WO2012169484A1 - Procédé de fabrication de structure stratifiée - Google Patents

Procédé de fabrication de structure stratifiée Download PDF

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Publication number
WO2012169484A1
WO2012169484A1 PCT/JP2012/064428 JP2012064428W WO2012169484A1 WO 2012169484 A1 WO2012169484 A1 WO 2012169484A1 JP 2012064428 W JP2012064428 W JP 2012064428W WO 2012169484 A1 WO2012169484 A1 WO 2012169484A1
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WO
WIPO (PCT)
Prior art keywords
base material
electromagnetic wave
wave treatment
copolymer
laminated structure
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Application number
PCT/JP2012/064428
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English (en)
Japanese (ja)
Inventor
肥後　睦子
晶文 熊野
邦雄 大東
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
Publication of WO2012169484A1 publication Critical patent/WO2012169484A1/fr

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Classifications

    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • 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
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • 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
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B32B2038/168—Removing solvent
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/306—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being water-activatable
    • 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
    • C09J2475/00—Presence of polyurethane

Definitions

  • the present invention relates to a method for manufacturing a laminated structure.
  • Non-Patent Document 1 describes a method of obtaining a laminated structure in which a base material and a base material are bonded to each other with a water-based adhesive so as to be firmly bonded.
  • Various studies have been made on a method for obtaining a laminated structure in which a base material and a base material are bonded to each other with a water-based adhesive and are firmly bonded.
  • the present invention includes the following inventions.
  • a method for producing a laminated structure in which a first substrate, an adhesive layer, and a second substrate are laminated in this order (A) applying a water-based adhesive to the surface of the first base material, and thermally drying the first base material coated with the water-based adhesive; (B) applying a water-based adhesive to the surface of the second base material, and thermally drying the second base material coated with the water-based adhesive; (C) a step of applying an aqueous adhesive again to the heat-dried surface of at least one of the first base material and the second base material, and thermally drying the obtained base material; (D) including a step of bonding the surface of the first substrate dried with the aqueous adhesive and the surface of the second dried substrate coated with the aqueous adhesive; A method for producing a laminated structure in which at least one heat drying in the above (a) to (c) is an electromagnetic wave treatment.
  • [3] (a ′) applying a water-based adhesive to the surface of the first base material, and subjecting the first base material coated with the water-based adhesive to electromagnetic wave treatment, (B ′) applying a water-based adhesive to the surface of the second base material and subjecting the second base material coated with the water-based adhesive to electromagnetic wave treatment; (C ′) a step of applying an aqueous adhesive again to the surface subjected to electromagnetic wave treatment of at least one of the first base material and the second base material, and subjecting the obtained base material to electromagnetic wave treatment; (D ′) including a step of bonding the surface of the first base material subjected to the electromagnetic wave treatment to which the aqueous adhesive is applied and the surface of the second base material subjected to the electromagnetic wave treatment to which the aqueous adhesive is applied [1].
  • [4] The method for manufacturing a laminated structure according to any one of [1] to [3], wherein the electromagnetic wave treatment is performed with an electromagnetic wave in a frequency band of 2.45 ⁇ 0.02 GHz.
  • [5] The method for producing a laminated structure according to any one of [1] to [4], wherein the laminated structure obtained by bonding the first base material and the second base material is further subjected to electromagnetic wave treatment .
  • the bonding step is performed while applying heat, pressure, or both.
  • X .m is hydrogen atom or -SO 3 M (M represents an integer of .n 1-3 represents a hydrogen atom, NH 4, or an alkali metal) is an integer of 1 to 100.
  • the method for producing a laminated structure according to any one of [1] to [7], wherein the aqueous adhesive includes the following (A), (B), and (C).
  • Thermoplastic resin (C) Water [10]
  • the surfactant is a surfactant in which X is a hydrogen atom, and X Including two or more types of surfactants in which —SO 3 M is present, or including two or more types of surfactants in which X is a hydrogen atom and surfactants in which X is —SO 3 NH 4 [ The manufacturing method of the laminated structure as described in 8] or [9].
  • the thermoplastic resin is (1) a polymer having at least one structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms, (2) a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms, an ⁇ -olefin having 2 to 20 carbon atoms different from the ⁇ -olefin having 2 to 20 carbon atoms, an ⁇ , ⁇ -unsaturated carboxylic acid ester, ⁇ A copolymer having a structural unit derived from one or more monomers selected from the group consisting of ⁇ -unsaturated carboxylic acid anhydride and vinyl acetate, (3) 1 selected from the group consisting of a structural unit derived from ethylene, an ⁇ -olefin having 3 to 20 carbon atoms, an ⁇ , ⁇ -unsaturated carboxylic acid ester, an ⁇ , ⁇ -unsaturated carboxylic acid anhydride, and vinyl acetate.
  • a copolymer having a structural unit derived from a monomer of at least one species (4) Copolymer having a structural unit derived from ethylene and a structural unit derived from one or more monomers selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acid esters and ⁇ , ⁇ -unsaturated carboxylic acids Coalescence, (5) Ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer, ethylene-propylene- An ⁇ -olefin copolymer such as 1-butene copolymer or a modified product thereof; or a mixture of two or more of these, (6) Ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene
  • thermoplastic resin has a melting point of 60 to 110 ° C.
  • aqueous adhesive further contains a polyurethane resin or a water-insoluble polyurethane resin.
  • a terpene system wherein the aqueous adhesive is further selected from the group consisting of terpene polymers, terpene phenols, ⁇ -pinene polymers, aromatic modified terpene polymers, ⁇ -pinene polymers, and terpene hydrogenated resins.
  • the water-based adhesive is further selected from the group consisting of polyurethane resin, terpene polymer, terpene phenol, ⁇ -pinene polymer, aromatic modified terpene polymer, ⁇ -pinene polymer, and terpene hydrogenated resin.
  • the aqueous adhesive further comprises an isocyanate selected from the group consisting of diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI) and oligomers or polymers thereof.
  • MDI diphenylmethane diisocyanate
  • TDI tolylene diisocyanate
  • HDI hexamethylene diisocyanate
  • XDI xylene diisocyanate
  • the surfactant contains 0.1 to 50 parts by weight, 0.1 to 20 parts by weight, or 0.1 to 10 parts by weight with respect to 100 parts by weight of the total resin constituting the aqueous emulsion.
  • the surfactant is a surfactant represented by the formula (A) and a surfactant represented by the formula (B) in a mass ratio of 1 to 99:99 to 1, 5 to 95. : 95-5, 10-90: 90-10, 30: 70-90: 10, 40: 60-90: 10 or 50: 50-90: 10, any one of [8]-[20]
  • the manufacturing method of laminated structure as described in any one of.
  • thermoplastic resin After polymerization of the thermoplastic resin, after the resin is dispersed in an aqueous medium, an aqueous adhesive obtained by an emulsification method, a forced emulsification method, a self-emulsification method or a phase inversion emulsification method is used [8].
  • the method for producing a laminated structure of the present invention is a method for producing a laminated structure in which a first substrate, an adhesive layer, and a second substrate are laminated in this order, (A) applying a water-based adhesive to the surface of the first base material, and thermally drying the first base material coated with the water-based adhesive; (B) applying a water-based adhesive to the surface of the second base material, and thermally drying the second base material coated with the water-based adhesive; (C) a step of applying an aqueous adhesive again to the heat-dried surface of at least one of the first base material and the second base material, and thermally drying the obtained base material; (D) The process of bonding the surface by which the water-based adhesive of the said 1st base material heat-dried and the surface to which the water-based adhesive of the said 2nd base material apply
  • first base material and the second base material include films and sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing, shoes, and the like.
  • Specific materials include wood-based materials such as wood, plywood, medium density fiberboard (MDF), particleboard, and fiberboard; cellulosic materials such as cotton cloth, cotton-containing fibers, linen, and rayon; polyethylene (derived from ethylene) Polyolefins having a structural unit as a main component), polypropylene (polyolefin having a structural unit derived from propylene as a main component), polystyrene (polyolefin having a structural unit derived from styrene as a main component), polycarbonate, acrylonitrile -Butadiene-styrene copolymer (ABS resin), (meth) acrylic resin polyester, polyether, polyvinyl chloride, polyurethane, foamed urethane, ethylene / vinyl
  • the first base material and the second base material may be a composite material composed of a plurality of materials.
  • an inorganic filler such as talc, silica and activated carbon, a kneaded molded product of carbon fiber or the like and a plastic material may be used.
  • polyurethane is a polymer crosslinked by a urethane bond, and is usually obtained by reaction of alcohol (—OH) and isocyanate (—NCO).
  • the urethane foam is a polyurethane foamed with a volatile solvent such as carbon dioxide or freon produced by a reaction between isocyanate and water used as a crosslinking agent.
  • Semi-rigid polyurethane is used for automobile interiors, and hard polyurethane is used for paints.
  • the cotton-containing fiber may be 100% cotton fiber, or may be a blended fiber of cotton and other natural fibers and / or chemical fibers.
  • Other natural fibers include wool, silk, hemp and the like.
  • Chemical fibers include synthetic fibers (for example, polyamide fibers such as polyester and nylon), semi-synthetic fibers (cellulose fibers such as acetate, protein fibers such as promix), regenerated fibers (rayon, cupra, polynosic, etc.) Cellulosic fibers), inorganic fibers (carbon fibers, glass fibers) and the like.
  • the first base material and the second base material can take various forms such as a film, a block, a fiber (for example, a woven fabric, a knitted fabric, a non-woven fabric, a knitted fabric, a felt), and a foam.
  • the footwear, the insole, the outer bottom, etc. of footwear including men's shoes and women's shoes such as sports shoes, town shoes, business shoes, and industrial work shoes, etc.
  • Form and material eg, polyolefin, EVA, nylon, cotton-containing fiber, synthetic leather, etc.
  • the surface of the first base material and / or the second base material may be smooth or may have irregularities.
  • attachment such as an adhesive agent
  • examples of the primer treatment include blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, anchor layer formation, and the like.
  • the surface of the first substrate and / or the second substrate may be subjected to a primer treatment.
  • a water-based adhesive may be applied and dried as a primer treatment.
  • the application of the water-based adhesive here can use the above-mentioned method, and drying may use any of the methods described below, but in particular, non-thermal drying such as natural drying or air drying, or usually It is preferable to perform drying using a hot air circulation type oven, infrared ray or far infrared ray heater.
  • the aqueous adhesive to be used may be only one kind or two or more kinds of twice treatment. Further, different aqueous adhesives may be used in the first and second substrates, but it is preferable to use the same one.
  • the water-based adhesive applied to the first base material and the second base material may not be the same water-based adhesive, but it is preferable to use the same water-based adhesive in consideration of the adhesiveness of both.
  • the thickness of the aqueous adhesive to be applied can be appropriately adjusted depending on the composition of the aqueous adhesive to be used, the material and form of the substrate, and the like.
  • the thickness after heat drying is about 0.01 to 300 ⁇ m, preferably about 0.01 to 200 ⁇ m, more preferably about 0.2 to 200 ⁇ m.
  • Drying may be natural drying, non-thermal drying such as air drying, or drying using a normal hot-air circulating oven, infrared or far-infrared heater, electromagnetic waves (for example, electromagnetic waves having a frequency band of 2.45 ⁇ 0.02 GHz) It can be performed by heat drying such as drying using an irradiation apparatus or a microwave oven.
  • the first substrate and the second substrate, or both be subjected to electromagnetic wave treatment.
  • the electromagnetic wave treatment the water contained in the aqueous adhesive (as will be described later, the solvent if present) can be removed to form an adhesive layer.
  • any method can be used as long as it can irradiate the surface of the first base material coated with the aqueous adhesive or the surface of the second base material coated with the aqueous adhesive.
  • an electromagnetic wave device that can emit an electromagnetic wave having a frequency band of 2.45 ⁇ 0.02 GHz, specifically, a microwave oven or the like can be used.
  • the output and time of the electromagnetic wave treatment can be appropriately adjusted according to the characteristics of the substrate, the composition of the aqueous adhesive used, and the like.
  • the output is in the range of about 1 W to 20 kW, preferably about 100 W to 20 kW, and more preferably about 300 W to 20 kW.
  • the time is about 1 second to 1 hour, preferably about 5 seconds to 30 minutes, and more preferably about 5 seconds to 10 minutes.
  • the electromagnetic wave treatment may be performed only once or may be performed twice or more. In this case, different frequency bands may be combined. Also, when performing electromagnetic wave treatment on both the first base material and the second base material, different frequency bands may be combined.
  • the first substrate or the second substrate is dried by standing (natural drying) instead of the electromagnetic wave treatment or before and after the electromagnetic wave treatment, or by heat drying using a normal hot-air circulating oven, infrared heater, or the like. May be performed.
  • the drying temperature and time can be appropriately adjusted according to the characteristics of the substrate, the composition of the aqueous adhesive used, and the like.
  • the temperature is about 30 to 150 ° C., preferably about 40 to 85 ° C.
  • the time is about 1 second to 1 hour, preferably about 5 seconds to 30 minutes, and more preferably about 5 seconds to 10 minutes.
  • step (a) or step (b) may be performed first.
  • the adhesive layer after heat drying, in particular electromagnetic wave treatment usually does not contain water (or a solvent if present) as described below, even if it is contained. It is about 3% by weight or less of the total weight of the layer.
  • step (c) an aqueous adhesive is applied to the surfaces of the first substrate and the second substrate, and after heat drying, for example, electromagnetic wave treatment (that is, the first time),
  • step (c) an aqueous adhesive is applied again to the surface on which at least one of the first base material and the second base material is applied, and the obtained base material is heat-dried.
  • electromagnetic wave processing is performed (that is, the second time).
  • the application of the aqueous adhesive and the heat drying (for example, electromagnetic wave treatment) again (second time) can be performed in the same manner as the above-described conditions (that is, the first condition).
  • the application and heat drying (for example, electromagnetic wave treatment) of the previous (first time) aqueous adhesive and the application and heat drying (for example, electromagnetic wave treatment) of the aqueous adhesive again (for the second time) are not necessarily the same conditions.
  • the type of water-based adhesive, coating method, coating thickness, heat drying method and conditions for example, temperature, time, output and time of electromagnetic wave treatment, presence or absence of preheating before and after electromagnetic wave treatment and its The conditions etc. may be changed as appropriate.
  • the application and heat drying (for example, electromagnetic wave treatment) of the second aqueous adhesive in the step (c) may be performed only once on at least one of the first base material and the second base material, Furthermore, you may perform 1 time or more of application
  • the above-mentioned non-thermal drying for example, standing, natural drying
  • heat drying using a normal hot air circulation type oven, an infrared heater or the like may be performed.
  • (i-4) is preferable, and more preferably, drying after applying the first (first) aqueous adhesive is performed by electromagnetic wave treatment, and again (second) application of the aqueous adhesive is performed.
  • the electromagnetic wave treatment is performed on both surfaces of the first base material and the second base material in the same manner as the application (first time) of the aqueous adhesive and the electromagnetic wave treatment.
  • a mechanical operation or manual operation is performed. Any of the methods may be used.
  • heat, pressure or both may be applied.
  • the heat load may be performed using the above-described normal hot air circulation type oven, infrared heater, microwave oven, or the like.
  • the electromagnetic wave treatment is preferably performed again on the obtained laminated structure.
  • the electromagnetic wave treatment conditions are the same as described above.
  • water-based adhesive used in the method for producing a laminated structure of the present invention contains water as a solvent, an adhesive, a pressure-sensitive adhesive, an adhesive modifier, a heat sealant, a paint, a primer for coating, an ink Any material capable of exhibiting the functions of the binder, the pressure-sensitive adhesive, the emulsion modifier, and the like can be used. Especially, what contains the polymer which has adhesiveness is preferable, and what contains a thermoplastic polymer is preferable.
  • polystyrene resin examples include polyolefin resin, acrylic resin (PMMA), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polytetrafluoroethylene (PTFE), and acrylonitrile.
  • PMMA acrylic resin
  • PVC polyvinyl chloride
  • PS polystyrene
  • PVAc polyvinyl acetate
  • PTFE polytetrafluoroethylene
  • ABS resin butadiene styrene resin
  • AS resin AS resin
  • the polymer contained in the aqueous adhesive is more preferably one containing a polymer having one or more structural units derived from an ⁇ -olefin having 2 to 20 carbon atoms.
  • the ⁇ -olefin having 2 to 20 carbon atoms include ethylene (C2), propylene (C3), 1-butene (C4), 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-octene, Nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, vinylcyclohexane, etc.
  • Preferred are ethylene, propylene, 1-butene and the like.
  • Polymers containing structural units derived from ⁇ -olefins having 2 to 20 carbon atoms include polyethylene (PE), high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), polypropylene (PP), etc.
  • Homopolymer or modified product thereof ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer
  • An ⁇ -olefin copolymer such as ethylene-propylene-1-butene copolymer or a modified product thereof, a copolymer with a copolymerizable monomer or a modified product thereof; or a mixture of two or more of these. It is preferable.
  • the copolymerizable monomer and ⁇ -olefin may be used alone or in combination of two or more.
  • the form of the copolymer may be any of random copolymerization, block copolymerization, graft copolymerization, and the like. These may be those having a low molecular weight or a high molecular weight such as peroxide.
  • the ⁇ -olefin-based polymer has a total structural unit of 100 mol%, for example, a structural unit derived from propylene: a structural unit derived from 1-butene, preferably 71 to 99 mol%: 1 to 29 mol%. Or a modified product thereof, more preferably 80 to 99 mol%: 1 to 20 mol%, or more preferably 90 to 99 mol%: 1 to 10 mol. % Of copolymers or modified products thereof.
  • This copolymer is preferably a copolymer in which substantially no melting peak is observed.
  • the fact that a melting peak is not substantially observed means that a crystal melting peak having a crystal melting heat amount of 1 J / g or more is not observed by differential scanning calorimetry (DSC) in a temperature range of ⁇ 100 to 200 ° C.
  • a structural unit derived from ethylene a copolymer containing a structural unit derived from propylene, preferably 5 to 20 mol%: 80 to 95 mol%, or a modified product thereof, more preferably 5 to 19 mol%: A copolymer containing 81 to 95 mol% or a modified product thereof, and more preferably a copolymer containing 10 to 19 mol%: 81 to 90 mol% or a modified product thereof.
  • This copolymer is preferably a copolymer in which a melting peak is observed.
  • a melting peak is observed by a differential scanning calorimetry (DSC) in the temperature range of ⁇ 100 to 200 ° C., a crystal melting peak with a crystal melting heat of 1 J / g or more or a crystal with a crystallization heat of 1 J / g or more. This means that a chemical peak is observed.
  • DSC differential scanning calorimetry
  • a structural unit derived from ethylene a structural unit derived from propylene: a structural unit derived from 1-butene, preferably a copolymer containing 1 to 99 mol%: 99 to 1 mol%: 99 to 1 mol% or a modification thereof More preferably, it is a copolymer or a modified product thereof containing 5 to 80 mol%: 90 to 2 mol%: 90 to 1 mol%, more preferably 10 to 40 mol%: 85 to 5 mol%: Examples thereof include a copolymer containing 60 to 2 mol% or a modified product thereof. This copolymer is preferably a copolymer in which no melting peak is observed.
  • copolymers can be produced using, for example, a known single site catalyst (metallocene, etc., for example, see Japanese Patent Application Laid-Open Nos. 58-19309 and 60-35005). For example, see European Patent Publication No. 12111287).
  • propylene-1-butene copolymer or a modified product thereof and the ethylene-propylene copolymer or the modified product thereof are preferably 1 to 99:99 to 1, more preferably 5 to 95 by weight ratio. : 95-5, more preferably 10-90: 90-10 may be used.
  • modified products of ⁇ -olefin polymers include modified products of ⁇ , ⁇ -unsaturated carboxylic acids.
  • the amount of modification in this case is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.2 to 4 parts by weight with respect to 100 parts by weight of the ⁇ -olefin polymer. It is.
  • 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.). These ⁇ , ⁇ -unsaturated carboxylic acids may be used in combination. Of these, ⁇ , ⁇ -unsaturated carboxylic acid anhydride is preferable, and maleic anhydride is more preferable.
  • Such a modified product is a method in which an ⁇ -olefin polymer is melted and then modified by adding ⁇ , ⁇ -unsaturated carboxylic acid or the like, and the ⁇ -olefin polymer is dissolved in a solvent such as toluene or xylene.
  • a solvent such as toluene or xylene.
  • the known method include a method in which an ⁇ , ⁇ -unsaturated carboxylic acid is added and modified after dissolution.
  • the modified product contains a structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid anhydride, the acid anhydride group may be retained or the ring-opened one may be retained. Both the formed and ring-opened ones may be contained.
  • the ⁇ -olefin polymer may be a copolymer of ethylene and one or more ⁇ -olefins having 3 to 20 carbon atoms, a modified product of this copolymer, or a mixture thereof. preferable.
  • Examples of the copolymerizable monomer include unsaturated carboxylic acid or anhydride, metal salt of ⁇ , ⁇ -unsaturated carboxylic acid, ⁇ , ⁇ -unsaturated carboxylic acid ester, vinyl ester, vinyl ester saponified product, cyclic olefin, Examples include vinyl aromatic compounds, polyene compounds (such as dienes), (meth) acrylonitrile, halogenated vinyls, and halogenated vinylidenes. You may use these individually or in combination of 2 or more types.
  • acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid
  • acrylate and methacrylate are collectively referred to as (meth) acrylate.
  • Examples of unsaturated carboxylic acids or anhydrides include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and unsaturated dicarboxylic acid half esters and half amides. Is mentioned. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.
  • Examples of the metal salt of ⁇ , ⁇ -unsaturated carboxylic acid include sodium salt and magnesium salt of (meth) acrylic acid.
  • Examples of ⁇ , ⁇ -unsaturated carboxylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl acrylate, Examples include 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, vinyl versatate, and the like. Of these, vinyl acetate is preferred.
  • vinyl ester saponified product examples include vinyl alcohol obtained by saponifying vinyl ester with a basic compound or the like.
  • cyclic olefin examples include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano--but
  • vinyl aromatic compound examples include styrene, ⁇ -methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, 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- Hexyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3- Hexadiene, 2-methyl-1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene, 2,3- Examples thereof include 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-cyclopentadiene, 2,3- Dimethyl-1,3-cyclohexadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1-fluoro-1,3-butadiene, 2-chloro-1,3-pentadiene 2-chloro-1,3-cyclopentadiene, 2-chloro-1,3-cyclohexadiene, and the like.
  • Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9 -Decadiene, 1,13-tetradecadiene, 1,5,9-decatriene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4 -Ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl-1,4 -Heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethy
  • Examples of the alicyclic nonconjugated polyene compound include vinylcyclohexane, vinylcyclohexene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, and 5-isopropenyl-2-norbornene.
  • aromatic non-conjugated polyene compound examples include divinylbenzene and vinylisopropenylbenzene.
  • modified product of the copolymer with the copolymerizable monomer examples include a modified product of ⁇ , ⁇ -unsaturated carboxylic acids as described above.
  • the modification amount in this case is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.2 to 0.2 parts by weight with respect to 100 parts by weight of the copolymer with the copolymerizable monomer. 4 parts by weight.
  • the polymer having at least one structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is preferably a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms and the ⁇ -olefin having 2 to 20 carbon atoms.
  • ⁇ -olefins having 2 to 20 carbon atoms Derived from one or more monomers selected from the group consisting of ⁇ -olefins having 2 to 20 carbon atoms, ⁇ , ⁇ -unsaturated carboxylic acid esters, ⁇ , ⁇ -unsaturated carboxylic acid anhydrides and vinyl acetate different from A copolymer having a structural unit, more preferably an ethylene-derived structural unit, an ⁇ -olefin having 3 to 20 carbon atoms, an ⁇ , ⁇ -unsaturated carboxylic acid ester, an ⁇ , ⁇ -unsaturated carboxylic acid anhydride.
  • Ether and alpha is a copolymer having a structural unit derived from one or more monomers selected from the group consisting of ⁇ - unsaturated carboxylic acid.
  • a copolymer of a monomer copolymerizable with ⁇ -olefin specifically, (i) an ethylene-vinyl acetate copolymer, a saponified product or a partially saponified product thereof, or a maleic anhydride-modified product of an ethylene-vinyl acetate copolymer, (ii) an ethylene- (meth) acrylic acid copolymer, (iii) ethylene- (meth) acrylate copolymer such as ethylene-glycidyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, (iv) ethylene-alicyclic ⁇ -olefin copolymers such as ethylene-vinylcyclohexane, (v) ethylene-vinyl acetate- (meth) acrylate copolymers such as ethylene-vinyl acetate copolymer-glycidyl (meth) acrylate
  • a polymer having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms, particularly a copolymer of the above (i) to (vii) has a melt flow rate of 0.01 to 500 g at 190 ° C. under a load of 2160 g. / 10 minutes is preferable, and 0.01 to 400 g / 10 minutes is more preferable.
  • the polymer having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms, particularly the copolymer of (i) to (vii) above, preferably has a melting point of 60 to 200 ° C. ° C is more preferable, and 60 to 110 ° C is more preferable. When a polymer having a melting point in this range is used, the permeability or adhesion of the aqueous adhesive to the adherend can be further improved.
  • ethylene-vinyl acetate copolymer saponified product or partially saponified product thereof, or maleic anhydride modified product of ethylene-vinyl acetate copolymer, (ii) ethylene- (meth) acrylic Acid copolymer, (iii) ethylene- (meth) acrylate copolymer, (v) ethylene-vinyl acetate- (meth) acrylate copolymer, (vi) ethylene- (meth) acrylate-maleic anhydride copolymer (Vii) ethylene- (meth) acrylate- (meth) acrylate copolymer, more preferably (ia) ethylene-vinyl acetate copolymer, (ii) ethylene- (meth) acrylic acid copolymer, (iii) ethylene- (meth) acrylate copolymer, (v) ethylene-vinyl acetate- (meth) acrylate copolymer
  • the content of the polymer can be appropriately adjusted depending on, for example, the type of polymer used, the purpose of use, the performance to be obtained, and the like.
  • it is preferably 1 to 60% by weight with respect to the total amount of the water-based adhesive. %, More preferably 3 to 60% by weight, 3 to 50% by weight, still more preferably 5 to 55% by weight.
  • Aqueous adhesive used in the present invention may contain other resins other than the polymer having the structural unit derived from ⁇ - olefin having 2 to 20 carbon atoms as described above.
  • other resins include polyolefin resins, acrylic resins (PMMA), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polytetrafluoroethylene (PTFE), acrylonitrile butadiene styrene resin (ABS resin), and various ones of such polymers and copolymers and their modified products such as aS resin. These may be used alone or in combination of two or more.
  • resin which exhibits the function as an adhesive resin or a tackifier.
  • resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and Examples thereof include hydrogenated resins, other petroleum resins, coumarone resins, indene resins, polyurethane resins, and the like.
  • rosin polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarized rosin and their glycerin ester, pentaerythritol ester, methyl ester, triethylene glycol ester, phenol modified product and ester thereof Rosins such as fluorides; terpene polymers, terpene phenols, ⁇ -pinene polymers, aromatic modified terpene polymers, ⁇ -pinene polymers, terpene hydrogenated resins, and other terpene resins; C5 petroleum fractions Petroleum resins obtained by polymerizing styrene, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and hydrogenated resins thereof; petroleum resins such as maleic acid modified products and fumaric acid modified products; polyisocyanate compounds and polyols described later A compound and, if necessary, a poly Examples thereof include urethane resin.
  • Terpene resins and polyurethane resins are preferable.
  • Terpene resins are YS Resin PX / PXN, YS Polyster, Mighty Ace, YS Resin TO / TR, Clearon P / M / K (manufactured by Yashara Chemical Co., Ltd.), Tamanoru 803L / 901 (manufactured by Arakawa Chemical Co., Ltd.), Teltac 80 (Japan) Any of those commercially available as Terpen Chemical Co., Ltd.) can be used.
  • the polyurethane resin is preferably in the form of an aqueous emulsion in which polyurethane is dispersed in water. That is, the polyurethane may be either water-soluble or water-insoluble, but is preferably water-insoluble.
  • the polyurethane resin can be obtained by reacting a polyisocyanate compound and a polyol compound, and if necessary, other compounds. Examples of the reaction include methods such as an acetone method, a prepolymer mixing method, a ketimine method, and a hot melt dispersion method.
  • polyisocyanate compound examples include organic polyisocyanate compounds having two or more isocyanate groups in the molecule, which are used for ordinary polyurethane production.
  • organic polyisocyanate compounds having two or more isocyanate groups in the molecule, which are used for ordinary polyurethane production.
  • polyol compound examples include compounds having two or more hydroxyl groups in the molecule, which are used for the production of ordinary polyurethane.
  • polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, glycerin; polyethylene glycol, polypropylene glycol, polytetramethylene ether Polyether polyols such as glycol; adipic acid, sebacic acid, itaconic acid, maleic anhydride, terephthalic acid, isophthalic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid Dicarboxylic acids such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-
  • Polyester polyols such as polycaprolactone polyol and poly ⁇ -methyl- ⁇ -valerolactone; polybutadiene polyols or hydrogenated products thereof, polycarbonate polyols, polythioether polyols, polyacrylate polyols, etc. .
  • the polyurethane resin preferably has a hydrophilic group in the molecule in order to improve dispersion stability in water.
  • a polyurethane containing a hydrophilic group in its molecule is called an ionomer structure and has a surface-active ability in itself. Therefore, there exists a tendency which is easy to disperse
  • anionic groups such as a sulfonyl group and a carboxyl group are preferable, and a sulfonyl group is more preferable. This is because there is a tendency to further improve the water resistance of an aqueous emulsion obtained by emulsion polymerization of monomers.
  • the anionic group is preferably neutralized by a neutralizing agent.
  • the neutralizing agent include tertiary amine compounds such as triethylamine and trietalamine; inorganic alkali compounds such as sodium hydroxide; ammonia and the like.
  • hydrophilic group In order to introduce a hydrophilic group into the molecule, it is preferable to use the following compounds during the production of polyurethane.
  • the compound include a nonionic hydrophilic group such as a structural unit derived from polyethylene glycol in the molecule, and a sulfonyl group, carboxyl group, hydroxyl group, primary amino group (—NH 2 ), secondary amino group ( ⁇ NH) and the like (hereinafter also referred to as “hydrophilic group-containing compound”) having at least one active hydrogen having reactivity with an isocyanate group.
  • hydrophilic group-containing compound examples include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, and N- (2-aminoethyl) -2.
  • a sulfonic acid-containing compound such as aminoethylsulfonic acid; a carboxylic acid-containing compound such as 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, and 2,2-dimethylolvaleric acid. You may use these individually or in combination of 2 or more types.
  • the polyurethane resin When the polyurethane resin is produced as an aqueous emulsion, it is a compound different from the hydrophilic group-containing compound for the purpose of chain extension, molecular weight adjustment, etc., if necessary, and contains active hydrogen capable of reacting with an isocyanate compound in the molecule.
  • a compound to be used may be used in combination. Examples of such compounds include polyvalent amine compounds such as ethylenediamine, 1,4-butanediamine, and 1,6-hexanediamine; tertiary amine-containing polyhydric alcohols such as triethanolamine, methanol, ethanol, and butanol. And monoalcohols.
  • polyurethane resin a commercially available polyurethane aqueous emulsion or a commercially available water-soluble urethane resin may be used as it is.
  • a polyurethane dispersion or polyurethane aqueous solution in which a polyurethane resin is dispersed or dissolved in water can be mentioned.
  • the polyurethane resin content in the polyurethane dispersion may be about 10 to 70% by weight, preferably about 20 to 60% by weight, more preferably about 30 to 60% by weight, and even more preferably about 30 to 55% by weight.
  • the polyurethane dispersion may further contain an organic solvent not containing an isocyanate reactive group, for example, ethyl acetate, acetone, methyl ethyl ketone, N-methylpyrrolidone and the like.
  • the amount of the organic solvent is not particularly limited, but can be 0.1 to 100 parts by weight with respect to 100 parts by weight of the nonvolatile content in the polyurethane dispersion.
  • water-soluble urethane resin for example, manufactured by Sumitomo Bayer Urethane Co., Ltd .; Dispacol U-42, U-53, U-54, U-56, KA-8484, KA-8484, KA-8755, KA-8756 KA-8766, manufactured by DIC Corporation; Hydran HW-111, HW-311, HW-333, HW-350, HW-337, HW-374, AP-20, AP-60LM, AP-80, Sanyo Chemical Manufactured by Kogyo Co., Ltd .; Uprene UXA-306, UXA-307, Permarin UA-150, Permarin UA-200, Permarin UA-300, Permarin UA-310, Eucort UWS-145, Daiichi Kogyo Seiyaku Co., Ltd .; Super Flex 107M, 110, 126, 130, 150, 160, 300, 361, 370, 410, 420,
  • the content thereof is preferably 1 to 99% by weight, more preferably 3 to 99% by weight, and still more preferably based on the total amount of the water-based adhesive. 5 to 90% by weight.
  • the polymer: other resin (non-volatile content weight ratio) is preferably 5:95 to 95: 5, more preferably 5:95 to 90:10, and still more preferably 10:50 to 80: 20.
  • These resins may be emulsions or emulsified together with a polymer having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms.
  • the aqueous adhesive preferably further contains a surfactant that generally acts as an emulsifier.
  • surfactants include cationic, anionic, amphoteric and nonionic surfactants. Among them, anionic or nonionic surfactants are preferable. In particular, those having the structure of the following formula (I) are preferred.
  • Surfactants may be used alone or in combination of two or more, but it is preferable to use two or more in combination. Among these, it is more preferable to use two or more kinds of surfactants having the structure of the formula (I).
  • X represents a hydrogen atom or —SO 3 M (M is a hydrogen atom, NH 4 or an alkali metal).
  • N represents an integer of 1 to 3.
  • m represents an integer of 1 to 100.
  • X in the formula (I) is a hydrogen atom, —SO 3 M (M is a hydrogen atom, —NH 4 or an alkali metal), that is, sulfuric acid, sulfate (for example, an alkali metal salt such as ammonium salt or sodium), etc.
  • a hydrogen atom, —SO 3 H or —SO 3 NH 4 is preferable.
  • X is a combination of a hydrogen atom and —SO 3 H, a combination of a hydrogen atom and —SO 3 NH 4 , or a combination of —SO 3 H and —SO 3 NH 4 . Of these, a combination of a hydrogen atom and —SO 3 NH 4 is preferable.
  • Latemul AD-25 manufactured by Kao Corporation
  • Latemuru E-1000A manufactured by Kao Corporation
  • Neugen EA-177 Daniichi Kogyo Seiyaku Co., Ltd.
  • the aqueous adhesive may contain a surfactant other than the surfactant represented by the formula (I).
  • the anionic surfactants include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyls. Examples include sulfosuccinate.
  • cationic surfactants include alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt, alkylpyridium salts such as cetylpyridium salt and decylpyridium salt, oxyalkylenetrialkylammonium salt, dioxyalkylenedialkylammonium salt , Allyl trialkyl ammonium salt, diallyl dialkyl ammonium salt and the like.
  • alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt
  • alkylpyridium salts such as cetylpyridium salt and decylpyridium salt
  • oxyalkylenetrialkylammonium salt such as cetylpyridium salt and decylpyridium salt
  • dioxyalkylenedialkylammonium salt dioxyalkylenedialkylammonium salt
  • Allyl trialkyl ammonium salt diallyl
  • Nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene propylene ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid esters, ethylene oxide propylene oxide block copolymers, polyoxyethylene fatty acid amides, and ethylene oxide.
  • -A compound having a polyoxyethylene structure such as a propylene oxide copolymer or a sorbitan derivative such as a polyoxyethylene sorbitan fatty acid ester.
  • amphoteric surfactants include lauryl betaine and lauryl dimethylamine oxide.
  • the content of the surfactant is usually 0.1 to 50 parts by weight, preferably 0.1 to 20 parts by weight, and more preferably 0 to 100 parts by weight of the resin constituting the aqueous adhesive. a .1 to 10 parts by weight.
  • the aqueous adhesive used in the present invention contains a surfactant other than the surfactant represented by the formula (I)
  • the surfactant represented by the formula (I) and the formula (I) The total content of surfactants other than the surfactants represented is usually 0.1 to 50 parts by weight, preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the resin constituting the aqueous adhesive. a 20 parts by weight, more preferably 0.1 to 10 parts by weight.
  • the weight ratio is preferably 1 to 99:99 to 1, more preferably 5 to 95:95 to 5, more preferably 10 to 90:90 to 10, particularly 30:70 to 90:10, 40:60 to 90:10, 50:50 to 90:10.
  • the aqueous adhesive preferably further contains a basic compound.
  • a basic compound what can neutralize a carboxyl group is preferable, for example, ammonia, an organic amine compound, a metal hydroxide, etc. are mentioned.
  • it is ammonia or an organic amine compound.
  • an organic amine compound having a boiling point of 200 ° C. or less can be easily dispersed by ordinary drying, and when forming a coating film using an aqueous adhesive, the water resistance and alkali resistance of the coating film are maintained / It can be improved and is preferable.
  • 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, N-ethylmorpholine and the like. Of these, N, N-dimethylethanolamine and the like are preferable.
  • Examples of the metal hydroxide include lithium hydroxide, potassium hydroxide, sodium hydroxide and the like.
  • the content thereof is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight with respect to 100 parts by weight of the resin constituting the aqueous adhesive. Part, more preferably 2 to 10 parts by weight.
  • the aqueous adhesive used in the present invention preferably does not contain a solvent, but in some cases, in addition to water, for example, an aromatic hydrocarbon such as toluene and xylene; an aliphatic hydrocarbon such as hexane; Esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, and n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and the like Glycol solvent, methyl cellosolve, cellosolve, butyl cellosolve, dioxane, MTBE (methyl tertiary butyl ether), cellsolve solvent such as butyl carbitol, diethylene glycol monomethyl ether, triethylene glycol Glycol solvents such
  • the water-based adhesive used in the present invention usually contains water. Furthermore, phenol stabilizers, phosphite stabilizers, amine stabilizers, amide stabilizers, anti-aging agents, weathering stabilizers, anti-settling agents, as required, without compromising the intended properties of the water-based adhesive.
  • Stabilizers antioxidants, heat stabilizers, light stabilizers; thixotropic agents, thickeners, dispersants, antifoaming agents, viscosity modifiers, weathering agents, pigments, pigment dispersants, antistatic agents, Additives such as lubricants, nucleating agents, flame retardants, oil agents, dyes, curing agents, crosslinking agents; transition metal compounds such as titanium oxide (rutile type) and zinc oxide; pigments such as carbon black; glass fibers, carbon fibers, titanium Potassium acid fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass flake, barium sulfate, clay, kaolin, fine powder silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide , Aluminum oxide, magnesium oxide, alumina, inorganic, such as celite, may contain optional components such as organic fillers.
  • water As the water contained in the aqueous adhesive used in the present invention, tap water, ion-exchanged water or the like is generally used. In order to further improve the stability of the water-based adhesive, a water-soluble resin such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, or hydroxyethyl cellulose may be added.
  • the water content is, for example, 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 45% by weight or more, and preferably 45% by weight or more based on the total amount of the aqueous adhesive. It is 85 weight% or less, More preferably, it is 80 weight% or less, More preferably, it is 70 weight% or less.
  • Thickeners can be used to adjust the viscosity of the formulation.
  • As a thickener manufactured by ADEKA Corporation; Adecanol UH-140S, UH-420, UH-438, UH-450VF, UH-462, UH-472, UH-526, UH-530, UH-540, UH -541VF, UH-550, UH-752, H-756VF, manufactured by San Nopco; SN thickener 920, 922, 924, 926, 929-S, A-801, A-806, A-812, A-813, A -818, 621N, 636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636, 4050 and the like.
  • the dispersant can be used for improving the wettability of the coated substrate.
  • a dispersant manufactured by ADEKA Corporation; Adeka Coal W-193, W-287, W-288, W-304, manufactured by BYK; BYK-333, BYK-345, BYK-346, BYK-347, BYK -348, BYK-349, BYK-378, manufactured by San Nopco; Nopco wet 50, SN wet 366, Nopco 38-C, SN disperse sand 5468, 5034, 5027, 5040, 5020 and the like.
  • the curing agent examples include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI), and oligomers or polymers thereof, which are isocyanate curing agents.
  • MDI diphenylmethane diisocyanate
  • TDI tolylene diisocyanate
  • HDI hexamethylene diisocyanate
  • XDI xylene diisocyanate
  • oligomers or polymers thereof which are isocyanate curing agents.
  • Sumika Bayer Urethane Sumidur 44V20, Sumidur N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547 and the like can be mentioned.
  • the curing agent is preferably 0.1 to 20 parts by weight, more preferably
  • a method for producing an aqueous adhesive a method known in the art, for example, a post-emulsification method (for example, forced emulsification method, self-emulsification method, phase inversion emulsification method) after polymerizing the resin and dispersing the resin in an aqueous medium. Etc.).
  • a post-emulsification method for example, forced emulsification method, self-emulsification method, phase inversion emulsification method
  • a surfactant, water and / or solvent are added to the reactor, and heated and stirred.
  • a resin to be emulsified, and optionally a solvent are added to a kneader, stirring, heating and melting, and a surfactant, water and / or Examples thereof include a method of adding a solvent, heating and stirring, and optionally adding water and / or a solvent before and after this and stirring.
  • water is introduced at least once.
  • a container preferably sealed and / or sealed
  • a heating device capable of being heated
  • a stirrer capable of applying a shearing force or the like to the contents.
  • Pressure vessel A normal stirrer can be used.
  • a pressure vessel include a pressure-resistant autoclave with a stirrer. Stirring may be performed, for example, at normal pressure or reduced pressure.
  • the rotational speed of the stirrer can be set at, for example, about 50 to 1000 rpm. If necessary, it is preferable to increase the rotational speed as the dispersion / stirring of the aqueous adhesive proceeds.
  • the heating is usually performed at 50 to 200 ° C, preferably 60 to 150 ° C, more preferably 70 to 100 ° C.
  • the solvent is preferably distilled off from the obtained dispersion (preferably reduced pressure or pressurized distillation).
  • the degree of pressure reduction or pressurization is about ⁇ 0.001 to 1 MPa, preferably about ⁇ 0.001 to 0.5 MPa.
  • examples of the kneader include a roll mill, a kneader, an extruder, an ink roll, and a Banbury mixer.
  • an extruder or a multi-screw extruder having one or more screws in the casing may be used.
  • a resin to be emulsified and a surfactant are mixed, and this is continuously fed from the hopper or feed port of the extruder, and this is heated, melted and kneaded, and further compressed by the extruder.
  • Water is supplied from at least one supply port provided in a zone, a metering zone, a deaeration zone, and the like, and after being kneaded with a screw, it is continuously extruded from a die.
  • the surfactant is preferably used within a desired range. However, when the surfactant is used in excess, it is optionally excessive from the obtained water-based adhesive.
  • the surfactant may be separated and removed. Separation and removal of the surfactant may be performed, for example, by using a centrifuge, a filter having an average pore size smaller than the average particle size of the aqueous adhesive (preferably having an average pore size of 0.05 to 0.5 ⁇ m). And a method using an ultrafiltration membrane).
  • the obtained water-based adhesive it is preferable to cool the obtained water-based adhesive.
  • the water-based adhesive containing the fine particle of a resin composition is obtained.
  • the cooling is not particularly required to be performed at a low temperature, and a method of leaving it at room temperature can be mentioned. Thereby, a fine and homogeneous aqueous adhesive can be obtained without agglomeration of resin or the like during the cooling process.
  • the particle size of the dispersoid contained in the aqueous adhesive is usually 10 ⁇ m or less, preferably 0.01 to 10 ⁇ m, more preferably 0.01 to 2 ⁇ m, and still more preferably 0.01 to 1 ⁇ m, based on the number.
  • the standing stability is good.
  • the particle size based on the number is a particle size corresponding to 50% of the value of the cumulative particle size distribution on the number basis. Unless otherwise specified, it means the value of the median diameter measured on the basis of the number, and the volume-based median diameter means a particle diameter in which the value of the cumulative particle size distribution corresponds to 50% on the volume basis. As long as it means the value of the median diameter measured on the basis of the number. Moreover, you may filter using the filter etc.
  • the particle diameters of the dispersoids are preferably approximately the same. As the same degree, for example, it is preferably within ⁇ 50%, more preferably within ⁇ 30% of the particle size of the polymer having a structural unit derived from ⁇ -olefin.
  • the peak observed in (ii) was a crystallization peak, and the presence or absence of a crystallization peak with a peak area of 1 J / g or more was confirmed.
  • the temperature was increased from ⁇ 100 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min.
  • the peak observed in (iii) was the melting peak of the crystal, and the presence or absence of a melting peak with a peak area of 1 J / g or more was confirmed.
  • Melt flow rate (MFR) According to JIS-K-7210, the measurement was performed under the conditions of a load of 2.16 kgf and a temperature of 130 ° C.
  • the modified amount of maleic anhydride is obtained by dissolving 1.0 g of a sample in 20 ml of xylene, dropping the sample solution into 300 ml of methanol while stirring to reprecipitate the sample, and then collecting the sample. After vacuum drying (80 ° C., 8 hours), a film having a thickness of 100 ⁇ m was prepared by hot pressing, the infrared absorption spectrum of the obtained film was measured, and the amount of maleic anhydride modification was determined by absorption near 1780 cm ⁇ 1. Was quantified.
  • Nonvolatile content It was measured by a measuring method according to JIS K-6828.
  • Particle size of aqueous emulsion This is a value measured with a laser diffraction particle size measuring device LA-950V2 manufactured by HORIBA. Unless otherwise specified, the particle diameter is a median diameter value measured on a number basis.
  • Example of production of copolymer (B-1-1) 386 parts of vinylcyclohexane (hereinafter sometimes referred to as VCH) and 3640 parts of toluene were charged into a SUS reactor substituted with argon. After raising the temperature to 50 ° C., ethylene was charged while being pressurized at 0.6 MPa.
  • VCH vinylcyclohexane
  • copolymer (B-1-2) ⁇ Example of production of copolymer (B-1-2)> To 100 parts of the obtained copolymer (B-1-1) copolymer, 0.4 part of maleic anhydride and 0.04 part of 1,3-bis (t-butylperoxyisopropyl) benzene were added. After sufficiently premixed, it was supplied from the supply port of the twin screw extruder and melt kneaded to obtain a copolymer (B-1-2). The temperature of the melt kneading part of the extruder was divided into two stages, the first half and the latter half, and the melt kneading was performed at a temperature setting of 180 ° C. in the first half and 260 ° C. in the second half. Copolymer (B-1-2) had a maleic acid graft amount of 0.2% and an MFR of 180 g / 10 min (190 ° C., load: 2.16 kgf).
  • Example of production of copolymer (B-3-1)> A 2 l separable flask reactor was equipped with a stirrer, thermometer, dropping funnel and reflux condenser to reduce the pressure, and the gas in the reactor was replaced with nitrogen. Into this flask, 1 l of dried toluene was introduced as a polymerization solvent. Here, propylene 8 NL / min and 1-butene 0.5 NL / min were continuously fed at normal pressure, and the solvent temperature was 30 ° C.
  • TIBA triisobutylaluminum
  • dimethylsilyl (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-) was used as a polymerization catalyst.
  • TIBA triisobutylaluminum
  • 0.005 mmol of 5-methyl-2-phenoxy) titanium dichloride was added to the reactor.
  • 0.025 mmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added to the reactor to initiate polymerization.
  • a propylene-1-butene copolymer (B-3-1) having a propylene content of 96 mol% was obtained.
  • the obtained polymer had an intrinsic viscosity [ ⁇ ] of 2.1 dl / g and a molecular weight distribution (Mw / Mn) of 2.5.
  • Mw / Mn molecular weight distribution
  • the obtained dispersion was put into a 2 L eggplant flask, evaporated under reduced pressure using an evaporator, and filtered through a 200 mesh nylon net to obtain an aqueous emulsion containing the polymer (B-1-2) and a surfactant. It was.
  • the obtained aqueous emulsion (E-1) had a particle size (number basis) of 0.61 ⁇ m and a non-volatile content concentration of 36%.
  • aqueous emulsion was produced in the same manner as ⁇ Aqueous emulsion production example 1> except that 100 parts of the polymer (B-2-1) was used as the copolymer.
  • the obtained aqueous emulsion (E-2) had a particle size (number basis) of 0.25 ⁇ m and a nonvolatile content concentration of 38%.
  • aqueous emulsion was produced in the same manner as in ⁇ Aqueous emulsion production example 1> except that 100 parts of the polymer (B-2-2) was used as the copolymer.
  • the obtained aqueous emulsion (E-3) had a particle size (number basis) of 0.22 ⁇ m and a nonvolatile content concentration of 39%.
  • aqueous emulsion was produced in the same manner as ⁇ Aqueous emulsion production example 1> except that 100 parts of the polymer (B-2-3) was used as the copolymer.
  • the obtained aqueous emulsion (E-4) had a particle size (number basis) of 0.21 ⁇ m and a non-volatile content concentration of 36%.
  • aqueous emulsion An aqueous emulsion was produced in the same manner as ⁇ Aqueous emulsion production example 1> except that 100 parts of the polymer (B-2-4) was used as the copolymer.
  • the obtained aqueous emulsion (E-5) had a particle size (number basis) of 0.13 ⁇ m and a nonvolatile content concentration of 36%.
  • aqueous emulsion was produced in the same manner as in ⁇ Aqueous emulsion production example 1> except that 100 parts of the polymer (B-3-2) was used as the copolymer.
  • the obtained aqueous emulsion (E-6) had a particle size (number basis) of 0.33 ⁇ m and a nonvolatile content concentration of 34%.
  • aqueous emulsion was produced in the same manner as ⁇ Aqueous emulsion production example 1> except that 50 parts of the polymer (B-2-2) and 50 parts of the polymer (B-3-2) were used as the copolymer.
  • the obtained aqueous emulsion (E-7) had a particle size (number basis) of 0.21 ⁇ m and a nonvolatile content concentration of 35%.
  • aqueous emulsion was produced in the same manner as in ⁇ Aqueous emulsion production example 1> except that 100 parts of polymer (B-4-1) [BONDINE HX8140 (manufactured by ARKEMA)] was used as the copolymer.
  • the obtained aqueous emulsion (E-8) had a particle size (number basis) of 0.09 ⁇ m and a nonvolatile content concentration of 40%.
  • aqueous emulsion was produced in the same manner as ⁇ Aqueous emulsion production example 1> except that 100 parts of the polymer (B-4-2) [BONDINE AX8390 (manufactured by ARKEMA)] was used as the copolymer.
  • the obtained aqueous emulsion (E-9) had a particle size (on a number basis) of 0.11 ⁇ m and a nonvolatile content concentration of 42%.
  • ⁇ Production Example 10 of Aqueous Emulsion> ⁇ Aqueous emulsion except that 67 parts of polymer (B-4-2) and 33 parts of adhesive resin (terpene phenol, Tamanol 803L, manufactured by Arakawa Chemical Co., Ltd.) are used instead of 100 parts of polymer (B-1-2).
  • An aqueous emulsion (E-10) was produced in the same manner as in Production Example 1>.
  • the obtained aqueous emulsion had a particle size (on a number basis) of 0.10 ⁇ m and a nonvolatile content concentration of 41%.
  • aqueous emulsion (E-11) was produced in the same manner as in ⁇ Aqueous emulsion production example 1> except that 100 parts of the polymer (B-4-3) [BONDINE HX8290 (manufactured by ARKEMA)] was used as the copolymer. .
  • the obtained aqueous emulsion had a particle size (number basis) of 0.18 ⁇ m and a nonvolatile content concentration of 39%.
  • ⁇ Production Example 12 of aqueous emulsion> Instead of using 100 parts of the polymer (B-1-2), 50 parts of the polymer (B-4-3) and 50 parts of an adhesive resin (terpene phenol, Tamanol 803L, manufactured by Arakawa Chemical Co., Ltd.) are used.
  • Emulsion Production Example 1> An aqueous emulsion (E-12) was produced in the same manner. The obtained aqueous emulsion had a particle size (number basis) of 0.20 ⁇ m and a nonvolatile content concentration of 33%.
  • aqueous emulsion (as in Aqueous Emulsion Production Example 1) except that 100 parts of the polymer (B-4-4) [BONDINE LX4110 (manufactured by ARKEMA)] was used as the copolymer and the reaction temperature was 90 ° C. E-13) was produced.
  • the obtained aqueous emulsion had a particle size (number basis) of 0.08 ⁇ m and a nonvolatile content concentration of 44%.
  • ⁇ Production Example 14 of Aqueous Emulsion> instead of 100 parts of the polymer (B-1-2), 75 parts of the polymer (B-4-4) and 25 parts of an adhesive resin (terpene phenol, Tamanol 803L, manufactured by Arakawa Chemical Co., Ltd.) were used, and the reaction temperature was 90.
  • An aqueous emulsion (E-14) was produced in the same manner as in ⁇ Preparation Example 1 of Aqueous Emulsion> except that the temperature was changed to 0 ° C.
  • the obtained aqueous emulsion had a particle size (on a number basis) of 0.20 ⁇ m and a nonvolatile content concentration of 34%.
  • EVA ethylene / vinyl acetate
  • the particle size of this aqueous emulsion was 1.7 ⁇ m, and the nonvolatile content concentration was 50%.
  • An aqueous emulsion (E-28) was formulated by mixing an aqueous emulsion (E-11) with an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) at a nonvolatile content ratio of 67 parts: 33 parts. Manufactured.
  • An aqueous emulsion (E-30) was formulated by mixing an aqueous emulsion (E-8) with an aqueous emulsion of terpene phenol (Tamanol E-200NT, Arakawa Chemical Co., Ltd.) in a nonvolatile content ratio of 67 parts: 33 parts. Manufactured.
  • An aqueous emulsion (E-32) was prepared by blending an aqueous emulsion (E-31) and an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) at a nonvolatile content ratio of 67:33. .
  • ⁇ Production Example 33 of Aqueous Emulsion> Instead of using 100 parts of the polymer (B-1-2), 50 parts of the propylene / butylene copolymer (B-3-2) and 50 parts of the ethylene / propylene copolymer (B-2-4) were used.
  • An aqueous emulsion (E-33) was produced in the same manner as in ⁇ Aqueous emulsion production example 1>.
  • the obtained aqueous emulsion (E-33) had a particle size of 0.2 ⁇ m (number basis) and a nonvolatile content of 34%.
  • ⁇ Production Example 35 of Aqueous Emulsion> The temperature in the cell of Labo Plast Mill Micro (manufactured by Toyo Seiki) was set to 95 ° C. In this cell, 3.12 g of the copolymer (B-1-2) was sealed and stirred at 300 rpm for 3 minutes. The maximum shear rate at this time was 1173 sec- 1 . Thereafter, 0.46 g of oxyethyleneoxypropylene block copolymer (weight average molecular weight 15500: Pluronic F108: manufactured by Asahi Denka Co., Ltd.) is added as an emulsifier together with 0.21 g of water, and the temperature in the cell is kept at 95 ° C.
  • oxyethyleneoxypropylene block copolymer weight average molecular weight 15500: Pluronic F108: manufactured by Asahi Denka Co., Ltd.
  • the mixture was kneaded at 300 rpm for 3 minutes (shear rate 1173 sec- 1 ). After kneading, the content was taken out and stirred and dispersed in a container containing warm water of about 70 ° C. to obtain an aqueous emulsion (E-35) having a volume-based median diameter of dispersoid of 0.43 ⁇ m.
  • Copolymer U1 Ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE HX8290, manufactured by ARKEMA, melting point: 81 ° C.)
  • Copolymer U2 ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE LX4110, manufactured by ARKEMA, melting point: 107 ° C.)
  • Copolymer U3 ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE HX8210, manufactured by ARKEMA, melting point: 100 ° C.)
  • Surfactant 1 Compound represented by the above formula (A) (Latemul E-1000A, 30% aqueous solution, manufactured by Kao Corporation)
  • Surfactant 2 Compound represented by the above formula (B) (Neugen EA-177, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
  • aqueous Emulsion An aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.), a polyurethane emulsion (manufactured by SBU, Dispacol U-54), an isocyanate (manufactured by SBU, Desmodur N3300)
  • An aqueous emulsion (E-39) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 100 parts: 5 parts.
  • aqueous Emulsion An aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.), a polyurethane emulsion (manufactured by SBU, Dispacol U-54), an isocyanate (manufactured by SBU, Desmodur N3300)
  • An aqueous emulsion (E-40) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 200 parts: 10 parts.
  • aqueous Emulsion An aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.), a polyurethane emulsion (manufactured by SBU, Dispacol U-54), an isocyanate (manufactured by SBU, Desmodur N3300)
  • An aqueous emulsion (E-41) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 1600 parts: 41 parts.
  • aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.), a polyurethane emulsion (manufactured by SBU, Dispacol U-54), an isocyanate (manufactured by SBU, Desmodur N3300)
  • An aqueous emulsion (E-42) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 100 parts: 15 parts.
  • aqueous Emulsion An aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.), a polyurethane emulsion (manufactured by SBU, Dispacol U-54), an isocyanate (manufactured by SBU, Desmodur N3300)
  • An aqueous emulsion (E-43) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 200 parts: 20 parts.
  • aqueous emulsion (E-44) was obtained by blending a polyurethane emulsion (SBU, Dispacol U-54) and isocyanate (SBU, Desmodur N3300) at a nonvolatile content ratio of 100 parts: 5 parts. It was.
  • SBU polyurethane emulsion
  • SBU Desmodur N3300
  • Aqueous emulsion (E-36), polyurethane emulsion (manufactured by SBU, Dispacol U-54), and isocyanate (manufactured by SBU, Desmodur N3300) are blended so that the nonvolatile content ratio is 100 parts: 100 parts: 5 parts.
  • an aqueous emulsion (E-45) was obtained.
  • Aqueous emulsion (E-36), polyurethane emulsion (manufactured by SBU, Dispacol U-54), and isocyanate (manufactured by SBU, Desmodur N3300) are blended so that the nonvolatile content ratio is 100 parts: 200 parts: 10 parts.
  • an aqueous emulsion (E-46) was obtained.
  • Copolymer P1 C 2 (ethylene) / EVA (ethylene / vinyl acetate copolymer) / MAH (maleic anhydride) copolymer (OREVAC T9314, manufactured by ARKEMA)
  • Copolymer P2 C 2 / EVA / MAH copolymer (OREVAC T9318, manufactured by ARKEMA)
  • Copolymer Q1 MAH modified-EVA (OREVAC G18211, manufactured by ARKEMA) Copolymer
  • R2 EVA part saponification product (Mersen H6410M, manufactured by Tosoh Corporation)
  • R3 EVA partly saponified product (Mersen H6820, manufactured by Tosoh Corporation)
  • R4 EVA part saponification product (Mersen H6822X, manufactured by Tosoh Corporation)
  • Test Examples 15 to 63 all of the water-based emulsions (E-15) to (E-35) are homogeneously dispersed by visual observation, and no aggregation, precipitation, phase separation or the like occurs during long-term storage. Showed good stability. Further, when the aqueous emulsions (E-36) to (E-63) were evaluated for stability for 5 days in the same manner as described above, no aggregation, precipitation, or phase separation was observed. State.
  • Example A Evaluation 1 of Adhesiveness of Aqueous Adhesive to M-EVA>
  • Table 5 shows Adecanol UH-420 (manufactured by ADEKA) as a thickener and Nopco Wet 50 (manufactured by San Nopco) as a dispersant in each of the water-based emulsions (nonvolatile content ratio) obtained in the production examples of water-based emulsions.
  • the stated amount was added, and the mixture was prepared with water so that the non-volatile content of the formulation was 40%, and stirred with a three-one motor to obtain an aqueous adhesive.
  • the obtained water-based adhesive of Table 5 was applied to 100% cotton canvas using a glass rod (coating amount: weight after drying about 60 g / m 2 ), and then naturally dried for 20 minutes. It was put in a microwave oven (manufactured by panasonic, NE-EH212, frequency 2.455 GHz), and subjected to electromagnetic wave treatment at 750 W for 30 seconds.
  • each water-based adhesive was bonded to a bar coater No. 75 (coil diameter: 75 ⁇ 25 ⁇ m) was applied to M-EVA (ethylene / vinyl acetate copolymer foam) (coating amount: weight after drying about 70 g / m 2 ), and obtained.
  • M-EVA was placed in a microwave oven and subjected to electromagnetic wave treatment at 750 W for 110 seconds.
  • each aqueous adhesive was applied to each of cotton canvas and M-EVA (cotton canvas coating amount: weight after drying about 40 g / m 2 , M-EVA coating amount: weight after drying about 80 g / m 2 ),
  • the obtained cotton canvas and M-EVA were put in a microwave oven and subjected to electromagnetic wave treatment at 750 W for 30 seconds.
  • the coated surfaces of cotton canvas and M-EVA water-based adhesive were bonded together and pressure-bonded.
  • the cotton / adhesive layer / M-EVA laminated structure thus obtained was again placed in a microwave oven and subjected to electromagnetic wave treatment at 750 W for 110 seconds. Immediately removed from the microwave and crimped by hand.
  • Example B Evaluation 2 of Adhesiveness of Aqueous Adhesive to M-EVA>
  • Table 6 shows Adecanol UH-756VF (manufactured by ADEKA) as a thickener and Nopco Wet 50 (manufactured by San Nopco) as a dispersant.
  • the obtained water-based adhesive B2 was applied to 100% cotton canvas using a glass rod (application amount: weight after drying about 130 g / m 2 ) and air-dried for 20 minutes.
  • the resulting canvas was microwaved (Microelectronics company make, 9KW microwave oven, frequency 2.45GHz) It put into electromagnetic waves for 30 seconds at 3000W. Also, water-based adhesive B1 was applied to bar coater No. 75 was used to coated on the M-EVA (coating amount: weight after drying about 30 g / m 2) was placed and the resulting M-EVA microwave was 110 seconds electromagnetic wave treatment at 3000W.
  • water-based adhesive B2 was applied to each of cotton canvas and M-EVA (cotton canvas coating amount: weight after drying about 60 g / m 2 , M-EVA coating amount: weight after drying about 30 g / m 2 ),
  • the obtained cotton canvas and M-EVA were placed in a microwave oven and subjected to electromagnetic wave treatment at 3000 W for 15 seconds. Subsequently, the coated surfaces of cotton canvas and M-EVA water-based adhesive were bonded together and pressure-bonded.
  • the cotton / adhesive layer / M-EVA laminated structure thus obtained was again placed in a microwave oven and subjected to electromagnetic wave treatment at 3900 W for 120 seconds. Immediately removed from the microwave and crimped by hand.
  • the obtained laminated structure was allowed to stand at room temperature for 24 hours, and the adhesion of the laminated structure was evaluated by the same method and evaluation criteria as described above. The results are shown in Table 6.
  • Example C Evaluation 3 of Adhesiveness of Water-based Adhesive to M-EVA>
  • Table 7 shows Adecanol UH-756VF (manufactured by ADEKA) as a thickener and Nopco Wet 50 (manufactured by San Nopco) as a dispersant in each emulsion (nonvolatile content ratio) obtained in the production example of the aqueous emulsion. (Non-volatile content ratio, unit: parts by weight) and water so that the non-volatile content of the formulation is 40%, and the mixture is stirred with a three-one motor to produce water-based adhesive C1 and water-based adhesive C2.
  • ADEKA Adecanol UH-756VF
  • Nopco Wet 50 manufactured by San Nopco
  • the obtained water-based adhesive C2 shown in Table 7 was applied to 100% cotton canvas using a glass rod (weight application amount after drying: about 130 g / m 2 ), and naturally dried for 20 minutes.
  • the canvas was subjected to electromagnetic wave treatment in a microwave oven at 3000 W for 30 seconds.
  • each water-based adhesive C1 shown in Table 7 was replaced with a bar coater No. 75 was applied to M-EVA (weight application amount after drying: about 30 g / m 2 ), and the obtained M-EVA was placed in a microwave oven and subjected to electromagnetic wave treatment at 5000 W for 170 seconds.
  • a water-based adhesive C2 was applied to each of the obtained cotton canvas and M-EVA (cotton canvas coating amount: weight after drying about 70 g / m 2 , M-EVA coating amount: weight after drying about 30 g / m 2 ), These cotton canvases were placed in a hot air oven at 80 ° C. for about 15 minutes, and M-EVA was placed in a hot air oven at 80 ° C. for about 10 minutes, and the coated surfaces of the aqueous adhesive were bonded together while hot.
  • the obtained cotton / adhesive layer / M-EVA laminate structure was again put into a hot air dryer, heat-treated at 80 ° C. for 10 minutes, taken out from the dryer, and then pressure-bonded by hand.
  • the obtained laminated structure was allowed to stand at room temperature for 24 hours, and the adhesion of the laminated structure was evaluated by the same method and evaluation criteria as described above. The results are shown in Table 7.
  • Example D Evaluation 4 of adhesion of water-based adhesive to M-EVA>
  • Adecanol UH-420 manufactured by ADEKA
  • Nopco Wet 50 manufactured by San Nopco
  • Table 8 nonvolatile content ratio, unit: parts by weight
  • the obtained water-based adhesive D in Table 8 was applied to 100% cotton canvas using a glass rod (coating amount: weight about 130 g / m 2 after drying) and air-dried for 1 hour. Also, the same water-based adhesive D applied to cotton was applied to the bar coater No. 75 was applied to M-EVA (foamed ethylene / vinyl acetate copolymer) (weight applied amount after drying: about 30 g / m 2 ), and the obtained M-EVA was naturally dried for 1 hour.
  • M-EVA fuoamed ethylene / vinyl acetate copolymer
  • Example F Evaluation 5 of adhesion and heat resistance of water-based adhesive to M-EVA>
  • terpene phenol as the adhesive resin 1 was added to the aqueous emulsions (E-36) to (E-38) (nonvolatile content ratio, unit: parts by weight) obtained in the production examples of the aqueous emulsion.
  • An aqueous emulsion (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) and an aqueous urethane emulsion (Disco Pearl U-54, manufactured by SBU) as the adhesive resin 2 were blended so that the nonvolatile content ratio was 100: 100: 100.
  • Adecanol UH-756VF (manufactured by ADEKA) was added as a thickener
  • Nopco Wet 50 (manufactured by San Nopco) was added as a dispersant
  • Desmodur N3300 (manufactured by SBU) was added as a crosslinking agent. After preparing with water so that the non-volatile content was 40%, the mixture was stirred with a three-one motor to obtain aqueous adhesives F1 to F10.
  • the obtained water-based adhesive (F10) in Table 9-1 was applied to 100% cotton canvas using a glass rod (coating amount: weight after drying: about 130 g / m 2 ), and after natural drying for 20 minutes, The electromagnetic wave treatment was performed at 3000 W for 30 seconds.
  • each of the water-based adhesives (F1) to (F9) was given a bar coater No. 75 was applied to M-EVA (ethylene / vinyl acetate copolymer foam) (coating amount: weight after drying: about 30 g / m 2 ), and the obtained M-EVA was heated at 3000 W for 110 seconds. Processed.
  • the aqueous adhesive (F10) was applied to cotton canvas and M-EVA using a glass rod (cotton canvas coating amount: weight after drying: about 70 g / m 2, M-EVA coating amount: weight after drying: about 70 g / m m 2 ), and M-EVA was subjected to electromagnetic wave treatment at 3000 W for 15 seconds. Subsequently, the coated surfaces of the cotton canvas and the M-EVA aqueous adhesive were bonded to each other and subjected to electromagnetic wave treatment at 3900 W for 120 seconds. Then, it crimped
  • Example H Evaluation 7 for Adhesion of Water-based Adhesive to M-EVA / Synthetic Leather> Table 10 shows Adecanol UH-756VF (manufactured by ADEKA) as a thickener and Nopco Wet 50 (manufactured by San Nopco) as a dispersant in each emulsion (nonvolatile content ratio) obtained in the aqueous emulsion production example. (Non-volatile content ratio, unit: parts by weight), and prepared with water so that the non-volatile content of the formulation is 40%, and stirred with a three-one motor, water-based adhesive H1 and water-based adhesive H2 Obtained.
  • the obtained water-based adhesive H-1 in Table 10 was applied to bar coater No. 75 was applied to M-EVA (weight application amount after drying: about 30 g / m 2 ), and the obtained M-EVA was placed in a microwave oven and subjected to electromagnetic wave treatment at 3000 W for 110 seconds.
  • Aqueous adhesives H-1 and H-2 were applied to each of the obtained M-EVA and synthetic leather (the amount of H-2 applied to the synthetic leather: weight after drying: about 30 g / m 2 , applied to M-EVA) H-1 coating amount: weight after drying of about 30 g / m 2 ), the obtained synthetic leather and M-EVA were placed in a microwave oven and subjected to electromagnetic wave treatment at 3000 W for 15 seconds.
  • a laminated structure having excellent adhesion can be produced.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention a pour objectif de fabriquer une structure stratifiée dotée d'une excellente adhérence. Plus précisément, l'invention concerne un procédé de fabrication de structure stratifiée selon lequel un premier matériau de base, une couche adhésive et un second matériau de base sont stratifiés dans cet ordre. Le procédé de l'invention inclut : (a) une étape au cours de laquelle un adhésif aqueux est appliqué à la surface du premier matériau de base, puis le premier matériau de base sur lequel l'adhésif aqueux a été appliqué est séché à la chaleur; (b) une étape au cours de laquelle l'adhésif aqueux est appliqué à la surface du second matériau de base, puis le second matériau de base sur lequel l'adhésif aqueux a été appliqué est séché à la chaleur; (c) une étape au cours de laquelle l'adhésif aqueux est à nouveau appliqué sur au moins l'une des faces séchées desdits premier et second matériaux de base, et les matériaux de bases obtenus sont séchés à la chaleur; et (d) une étape au cours de laquelle lesdites faces des premier et second matériaux de base sur lesquelles ont été appliqué l'adhésif aqueux puis séchées à la chaleur, sont collées. Au moins un séchage à la chaleur desdites étapes (a) à (c), consiste en un traitement par ondes électromagnétiques.
PCT/JP2012/064428 2011-06-10 2012-06-05 Procédé de fabrication de structure stratifiée WO2012169484A1 (fr)

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JP2009235289A (ja) * 2008-03-28 2009-10-15 Unitika Ltd 水性分散体および積層体
JP2009298154A (ja) * 2009-09-17 2009-12-24 Dic Corp 繊維積層体の製造方法及びそれにより得られる合成皮革
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JPH02127491A (ja) * 1988-11-04 1990-05-16 Dai Ichi Kogyo Seiyaku Co Ltd 水系接着剤組成物
JPH03277680A (ja) * 1990-01-19 1991-12-09 Arakawa Chem Ind Co Ltd 水性エマルジョン型接着剤組成物
JP2004051884A (ja) * 2002-07-23 2004-02-19 Unitika Ltd 水性分散液および接着剤
JP2011500314A (ja) * 2007-10-17 2011-01-06 株式会社ブリヂストン タイヤ製造のための水系接着剤混合物の塗布方法
JP2009227913A (ja) * 2008-03-25 2009-10-08 Denki Kagaku Kogyo Kk 樹脂組成物およびその製造方法
JP2009235289A (ja) * 2008-03-28 2009-10-15 Unitika Ltd 水性分散体および積層体
JP2009298154A (ja) * 2009-09-17 2009-12-24 Dic Corp 繊維積層体の製造方法及びそれにより得られる合成皮革

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