表1-10に記載する。
攪拌機、温度計、還流冷却管を備えたセパラブルフラスコ反応容器に、塩素化ゴム1(ペルグートS20(Bayer社))10部、重合性基を有する化合物として、メタクリル酸ドデシル(東京化成工業社)60部、1,6-ヘキサンジオールジメタクリレート(東京化成工業社)30部及び有機溶媒1(トルエン(和光純薬工業社、試薬特級))を20部仕込み、60℃にて攪拌して溶解し室温に冷却した。
界面活性剤2(ラテムル(登録商標)E-1000A(30%水溶液、花王社))5部をイオン交換水100部に入れ、60℃で撹拌して溶解し、界面活性剤2のイオン交換水溶液を調製した。
室温にて、塩素化ゴム1、重合性基を有する化合物及びトルエンの混合液に、界面活性剤2のイオン交換水溶液、塩基性化合物1としてN,N-ジメチルエタノールアミン2部(東京化成工業社)を添加し、撹拌して混合した。これに、光重合開始剤1(2-ヒドロキシ-2-メチルプロピオフェノン(東京化成工業社))5部を添加し、撹拌して混合した。次いで、攪拌機ホモミキサーMARKIIを取り付けたTKロボミクス((株)PRIMIX製)を準備した。得られた混合物を16000rpmで2分間攪拌して乳白色の水性エマルションを得た。次いで、高圧ホモジナイザー((株)エスエムテー製)LAB1000を用い、800barにて1回処理を行って得られた水性エマルションを200メッシュナイロン網にて濾過し、水性エマルション(E-61)を得た。添加した各成分を表1-11に記載する。
製造例61で使用した光重合開始剤1を使用しないこと以外は、製造例61と同様の方法で、表1-11に示す質量部の塩素化ゴム、重合性基を有する化合物、界面活性剤、塩基性化合物1、有機溶剤及びイオン交換水を使用して、水性エマルション(E-61)~(E-66)を得た。
攪拌機、温度計、還流冷却管を備えたセパラブルフラスコ反応容器に、塩素化ゴム1(ペルグートS20(Bayer社))10部、重合性基を有する化合物として、メタクリル酸ドデシル(東京化成工業社)60部及び1,6-ヘキサンジオールジメタクリレート(東京化成工業社)30部を仕込み、60℃にて攪拌して溶解し室温に冷却した。
界面活性剤1(アクアロンKH-10(第一工業製薬社)3部をイオン交換水100部に入れ、60℃で撹拌して溶解し、界面活性剤1のイオン交換水溶液を調整した。
室温にて、塩素化ゴム1と重合性基を有する化合物の混合液に、界面活性剤1のイオン交換水溶液、塩基性化合物1としてN,N-ジメチルエタノールアミン2部(東京化成工業社)を添加し、撹拌して混合した。次いで、攪拌機ホモミキサーMARKIIを取り付けたTKロボミクス((株)PRIMIX製)を準備した。得られた混合物を5000rpmで2分間攪拌して乳白色の水性エマルションを得た。得られた水性エマルションを200メッシュナイロン網にて濾過し、水性エマルション(E-67)を得た。添加した各成分を表1-12に記載する。
表1-12に示す質量部の塩素化ゴム、重合性基を有する化合物、界面活性剤、塩基性化合物1及びイオン交換水を使用して、製造例67と同様にして水性エマルション(E-68)~(E-69)を得た。
製造例11で使用した塩素化ゴム1に重合体1(ショウプレンW(昭和電工社))を使用したこと以外は製造例11と同様にして水性エマルション(S-1)を得た。
製造例11で使用した塩素化ゴム1に重合体2(ショウプレンAF(昭和電工社))を使用したこと以外は製造例11と同様にして水性エマルション(S-2)を得た。
製造例65で使用した塩素化ゴム1に重合体1(ショウプレンW(昭和電工社))を使用したこと以外は製造例65と同様にして水性エマルション(S-3)を得た。
表2-1~表2-7に示す質量部の、水性エマルション、光重合開始剤、レベリング剤1(BYK(登録商標)-349、ビックケミー・ジャパン社)、イオン交換水を加え、スリーワンモーターで攪拌し、製造例で得られた水性エマルションを含む水系接着剤(F1)~(F70)を得た。
なお、以降、本発明の水性エマルションの一実施形態として、接着剤としてより適した添加剤をさらに含有する形態を「水系接着剤」と記載している。
表2-8に示す質量部の、水性エマルション、光重合開始剤、重合性基を有する化合物、光安定剤、レベリング剤1(BYK(登録商標)-349、ビックケミー・ジャパン社)、架橋剤、有機溶剤及びイオン交換水を混合し、スリーワンモーターで攪拌し、製造例で得られた水性エマルションを含む水系接着剤(F71)~(F80)を得た。
攪拌機、温度計、還流冷却管を備えたセパラブルフラスコ反応容器に、塩素化ゴム1(ペルグートS20(Bayer社))10部、重合体3(VINNOL E15/45(独Wacker Chemie AG社))1部、重合性基を有する化合物として、メタクリル酸ドデシル(東京化成工業社)60部及び1,6-ヘキサンジオールジメタクリレート(東京化成工業社)30部を仕込み、60℃にて攪拌して溶解し室温に冷却した。
界面活性剤1(アクアロンKH-10(第一工業製薬社)3部をイオン交換水100部に入れ、60℃で撹拌して溶解し、界面活性剤1のイオン交換水溶液を調製した。
室温にて、塩素化ゴム1と重合性基を有する化合物との混合液に、界面活性剤1のイオン交換水溶液、塩基性化合物1としてN,N-ジメチルエタノールアミン2部(東京化成工業社)を添加し、撹拌して混合した。次いで、攪拌機ホモミキサーMARKIIを取り付けたTKロボミクス((株)PRIMIX製)を準備した。得られた混合物を16000rpmで2分間攪拌して乳白色の水性エマルションを得た。次いで、高圧ホモジナイザー((株)エスエムテー製)LAB1000を用い、800barにて1回処理を行って得られた水性エマルションを200メッシュナイロン網にて濾過し、水性エマルション(E-70)を得た。添加した各成分を表2-9に記載する。
表2-10に示す質量部の、水性エマルション、樹脂水性分散体、光重合開始剤、レベリング剤1(BYK(登録商標)-349、ビックケミー・ジャパン社)、イオン交換水を混合し、スリーワンモーターで攪拌し、製造例で得られた水性エマルションを含む水系接着剤(F81)~(F87)を得た。
表2-11及び表2-12に示す質量部の光重合開始剤又は蛍光増白剤を塩素化ゴム1と同時に添加し、表2-11及び表2-12に示す質量部の塩素化ゴム、重合性基を有する化合物、界面活性剤、塩基性化合物1及びイオン交換水を添加したこと以外は、製造例4と同様にして水性エマルション(E-71)~(E107)を得た。
表2-13に示す質量部の、水性エマルション、光重合開始剤、レベリング剤1(BYK(登録商標)-349、ビックケミー・ジャパン社)、イオン交換水を加え、スリーワンモーターで攪拌し、製造例で得られた水性エマルションを含む水系接着剤(F88)~(F124)を得た。
ポリウレタンエマルション(ディスパコール(登録商標)U-54、住化バイエルウレタン(株))、イソシアナート(デスモジュール(登録商標)N3300、住化バイエルウレタン(株))、レベリング剤1(BYK(登録商標)-349、ビックケミー・ジャパン(株))を、不揮発分比で100部:5部:1部になるように混合して水性エマルション(E200)を得た。
表2-14に示す質量部の、水性エマルション、光重合開始剤、レベリング剤1(BYK(登録商標)-349、ビックケミー・ジャパン社)及びイオン交換水を混合し、スリーワンモーターで攪拌し、水系接着剤(H1)~(H3)を得た。
水系接着剤(F1)を、はけを用いて、第1の基材であるM-EVA(エチレン-酢酸ビニル共重合体の発泡体)に塗布(塗布量:乾燥後重量約 3g/m2)し、70℃で5分間乾燥し、コンベア式UV照射装置(アイグラフィックス株式会社製、アイグランデージECS-4011GX)で、紫外線を照射してM-EVA(A)を得た。(ランプ:高圧水銀ランプ、ランプ出力:3kW、ランプ高さ:110mm、コンベアスピード:276m/min、積算光量:1100mJ/cm2(紫外線積算光量計UVICURE PLUS II、UV-A測定値、FusionUV Systems Japan K.K.社)
続いて、軟質ポリ塩化ビニル及びM-EVA(A)に水性エマルション(E200)を、はけを用いて塗布し(塗布量:乾燥後重量約50g/m2)、70℃で5分間オーブン乾燥した。その後、得られた軟質ポリ塩化ビニルとM-EVA(A)の、水性エマルション(E200)の塗布面同士を貼り合せ、手で圧着し、さらにプレスにて3MPaで20秒間圧着した。これによって、軟質ポリ塩化ビニルとE200からなる接着層と紫外線を照射された接着剤層と第1の基材であるM-EVAとをこの順に積層した積層体(1)を得た。
○:剥離強度55N/inch以上。
×:剥離強度55N/inch未満。
評価例1の水系接着剤(F1)を、水系接着剤(F1)~(F37)及び(F39)~(F80)のいずれかに変更したこと以外は評価例1と同様にして積層体(2)~(79)を得た。
評価例1と同様にして、積層体の接着性を評価した。その結果を表3-1~表3-8に示す。
評価例1の水系接着剤(F1)を、水系接着剤(F38)に変更し、M-EVAへの水系接着剤の塗布量を約1g/m2に変更したこと以外は評価例1と同様にして積層体(80)を得た。
評価例1と同様にして、積層体の接着性を評価した。その結果を表3-9に示す。
評価例1の水系接着剤(F1)を、水系接着剤(F70)に変更し、紫外線を照射1回照射した(ランプ:高圧水銀ランプ、ランプ出力:3kW、ランプ高さ:110mm、コンベアスピード:276m/min、積算光量:1100mJ/cm2(紫外線積算光量計UVICURE PLUS II、UV-A測定値、FusionUV Systems
Japan K.K.社)のち、さらに同じ条件の紫外線を1回照射したこと以外は評価例1と同様にして積層体(81)を得た。
評価例1と同様にして、積層体の接着性を評価した。その結果を表3-10に示す。
水系接着剤(F1)を、はけを用いて、M-EVA(エチレン-酢酸ビニル共重合体の発泡体)に塗布(塗布量:乾燥後重量約 3g/m2)し、70℃で5分間乾燥し、コンベア式UV照射装置(アイグラフィックス株式会社製、アイグランデージECS-4011GX)で、紫外線を照射してM-EVA(A)を得た。(ランプ:高圧水銀ランプ、ランプ出力:3kW、ランプ高さ:110mm、コンベアスピード:276m/min、積算光量:1100mJ/cm2(紫外線積算光量計UVICURE PLUS II、UV-A測定値、FusionUV Systems Japan K.K.社)
続いて、綿帆布(城北工業社)に水性エマルション(E200)を、はけを用いて塗布し(塗布量:乾燥後重量約50g/m2)、70℃で5分間オーブン乾燥し、綿帆布(A)を得た。得られた綿帆布(A)及びM-EVA(A)に水性エマルション(E200)を、はけを用いて塗布し(塗布量:乾燥後重量約50g/m2)、70℃で5分間オーブン乾燥した。その後、得られた綿帆布(A)とM-EVA(A)の、水性エマルション(E200)の塗布面同士を貼り合せ、手で圧着し、さらにプレスにて3MPaで20秒間圧着した。これによって、綿帆布とE200からなる接着層と紫外線を照射された接着層とM-EVAとをこの順に積層した積層体(82)を得た。
水系接着剤(F1)を、はけを用いて、M-EVA(エチレン-酢酸ビニル共重合体の発泡体)に塗布(塗布量:乾燥後重量約 3g/m2)し、70℃で5分間乾燥し、コンベア式UV照射装置(アイグラフィックス株式会社製、アイグランデージECS-4011GX)で、紫外線を照射してM-EVA(A)を得た。(ランプ:高圧水銀ランプ、ランプ出力:3kW、ランプ高さ:110mm、コンベアスピード:276m/min、積算光量:1100mJ/cm2(紫外線積算光量計UVICURE PLUS II、UV-A測定値、FusionUV Systems Japan K.K.社)
続いて、ゴム基材(神栄化工社)にトリクロロイソシアヌル酸のアセトン溶液(2質量%)をはけで塗布し(塗布量:乾燥後重量約0.5g/m2)、70℃で5分間オーブン乾燥し、ゴム基材(A)を得た。得られたゴム基材(A)及びM-EVA(A)に水性エマルション(E200)を、はけを用いて塗布し(塗布量:乾燥後重量約50g/m2)、70℃で5分間オーブン乾燥した。その後、得られたゴム基材(A)とM-EVA(A)の、水性エマルション(E200)の塗布面同士を貼り合せ、手で圧着し、さらにプレスにて3MPaで20秒間圧着した。これによって、ゴム基材(A)とE200からなる接着層と紫外線を照射された接着層とM-EVAとをこの順に積層した積層体(83)を得た。
水系接着剤(F1)を、はけを用いて、M-EVA(エチレン-酢酸ビニル共重合体の発泡体)に塗布(塗布量:乾燥後重量約 3g/m2)し、70℃で5分間乾燥し、コンベア式UV照射装置(アイグラフィックス株式会社製、アイグランデージECS-4011GX)で、紫外線を照射してM-EVA(A)を得た。(ランプ:高圧水銀ランプ、ランプ出力:3kW、ランプ高さ:110mm、コンベアスピード:276m/min、積算光量:1100mJ/cm2(紫外線積算光量計UVICURE PLUS II、UV-A測定値、FusionUV Systems Japan K.K.社)
続いて、合成皮革(城北工業社)及びM-EVA(A)に水性エマルション(E200)を、はけを用いて塗布し(塗布量:乾燥後重量約50g/m2)、70℃で5分間オーブン乾燥した。その後、得られた合成皮革(城北工業社)とM-EVA(A)の、水性エマルション(E200)の塗布面同士を貼り合せ、手で圧着し、さらにプレスにて3MPaで20秒間圧着した。これによって、合成皮革(城北工業社)とE200からなる接着層と紫外線を照射された接着層とM-EVAとをこの順に積層した積層体(84)を得た。
○:剥離強度55N/inch以上。
×:剥離強度55N/inch未満。
製造例4で得られた水性エマルション(E-4)1.01gを、イオン交換水で10倍に希釈しメンブランフィルター1(ADVANTEC TOYO社製、ニトロセルロース製、孔径0.45μm)を用いて濾過し、濾液を得た。得られた濾液にメタノールを添加すると沈殿物が生じた。沈殿を、メンブランフィルター2(ADVANTEC TOYO社製、PTFE製、孔径0.50μm)を用いて濾取し、さらにメタノール(和光純薬工業社、試薬特級)でメンブランフィルター2とメンブランフィルター2に付着した沈殿を洗浄した。メンブランフィルター2とメンブランフィルター2付着した沈殿を22℃で24時間減圧乾燥(10hPa)し、THFでメンブランフィルター2付着した沈殿を溶解した。得られたTHF溶液のGPC測定及びTHF溶液を乾固することで得られた物質のIR測定を行った。その結果、塩素化ゴム1が検出された。製造例4で得られた水性エマルションに含まれる塩素化ゴム1の100質量部のうち、濾過後の水性エマルションに含まれていた塩素化ゴム1の質量はGPC測定結果から算出した結果、96質量%であった。
製造例4の水性エマルションを70℃30分で乾燥して得られた組成物のせん断粘度を、コーンプレート(アングル2°)を用いた回転式レオメーターで25℃、せん断速度1s-1で測定した。せん断粘度は23Pa・sであった。
製造例14の水性エマルションを70℃30分で乾燥して得られた組成物のせん断粘度を、コーンプレート(アングル2°)を用いた回転式レオメーターで25℃、せん断速度1s-1で測定した。せん断粘度は46Pa・sであった。
製造例28の水性エマルションを70℃30分で乾燥して得られた組成物のせん断粘度を、コーンプレート(アングル2°)を用いた回転式レオメーターで56℃、せん断速度1s-1で測定した。せん断粘度は12Pa・sであった。
評価例1において、第1の基材として用いた「M-EVA(エチレン-酢酸ビニル共重合体の発泡体)」を下記表3-12の「第1の基材」の欄に示す基材に代えたことが異なる他は評価例1と同様にして積層体89~91を得た。
○:剥離強度55N/inch以上。
×:剥離強度55N/inch未満。
PE/EVA=60/40:ポリエチレン/エチレン-酢酸ビニル共重合体を60/40(PE/EVA=60/40)で重合させた発泡体
PE/SEBS=50/50:ポリエチレン/スチレン-エチレン-ブチレン-スチレンブロック共重合体を50/50(PE/SEBS=50/50)で重合させた発泡体
SBBS:スチレン-ブタジエン-ブチレン-スチレンブロック共重合体(SBBS)で重合させた発泡体
評価例1の水系接着剤(F1)を、水系接着剤(F81)~(F87)のいずれかに変更したこと以外は評価例1と同様にして積層体(92)~(98)を得た。
評価例1と同様にして、積層体の接着性を評価した。その結果を表3-13に示す。
○:剥離強度55N/inch以上。
×:剥離強度55N/inch未満。
評価例1の水系接着剤(F1)を、水系接着剤(F88)~(F124)のいずれかに変更したこと以外は評価例1と同様にして積層体(99)~(135)を得た。
評価例1と同様にして、積層体の接着性を評価した。その結果を表3-14に示す。
○:剥離強度55N/inch以上。
×:剥離強度55N/inch未満。
評価例1の水系接着剤(F1)を、水系接着剤(H1)~(H3)のいずれかに変更したこと以外は評価例1と同様にして比較積層体(1)~(3)を得た。
評価例1と同様にして、積層体の接着性を評価した。その結果を表3-15に示す。
Claims (22)
- 塩素原子含有量が45質量%以上である塩素化ゴムと、1種以上の重合性基を有する化合物と、水とを含む水性エマルション。
- 前記塩素化ゴム100質量部に対する、前記重合性基を有する化合物の含有量が50~10000質量部である請求項1に記載の水性エマルション。
- 水を分散媒として含み、
前記塩素化ゴムと前記重合性基を有する化合物との混合物を分散質として含む請求項1又は2に記載の水性エマルション。 - 分散質が液体状である請求項1~3のいずれかに記載の水性エマルション。
- 前記塩素化ゴムの少なくとも一部が分散質に溶解している請求項1~4のいずれかに記載の水性エマルション。
- 前記塩素化ゴムの少なくとも一部が前記重合性基を有する化合物に溶解した溶液を、分散質として含む請求項1~5のいずれかに記載の水性エマルション。
- 前記重合性基を有する化合物が23℃大気圧下で液体である請求項1~6のいずれかに記載の水性エマルション。
- 前記重合性基を有する化合物が、エチレン性不飽和二重結合を有する化合物である請求項1~7のいずれかに記載の水性エマルション。
- さらに、界面活性剤を含む請求項1~8のいずれかに記載の水性エマルション。
- さらに、光重合開始剤を含む請求項1~9のいずれかに記載の水性エマルション。
- さらに、光安定剤を含む請求項1~10のいずれかに記載の水性エマルション。
- さらに、紫外線硬化性オリゴマーを含む請求項1~11のいずれかに記載の水性エマルション。
- さらに、蛍光増白剤を含む請求項1~12のいずれかに記載の水性エマルション。
- さらに、レベリング剤を含む請求項1~13のいずれかに記載の水性エマルション。
- 前記分散質の体積基準のメジアン径が10μm以下である請求項3~14のいずれかに記載の水性エマルション。
- 前記塩素化ゴムがカルボキシ基及びカルボン酸無水物構造を有さない請求項1~15のいずれかに記載の水性エマルション。
- 前記塩素化ゴムの質量部と前記重合性基を有する化合物の質量部との合計量が、前記塩素化ゴムと前記重合性基を有する化合物と水の質量部の合計量に対して、0.1質量%~70質量%である請求項1~16のいずれかに記載の水性エマルション。
- 請求項1~17のいずれかに記載の水性エマルションによって形成される塗布膜。
- 請求項18に記載の塗布膜の硬化物。
- オレフィン系重合体からなる第1の基材の上に、請求項19に記載の硬化物と、さらにその上に一層以上の接着剤層と、第2の基材とがこの順に積層された積層体。
- エチレン・酢酸ビニル共重合体からなる第1の基材の上に、請求項19に記載の硬化物と、さらにその上に一層以上の接着剤層と、第2の基材とがこの順に積層された積層体。
- 前記接着剤層と前記第2の基材とが請求項19に記載の硬化物を介して積層されている請求項20又は21に記載の積層体。
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| CN109843935A (zh) * | 2016-10-28 | 2019-06-04 | 住友化学株式会社 | 分散液 |
| KR20190077342A (ko) | 2016-10-28 | 2019-07-03 | 스미또모 가가꾸 가부시끼가이샤 | 분산액 |
| CN109843935B (zh) * | 2016-10-28 | 2021-07-27 | 住友化学株式会社 | 分散液 |
| JP2018070768A (ja) * | 2016-10-28 | 2018-05-10 | 住友化学株式会社 | 分散液 |
| WO2018079634A1 (ja) * | 2016-10-28 | 2018-05-03 | 住友化学株式会社 | 分散液 |
| EP4023730A4 (en) * | 2019-08-28 | 2023-09-13 | Hanwha Solutions Corporation | AQUEOUS FLAME-RETARDANT ADHESIVE COMPOSITION AND METHOD FOR PRODUCING THE SAME |
| US12331220B2 (en) | 2019-08-28 | 2025-06-17 | Hanwha Solutions Corporation | Aqueous flame retardant adhesive composition and method for preparing the same |
| WO2024075829A1 (ja) * | 2022-10-06 | 2024-04-11 | 株式会社クラレ | 組成物、懸濁重合用分散剤、及びビニル系重合体の製造方法 |
| WO2024210066A1 (ja) * | 2023-04-06 | 2024-10-10 | 株式会社クラレ | 溶液、分散剤、ビニル化合物重合体の製造方法、及び溶液の製造方法 |
| JPWO2024210066A1 (ja) * | 2023-04-06 | 2024-10-10 | ||
| JP7811667B2 (ja) | 2023-04-06 | 2026-02-05 | 株式会社クラレ | 溶液、分散剤、ビニル化合物重合体の製造方法、及び溶液の製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI664252B (zh) | 2019-07-01 |
| KR102483804B1 (ko) | 2022-12-30 |
| CN106459241B (zh) | 2019-03-01 |
| KR20170028308A (ko) | 2017-03-13 |
| TW201606002A (zh) | 2016-02-16 |
| JPWO2015194611A1 (ja) | 2017-06-08 |
| CN106459241A (zh) | 2017-02-22 |
| JP6902194B2 (ja) | 2021-07-14 |
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