WO2018079634A1 - 分散液 - Google Patents

分散液 Download PDF

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Publication number
WO2018079634A1
WO2018079634A1 PCT/JP2017/038601 JP2017038601W WO2018079634A1 WO 2018079634 A1 WO2018079634 A1 WO 2018079634A1 JP 2017038601 W JP2017038601 W JP 2017038601W WO 2018079634 A1 WO2018079634 A1 WO 2018079634A1
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Prior art keywords
compound
meth
acrylate
dispersion
weight
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PCT/JP2017/038601
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English (en)
French (fr)
Japanese (ja)
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WO2018079634A8 (ja
Inventor
能宜 岡田
中島　秀人
順次 森本
Original Assignee
住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN201780066765.7A priority Critical patent/CN109843935B/zh
Priority to KR1020197011158A priority patent/KR102412701B1/ko
Publication of WO2018079634A1 publication Critical patent/WO2018079634A1/ja
Publication of WO2018079634A8 publication Critical patent/WO2018079634A8/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
    • 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
    • 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
    • B32B27/30—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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers

Definitions

  • the present invention relates to a dispersion.
  • Patent Document 1 describes an aqueous resin composition containing an acid-modified chlorinated polyolefin that can be used as an adhesive or a primer.
  • Patent Document 2 describes an aqueous emulsion excellent in adhesiveness, which contains a chlorinated rubber having a chlorine atom content of 45% by weight or more, a compound having one or more polymerizable groups, and water. Has been. However, such an aqueous emulsion does not always have sufficient adhesion when used after long-term storage.
  • the problem to be solved by the present invention is to provide a dispersion exhibiting excellent adhesiveness even when used after long-term storage.
  • a dispersion liquid containing water as a dispersion medium and containing a compound having a chlorinated rubber and a polymerizable group as a dispersoid The total amount of the chlorinated rubber and the compound having a polymerizable group is 1 to 60% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group and water, 30 mL of the dispersion liquid is poured into a 100 mL container, and a measurement sample is prepared by stirring for 1 minute at a rotation speed of 800 rpm and a rotation speed of 2,000 rpm using a rotation and revolution stirrer.
  • Back-scattered light by pouring into a sample cell, irradiating the measurement sample in the sample cell with incident light having a wavelength of 880 nm, and detecting back-scattered light from the measurement sample at a position of 45 ° to the incident light
  • the intensity (%) measurement was started within 10 minutes from the preparation of the measurement sample, and the backscattering was measured 30 minutes after the start of measurement at each of the top, middle and bottom of the measurement sample in the sample cell.
  • the maximum value ⁇ (%) of the absolute value of the amount of change in the backscattered light intensity (%) measured 24 hours after the start of measurement with respect to the light intensity (%) is expressed by the following formulas (I) to (III) ⁇ (upper part) ⁇ 20 (I) ⁇ (intermediate part) ⁇ 5 (II) ⁇ (bottom) ⁇ 10 (III) [Wherein, ⁇ (upper part) represents the maximum value ⁇ (%) at the upper part of the measurement sample, ⁇ (middle part) represents the maximum value ⁇ (%) at the intermediate part of the measurement sample, and ⁇ ( Bottom) shows the maximum value ⁇ (%) at the bottom of the measurement sample, and the top, middle, and bottom of the measurement sample show the height of the measurement sample in the sample cell excluding the meniscus portion from the top. The part of the measurement sample divided by 1/3 is shown. ] A dispersion that meets the requirements of
  • the amount of the chlorinated rubber is 1 to 30 parts by weight relative to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
  • the amount of the chlorinated rubber is 3 to 25 parts by weight with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
  • the amount of the chlorinated rubber is 5 to 20 parts by weight with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
  • the amount of the chlorinated rubber is 0.01 to 18% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group, and water.
  • the amount of the chlorinated rubber is 0.1 to 10% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group, and water.
  • the amount of the chlorinated rubber is 0.2 to 5% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group, and water. The dispersion described.
  • the amount of the compound having a polymerizable group and a cyclic structure is 1 to 60% by weight in the total of the compound having a polymerizable group, according to any one of the above [29] to [32] Dispersion.
  • the amount of the compound having a polymerizable group and a cyclic structure is 3 to 40% by weight in the total of the compound having a polymerizable group, according to any one of the above [29] to [32] Dispersion.
  • the amount of the compound having a polymerizable group and a cyclic structure is 5 to 20% by weight in the total of the compound having a polymerizable group, according to any one of the above [29] to [32] Dispersion.
  • the amount of the compound having a polymerizable group and having no cyclic structure is 0.4 to 50% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group, and water.
  • the aforementioned [29], wherein the amount of the compound having a polymerizable group and having no cyclic structure is 1 to 25% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water.
  • the dispersion liquid according to any one of [35].
  • the compound having a polymerizable group and having no cyclic structure is at least one selected from the group consisting of dodecyl (meth) acrylate and 1,6-hexanediol di (meth) acrylate.
  • the dispersion liquid as described in any one of.
  • the compound having a polymerizable group and a cyclic structure is selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate.
  • the aforementioned [29], wherein the compound having a polymerizable group and a cyclic structure is at least one selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate.
  • any one of [1] to [41], wherein the compound having a polymerizable group is at least one selected from the group consisting of a compound having an ethylenically unsaturated bond, an epoxy compound, and an oxetane compound.
  • the dispersion liquid described in 1. [49] The dispersion according to any one of [1] to [41], wherein the compound having a polymerizable group is a compound having an ethylenically unsaturated bond.
  • [52] The dispersion according to any one of [1] to [51], further including a surfactant.
  • the dispersion of the present invention can adhere to an adherend with sufficient strength even when used after long-term storage.
  • the dispersion of the present invention contains water as a dispersion medium, and contains a chlorinated rubber and a compound having a polymerizable group as a dispersoid.
  • the dispersion of the present invention is useful as an aqueous adhesive, a primer, or a raw material thereof.
  • the dispersion (dispersion) of the present invention may be a suspension (suspension) in which the dispersoid is solid, or may be an emulsion (emulsion) in which the dispersoid is liquid, and some of the dispersoid is solid.
  • the remaining dispersoid may be a liquid dispersion.
  • the dispersion of the present invention is preferably an emulsion in which the dispersoid is a liquid, or a part of the dispersoid is a solid and the remaining dispersoid is a liquid, more preferably An emulsion in which the dispersoid is liquid.
  • the dispersion of the present invention it is preferable that at least a part of the chlorinated rubber is dissolved in the liquid dispersoid.
  • that at least a part of the chlorinated rubber is dissolved in the liquid dispersoid means that when the dispersion is filtered through a filter having a pore size of about 0.50 ⁇ m, at least a part of the chlorinated rubber is in the filtrate.
  • the chlorinated rubber contained in the filtrate is preferably 1 part by weight or more, more preferably 10 parts by weight or more, and further preferably 30 parts by weight or more with respect to 100 parts by weight of the chlorinated rubber contained in the dispersion before filtration. More preferably, it is 70 parts by weight or more. It is particularly preferable that all of the chlorinated rubber is dissolved in the liquid dispersoid (that is, all of the chlorinated rubber is contained in the filtrate).
  • the compound having a polymerizable group is liquid at 23 ° C. and atmospheric pressure, and all the compounds having a polymerizable group are at 23 ° C. and atmospheric pressure. More preferably, it is liquid.
  • at least a part of the chlorinated rubber has a polymerizable group that is liquid at 23 ° C. and atmospheric pressure (hereinafter sometimes abbreviated as “compound having a polymerizable group that is liquid”). It is preferable that the chlorinated rubber is dissolved in the solvent, and it is more preferable that the entire chlorinated rubber is dissolved in the compound having a polymerizable group that is liquid.
  • the fact that at least a part of chlorinated rubber is dissolved in a compound having a polymerizable group that is liquid means that a mixture of a chlorinated rubber and a compound having a polymerizable group that is liquid is filtered with a filter having a pore diameter of about 0.50 ⁇ m. It means that at least a part of the chlorinated rubber is contained in the filtrate when filtered.
  • the chlorinated rubber contained in the filtrate is preferably 1 part by weight or more, more preferably 10 parts by weight or more, and further preferably 30 parts by weight or more with respect to 100 parts by weight of the chlorinated rubber contained in the dispersion before filtration. More preferably, it is 70 parts by weight or more. It is particularly preferable that all of the chlorinated rubber is dissolved in the liquid dispersoid (that is, all of the chlorinated rubber is contained in the filtrate).
  • the mixing temperature for preparing the mixture of the chlorinated rubber and the compound having a polymerizable group is usually 25 to 100 ° C., and the mixing time is preferably as short as possible.
  • the mixer used for this purpose include a Banbury mixer, a Henschel mixer, and a homomixer.
  • the total amount of the chlorinated rubber and the compound having a polymerizable group is 1 to 60% by weight, preferably 3 to 30% by weight, more preferably 5% in the total of the chlorinated rubber, the compound having a polymerizable group and water. ⁇ 15 wt%. Adhesiveness will become favorable by making the total amount of the compound which has chlorinated rubber and a polymeric group into the said range.
  • the dispersion of the present invention was prepared by pouring 30 mL of the dispersion into a 100 mL container, and stirring for 1 minute under the conditions of a rotation speed of 800 rpm and a rotation speed of 2,000 rpm using a rotation and revolution stirrer.
  • the measurement sample is poured into a cylindrical sample cell having a diameter of 25 mm, the measurement sample in the sample cell is irradiated with incident light having a wavelength of 880 nm, and backscattered light from the measurement sample is emitted at a position of 45 ° with respect to the incident light.
  • the measurement of the backscattered light intensity (%) by detection is started within 10 minutes from the preparation of the measurement sample, and the measurement is started at each of the top, middle and bottom of the measurement sample in the sample cell.
  • the maximum value ⁇ (%) of the absolute value of the amount of change in the backscattered light intensity (%) measured 24 hours after the start of measurement with respect to the backscattered light intensity (%) measured 30 minutes later is Formulas (I) to (III): ⁇ (upper part) ⁇ 20 (I) ⁇ (intermediate part) ⁇ 5 (II) ⁇ (bottom) ⁇ 10 (III) [Wherein, ⁇ (upper part) represents the maximum value ⁇ (%) at the upper part of the measurement sample, ⁇ (middle part) represents the maximum value ⁇ (%) at the intermediate part of the measurement sample, and ⁇ ( Bottom) shows the maximum value ⁇ (%) at the bottom of the measurement sample, and the top, middle, and bottom of the measurement sample show the height of the measurement sample in the sample cell excluding the meniscus portion
  • the part of the measurement sample divided by 1/3 is shown.
  • One of the characteristics is to satisfy the above requirements.
  • the boundary between the upper part and the intermediate part of the measurement sample and the boundary between the intermediate part and the bottom part of the measurement sample are all included in the intermediate part of the measurement sample. Even if the dispersion liquid of the present invention satisfying such requirements is used after long-term storage, it can adhere to an adherend with sufficient strength.
  • a series of operations consisting of preparation of the measurement sample and measurement of the backscattered light intensity (%) is performed in an environment at 24-26 ° C. using an apparatus placed in an environment at 24-26 ° C.
  • preparation of the measurement sample that is, stirring of the dispersion liquid using a rotation / revolution stirrer
  • a dispersion liquid that is allowed to stand for 1 hour or more in an environment of 24 to 26 ° C. is used.
  • Examples of the rotation / revolution stirrer for preparing the measurement sample include “Rotation / revolution mixer: Awatori Nertaro ARE-310” manufactured by Sinky Corporation.
  • As an apparatus for measuring the amount of change in the backscattered light intensity (%) of the measurement sample for example, “turbiscan TOWER” manufactured by Formulation may be mentioned.
  • the “backscattered light intensity (%)” means “intensity of detected backscattered light with respect to the intensity of irradiated incident light (%)”. “The amount of change in the backscattered light intensity (%) measured 24 hours after the start of measurement relative to the backscattered light intensity (%) measured 30 minutes after the start of measurement” means “measurement It means a difference between the backscattered light intensity (%) measured 30 minutes after the start and the backscattered light intensity (%) measured 24 hours after the start of measurement.
  • the “maximum value in absolute value” means “a maximum value in a plurality of the absolute values calculated in each of the top, middle, and bottom of the measurement sample in the sample cell”.
  • the volume-based median diameter of the dispersoid in the dispersion is preferably 10 ⁇ m or less, more preferably 0.01 to 5 ⁇ m, still more preferably 0.01 to 2 ⁇ m, and still more preferably 0.01 ⁇ 1 ⁇ m. When the median diameter is within the above range, the standing stability of the dispersion is good.
  • the volume-based median diameter of the dispersoid means a particle diameter at which the integrated particle diameter distribution value is 50% on the volume basis. This median diameter can be measured with a laser diffraction particle diameter measuring apparatus LA-950V2 manufactured by HORIBA.
  • Chlorinated rubber means chlorinated natural rubber or synthetic rubber.
  • the chlorinated rubber may be one type or two or more types.
  • rubber means “uncrosslinked rubber” unless otherwise specified.
  • the chlorinated rubber used in the present invention may be a chlorinated rubber having a melting point or a chlorinated rubber having no melting point. It is preferable to use a chlorinated rubber having a melting point.
  • the melting point of the chlorinated rubber is preferably 100 ° C. or higher, more preferably 200 ° C. or higher, further preferably 240 ° C. or higher, preferably 350 ° C. or lower, more preferably 300 ° C. or lower.
  • the melting point of the chlorinated rubber can be measured by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • An example of the DSC apparatus is DSC-60 Plus manufactured by Shimadzu Corporation.
  • the chlorine atom content of the chlorinated rubber is preferably 45% by weight or more, more preferably 45 to 85% by weight, still more preferably 55 to 80% by weight.
  • chlorinated rubber those having no carboxy group and carboxylic anhydride structure are preferably used.
  • the dispersion liquid of the present invention containing such a chlorinated rubber is used as an aqueous adhesive, primer or raw material thereof, the concern about the decrease in water resistance of the coating film is extremely small and effective.
  • the chlorinated rubber is not particularly limited as long as it is chlorinated natural rubber or synthetic rubber.
  • chlorinated natural rubber chlorinated butadiene rubber, chlorinated butyl rubber, chlorinated isoprene rubber, butadiene / chlorinated cyclic conjugate Diene adducts, chlorinated butadiene styrene copolymers, brominated poly (2,3-dichloro-1,3-butadiene) and ⁇ -haloacrylonitrile-co-2,3-dichloro-1,3-butadiene copolymers Etc.
  • a chlorinated rubber synthesized from a raw material containing a monomer having 4 or more carbon atoms is preferred.
  • the chlorinated rubber is more preferably at least one selected from the group consisting of chlorinated natural rubber, chlorinated isoprene rubber and chlorinated butadiene rubber, more preferably chlorinated natural rubber, chlorinated isoprene rubber or chlorinated butadiene. It is rubber.
  • a conventionally known method can be adopted. For example, a method in which natural rubber or synthetic rubber is dissolved in a chlorinated organic solvent such as carbon tetrachloride or monochlorobenzene, or an organic solvent such as toluene, and chlorine gas is blown; the natural rubber or synthetic rubber is suspended or emulsified in water Injecting chlorine gas with water; Introducing chlorine gas while irradiating ultraviolet rays with natural rubber or synthetic rubber suspended or emulsified in water; Contacting natural rubber or synthetic rubber with liquid chlorine under low pressure And chlorinating directly.
  • a chlorinated organic solvent such as carbon tetrachloride or monochlorobenzene, or an organic solvent such as toluene
  • 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 polystyrene-reduced weight average molecular weight (Mw) of the chlorinated rubber is preferably 1,000 or more, more preferably 3,000 or more, further preferably 5,000 or more, particularly preferably 10,000 or more, preferably 400,000 or less, more preferably 200,000 or less.
  • Mw can be measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • chlorinated rubber for example, commercially available products and known methods or those manufactured according to the methods can be used.
  • Commercially available products include, for example, 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 (Covestro), Alloprene (registered trademark) R10, R20, R40 (manufactured by ICI UK).
  • Supercron registered trademark
  • CR-10 CR-20
  • Pergut S-40 Pergut S -90
  • Pergut S-130 Pergut S-170
  • Alloprene registered trademark
  • R10, R20, R40 manufactured by ICI UK.
  • the method of patent 2660478 is mentioned, for example.
  • the amount of the chlorinated rubber is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, still more preferably 5 to 20 parts by weight based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Part.
  • the amount of the chlorinated rubber is preferably 0.01 to 18% by weight, more preferably 0.1 to 10% by weight, and still more preferably 0.1% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water. 2 to 5% by weight.
  • (meth) acryl means “acryl and methacryl”
  • (meth) acryloyl” means “acryloyl and methacryloyl”.
  • Other expressions of “(meta)” have the same meaning.
  • the compound having a polymerizable group is preferably at least one selected from the group consisting of a compound having an ethylenically unsaturated bond, an epoxy compound, and an oxetane compound, and more preferably a compound having an ethylenically unsaturated bond.
  • the number of ethylenically unsaturated bonds in the compound having an ethylenically unsaturated bond is preferably 1 to 3, more preferably 1 to 2.
  • Examples of the compound having one ethylenically unsaturated bond include heterocyclic ethylenically unsaturated compounds (for example, N-vinyl-nitrogen-containing heterocycles such as N-vinylpyrrolidone, N-vinylpyridine and N-vinylcaprolactam).
  • heterocyclic ethylenically unsaturated compounds for example, N-vinyl-nitrogen-containing heterocycles such as N-vinylpyrrolidone, N-vinylpyridine and N-vinylcaprolactam.
  • heterocyclic (meth) acrylates 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, etc.), N, N′-dimethylacrylamide, alkoxy (poly) alkylene glycol (meth) acrylate (for example, methoxyethylene (meta) Acrylate, ethoxy-diethylene glycol (meth) acrylate, methoxypolyethylene (meth) acrylate, butoxypolyethylene (meth) acrylate, etc.), alkyl (meth) acrylate (for example, methyl (meth) acrylate, eth
  • Examples of the compound having one ethylenically unsaturated bond and having a cyclic structure include (meth) acrylate having an alicyclic skeleton (for example, cyclohexyl (meth) acrylate, 4 (1,1-dimethylethyl)) Cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, norbornylmethyl (meth) acrylate, phenylnorbornyl (meth) acrylate, cyanonor Bornyl (meth) acrylate, menthyl (meth) acrylate, fentyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] dec-8-yl (Meta
  • Examples of the compound having two ethylenically unsaturated bonds include di (meth) acrylate of 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, polyoxyalkylene glycol di- (Meth) acrylate (for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Liethylene glycol-propylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-
  • Examples of the compound having two ethylenically unsaturated bonds and having a cyclic structure include di (meth) acrylates (for example, 2,2) of adducts of alkylene oxide (for example, ethylene oxide, propylene oxide, etc.) of bisphenol A.
  • bifunctional epoxy resin for example, 2,2-bis (glycidyl oxyphe Le) propane (meth) acrylic acid adduct, bisphenol A diglycidyl ether methacrylic acid adduct, etc.
  • Examples of the compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, tris (acryloyloxy) isocyanurate, tris (2-acryloyloxyethyl) isocyanate Nurate, tris (2-hydroxyethyl) isocyanurate, tri (meth) acrylate, tris (hydroxypropyl) Isocyanurate of tri (meth)
  • the number of carbon atoms of the compound having an ethylenically unsaturated bond is preferably 5 to 25, more preferably 6 to 23, and still more preferably 8 to 20.
  • 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 diglycol Diether, brominated bisphenol A diglycidyl ether, brominated
  • epoxy compound aromatic epoxides and alicyclic epoxides are preferable and alicyclic epoxides are more preferable from the viewpoint of excellent curing speed.
  • oxetane compound examples include 2-hydroxymethyl-2-methyloxetane, 2-hydroxymethyl-2-ethyloxetane, 2-hydroxymethyl-2-propyloxetane, 2-hydroxymethyl-2-butyloxetane, 1,4 -Bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene and the like.
  • the compound having a polymerizable group may be solid or liquid at 23 ° C. and atmospheric pressure, and is preferably liquid.
  • the amount of the compound having a polymerizable group in the dispersion of the present invention is preferably 70 to 99 parts by weight, more preferably 75 to 97 parts, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Part by weight, more preferably 80 to 95 parts by weight.
  • the compound having a polymerizable group is preferably a mixture of a compound having a polymerizable group and not having a cyclic structure and a compound having a polymerizable group and a cyclic structure.
  • the compound having a polymerizable group and having no cyclic structure is preferably 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 1,6-hexane. It is at least one selected from the group consisting of diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate, and more preferably dodecyl (meth).
  • the compound having a polymerizable group and a cyclic structure is preferably at least selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate.
  • at least one selected from the group consisting of tricyclodecane dimethanol di (meth) acrylate is preferably at least selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate.
  • the compound having a polymerizable group is a mixture of a compound having a polymerizable group and not having a cyclic structure, and a compound having a polymerizable group and a cyclic structure
  • the compound has a polymerizable group and is cyclic
  • the amount of the compound having no structure is preferably 0.4 to 50% by weight, more preferably 1 to 25% by weight, and still more preferably 3% in the total of the chlorinated rubber, the compound having a polymerizable group and water.
  • the amount of the compound having a polymerizable group and a cyclic structure is preferably from 0.01 to 30% by weight, more preferably in the total of the chlorinated rubber, the compound having a polymerizable group and water. It is 0.1 to 15% by weight, more preferably 0.2 to 5% by weight.
  • the compound having a polymerizable group is a mixture of a compound having a polymerizable group and not having a cyclic structure, and a compound having a polymerizable group and a cyclic structure
  • the compound has a polymerizable group and is cyclic
  • the amount of the compound having no structure is preferably 40 to 99% by weight, more preferably 60 to 97% by weight, and still more preferably 80 to 95% by weight in the total of the compounds having a polymerizable group.
  • the amount of the compound having a polymerizable group and a cyclic structure is preferably 1 to 60% by weight, more preferably 3 to 40% by weight, and still more preferably in the total of the compound having a polymerizable group. Is from 5 to 20% by weight.
  • Water> There is no limitation in particular as water which the dispersion liquid of this invention contains, For example, tap water or deionized water is used.
  • the dispersion of the present invention may contain other components different from water, chlorinated rubber and the compound having a polymerizable group. Only 1 type may be used for another component and it may use 2 or more types together.
  • Other components include, for example, polymerization inhibitors, surfactants, photopolymerization initiators, light stabilizers, UV curable oligomers, fluorescent brighteners, leveling agents, basic compounds, organic solvents, crosslinking agents, photosensitizers.
  • Sensitizers other resins or rubbers different from chlorinated rubber, phenolic stabilizers, phosphite stabilizers, amine stabilizers, amide stabilizers, anti-aging agents, weathering stabilizers, preservatives, anti-settling agents , Antioxidant, heat stabilizer, thixotropic agent, thickener, 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 fiber, carbon fiber, potassium titanate fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass flake, barium sulfate , Clay, kaolin, finely divided silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, and fillers of inorganic or organic, such as Celite,
  • Polymerization inhibitor> There is no limitation in particular in a polymerization inhibitor, A well-known polymerization inhibitor can be used.
  • the polymerization inhibitor include hydroquinone, methylhydroquinone, monoesterified hydroquinone, 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- Examples include benzoquinone, 4-methoxyphenol, chloranil, pyrogallol, 2-oxydiphenylamine, and phenothiazine.
  • Examples of commercially available 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 has the effect of increasing the storage stability of the dispersion and ensuring curability.
  • the amount of the polymerization inhibitor in the dispersion is preferably 0.005 to 0.4 weight with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Parts, more preferably 0.01 to 0.4 parts by weight, even more preferably 0.01 to 0.3 parts by weight, still more preferably 0.02 to 0.3 parts by weight, still more preferably 0.02 to The amount is 0.2 parts by weight, particularly preferably 0.035 to 0.2 parts by weight.
  • the polymerization inhibitor a polymerization inhibitor that is soluble in a compound having a liquid polymerizable group is preferable.
  • the surfactant preferably acts as an emulsifier.
  • examples of the surfactant include a cationic, anionic, amphoteric or nonionic surfactant, and an anionic or nonionic surfactant is preferable.
  • Surfactants may be used alone or in combination of two or more.
  • anionic surfactant examples 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, etc.
  • Higher fatty acid ester sulfonates such as higher alkyl sulfonates and lauric acid ester sulfonates, dialkyl sulfosuccinates such as dioctyl sulfosuccinate, higher fatty acid amide sulfonates such as oleic acid amide sulfonic acid, dodecylbenzene sulfone Acid aryl, alkylaryl sulfonates such as diisopropylnaphthalene sulfonate, formalin condensates of alkyl aryl sulfonate, pentadecane-2-sulfate Higher alcohol sulfates such as dipolyoxyethylene dodecyl ether phosphates, polyoxyethylene alkyl phosphates such as lignin sulfonate, polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate, polyoxy Ethy
  • Examples of the cationic surfactant include alkylamine hydrochlorides such as dodecylamine hydrochloride, alkyl quaternary ammonium salts such as alkyldimethylbenzylammonium salt, alkylisoquinolinium salt and dialkylmorpholinium salt, benzethonium chloride, And polyalkylvinylpyridinium salts, alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt, alkylpyridium salts such as cetylpyridium salt and decylpyridium salt, oxyalkylenetrialkylammonium salt, dioxyalkylenedialkylammonium salt, Examples include allyltrialkylammonium salt, diallyldialkylammonium salt, 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 Lenalkylamine, polyoxyethylene alkanediol, alkoxy polyethylene glycol methacrylate, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene fatty acid amide, polyalkylene polyamine alkylene oxide adduct, polyalkylene polyimine alkylene oxide adduct, Examples include polyvinyl pyrrolidone, dicyandiamide polyalkylene polyamine condensate, polyethylene glycol, polyvinyl alcohol 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.
  • Examples of commercially available 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, Demal EP, Emulgen 102KG, Emulgen 104P, Emulgen 105, Emalgen 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,
  • the dispersion of the present invention preferably contains a surfactant.
  • the amount thereof is preferably 1 part by weight or more, preferably 30 parts by weight, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Below, more preferably 15 parts by weight or less, and still more preferably 10 parts by weight or less.
  • the photopolymerization initiator is a compound that generates active species by the action of light.
  • Examples of the photopolymerization initiator include 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 a photo base generator that generates a base by the action of light. It is done.
  • 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 compound examples include benzophenone, 4-methylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert -Butylperoxycarbonyl) 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).
  • acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
  • triazine compound examples include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -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 2,4-bis (t
  • photo radical generators can be used.
  • examples of commercially available photoradical generators include Irgacure (registered trademark) 1173, 907, 184, 651, 819, 250, 2959, 127, 754 and 369 (BASF Japan Co., Ltd.), Sequol (registered trademark).
  • Irgacure registered trademark 500 (1-hydroxy-cyclohexyl-phenyl-ketone / benzophenone: 50/50%
  • Irgacure registered trademark 1700
  • Irgacure® 1800 bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethylpentylphosphine oxide / 1-hydroxycyclohexyl-phenylketone: 25/75%)
  • BASF Japan Ltd. BASF Japan Ltd.
  • photoacid generator examples include sulfonic acid derivatives, onium salts, dicarboxylic imides, and the like.
  • sulfonic acid derivatives examples include disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, trifluoromethylsulfonates, benzoinsulfonates, and sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol. , Pyrogallol trisulfonates, benzyl sulfonates.
  • onium salts include tetrafluoroborate (BF 4 ⁇ ), hexafluorophosphate (PF 6 ⁇ ), hexafluoroantimonate (SbF 6 ⁇ ), hexafluoroarsenate (AsF 6 ⁇ ), hexachloroantimonate ( SbCl 6 ⁇ ), tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate, perchlorate ion (ClO 4 ⁇ ), trifluoromethanesulfonate ion (CF 3 SO 3 ⁇ ), fluorosulfonic acid ion (FSO 3-), include toluenesulfonate ion, trinitrobenzene sulfonate anion, a sulfonium salt and iodonium salts having an anion such as trinitrotoluene sulf
  • 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- Tetradecyloxy) phenyl] phenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium
  • onium salts examples include aromatic diazonium salts such as p-methoxybenzenediazonium and hexafluoroantimonate.
  • onium salts include, for example, Sun Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI-L160, SI -L110, SI-L147 (above, Sanshin Chemical Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990 (above, Union Carbide), Adekaoptomer SP-150, SP- 151, SP-170, SP-171, SP-172 (above, manufactured by ADEKA), Irgacure 261, Irgacure 250 (made by BASF), CI-2481, CI-2624, CI-2638, CI-2064 (above, Japan) Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (above, DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100,
  • Diaryliodonium salts that can be produced by the method can also be used. These may be used alone or in combination of two or more.
  • dicarboxylic imides examples include N- (methylsulfonyloxy) naphthalene-1,8-dicarboximide, N- (tosyloxy) naphthalene-1,8-dicarboximide, N-[(trifluoromethyl) sulfonyl Oxy] naphthalene-1,8-dicarboximide, N- (camphorsulfonyloxy) naphthalene-1,8-dicarboximide, N- (phenylsulfonyloxy) succinimide, N- (tosyloxy) succinimide, N-[(tri Fluoromethyl) sulfonyloxy] succinimide, N- (camphorsulfonyloxy) succinimide, N-[(trifluoromethyl) sulfonyloxy] phthalimide, N-[(trifluoromethyl) sulfonyloxy] phthalimide, N-[(
  • photobase generators 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 may be used alone or in combination of two or more.
  • the amount thereof is preferably from the viewpoint of stability, reactivity, and odor with respect to a total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group.
  • the amount is 0.01 parts by weight or more, preferably 40 parts by weight or less, more preferably 20 parts by weight or less, still more preferably 10 parts by weight or less, and still more preferably 5 parts by weight 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.
  • ultraviolet absorbers examples include salicylic acids (eg, phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, etc.), benzophenones (eg, 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'-dimethoxy Benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, etc.), benzotriazoles (for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5 ′) -Tert Butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) benzo
  • hindered amine light stabilizer examples 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-dicarbamate, etc.), and high molecular weight piperidine polycondensates (eg, dimethyl-1- (2-
  • the amount thereof is preferably 0.01 parts by weight or more, preferably 15 parts by weight with respect to a total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group.
  • the amount is not more than parts by weight, more preferably not more than 10 parts by weight, still more preferably not more than 5 parts by weight.
  • 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 (manufactured by Sartomer), U-4HA and U-6HA (Shin Nakamura Chemical Co., Ltd.) AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G and DAUA-167 (manufactured by Kyoeisha Chemical Co., Ltd.).
  • 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 (Cartomer). It is done.
  • These polyester acrylate oligomers may be used alone or in combination.
  • the amount thereof is preferably 0.01 parts by weight or more, preferably 100 parts by weight or more, preferably 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group. It is 20 parts by weight or less, more preferably 15 parts by weight or less, further preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less.
  • optical brightener examples include dialkylaminocoumarin, bisdimethylaminostilbene, bismethylaminostilbene, 4-alkoxy-1,8-naphthalenedicarboxylic acid-N-alkylimide, bisbenzoxazolylethylene, 1,4 -Bis (2-benzoxazolyl) naphthalene, dialkylstilbene and the like.
  • fluorescent whitening agents 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 amount thereof is preferably 0.01 parts by weight or more, preferably 100 parts by weight or more, preferably 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. 5 parts by weight or less, more preferably 3 parts by weight or less, and still more preferably 1 part by weight or less.
  • Leveling agent> As a leveling agent, for example, Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, polyflow no. 95 (manufactured by Kyoeisha Chemical Industries), 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 EF-352
  • the amount thereof is preferably 1 part by weight or more, preferably 20 parts by weight or less, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. More preferably, it is 10 parts by weight or less, and further preferably 5 parts by weight or less.
  • ⁇ Basic compound> As a basic compound, ammonia, an organic amine compound, a metal hydroxide, etc. are mentioned, for example.
  • the basic compound is preferably ammonia or an organic amine compound.
  • Examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, Examples include 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine. Of these, N, N-dimethylethanolamine is preferred.
  • metal hydroxide examples include lithium hydroxide, potassium hydroxide and sodium hydroxide.
  • the amount thereof is preferably 0.01 parts by weight or more, preferably 20 parts per 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.
  • the amount is not more than parts by weight, more preferably not more than 10 parts by weight, still more preferably not more than 5 parts by weight.
  • Organic solvent examples 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; Alcohols such as ethanol, n-propanol, isopropyl alcohol and n-butanol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether and 3-methoxy-3 -Glycols such as methyl-1-butanol; methyl cellosolve, cellosolve, butyl cellosolve, dioxane, MTBE (methyl tertiary rib Ether) and butyl cellosolves of carbitol, ethylene glycol monomethyl
  • the amount of the organic solvent in the dispersion of the present invention is preferably 0 to 100 parts by weight, more preferably 0, from the viewpoint of odor etc. with respect to the total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group. -50 parts by weight, more preferably 0-30 parts by weight, still more preferably 0-10 parts by weight. It is particularly preferred that the dispersion of the present invention does not contain an organic solvent.
  • Crosslinking agent By including a crosslinking agent, there exists a tendency which adhesiveness, the water resistance of a contact bonding layer, and the solvent resistance of a contact bonding layer improve more.
  • the crosslinking agent include epoxy compounds, polyisocyanate compounds (particularly aliphatic polyisocyanate compounds), oxazoline compounds, aziridine compounds, carbodiimide compounds, active methylol compounds, active alkoxymethyl compounds, metal chelates, hydrazide compounds, hydrazines. Compounds and the like. Among these, aliphatic polyisocyanate compounds, carbodiimide compounds, oxazoline compounds, hydrazide compounds, and hydrazine compounds are preferable. Among these, an aqueous one (water-soluble or water-dispersible) is 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 thereof include Sumidur (registered trademark) N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547, 44V10 made by Sumika Covestrourethane.
  • carbodiimide compound examples include Nisshinbo Chemical Co., Ltd .: Carbodilite (SV-02, V-02, V-02-L, V-04, E-01, E-02) and the like.
  • hydrazide compounds include Otsuka Chemical Co., Ltd .: ADH (adipic acid dihydrazide), SDH (sebacic acid dihydrazide), DDH (dodecandiohydrazide), IDH (isophthalic acid dihydrazide), SAH (salicylic acid hydrazide) and the like. It is done.
  • hydrazine compound examples include Otsuka Chemical Co., Ltd .: hydrazine monohydrochloride, hydrazine dihydrochloride, hydrazine monohydrobromide, hydrazine carbonate, and the like.
  • the amount thereof is preferably 0.01 parts by weight or more, preferably 30 parts by weight with respect to a total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group. Part or less, more preferably 15 parts by weight or less, further preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less.
  • the photosensitizer can be appropriately selected according to the wavelength to be enhanced.
  • the effective excitation wavelength range of the photosensitizer is usually 450 nm or less, preferably 250 to 380 nm.
  • Examples of photosensitizers include triethanolamine, triisopropanolamine, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminoethylbenzoate, and isoacyl 4-dimethylaminobenzoate. Can be mentioned.
  • the amount is preferably 0.01 parts by weight or more, preferably 100 parts by weight or more, preferably 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group. It is 15 parts by weight or less, more preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less.
  • the dispersion of the present invention may contain another resin or rubber different from the chlorinated rubber as long as the effects of the present invention are not impaired. Any other resin or rubber may be used alone or in combination of two or more.
  • rubber means an elastomer having elasticity
  • resin means a thermoplastic resin or thermosetting resin that does not have elasticity.
  • Examples of other resins or rubbers include ethylene-vinyl ester copolymers, styrene-maleic acid copolymers, resins having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms and modified products, (meth) acrylic Resin, polystyrene, polyvinyl acetate, polyurethane, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-vinylidene chloride Polymer, vinylidene chloride- (meth) acrylic acid ester copolymer, vinylidene chloride-acrylonitrile copolymer, chlorinated resin having a structural unit derived from ⁇ -olefin having 2 to 20 carbon atoms, polyurea, acrylonitrile-butadiene -Styrene copolymer,
  • the ethylene-vinyl ester copolymer is a copolymer containing an ethylene unit and a vinyl ester unit.
  • the vinyl ester unit include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl ester of tertiary carboxylic acid having 8 to 10 carbon atoms and so-called vinyl versatate (for example, trade name: Veova (manufactured by Shell Chemical Co., Ltd.). Units derived from alkyl acid vinyl esters such as (registered trademark) 10).
  • the ethylene-vinyl ester copolymer may contain units derived from monomers copolymerizable with ethylene and vinyl esters, in addition to ethylene units and vinyl ester units.
  • this monomer include vinyl halides such as vinyl chloride, monomers having a small amount of functional groups such as amide groups, and (meth) acrylic acid esters.
  • an ethylene-vinyl acetate copolymer (hereinafter sometimes abbreviated as “EVA”) is preferable.
  • the ethylene-vinyl acetate copolymer has different properties depending on the vinyl acetate content and the like, but various vinyl acetate contents and shapes (films, blocks, fibers, foams) can be used.
  • the ethylene-vinyl acetate copolymer may contain olefin units other than ethylene units. Examples of the ethylene-vinyl acetate copolymer containing other olefin units include ethylene-octene-vinyl acetate copolymer, ethylene-butene-vinyl acetate copolymer, and ethylene-propylene-vinyl acetate copolymer. It is done.
  • Examples of the ethylene-vinyl ester copolymer include VINNOL® E15 / 45, E15 / 45M, E15 / 48A, H15 / 42, H15 / 50, H11 / 59, H14 / 36, H40 / 50, H40 / 55, and H40. / 60, H30 / 48M (Wacker Chemie AG) and the like.
  • the ethylene-vinyl ester copolymer may be in the form of an emulsion.
  • Such an emulsion may be produced by emulsion polymerization of monomers constituting the ethylene unit and the vinyl ester unit, or a commercially available product may be used.
  • Examples of the emulsion of the ethylene-vinyl ester copolymer include Sumikaflex (registered trademark) 201HQ, 303HQ, 355HQ, 400HQ, 401HQ, 408HQ, 410HQ, 450HQ, 455HQ, 456HQ, 460HQ, 465HQ, 467HQ, 7400HQ, 470HQ, 478HQ, 510HQ, 520HQ, 710, 752, 755, SDX-5100, 801HQ, 808HQ, 830, 850HQ, 900HL and 3950 (above, manufactured by Sumitomo Chemical Co., Ltd.), Vanflex OM-4000 and OM-4200 (above, (Manufactured by Kuraray Co., Ltd.), Polysol (registered trademark) EVA AD-2, AD-3, AD-4, AD-5, AD-51, AD-56, AD-59 and P-900 (above, Showa Polymer) (stock) ), Denka EVA TEX (registered trademark) # 20, # 30, # 40
  • Examples of the styrene-maleic acid copolymer include ARASTOR 700, 703S (manufactured by Arakawa Chemical Industry Co., Ltd.), SMA (registered trademark) 1000, SMA (registered trademark) 2000, SMA (registered trademark) 3000 (Cray Valley '). s).
  • Examples of the styrene-maleic acid copolymer emulsion include VE-1122 (manufactured by Seiko PMC Co., Ltd.).
  • 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.
  • 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-eicocene and vinylcyclohexane. Of these, ethylene and propylene are preferred.
  • 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), linear ⁇ -olefin homopolymers such as low density polyethylene, ultra high molecular weight polyethylene and polypropylene (PP), isotactic (isotactic) polypropylene, syndiotactic polypropylene and atactic polypropylene; ethylene-propylene copolymer, propylene-1 An ⁇ -olefin copolymer such as a butene copolymer, an ethylene-1-butene copolymer, an ethylene-1-octene copolymer, and an ethylene-1-hexene copolymer; and an ⁇ having 2 to 20 carbon atoms -Copolymerizable with olefin and ⁇ -olefin And a copolymer with a
  • the copolymer of an ⁇ -olefin having 2 to 20 carbon atoms and a monomer copolymerizable with the ⁇ -olefin may contain one type of unit derived from each, It may contain two or more types of units derived from.
  • Examples of monomers copolymerizable with an ⁇ -olefin having 2 to 20 carbon atoms include, for example, ⁇ , ⁇ -unsaturated carboxylic acids and their anhydrides, metal salts of ⁇ , ⁇ -unsaturated carboxylic acids, ⁇ , ⁇ -Unsaturated carboxylic acid esters, vinyl esters, vinyl ester saponified products, cyclic olefins, vinyl aromatic compounds, polyene compounds (dienes, etc.), (meth) acrylonitrile, vinyl halides, amides and halogenated vinylidenes, etc. It is done. These may be used alone or in combination.
  • Examples of the ⁇ , ⁇ -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 acid half ester, maleic acid half amide, itaconic acid half ester, itaconic acid half amide, and the like.
  • acrylic acid, methacrylic acid, maleic acid and maleic anhydride are preferred, and acrylic acid and maleic anhydride are particularly preferred.
  • 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.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl acrylate, Examples thereof include dimethyl maleate and esterified products of 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.
  • Examples of the vinyl ester saponified product 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 compound examples include styrene, ⁇ -methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, and Examples include vinyl naphthalene.
  • polyene compounds 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. Can be mentioned. These may have a substituent such as an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group.
  • Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2- Examples include methyl-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- Examples include 1,3-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, and 5-ethyl.
  • Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexane, vinylcyclohexene, 5-vinyl-2-norbornene, 1,4-divinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane, and methyltetrahydroindene. It is done.
  • 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 an ethylene unsaturated carboxylic acid copolymer such as an ethylene-acrylic acid copolymer and an ethylene-methacrylic acid copolymer, Ionomers in which some or all of the carboxyl groups of the ethylene-unsaturated carboxylic acid copolymer are neutralized with metal, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate Copolymer, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-isobutyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-isobutyl acrylate-methacrylic acid copolymer, ethylene- Ethylene-unsaturated carboxylic acid ester such as n-butyl acrylate
  • modified products having structural units derived from ⁇ -olefins having 2 to 20 carbon atoms include resins having structural units derived from ⁇ -olefins having 2 to 20 carbon atoms such as ⁇ , ⁇ -unsaturated carboxylic acids, etc.
  • denaturation by is mentioned.
  • the modification rate with ⁇ , ⁇ -unsaturated carboxylic acids and the like is preferably 0.1 to 10% by weight with respect to 100% by weight of the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms before modification, More preferably, it is 0.2 to 5% by weight, and still more preferably 0.2 to 4% by weight.
  • 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.).
  • ⁇ , ⁇ -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 of a resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is obtained by melting the resin and then adding an ⁇ , ⁇ -unsaturated carboxylic acid or the like to the melt.
  • the resin can be prepared by, for example, a method of dissolving the resin in an organic solvent such as toluene or xylene and then adding an ⁇ , ⁇ -unsaturated carboxylic acid or the like to the solution to modify the resin.
  • the chlorination rate of the chlorinated resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is preferably 5 to 80% by weight with respect to 100% by weight of the copolymer before modification, More preferably, it is 40 to 75% by weight, and further preferably 55 to 70% by weight.
  • Chlorination of a resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is obtained by dissolving or dispersing the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms in an organic solvent. It can be performed by a method of blowing chlorine gas into the chamber.
  • Examples of the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms and modified products thereof include, for example, Mersen (registered trademark) H-6410M, H-6051, H-6960, H-6820, and H-6822X ( Tosoh Corporation), EVAL (registered trademark) L171B, F171B, H171B, E105B and G156B (Kuraray Co., Ltd.), Soarnol (registered trademark) D2908, DT2904, DC3212, DC3203, E3808, ET3803, A4412, AT4403, BX, 16DX, D2908H4 and A4412H4 (Nippon Synthetic Chemical Industry Co., Ltd.), Soaredin (registered trademark) PG505 (Nippon Synthetic Chemical Industry Co., Ltd.), NISSO (registered trademark) PB (Nippon Soda Co., Ltd.), Polytail (registered trademark) H (Mitsubishi Chemical Corporation
  • 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, 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 (made in Japan) Chemicals Co., Ltd.), and the like.
  • the resin having a chlorinated ⁇ -olefin derived structural unit 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.).
  • the polyurethane may be foamed polyurethane or non-foamed polyurethane, but is preferably non-foamed polyurethane.
  • non-foamed polyurethanes water-soluble or water-dispersible polyurethanes are preferable.
  • a commercially available polyurethane can be used. Examples of commercially available polyurethanes include Nipponan (registered trademark) 3110, 3116, 3016, 3113, 3124, 3126, 3230 (Nippon Polyurethane Industry Co., Ltd.).
  • water-soluble or water-dispersible polyurethanes include, for example, Dispacol (registered trademark) U-42, U-53, U-54, U-56, KA-8484, KA-8484, KA-8755, KA- 8756 and KA-8766 (Sumitomo Covestrourethane Co., Ltd.), Hydran (registered trademark) HW-111, HW-311, HW-333, HW-350, HW-337, HW-374, AP-20, AP- 60LM and AP-80 (DIC Corporation), Uprene (registered trademark) UXA-306, UXA-307, Permarin UA-150, Permarin UA-200, Permarin UA-300, Permarin UA-310 and Ucourt UWS-145 ( Sanyo Chemical Industries, Ltd.), Superflex (registered trademark) 107M, 110, 126, 130 150, 160, 210, 300, 361, 370, 410, 420,
  • 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 Corporation), and the like.
  • Examples of the polyvinyl chloride emulsion include Vinibrand 701, 700, and 711 (Nisshin Chemical Industry Co., Ltd.).
  • Chlorinated polyvinyl chloride is obtained by chlorinating polyvinyl chloride by a chlorination method such as a gas phase or a liquid phase.
  • polyvinyl chloride include a homopolymer of vinyl chloride and a copolymer of vinyl chloride and other monomers.
  • other monomers include ethylene, propylene, alkyl vinyl ether, vinylidene chloride, vinyl acetate, acrylic acid ester, and maleic acid ester.
  • Examples of the chlorinated polyvinyl chloride include Sekisui PVC-HA (Sekisui Chemical Co., Ltd.).
  • Examples of the polyvinylidene chloride include SARAN X05253-16 (manufactured by Dow Chemical Co., Ltd.), Saran Wrap (registered trademark) resin (manufactured by Asahi Kasei Co., Ltd.), and the like.
  • Examples of the polyvinylidene chloride emulsion include Diofan 193D, A736, A036, A050, A063, B204, A115 (manufactured by Solvay).
  • Examples of the vinyl chloride-vinylidene chloride copolymer include IXAN SGA-1 (manufactured by Solvay).
  • vinylidene chloride- (meth) acrylic acid ester copolymer examples include IXAN PVS-109, 801, 815, Diofan A586, A602, A610 (manufactured by Solvay).
  • the chloroprene resin is a chloroprene homopolymer or a copolymer of chloroprene and other monomers.
  • the other monomer include isoprene, butadiene, dichlorobutadiene, styrene, acrylonitrile, acrylic acid ester, methacrylic acid ester, acrylic acid, methacrylic acid, itaconic acid, and the like.
  • the acid-modified chloroprene resin is obtained by graft copolymerizing the 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 the acid-modified chloroprene resin examples include Skyprene (registered trademark) G-42, G-40S, G-55, G-40, S-1, G-40T, B-30S, Y- 31 (Tosoh Corp.), Shoprene (Registered Trademark) W, AF, WHV, WXJ, WB (Showa Denko Co., Ltd.), and Denka Chloroprene (Registered Trademark) A-30, A-70, A-90, A -91, M-130L, DCR-11 (Denka 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), and Denkachloroprene (registered trademark) LA-50 and LC -501 (Denka Co., Ltd.).
  • brominated butyl rubber examples include JSR BROMOBUTYL 2255, 2244 (JSR), Exxon Bromobutyl 2255 (ExxonMobil Chemical).
  • modified rubber examples include a chlorinated or brominated modified copolymer of a copolymer of isomonoolefin and paramethylstyrene, and examples of commercially available products include Expro 50 (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.
  • the dispersion of the present invention may contain a water-soluble resin such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, and hydroxyethyl cellulose as another resin.
  • a water-soluble resin such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, and hydroxyethyl cellulose as another resin.
  • the dispersion of the present invention may contain a tackifying resin as another resin.
  • 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, 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 Rosins such as esterified products; terpene polymers such as terpene polymers, terpene phenols, ⁇ -pinene polymers, aromatic modified terpene polymers, ⁇ -pinene polymers, terpene hydrogenated resins, etc .; petroleum having 5 carbon atoms Petroleum resins obtained by polymerizing fractions, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms and their hydrogenated resins; petroleum resins such as maleic acid-modified products and fumaric acid-modified products, chlorinated paraffins, etc. It is done.
  • terpene resins examples include YS Resin PX, PXN, YS Polyster, Mighty Ace, YS Resin TO, TR and Clearon P, M, K (Yasuhara Chemical Co., Ltd.), Tamanoru 803L, 901 (Arakawa Chemical Industries, Ltd.) ) And Tertac 80 (Nippon Terpene Chemical Co., Ltd.).
  • terpene resin emulsion include Tamorol E-200NT and E100 (Arakawa Chemical Industries, Ltd.).
  • chlorinated paraffin examples include Enpara (registered trademark) 70, 50, AR-500 (Ajinomoto Fine Techno Co., Ltd.), Toyoparax (registered trademark) 250, 265, 270, 150, A50 (Tosoh Corp.), etc. Is mentioned.
  • the amount thereof is preferably 0.01 parts by weight or more, preferably 100 parts by weight or more, based on the total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group. Is 100 parts by weight or less, more preferably 50 parts by weight or less, still more preferably 30 parts by weight or less, and still more preferably 20 parts by weight or less.
  • a thickener can be used to adjust the viscosity of the dispersion.
  • the thickener include 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 (ADEKA), and SN thickeners 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 dispersion of the present invention can be produced by a method as described in the examples below. Hereafter, the manufacturing method of the dispersion liquid of this invention is demonstrated in detail.
  • the preliminary dispersion method is not particularly limited, and can be performed using known means and apparatuses.
  • known devices include a homomixer.
  • the number of stirring is preferably 5,000 to 20,000 rpm, more preferably 8,000 to 20,000 rpm, and the stirring time is preferably 2 to 10 minutes, more preferably 3 ⁇ 10 minutes. It is preferred to start stirring with the mixture at room temperature.
  • the obtained preliminary dispersion is homogenized using a high-pressure homogenizer.
  • the pressure of the high-pressure homogenizer is preferably 40 to 1,000 bar, more preferably 40 to 800 bar. If the pressure is less than 40 bar, fine dispersion of the dispersoid becomes insufficient. Conversely, even if the pressure exceeds 1,000 bar, fine dispersion of the dispersoid is not improved.
  • the number of homogenization treatments with a high-pressure homogenizer is preferably 2 to 10 times, more preferably 3 to 8 times. If the number of treatments is less than two, fine dispersion of the dispersoid becomes insufficient. Conversely, even if the number of treatments exceeds 10, the fine dispersion of the dispersoid is not improved. It is preferable to start the homogenization process by a high-pressure homogenizer after cooling the preliminary dispersion obtained by the homomixer to room temperature.
  • Examples of the high-pressure homogenizer include “LAB1000”, “LAB2000”, “15MR”, “G-MODEL”, “R-MODEL” manufactured by SMT Co., Ltd., and the like.
  • a diluted dispersion may be produced by adding water to the dispersion of the invention produced as described above and stirring. Moreover, you may add the other component (for example, leveling agent) to the dispersion liquid of this invention manufactured as mentioned above, and stir, and may manufacture the dispersion liquid containing another component.
  • the other component for example, leveling agent
  • the dispersion of the present invention is useful as an aqueous adhesive, a primer, or a raw material thereof.
  • this invention provides the coating film formed from the said dispersion liquid, and the hardened
  • this invention provides the laminated body by which the 1st base material, the said hardened
  • the first substrate is preferably made of an olefin polymer or an ethylene-vinyl acetate copolymer.
  • the cured product may further exist between the adhesive layer and the second substrate.
  • Examples of the material of the adherend to which the dispersion liquid of the present invention is applied, or the adherend (including the first base material and the second base material) on which the coating film and the cured product of the present invention are laminated include wood.
  • Wood materials such as plywood, medium density fiberboard (MDF), particle board, fiber board; cellulose materials such as cotton cloth, cotton-containing fibers, linen, rayon; (1) homopolymers and copolymers of ethylene; Olefin-based polymers such as propylene homopolymer and copolymer, (2) styrene homopolymer and copolymer, (3) polycarbonate, (4) acrylonitrile-butadiene-styrene copolymer (ABS resin), (5) Poly (meth) acrylic resin, (6) Polyester, (7) Polyether, (8) Polyvinyl chloride, (9) Foamed or non-foamed polyurethane, (10) Foamed Is an unfoamed ethylene-vinyl acetate copoly
  • the adherend may be made of one kind of material or may be made of two or more kinds of materials.
  • the adherend may be a kneaded molded product of the plastic material and a filler such as talc, silica, activated carbon, or carbon fiber.
  • the dispersion liquid of the present invention includes adhesion between cellulosic material and plastic material, polyvinyl chloride, ethylene-vinyl acetate copolymer, cotton-containing fiber, polyamide resin, olefin polymer, polyurethane. , Rubber or cross-linked rubber, and synthetic leather can be suitably used for adhesion.
  • the shape of the adherend include a film, a sheet, and a block shape, and an adherend having a film or sheet shape is preferable.
  • olefin polymer examples include resins having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms described in ⁇ Other resin or rubber> and modified products. Moreover, as a plastic material, what was demonstrated by ⁇ other resin or rubber> is mentioned, for example.
  • Cotton-containing fibers may be 100% cotton fibers, or may be blended fibers of cotton and other natural fibers and / or chemical fibers. Examples of other natural fibers include wool, silk and hemp.
  • Examples of chemical fibers include synthetic fibers (for example, polyester fibers and polyamide fibers), semi-synthetic fibers (for example, cellulose fibers such as acetate, protein fibers such as promix), and regenerated fibers (for example, rayon, And cellulose fibers such as cupra and polynosic) and inorganic fibers (for example, carbon fibers and glass fibers).
  • Examples of the shape of the cotton-containing fiber include woven fabric, knitted fabric, nonwoven fabric, knitted fabric, felt, film, and block shape.
  • polyamide-based resin examples include polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11 and polyamide 12.
  • the shape of the polyamide resin may be any of a film, a block, a fiber, or a foam.
  • Examples of rubber or cross-linked rubber include thermoplastic rubbers; natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber and other diene rubbers; butyl rubber, ethylene-propylene rubber And non-diene rubbers such as ethylene-propylene-diene rubber, silicone rubber and fluororubber; and cross-linked products thereof.
  • the rubber or the crosslinked rubber 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. may be used in combination. Good.
  • Synthetic leather includes both synthetic leather and artificial leather in the narrow sense. That is, the synthetic leather may be a synthetic leather obtained by applying a synthetic resin to a natural or synthetic fabric or the like, or may be an artificial leather obtained by impregnating a synthetic resin into a fabric (usually a nonwoven fabric) such as microfiber, Artificial leather obtained by impregnating a synthetic resin into a fabric (usually a nonwoven fabric) such as microfiber and further applying the synthetic resin may be used.
  • these synthetic resins include polyurethane resins, polyamide resins, polyamino acid resins, and the like, and polyurethane resins are preferable.
  • the dispersion of the present invention can be used effectively for adhesion of adherends such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing and shoes.
  • the dispersion liquid of the present invention is used for constituting materials (covers) such as a hood, an insole, and an outer bottom in footwear such as men's shoes such as sports shoes, town shoes, and business shoes, women's shoes, and industrial work shoes. It is suitable as an adhesive, a primer or a raw material thereof for adhering the body.
  • the surface of these adherends may be smooth or may have irregularities. Moreover, in order to improve adhesiveness, you may surface-treat to a to-be-adhered body. Examples of the surface treatment include primer treatment, blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and anchor layer formation.
  • the manufacturing method of the laminated body of this invention mentioned above is demonstrated.
  • the dispersion is applied to the surface of the first substrate, optionally the second substrate.
  • Application may be performed by a known method.
  • Known methods include, 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.
  • the application and drying of the dispersion may be performed only once, or may be performed twice or more.
  • the application and drying methods may be combined with each other, or different methods may be combined.
  • the coating film After applying the dispersion liquid to the first substrate, the coating film may be dried or heat-treated, and then electromagnetic waves may be irradiated.
  • the heating temperature is, for example, about 30 to 150 ° C., preferably about 40 to 80 ° C.
  • the heating time is, for example, about 1 second to 1 hour, preferably about 5 seconds to 30 minutes, and more preferably about 5 seconds to 10 minutes.
  • the coating film may be allowed to stand (natural drying) before and after drying or heat treatment of the coating film. It is preferable to form a cured product of the coating film by irradiating the coating film formed from the dispersion with electromagnetic radiation (particularly, ultraviolet rays).
  • examples of the light source therefor 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 ultrahigh pressure mercury lamp, and a low pressure mercury lamp are preferable.
  • the peak illuminance of electromagnetic radiation is preferably 5 to 2000 mW / cm 2 , more preferably 10 to 2000 mW / cm 2 .
  • Integrated irradiation dose is preferably 20 ⁇ 3000mJ / cm 2, more preferably 100 ⁇ 2500mJ / cm 2.
  • a surface treatment may be applied to the first substrate.
  • the surface treatment include primer treatment, 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.
  • cured material obtained from it can be ensured by reducing the water
  • the thickness of the coated film after drying is preferably about 0.01 to 300 ⁇ m, more preferably about 0.01 to 200 ⁇ m, and still more preferably about 0.01 to 50 ⁇ m.
  • a liquid adhesive is applied to at least one of the first substrate and the second substrate to which the dispersion is applied, and is dried or heat-treated.
  • These application and drying or heat treatment may be performed only once on at least one of the first base material and the second base material, but both the application and heat drying of the adhesive may be performed on both of them.
  • the application method of the adhesive, the thickness of the coating film after drying, the method of drying or heat treatment, conditions such as temperature and time, etc. can be changed as appropriate. The same conditions as the dispersion application described above may be selected, or different conditions may be selected.
  • the same adhesive may be applied to the first substrate and the second substrate, or different adhesives may be applied. May be. In order to adhere the first substrate and the second substrate satisfactorily, it is preferable to use the same adhesive.
  • the adhesive may be the dispersion used above or a commercially available adhesive.
  • 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.
  • the thickness of the adhesive layer is preferably about 0.01 to 300 ⁇ m, more preferably about 0.01 to 200 ⁇ m.
  • the adherend Prior to applying the liquid adhesive to the adherend (first substrate and / or second substrate), the adherend may be subjected to the surface treatment described above.
  • the method for bonding the first substrate and the second substrate to which the dispersion and / or the adhesive is applied is not particularly limited, and these may be bonded by mechanical operation or manually. During bonding, heat, pressure, or both may be applied. In the case of heating, it is necessary to set the heating within a temperature range in which the first base material, the second base material, and the adhesive layer do not deteriorate, and the heating temperature is preferably about 120 ° C. or less, more preferably It is about 100 ° C. or lower. Heating can be performed using a normal hot air circulating oven, an infrared heater, a microwave oven, or the like.
  • the pressure is, for example, about 100 g / cm 2 or more and less than the pressure at which the shapes of the first base material and the second base material are deformed.
  • the time is, for example, about 1 second to 10 days.
  • the first base material and the second base material include those similar to the adherend described above.
  • the first substrate is preferably a substrate made of an olefin polymer or an ethylene-vinyl acetate copolymer.
  • the second base material is preferably a base material selected from the group consisting of polyvinyl chloride, synthetic leather, rubber, cotton-containing fibers, and polyolefin polymers.
  • the adhesive layer can be obtained, for example, by applying a liquid polyurethane adhesive, a liquid rubber adhesive, a liquid acrylic adhesive, or a liquid epoxy adhesive, and removing water, an organic solvent, or the like.
  • liquid polyurethane adhesive examples include the above-described water-soluble or water-dispersible polyurethane.
  • liquid 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.
  • liquid adhesives containing rubber components such as block copolymer rubber (SBS), butadiene-acrylonitrile copolymer rubber (NBR), and butadiene rubber (BR). Only 1 type may be used for a rubber component and it may use 2 or more types together.
  • an adhesion-imparting resin such as rosin resin, terpene resin, and petroleum resin may be added to the rubber adhesive.
  • liquid acrylic adhesive examples include a liquid containing a copolymer of an acrylic ester and / or methacrylic ester as an adhesive component, a functional group-containing monomer, and a monomer intended to improve cohesion.
  • An adhesive is mentioned.
  • An isocyanate crosslinking agent, a chelate crosslinking agent, an epoxy crosslinking agent, or the like may be added to the liquid acrylic adhesive.
  • 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-containing monomer 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 Hydroxyethyl ester, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc.
  • acrylic acid or hydroxyalkyl ester of methacrylic acid acrylamide, methacrylamide, diacetone (meth) acrylamide, N-methylolacrylamide, N-methylol N-substituted or unsubstituted acrylamide such as methacrylamide, N-butoxymethylacrylamide, N-butoxymethacrylamide; acrylic acid such as glycidyl methacrylate and glycidyl methacrylate Or, preferred examples include glycidyl ester of methacrylic acid; acrylonitrile and the like.
  • liquid epoxy adhesive examples include a liquid adhesive containing an epoxy resin having one or more epoxy groups per molecule on average.
  • the epoxy resin include an epoxy resin obtained from bisphenol A and epichlorohydrin, a polyglycidyl ether obtained from bisphenol F and epichlorohydrin, or hydrogenated bisphenol A and epichlorohydrin.
  • 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 may be used alone or in combination of two or more.
  • Liquid polyurethane adhesives, liquid rubber adhesives, liquid acrylic adhesives and liquid epoxy adhesives may be in the form of solutions, dispersions or emulsions, and hot melt adhesives used in the molten state An agent may be used.
  • the adhesive constituting the adhesive layer may contain another component (for example, resin) different from the above-described components.
  • resin for example, resin
  • the resin that the adhesive may contain include, for example, an olefin 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 copolymer
  • AS resin acrylonitrile-butadiene-styrene copolymer
  • modified products of the resin may be used alone or in combination of two or more.
  • examples of the resin that the adhesive may contain include a tackifier resin.
  • tackifying 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 hydrogens thereof.
  • examples thereof include additive resins, other petroleum-based resins, coumarone resins, indene resins, polyurethane resins, and the like.
  • the adhesive may contain examples, for example, surfactants, photopolymerization initiators, light stabilizers, ultraviolet curable oligomers, fluorescent brighteners, leveling agents, basic compounds, and organic compounds.
  • the chlorine atom content of the chlorinated rubber is a value measured by a flask combustion-ion chromatography method.
  • the median diameter (volume basis) of the dispersoids described in the following table is a value measured with a laser diffraction particle diameter measuring apparatus LA-950V2 manufactured by HORIBA Corporation.
  • a measurement sample is prepared from the dispersions produced in Examples and Comparative Examples described later, and the measurement is started within 10 minutes from the sample preparation, and the upper part of the measurement sample in the sample cell;
  • the amount of change in backscattered light intensity (%) measured 24 hours after the start of measurement, relative to the backscattered light intensity (%) measured 30 minutes after the start of measurement at each of the intermediate part and the bottom part The maximum value ⁇ in absolute value was calculated and evaluated according to the following criteria. The results are shown in the table below. ⁇ : All the requirements of the above formulas (I) to (III) are satisfied. ⁇ : Does not satisfy any or all of the requirements of the above formulas (I) to (III).
  • Chlorinated rubber 1 Pergut S20 (Covestro, chlorine atom content: 64.5% or more, melting point: 250 ° C., weight average molecular weight (Mw) in terms of polystyrene: 75,000, carboxy group and carboxylic anhydride structure Chlorinated rubber that does not have) Compound 1 having polymerizable group: dodecyl methacrylate (containing 970 ppm 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.) Compound having a polymerizable group 2: 1,6-hexanediol dimethacrylate (containing 60 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.) Compound having polymerizable group 3: 2-phenoxyethylene glycol methacrylate (containing 100 ppm of 4-methoxyphenol, Shin-Naka
  • Surfactant 1 (5 parts) was placed in ion-exchanged water (300 parts) and stirred at 60 ° C. to prepare an aqueous solution of surfactant 1 (hereinafter referred to as “solution 2”).
  • solution 2 was added to solution 1 and stirred to prepare a mixture. Subsequently, the obtained mixture was stirred at 16,000 rpm for 5 minutes at room temperature using TK Robotics (manufactured by PRIMIX Co., Ltd.) equipped with a homomixer MARKII to obtain a milky white emulsion. After cooling the dispersion to room temperature, homogenization was performed 4 times using a high-pressure homogenizer “LAB1000” manufactured by SMT Co., Ltd. at 800 bar, and the resulting emulsion was filtered through a 200 mesh nylon net. A dispersion E1 which is an emulsion was obtained. The obtained dispersion E1 had a nonvolatile content concentration of 25%.
  • Dispersion E6 was produced using a solution to which the amount of fluorescent whitening agent shown in Table 1 was added.
  • Dispersion E7 was produced without using a photopolymerization initiator.
  • aqueous adhesives F1 to F12 Any one of dispersions E1 to E12, leveling agent 1 (BYK (registered trademark) -349, Big Chemie Japan), and ion-exchanged water in the amounts shown in Table 2 are mixed, stirred with a three-one motor, and mixed with milk. Water-based adhesives F1 to F12 as turbid liquids were obtained. In Examples 1 to 7 and Comparative Examples 1 to 5 and later, a dispersion that further contains a leveling agent and is suitable as an adhesive is referred to as an “aqueous adhesive”.
  • Example 8 Production of laminate 1>
  • the water-based adhesive F1 was allowed to stand at 50 ° C. for 7 days in a blowing constant temperature incubator, and then applied to a foam of ethylene-vinyl acetate copolymer (EVA) as a first substrate using a brush ( Weight per unit area of the coated film after drying: about 3 g / m 2 ), dried at 70 ° C. for 5 minutes, and irradiated with ultraviolet rays using a conveyor type UV irradiation device (Eye Graphics Co., Ltd., Eye Grandage ECS-4011GX).
  • EVA ethylene-vinyl acetate copolymer
  • the adhesive 1 was applied to a cotton canvas (Johoku Kogyo Co., Ltd.) as the second substrate using a brush (weight per unit area of the coated film after drying: about 50 g / m 2 ), It was oven dried at 70 ° C. for 5 minutes to obtain a laminate of cotton canvas and adhesive layer.
  • Adhesive 1 is applied to the surface on the cured product side of the laminate of EVA and cured product obtained as described above, and the surface on the adhesive layer side of the laminate of cotton canvas and adhesive layer, respectively.
  • the film was applied using a brush (weight per unit area of the coated film after drying: about 50 g / m 2 ), and oven-dried at 70 ° C. for 5 minutes. Thereafter, the adhesive layers of the obtained EVA, cured product and adhesive layer laminate and cotton canvas and adhesive layer laminate were bonded together, pressure-bonded by hand, and further pressed at 3 MPa at 20 MPa.
  • the laminated body 1 which is a laminated body of EVA (1st base material), hardened
  • Examples 9 to 14 and Comparative Examples 6 to 10 Production of Laminates 2 to 12> EVA (first substrate), cured product, adhesive layer, cotton canvas (second), except that the water-based adhesive F1 was changed to any one of the water-based adhesives F2 to F12. Laminated bodies 2 to 12 which are laminated bodies with the base material) were obtained.
  • ⁇ Test Example 1 Evaluation of initial adhesiveness> The laminate is allowed to stand at room temperature for 5 minutes after the production, and is then laminated using a tensile tester (manufactured by Shimadzu Corp., Autograph) under the conditions of a peeling rate of 50 mm / min, a peeling angle of 180 degrees, and room temperature. The peel strength between EVA (first substrate) and cotton canvas (second substrate) was measured, and the initial adhesion was evaluated according to the following criteria. The results are shown in Table 3. ⁇ : Peel strength is 45 N / inch or more ⁇ : Peel strength is less than 45 N / inch
  • Types of laminates produced in Examples 8 to 14 and Comparative Examples 6 to 10 results of evaluation of types of water-based adhesive used and the amount of change in backscattered light intensity; and results of evaluation of initial adhesiveness and final adhesiveness Is shown in Table 3 below.
  • the laminates 1 to 7 manufactured using the water-based adhesives F1 to F7 that satisfy the requirements for the amount of change in the backscattered light intensity of the present invention are the water-based adhesives that do not satisfy the requirements for the amount of change in the backscattered light intensity of the present invention.
  • the initial adhesiveness and final adhesiveness were good.
  • the dispersion of the present invention is useful as an aqueous adhesive, a primer, or a raw material thereof.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
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JPH0559188A (ja) * 1991-08-29 1993-03-09 Dainippon Ink & Chem Inc 塩素化ポリオレフイン樹脂水性分散液の製造方法
JPH0892524A (ja) * 1994-09-19 1996-04-09 Nippon Shokubai Co Ltd 水性複合樹脂分散液およびその製造方法
JP2007091997A (ja) * 2005-09-30 2007-04-12 Dainippon Ink & Chem Inc 一液型水性コーティング剤、その製造方法および塗装物
WO2015194611A1 (ja) * 2014-06-20 2015-12-23 住友化学株式会社 水性エマルション並びに塗膜、硬化物及び積層体

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JP5011669B2 (ja) 2005-07-22 2012-08-29 東洋紡績株式会社 水性樹脂組成物およびその製造方法
KR20170028310A (ko) * 2014-06-20 2017-03-13 스미또모 가가꾸 가부시끼가이샤 수성 에멀션 그리고 도막, 경화물 및 적층체
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JPH0559188A (ja) * 1991-08-29 1993-03-09 Dainippon Ink & Chem Inc 塩素化ポリオレフイン樹脂水性分散液の製造方法
JPH0892524A (ja) * 1994-09-19 1996-04-09 Nippon Shokubai Co Ltd 水性複合樹脂分散液およびその製造方法
JP2007091997A (ja) * 2005-09-30 2007-04-12 Dainippon Ink & Chem Inc 一液型水性コーティング剤、その製造方法および塗装物
WO2015194611A1 (ja) * 2014-06-20 2015-12-23 住友化学株式会社 水性エマルション並びに塗膜、硬化物及び積層体

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