Classifications

• • 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
• • 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
• • 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
• • 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
• • 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
• • 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
• • 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
• • 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
• • 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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