WO2022209918A1 - Polyolefin adhesive composition and multilayer body - Google Patents

Polyolefin adhesive composition and multilayer body Download PDF

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Publication number
WO2022209918A1
WO2022209918A1 PCT/JP2022/012057 JP2022012057W WO2022209918A1 WO 2022209918 A1 WO2022209918 A1 WO 2022209918A1 JP 2022012057 W JP2022012057 W JP 2022012057W WO 2022209918 A1 WO2022209918 A1 WO 2022209918A1
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WO
WIPO (PCT)
Prior art keywords
acid
mass
adhesive composition
modified polyolefin
eva
Prior art date
Application number
PCT/JP2022/012057
Other languages
French (fr)
Japanese (ja)
Inventor
桃子 福田
Original Assignee
東洋紡株式会社
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Filing date
Publication date
Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to JP2022564395A priority Critical patent/JPWO2022209918A1/ja
Priority to CN202280025851.4A priority patent/CN117083359A/en
Priority to KR1020237036922A priority patent/KR20230164114A/en
Publication of WO2022209918A1 publication Critical patent/WO2022209918A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—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 modified by chemical after-treatment
    • C09J123/28—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 modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C09J123/286—Chlorinated polyethylene
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J123/26—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 modified by chemical after-treatment
    • C09J123/28—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 modified by chemical after-treatment by reaction with halogens or compounds containing halogen

Definitions

  • the present invention is an adhesive that exhibits excellent adhesion to substrates containing polyolefin resins, such as polypropylene, polyethylene, and ethylene-vinyl acetate copolymer (EVA) as the main component, without using a curing agent or ultraviolet rays. It relates to an agent composition.
  • polyolefin resins such as polypropylene, polyethylene, and ethylene-vinyl acetate copolymer (EVA) as the main component, without using a curing agent or ultraviolet rays. It relates to an agent composition.
  • Polyolefin resins are relatively inexpensive and have excellent performance, such as chemical resistance, water resistance, and heat resistance, and are widely used in automobile parts, home appliances, household goods, containers, etc.
  • polyolefin resins are crystalline and do not have highly reactive functional groups on their surfaces, making it difficult to adhere to or paint polyolefin resin substrates.
  • EVA ethylene-vinyl acetate copolymer
  • EVA is used in the midsole of sports shoes, etc., and is a base material with excellent cushioning properties and light weight. good adhesion is also required.
  • Patent Document 1 describes a chlorine-free resin composition comprising a polymer of a thermoplastic elastomer and a copolymerizable monomer, and an organic solvent, as a primer for bonding footwear parts.
  • Patent Document 2 describes an adhesive composition containing a polychloroprene-polymethyl methacrylate graft copolymer and an (ethylene-vinyl acetate copolymer)-polymethyl methacrylate graft copolymer.
  • these adhesives are solvent-based ones dissolved in an organic solvent, have a low flash point, and cannot be said to be highly safe.
  • Patent Document 3 a photopolymerizable monomer is added and UV irradiation is performed to improve adhesiveness.
  • the introduction of a large-scale machine for ultraviolet irradiation is necessary, and ultraviolet rays may lead to yellowing of the base material and deterioration of properties, so adhesives that do not require ultraviolet irradiation are desired.
  • the present invention was made against the background of such problems of the prior art. Accordingly, it is an object of the present invention to provide an adhesive composition that exhibits excellent adhesion to low-polarity polyolefin substrates such as polypropylene and EVA.
  • chlorinated modified polyolefin (A) used in the present invention is not limited, it is preferably modified at least one of polyethylene, polypropylene and propylene/ ⁇ -olefin copolymer.
  • the chlorinated modified polyolefin (A) is more preferably modified polypropylene or propylene/ ⁇ -olefin copolymer.
  • the propylene/ ⁇ -olefin copolymer is mainly composed of propylene and is copolymerized with an ⁇ -olefin.
  • the ⁇ -olefin for example, one or several of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate and the like can be used.
  • ethylene and 1-butene are preferred, and ethylene and 1-butene are particularly preferred.
  • the propylene content in the polyolefin of the chlorinated modified polyolefin (A) is preferably 60% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, and 90% by mass. It is more preferable that it is above.
  • the chlorinated modified polyolefin (A) used in the present invention is not limited, but from the viewpoint of adhesiveness, at least one of polyethylene, polypropylene and propylene/ ⁇ -olefin copolymer contains ⁇ , ⁇ -unsaturated carboxylic acid and Those obtained by grafting at least one of its anhydrides are preferred.
  • at least one ⁇ , ⁇ -unsaturated carboxylic acid and its acid anhydride include maleic acid, itaconic acid, citraconic acid and their acid anhydrides. Among these, acid anhydrides are preferred, and maleic anhydride is more preferred.
  • maleic anhydride-modified polypropylene maleic anhydride-modified propylene/ethylene copolymer
  • maleic anhydride-modified propylene/1-butene copolymer maleic anhydride-modified propylene/ethylene/1-butene copolymer, etc.
  • These modified polyolefins can be used singly or in combination of two or more.
  • the content of the ⁇ , ⁇ -unsaturated carboxylic acid and its acid anhydride in the chlorinated modified polyolefin (A) is preferably in the range of 0.01 to 20 mass%, preferably 0.3 to More preferably in the range of 10% by weight, most preferably in the range of 1-5% by weight. If the content is less than 0.01% by mass, the chlorinated modified polyolefin resin may not develop adhesiveness due to the lack of polar groups. This is not preferable as it may reduce the force.
  • the chlorine content of the chlorinated modified polyolefin (A) ranges from 10 to 40% by mass. It is preferably 15 to 38% by mass, more preferably 20 to 35% by mass, particularly preferably 21 to 33% by mass, and most preferably 25 to 30% by mass.
  • the amount is 10% by mass or more, the wettability to the substrate tends to be good and the adhesiveness tends to be good.
  • it exceeds 40% by mass the flexibility of the resin may be impaired, leading to a decrease in adhesiveness.
  • the weight average molecular weight (Mw) of the chlorinated modified polyolefin (A) is preferably in the range of 10,000 to 200,000. More preferably in the range of 20,000 to 180,000, still more preferably in the range of 30,000 to 160,000, particularly preferably in the range of 40,000 to 140,000, most preferably 50 ,000 to 120,000.
  • Mw weight average molecular weight
  • the melting point of the chlorinated modified polyolefin (A) is preferably 80° C. or lower, more preferably 70° C. or lower, particularly preferably 60° C. or lower, and most preferably has no melting point.
  • having no melting point means that the heat of fusion ( ⁇ H) at the melting point is 5 J/g or less as measured by a differential scanning calorimeter (DSC).
  • the chlorinated polyolefin used in the present invention can be produced by a known method.
  • chlorinated polyolefin is dissolved in a chlorinated solvent, and under irradiation with ultraviolet rays or in the presence of a catalyst containing a peroxide such as benzoyl peroxide, in a solution state or in a heterogeneously dispersed state. It can be obtained by blowing in chlorine gas at a temperature of 50 to 150° C. under normal pressure or pressure to cause a reaction.
  • Water used in the present invention is usually tap water or ion-exchanged water.
  • the adhesive composition of the present invention preferably contains water in an adhesive composition of 10 to 98% by mass, more preferably 20 to 90% by mass, particularly preferably 30 to 70% by mass, and 40 to 60% by mass. % is more preferred.
  • Acid (C) used in the present invention is preferably an organic acid.
  • organic acids carboxylic acids, amino acids, organic sulfonic acids, acid anhydrides and the like can be used.
  • the acid anhydride may generate an acid by hydrolysis after addition.
  • acids include formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, arachidic acid, behenic acid, Lignoceric acid, acrylic acid, methacrylic acid, crotonic acid, methaconic acid, mesaconic acid, citraconic acid, butyric acid, valeric acid, hexanoic acid, malonic acid, glutaric acid, oxalic acid, lactic acid, succinic acid, fumaric acid, malic acid, tartaric acid , citric acid, salicylic acid, p-coumaric acid, caffeic acid, ferulic acid, chlorogenic acid, quinic acid, orotic acid, glycolic acid, gluconic acid, stearic acid, benzoic acid, glyoxylic acid, etc., which are
  • the pKa (acid dissociation constant) is preferably 4.8 or less, more preferably 4.0 or less, and particularly preferably. is an acid of 3.8 or less, such as formic acid. Moreover, when it has multiple pKa, at least one of the multiple pKa should be 4.8 or less. Furthermore, when two or more acids (C) are used, at least one is preferably 4.8 or less.
  • the acid (C) is preferably 0.1 to 100 parts by mass, more preferably 1 to 80 parts by mass, particularly preferably 3 to 60 parts by mass, relative to 100 parts by mass of the chlorinated modified polyolefin (A). , more preferably 5 to 50 parts by mass.
  • the acid (C) may be added to the dispersion medium before emulsification of the adhesive in the emulsification method described later, or may be added after emulsification.
  • the emulsifier (D) used in the present invention includes, for example, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl cetyl ether, polyoxyethylene alkylphenyl ethers, polyoxyethyl alkyls, polyoxyethylene alkylaryl ethers, polyethylene Nonionic surfactants such as alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, poly(oxyethylene-oxypropylene) block copolymers; higher alkyl sulfates, alkyl and aryl polyoxyethylene sulfates Anionic surfactants such as salts, higher fatty acid salts, alkylarylsulfonates, and alkylphosphoric acid ester salts are included.
  • polyoxyethylene alkyl ethers such as polyoxyethylene oleyl cetyl ether, polyoxyethylene alkylphenyl ethers, polyoxyethyl alkyls, polyoxyethylene al
  • the HLB value of the emulsifier is preferably in the range of 1-20, more preferably in the range of 10-19.
  • the above emulsifiers may be used alone or in combination of two or more.
  • the amount of the emulsifier (D) used is preferably 30 parts by mass or less, particularly 20 parts by mass or less per 100 parts by mass of the chlorinated modified polyolefin (A). Moreover, 0.5 mass part or more is preferable.
  • Organic solvent (E) used in the present invention dissolves the chlorinated modified polyolefin (A).
  • aromatic hydrocarbons such as benzene, toluene, and xylene
  • aliphatic hydrocarbons such as hexane, heptane, octane, and decane
  • Alicyclic hydrocarbons such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol and other alcohol solvents, acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone,
  • ketone solvents cellosolves such as methyl cellosolve and ethyl cellosolve, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl propionate, and butyl formate, ethylene glycol mono-n-butyl ether , ethylene glycol monoiso-butyl ether, ethylene glycol monotert-butyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoiso-butyl ether, triethylene glycol mono-n-butyl ether, tetraethylene glycol mono-n-butyl ether, etc.
  • cellosolves such as methyl cellosolve and ethyl cellosolve
  • ester solvents such as methyl acetate, ethyl acetate, butyl acetate, propyl acetate, amyl
  • a mixed solvent of an alicyclic hydrocarbon such as methylcyclohexane or ethylcyclohexane and a polar solvent such as butyl acetate or methylethylketone is preferable in terms of working environment and drying property.
  • the organic solvent (E) is preferably 1 part by mass or more, more preferably 100 parts by mass or more, and preferably 1500 parts by mass or more with respect to 100 parts by mass of the chlorinated modified polyolefin (A). More preferably, it is particularly preferably 2000 parts by mass or more. Also, it is preferably 15,000 parts by mass or less, more preferably 10,000 parts by mass or less, even more preferably 8,000 parts by mass or less, and most preferably 6,000 parts by mass or less. If it is less than the above range, the wettability and adhesiveness to the substrate may be deteriorated, and if it exceeds the above range, it may be disadvantageous in terms of production cost and transportation cost.
  • the adhesive of the present invention preferably does not contain a curing agent.
  • the content of not containing a curing agent is 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less based on 100 parts by mass of the chlorinated modified polyolefin resin (A).
  • ⁇ Adhesive> To obtain the adhesive of the present invention, it is necessary to emulsify using the chlorinated modified polyolefin, emulsifier, water and acid.
  • a method for emulsification a known method such as a forced emulsification method, a self-emulsification method, or a phase inversion emulsification method can be used.
  • a forced emulsification method in the present invention, an aqueous solution in which a predetermined amount of an emulsifier is dissolved is placed in a container in which an emulsifier such as a homomixer is set, and emulsification is performed while gradually adding chlorinated modified polyolefin therein. .
  • the resin it is necessary to dissolve the resin in advance in an organic solvent, or at least to swell or disperse it in water so that the resin can be sufficiently emulsified and dispersed in water. Otherwise, the desired particle size cannot be obtained because sufficient stirring power will not be applied to the system.
  • the organic solvent previously added to the system may be removed by concentration under reduced pressure to the extent that the adhesiveness of the adhesive is not impaired.
  • the method of applying the adhesive to the substrate in the present invention is not particularly limited, but examples include a method of applying absorbent cotton or cloth impregnated with the adhesive to the substrate, and a method of coating using a spray. .
  • the ethylene-vinyl acetate copolymer (EVA) base material used in the present invention may be EVA alone, or may be a mixture of EVA and a resin or component other than EVA.
  • the shape of the substrate includes various shapes such as film, sheet, block and foam, preferably foam.
  • thermoplastic elastomer substrate used in the present invention is not particularly limited, but examples of thermoplastic elastomers include polyolefin-based, polyurethane-based, polystyrene-based, vinyl chloride-based, polyester-based, polyamide-based, and polybutadiene-based materials. From the viewpoint of adhesiveness, a polyurethane-based thermoplastic elastomer substrate is preferable.
  • the rubber base material used in the present invention is not particularly limited, but includes natural rubber, nitrile rubber, styrene-butadiene rubber, and the like, and may contain antioxidants, plasticizers, pigments, inorganic particles, and the like.
  • a laminate containing an adhesive layer obtained by the adhesive composition of the present invention can be obtained, for example, by coating the adhesive composition of the present invention on the surface of a base material, and using the formed coating film as an adhesive layer for other materials.
  • the adhesive composition of the present invention may be applied to the surface of a base material, the resulting coating film may be used as a primer layer, and a conventionally known adhesive may be applied thereon to form an adhesive layer.
  • Laminates can also be obtained by bonding materials.
  • Conventionally known adhesives include, for example, ethylene/vinyl acetate copolymer resin adhesives, modified ethylene/vinyl acetate copolymer resin adhesives, acrylic resin adhesives, urethane resin adhesives, and polyolefin resin adhesives.
  • Examples include adhesives, modified polyolefin adhesives, synthetic rubber adhesives such as polychloroprene, and rosin resin adhesives.
  • These adhesives may be solvent-based, water-based, or hot-melt-based, but water-based adhesives are preferably used in view of the risk of fire and environmental hygiene.
  • Example 1 (Preparation of adhesive composition) 100 g of the chlorinated modified polyolefin resin (A-1) obtained in Production Example 1 and 30 g of formic acid were added to 2000 g of an ethylcyclohexane/butyl acetate mixed solvent and stirred at 60° C. for 2 hours to obtain a chlorinated modified polyolefin resin solution. Further, 20 g of an emulsifier (Noigen EA-177D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., a nonionic surfactant) was added to 2000 g of ion-exchanged water, and the mixture was stirred at 60° C. for 2 hours to obtain an aqueous emulsifier solution.
  • an emulsifier Noigen EA-177D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., a nonionic surfactant
  • the resulting chlorinated modified polyolefin resin solution and emulsifier aqueous solution were added to a 1 L tall beaker and stirred at room temperature at 8,000 rpm for 5 minutes using a high-speed stirrer (CLEARMIX CLM-0.8S: manufactured by M-Technic Co., Ltd.). and an adhesive composition 1 was obtained.
  • Examples 2 to 16 and Comparative Examples 1 to 4 An adhesive composition was prepared in the same manner as in Example 1 with changes shown in Tables 2 and 3, and each evaluation was carried out.
  • the modified polyolefin resin was dissolved in chloroform and subjected to FT-IR measurement, and based on the calibration curve, the amount of acid modification by maleic anhydride was determined from the absorbance of the stretching peak (1780 cm -1 ) of the carbonyl bond of maleic anhydride. .
  • EVA/thermoplastic elastomer test pieces Foamed EVA sheet [ethylene/vinyl acetate copolymer foam, size 100mm x 30mm x 10mm cube] is used as the EVA base material, and TPU base material (urethane thermoplastic elastomer) is used as the thermoplastic elastomer base material. sheet size 100 mm x 10 mm x 2 mm) was used.
  • the EVA base material is previously degreased with MEK and dried at 60° C. for 3 minutes using a warm air dryer. After drying, the EVA substrate was placed in a hot air dryer and preheated at 60° C.
  • the adhesive composition was applied to the EVA substrate.
  • the adhesive composition soaked in absorbent cotton was applied to the entire surface of the substrate.
  • the coated surface was dried at 60° C. for 3 minutes using a hot air dryer to obtain an EVA base material laminated with an adhesive layer.
  • a polyurethane adhesive (DISPERCOL U54, manufactured by Covestro) was applied to the surface of each of the EVA and TPU substrates with a brush so that the film thickness after drying was 200 ⁇ m, followed by drying with a hot air dryer. dried for a minute.
  • ⁇ T-type peel test> The test piece was cut into a size of 100 mm ⁇ 10 mm, and the adhesion was evaluated by the T-type peel test according to the following criteria. Based on the test method of ASTM-D1876-61, using Tensilon RTM-100 manufactured by Orientec Corporation, the peel strength was measured at a tensile speed of 50 mm/min under an environment of 25°C. The peel strength between the EVA substrate and the TPU substrate (kgf/cm) was the average value of five test values.
  • ⁇ Adhesion Evaluation Criteria> ⁇ (particularly excellent in practical use): 5.0 kgf/cm or more or EVA breaks. Material failure means that the EVA substrate is destroyed without peeling at the EVA substrate/TPU interface. ⁇ (Practical): 3.0 kgf/cm or more and less than 5.0 kgf/cm ⁇ (Impossible): Less than 3.0 kgf/cm
  • the adhesive according to the present invention contains a chlorinated modified polyolefin (A) having a chlorine content of 10 to 40%, an emulsifier, water, and an acid, has good pot life, and is high even without ultraviolet irradiation. Adhesive strength can be expressed. Therefore, a laminate of a polyolefin base material and a thermoplastic elastomer or rubber formed from the adhesive of the present invention can be used not only in fields such as automobile interior parts, furniture materials, and building interior materials, but also footwear and sports shoes. It is also widely available as a bottom adhesive and primer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

[Problem] To provide an adhesive composition that exhibits excellent adhesion to a base material, which is mainly composed of a polyolefin resin such as a polypropylene, a polyethylene and an ethylene-vinyl acetate copolymer (EVA), without using a curing agent, ultraviolet light or the like. [Solution] An adhesive composition which contains (A) a chlorinated modified polyolefin that has a chlorine content of 10% by mass to 40% by mass, (B) water and (C) an acid.

Description

ポリオレフィン系接着剤組成物及び積層体Polyolefin adhesive composition and laminate
　本発明は、ポリオレフィン系樹脂、例えばポリプロピレンやポリエチレン、エチレン・酢酸ビニル共重合体（EVA）を主成分とする基材に対し、硬化剤や紫外線などを用いることなく優れた接着性を発現する接着剤組成物に関する。 The present invention is an adhesive that exhibits excellent adhesion to substrates containing polyolefin resins, such as polypropylene, polyethylene, and ethylene-vinyl acetate copolymer (EVA) as the main component, without using a curing agent or ultraviolet rays. It relates to an agent composition.
　ポリオレフィン系樹脂は比較的安価で優れた性能、例えば、耐薬品性、耐水性、耐熱性等を有し、自動車部品、家電、生活用品、容器類等に幅広く利用されている。しかし、このような特徴を有していながら、ポリオレフィン系樹脂は結晶性で表面に反応性に富んだ官能基を有しないため、ポリオレフィン系樹脂基材に対して接着や塗装を施すことは困難である。例えば、エチレン・酢酸ビニル共重合体（ＥＶＡ）はスポーツシューズ等のミッドソールに使用され、クッション性や軽量性等に優れた基材であるが、衝撃や曲げ応力に耐えうる基材同士の強固な接着性も求められている。特許文献１には履物用部品接着用プライマーとして、熱可塑性エラストマーと共重合性モノマーとの重合体及び有機溶媒からなる、塩素を含有しない樹脂組成物が記載されている。特許文献２には、ポリクロロプレン－ポリメタクリル酸メチルグラフト共重合体、及び（エチレン－酢酸ビニル共重合体）－ポリメタクリル酸メチルグラフト共重合体を含有する接着剤組成物が記載されている。しかし、これらの接着剤は有機溶剤で溶解した溶剤系のものであり、引火点が低く、安全性の高いものであるとは言えない。 Polyolefin resins are relatively inexpensive and have excellent performance, such as chemical resistance, water resistance, and heat resistance, and are widely used in automobile parts, home appliances, household goods, containers, etc. However, despite these characteristics, polyolefin resins are crystalline and do not have highly reactive functional groups on their surfaces, making it difficult to adhere to or paint polyolefin resin substrates. be. For example, ethylene-vinyl acetate copolymer (EVA) is used in the midsole of sports shoes, etc., and is a base material with excellent cushioning properties and light weight. good adhesion is also required. Patent Document 1 describes a chlorine-free resin composition comprising a polymer of a thermoplastic elastomer and a copolymerizable monomer, and an organic solvent, as a primer for bonding footwear parts. Patent Document 2 describes an adhesive composition containing a polychloroprene-polymethyl methacrylate graft copolymer and an (ethylene-vinyl acetate copolymer)-polymethyl methacrylate graft copolymer. However, these adhesives are solvent-based ones dissolved in an organic solvent, have a low flash point, and cannot be said to be highly safe.
　さらに、特許文献３においては、光重合性モノマーを添加し紫外線照射により接着性向上を図っている。しかしながら、紫外線照射のための大がかりな機械の導入が必要であり、紫外線による基材の黄変や特性低下につながりかねないことから、紫外線照射不要の接着剤が求められている。 Furthermore, in Patent Document 3, a photopolymerizable monomer is added and UV irradiation is performed to improve adhesiveness. However, the introduction of a large-scale machine for ultraviolet irradiation is necessary, and ultraviolet rays may lead to yellowing of the base material and deterioration of properties, so adhesives that do not require ultraviolet irradiation are desired.
特開２００５-２９０３１３号公報JP-A-2005-290313 特開２００４-３５９７８８号公報JP-A-2004-359788 特開２０２０-１２２１６６号公報JP 2020-122166 A
　本発明は、かかる従来技術の課題を背景になされたものである。すなわち、本発明の目的は、ポリプロピレンやEVAのような極性の低いポリオレフィン基材への接着に優れた接着剤組成物を提供することにある。 The present invention was made against the background of such problems of the prior art. Accordingly, it is an object of the present invention to provide an adhesive composition that exhibits excellent adhesion to low-polarity polyolefin substrates such as polypropylene and EVA.
　上記課題を達成するため、本発明者らは鋭意検討し、塩素含量が１０-４０質量％の塩素化変性ポリオレフィン（A）、水（B）、及び酸（C）を含有する接着剤組成物が有効であることを見出し、以下の発明を提案するに至った。 In order to achieve the above objects, the present inventors have made intensive studies and found an adhesive composition containing chlorinated modified polyolefin (A) having a chlorine content of 10 to 40% by mass, water (B), and acid (C). is effective, and has proposed the following invention.
　本発明により、EVAのような極性の低い基材への接着において、紫外線照射や硬化剤を使用することなく高い接着強度を発現することができる。 According to the present invention, it is possible to develop high adhesive strength in bonding to low-polarity substrates such as EVA without using ultraviolet irradiation or curing agents.
　以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
＜塩素化変性ポリオレフィン（Ａ）＞
　本発明で用いる塩素化変性ポリオレフィン（Ａ）は限定的ではないが、ポリエチレン、ポリプロピレンおよびプロピレン・α－オレフィン共重合体の少なくとも１種に、変性がほどこされたものであることが好ましい。 <Chlorinated modified polyolefin (A)>
Although the chlorinated modified polyolefin (A) used in the present invention is not limited, it is preferably modified at least one of polyethylene, polypropylene and propylene/α-olefin copolymer.
　塩素化変性ポリオレフィン（Ａ）はポリプロピレンまたはプロピレン・α－オレフィン共重合体に変性がほどこされたものがより好ましい。プロピレン・α－オレフィン共重合体は、プロピレンを主体としてこれにα－オレフィンを共重合したものである。α－オレフィンとしては、例えば、エチレン、１－ブテン、１－ヘプテン、１－オクテン、４－メチル－１－ペンテン、酢酸ビニルなどを１種又は数種用いることができる。これらのα－オレフィンの中では、エチレン、１－ブテンが好ましく、特にエチレン及び１－ブテンを用いることが好ましい。 The chlorinated modified polyolefin (A) is more preferably modified polypropylene or propylene/α-olefin copolymer. The propylene/α-olefin copolymer is mainly composed of propylene and is copolymerized with an α-olefin. As the α-olefin, for example, one or several of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate and the like can be used. Among these α-olefins, ethylene and 1-butene are preferred, and ethylene and 1-butene are particularly preferred.
　塩素化変性ポリオレフィン（Ａ）はポリオレフィン中のプロピレン含有量が６０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、８０質量％以上であることが特に好ましく、９０質量％以上であることがさらに好ましい。 The propylene content in the polyolefin of the chlorinated modified polyolefin (A) is preferably 60% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, and 90% by mass. It is more preferable that it is above.
本発明で用いる塩素化変性ポリオレフィン（Ａ）は限定的ではないが、接着性の観点からポリエチレン、ポリプロピレン及びプロピレン・α－オレフィン共重合体の少なくとも１種に、α，β－不飽和カルボン酸及びその酸無水物の少なくとも１種をグラフトすることにより得られるものが好ましい。α，β－不飽和カルボン酸及びその酸無水物の少なくとも１種としては、例えば、マレイン酸、イタコン酸、シトラコン酸及びこれらの酸無水物が挙げられる。これらの中でも酸無水物が好ましく、無水マレイン酸がより好ましい。具体的には、無水マレイン酸変性ポリプロピレン、無水マレイン酸変性プロピレン・エチレン共重合体、無水マレイン酸変性プロピレン・１－ブテン共重合体、無水マレイン酸変性プロピレン・エチレン・１－ブテン共重合体等が挙げられ、これら変性ポリオレフィンを１種類又は２種類以上を組み合わせて使用することができる。 The chlorinated modified polyolefin (A) used in the present invention is not limited, but from the viewpoint of adhesiveness, at least one of polyethylene, polypropylene and propylene/α-olefin copolymer contains α,β-unsaturated carboxylic acid and Those obtained by grafting at least one of its anhydrides are preferred. Examples of at least one α,β-unsaturated carboxylic acid and its acid anhydride include maleic acid, itaconic acid, citraconic acid and their acid anhydrides. Among these, acid anhydrides are preferred, and maleic anhydride is more preferred. Specifically, maleic anhydride-modified polypropylene, maleic anhydride-modified propylene/ethylene copolymer, maleic anhydride-modified propylene/1-butene copolymer, maleic anhydride-modified propylene/ethylene/1-butene copolymer, etc. These modified polyolefins can be used singly or in combination of two or more.
　塩素化変性ポリオレフィン（Ａ）のα，β－不飽和カルボン酸およびその酸無水物の含有量は、塩素化変性ポリオレフィン樹脂中、０．０１～２０質量％の範囲内が好ましく、０．３～１０質量％ の範囲内がより好ましく、１～５質量％ の範囲内であることが最も好ましい。当該含有量が０．０１質量％ 未満であると、塩素化変性ポリオレフィン樹脂の極性基不足により接着性を発現しないおそれがあり、逆に、２０質量％ を超えると、ポリオレフィン樹脂基材への密着力が低下するおそれがあるので、好ましくない。 The content of the α,β-unsaturated carboxylic acid and its acid anhydride in the chlorinated modified polyolefin (A) is preferably in the range of 0.01 to 20 mass%, preferably 0.3 to More preferably in the range of 10% by weight, most preferably in the range of 1-5% by weight. If the content is less than 0.01% by mass, the chlorinated modified polyolefin resin may not develop adhesiveness due to the lack of polar groups. This is not preferable as it may reduce the force.
　塩素化変性ポリオレフィン（A）の塩素含量の範囲は１０～４０質量％である。好ましくは１５～３８質量％であり、より好ましくは２０～３５質量％であり、特に好ましくは２１～３３質量％であり、最も好ましくは２５～３０質量％である。１０質量％以上であると基材への濡れ性が良好になり接着性が良好となる傾向がある。一方４０質量％を越えると樹脂の柔軟性が損なわれ接着性低下につながる場合がある。 The chlorine content of the chlorinated modified polyolefin (A) ranges from 10 to 40% by mass. It is preferably 15 to 38% by mass, more preferably 20 to 35% by mass, particularly preferably 21 to 33% by mass, and most preferably 25 to 30% by mass. When the amount is 10% by mass or more, the wettability to the substrate tends to be good and the adhesiveness tends to be good. On the other hand, if it exceeds 40% by mass, the flexibility of the resin may be impaired, leading to a decrease in adhesiveness.
　塩素化変性ポリオレフィン（Ａ）の重量平均分子量（Ｍｗ）は、１０，０００～２００，０００の範囲であることが好ましい。より好ましくは２０，０００～１８０，０００の範囲であり、さらに好ましくは３０，０００～１６０，０００の範囲であり、特に好ましくは４０，０００～１４０，０００の範囲であり、最も好ましくは、５０，０００～１２０，０００の範囲である。１０，０００以上であると、凝集力が強くなり接着性が良好となる傾向がある。一方、２００，０００以下であると、流動性が良好となり接着する際の操作性が良好となる傾向がある。 The weight average molecular weight (Mw) of the chlorinated modified polyolefin (A) is preferably in the range of 10,000 to 200,000. More preferably in the range of 20,000 to 180,000, still more preferably in the range of 30,000 to 160,000, particularly preferably in the range of 40,000 to 140,000, most preferably 50 ,000 to 120,000. When it is 10,000 or more, there is a tendency for the cohesive force to become strong and the adhesiveness to become good. On the other hand, if it is 200,000 or less, the fluidity tends to be good, and the operability at the time of adhesion tends to be good.
塩素化変性ポリオレフィン（A）の融点は８０℃以下が好ましく、７０℃以下がより好ましく、６０℃以下が特に好ましく、融点を持たないことが最も好ましい。この場合の融点を持たないとは、示差走査熱量計（ＤＳＣ）測定により、融点の融解熱量（ΔＨ）が５Ｊ／ｇ以下であることを指す。 The melting point of the chlorinated modified polyolefin (A) is preferably 80° C. or lower, more preferably 70° C. or lower, particularly preferably 60° C. or lower, and most preferably has no melting point. In this case, having no melting point means that the heat of fusion (ΔH) at the melting point is 5 J/g or less as measured by a differential scanning calorimeter (DSC).
　本発明に用いられる塩素化ポリオレフィンは公知の方法で製造することができる。その製造法の一例としては、塩素化ポリオレフィンを塩素化溶媒中に溶解し、紫外線の照射下又は過酸化ベンゾイル等の過酸化物を含む触媒の存在下において、溶液状態で又は不均一分散状態で常圧又は加圧下に５０～１５０℃の温度で塩素ガスを吹き込み、反応させて得ることができる。 　The chlorinated polyolefin used in the present invention can be produced by a known method. As an example of its production method, chlorinated polyolefin is dissolved in a chlorinated solvent, and under irradiation with ultraviolet rays or in the presence of a catalyst containing a peroxide such as benzoyl peroxide, in a solution state or in a heterogeneously dispersed state. It can be obtained by blowing in chlorine gas at a temperature of 50 to 150° C. under normal pressure or pressure to cause a reaction.
＜水（B）＞
本発明で用いられる水は、通常、水道水またはイオン交換水が用いられる。
本発明の接着剤組成物は水を、接着剤組成物中に１０～９８質量％含有することが好ましく、２０～９０質量％がより好ましく、３０～７０質量％が特に好ましく、４０～６０質量％がさらに好ましい。 <Water (B)>
Water used in the present invention is usually tap water or ion-exchanged water.
The adhesive composition of the present invention preferably contains water in an adhesive composition of 10 to 98% by mass, more preferably 20 to 90% by mass, particularly preferably 30 to 70% by mass, and 40 to 60% by mass. % is more preferred.
<酸（C）>
本発明で用いられる酸（C）は、有機酸であることが好ましい。有機酸としては、カルボン酸、アミノ酸、有機スルホン酸、酸無水物等を使用することができる。ただし、酸無水物は添加後に加水分解によって酸を生成してもよい。酸の具体例としては、ギ酸、酢酸、プロピオン酸、ブチル酸、ペンタン酸、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、マルガリン酸、アラキジン酸、ベヘン酸、リグノセリン酸、アクリル酸、メタクリル酸、クロトン酸、メタコン酸、メサコン酸、シトラコン酸、酪酸、吉草酸、ヘキサン酸、マロン酸、グルタル酸、シュウ酸、乳酸、コハク酸、フマル酸、リンゴ酸、酒石酸、クエン酸、サリチル酸、p-クマル酸、コーヒー酸、フェルラ酸、クロロゲン酸、キナ酸、オロト酸、グリコール酸、グルコン酸、ステアリン酸、安息香酸、グリオキシル酸等が挙げられ、これらを単独で使用しても良いし、２種以上を任意に組み合わせて使用しても良い。中でも、EVA基材と熱可塑性エラストマー基材またはゴム基材との接着性向上において、ｐKa（酸解離定数）が４．８以下であれば好ましく、より好ましくは４．０以下であり、特に好ましくはギ酸などの３．８以下の酸である。また、ｐKaを複数有する場合、複数のｐKaのうち少なくとも一つが４．８以下であればよい。さらに酸（C）を２種以上用いる場合は、少なくとも一つが４．８以下であることが好ましい。 <Acid (C)>
Acid (C) used in the present invention is preferably an organic acid. As organic acids, carboxylic acids, amino acids, organic sulfonic acids, acid anhydrides and the like can be used. However, the acid anhydride may generate an acid by hydrolysis after addition. Specific examples of acids include formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, arachidic acid, behenic acid, Lignoceric acid, acrylic acid, methacrylic acid, crotonic acid, methaconic acid, mesaconic acid, citraconic acid, butyric acid, valeric acid, hexanoic acid, malonic acid, glutaric acid, oxalic acid, lactic acid, succinic acid, fumaric acid, malic acid, tartaric acid , citric acid, salicylic acid, p-coumaric acid, caffeic acid, ferulic acid, chlorogenic acid, quinic acid, orotic acid, glycolic acid, gluconic acid, stearic acid, benzoic acid, glyoxylic acid, etc., which are used alone may be used, or two or more may be used in any combination. Among them, in improving the adhesion between the EVA substrate and the thermoplastic elastomer substrate or the rubber substrate, the pKa (acid dissociation constant) is preferably 4.8 or less, more preferably 4.0 or less, and particularly preferably. is an acid of 3.8 or less, such as formic acid. Moreover, when it has multiple pKa, at least one of the multiple pKa should be 4.8 or less. Furthermore, when two or more acids (C) are used, at least one is preferably 4.8 or less.
　酸（C）は、塩素化変性ポリオレフィン（A）１００質量部に対して、０．１～１００質量部であることが好ましく、より好ましくは１～８０質量部、特に好ましくは３～６０質量部、さらに好ましくは５～５０質量部である。 The acid (C) is preferably 0.1 to 100 parts by mass, more preferably 1 to 80 parts by mass, particularly preferably 3 to 60 parts by mass, relative to 100 parts by mass of the chlorinated modified polyolefin (A). , more preferably 5 to 50 parts by mass.
　酸（C）は、例えば、後に述べる乳化法において接着剤の乳化前の分散媒に添加してもよいし、乳化後に添加してもよい。 For example, the acid (C) may be added to the dispersion medium before emulsification of the adhesive in the emulsification method described later, or may be added after emulsification.
＜乳化剤（D）＞
　本発明で用いる乳化剤（D）は、例えば、ポリオキシエチレンオレイルセチルエーテルなどのポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチルアルキル類、ポリオキシエチレンアルキルアリールエーテル類、ポリエチレンアルキルエステル類、ソルビタンアルキルエステル類、ポリオキシエチレンソルビタンアルキルエステル類、ポリ（ オキシエチレン－ オキシプロピレン） ブロックコポリマー類等のノニオン性界面活性剤； 高級アルキル硫酸エステル類、アルキル、アリールポリオキシエチレン硫酸エステル塩類、高級脂肪酸塩類、アルキルアリールスルフォン酸塩類、アルキルリン酸エステル塩類等のアニオン性界面活性剤等が挙げられる。
前記の乳化剤のＨＬＢ値は１～２０の範囲が好ましく、１０～１９の範囲がより好ましい。
　前記の乳化剤は、単独で使用しても２種以上を併用してもよい。乳化剤（D）の使用量は、塩素化変性ポリオレフィン（A）１００質量部に対して、３０質量部以下、特に２０質量部以下が好ましい。また、０．５質量部以上が好ましい。 <Emulsifier (D)>
The emulsifier (D) used in the present invention includes, for example, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl cetyl ether, polyoxyethylene alkylphenyl ethers, polyoxyethyl alkyls, polyoxyethylene alkylaryl ethers, polyethylene Nonionic surfactants such as alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, poly(oxyethylene-oxypropylene) block copolymers; higher alkyl sulfates, alkyl and aryl polyoxyethylene sulfates Anionic surfactants such as salts, higher fatty acid salts, alkylarylsulfonates, and alkylphosphoric acid ester salts are included.
The HLB value of the emulsifier is preferably in the range of 1-20, more preferably in the range of 10-19.
The above emulsifiers may be used alone or in combination of two or more. The amount of the emulsifier (D) used is preferably 30 parts by mass or less, particularly 20 parts by mass or less per 100 parts by mass of the chlorinated modified polyolefin (A). Moreover, 0.5 mass part or more is preferable.
＜有機溶剤(E)＞
　本発明で用いる有機溶剤（E）は、塩素化変性ポリオレフィン（Ａ）を溶解させる。具体的には、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素、ヘキサン、ヘプタン、オクタン、デカン等の脂肪族系炭化水素、シクロヘキサン、シクロヘキセン、メチルシクロヘキサン、エチルシクロへキサン、ブチルシクロヘキサン、アミルシクロヘキサン等の脂環族炭化水素、メタノール、エタノール、イソプロピルアルコール、ブタノール、ペンタノール、ヘキサノール、プロパンジオール、フェノール等のアルコール系溶剤、アセトン、メチルイソブチルケトン、メチルエチルケトン、ペンタノン、ヘキサノン、シクロヘキサノン、イソホロン、アセトフェノン等のケトン系溶剤、メチルセルソルブ、エチルセルソルブ等のセルソルブ類、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸アミル、プロピオン酸メチル、ギ酸ブチル等のエステル系溶剤、エチレングリコールモノn -ブチルエーテル、エチレングリコールモノi s o -ブチルエーテル、エチレングリコールモノt e r t - ブチルエーテル、ジエチレングリコールモノn -ブチルエーテル、ジエチレングリコールモノi s o -ブチルエーテル、トリエチレングリコールモノn -ブチルエーテル、テトラエチレングリコールモノn -ブチルエーテル等のグリコールエーテル系溶剤等を使用することができ、これら１種または２種以上を併用することができる。特に作業環境性、乾燥性から、メチルシクロへキサンやエチルシクロヘキサンのような脂環族炭化水素と酢酸ブチル、メチルエチルケトンのような極性溶剤の混合溶剤が好ましい。 <Organic solvent (E)>
The organic solvent (E) used in the present invention dissolves the chlorinated modified polyolefin (A). Specifically, for example, aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane, butylcyclohexane, and amylcyclohexane; Alicyclic hydrocarbons such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol and other alcohol solvents, acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone, etc. ketone solvents, cellosolves such as methyl cellosolve and ethyl cellosolve, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl propionate, and butyl formate, ethylene glycol mono-n-butyl ether , ethylene glycol monoiso-butyl ether, ethylene glycol monotert-butyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoiso-butyl ether, triethylene glycol mono-n-butyl ether, tetraethylene glycol mono-n-butyl ether, etc. can be used, and these can be used singly or in combination of two or more. In particular, a mixed solvent of an alicyclic hydrocarbon such as methylcyclohexane or ethylcyclohexane and a polar solvent such as butyl acetate or methylethylketone is preferable in terms of working environment and drying property.
　有機溶剤（E)は、塩素化変性ポリオレフィン（Ａ）１００質量部に対して、１質量部以上であることが好ましく、１００質量部以上であることがより好ましく、１５００質量部以上であることがさらに好ましく、２０００質量部以上であることが特に好ましい。また、１５０００質量部以下であることが好ましく、１００００質量部以下であることがより好ましく、８０００質量部以下であることがさらに好ましく、６０００質量部以下であることが最も好ましい。前記範囲未満では、基材への濡れ性や接着性が低下する場合があり、前記範囲を超えると製造コスト、輸送コストの面から不利となる場合がある。 The organic solvent (E) is preferably 1 part by mass or more, more preferably 100 parts by mass or more, and preferably 1500 parts by mass or more with respect to 100 parts by mass of the chlorinated modified polyolefin (A). More preferably, it is particularly preferably 2000 parts by mass or more. Also, it is preferably 15,000 parts by mass or less, more preferably 10,000 parts by mass or less, even more preferably 8,000 parts by mass or less, and most preferably 6,000 parts by mass or less. If it is less than the above range, the wettability and adhesiveness to the substrate may be deteriorated, and if it exceeds the above range, it may be disadvantageous in terms of production cost and transportation cost.
＜添加物＞
本発明の接着剤には、目的に応じて性能をさらに向上させるために、その他の樹脂、無機粒子、フィラー、顔料、染料等を添加することができる。 <Additives>
Other resins, inorganic particles, fillers, pigments, dyes and the like can be added to the adhesive of the present invention in order to further improve its performance depending on the purpose.
　本発明の接着剤は硬化剤を含有しないことが好ましい。硬化剤を含有しないとは、塩素化変性ポリオレフィン樹脂（A）１００質量部に対して３質量％以下であり、好ましくは１質量％以下、より好ましくは０．５質量%以下である。硬化剤を含有しないことで、硬化による貯蔵時における粘度の上昇が抑えられ、ロングラン生産時においても歩留まり良く生産を行うことができる。 The adhesive of the present invention preferably does not contain a curing agent. The content of not containing a curing agent is 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less based on 100 parts by mass of the chlorinated modified polyolefin resin (A). By not containing a curing agent, an increase in viscosity due to curing during storage can be suppressed, and production can be performed with a high yield even during long-run production.
＜接着剤＞
本発明の接着剤を得るには、上記塩素化変性ポリオレフィン、乳化剤、水、および酸を用いて乳化する必要がある。その方法としては、強制乳化法や自己乳化法、転相乳化法などの公知の方法で乳化することができる。例えば、強制乳化法では、本発明においてはホモミキサ－のような乳化器をセットした容器の中に乳化剤を所定量溶解した水溶液を入れ、その中に塩素化変性ポリオレフィンを徐々に加えながら乳化を行う。この際、同樹脂が充分水中に乳化分散できるように、有機溶剤でもって予め溶解するか又は、少なくとも膨潤あるいは分散状態にしておく必要がある。そうしないと充分な撹拌動力が系内に投下されないので希望する粒径が得られない。系内に予め添加した有機溶剤はその接着剤の接着性を損なわない範囲で減圧濃縮により除いてもよい。 <Adhesive>
To obtain the adhesive of the present invention, it is necessary to emulsify using the chlorinated modified polyolefin, emulsifier, water and acid. As a method for emulsification, a known method such as a forced emulsification method, a self-emulsification method, or a phase inversion emulsification method can be used. For example, in the forced emulsification method, in the present invention, an aqueous solution in which a predetermined amount of an emulsifier is dissolved is placed in a container in which an emulsifier such as a homomixer is set, and emulsification is performed while gradually adding chlorinated modified polyolefin therein. . At this time, it is necessary to dissolve the resin in advance in an organic solvent, or at least to swell or disperse it in water so that the resin can be sufficiently emulsified and dispersed in water. Otherwise, the desired particle size cannot be obtained because sufficient stirring power will not be applied to the system. The organic solvent previously added to the system may be removed by concentration under reduced pressure to the extent that the adhesiveness of the adhesive is not impaired.
本発明における接着剤を基材に塗工する方法としては、特に限定されないが、脱脂綿や布に接着剤を染み込ませたものを基材に塗る方法や、スプレーを用いて塗装する方法が挙げられる。 The method of applying the adhesive to the substrate in the present invention is not particularly limited, but examples include a method of applying absorbent cotton or cloth impregnated with the adhesive to the substrate, and a method of coating using a spray. .
＜エチレン-酢酸ビニル共重合体（EVA）基材＞
　本発明に用いられるエチレン－酢酸ビニル共重合体（EVA）基材は、EVA単体でもよく、EVA に加えてEVA以外の樹脂や成分がブレンドされたものでもよい。基材の形状はフィルム、シート、ブロック、発泡体等の種々のものが挙げられるが、好ましくは発泡体のものである。 <Ethylene-vinyl acetate copolymer (EVA) base material>
The ethylene-vinyl acetate copolymer (EVA) base material used in the present invention may be EVA alone, or may be a mixture of EVA and a resin or component other than EVA. The shape of the substrate includes various shapes such as film, sheet, block and foam, preferably foam.
＜熱可塑性エラストマー基材及びゴム基材＞
　本発明に用いられる熱可塑性エラストマー基材は、特に限定されないが、例えば熱可塑性エラストマーとして、ポリオレフィン系、ポリウレタン系、ポリスチレン系、塩化ビニル系、ポリエステル系、ポリアミド系、ポリブタジエン系などが挙げられる。接着性の観点から、ポリウレタン系の熱可塑性エラストマー基材が好ましい。
　本発明に用いられるゴム基材は、特に限定されないが、天然ゴム、ニトリルゴム、スチレンブタジエンゴムなどが挙げられ、酸化防止剤、可塑剤、顔料、無機粒子などを含んでいてもよい。 <Thermoplastic elastomer substrate and rubber substrate>
The thermoplastic elastomer substrate used in the present invention is not particularly limited, but examples of thermoplastic elastomers include polyolefin-based, polyurethane-based, polystyrene-based, vinyl chloride-based, polyester-based, polyamide-based, and polybutadiene-based materials. From the viewpoint of adhesiveness, a polyurethane-based thermoplastic elastomer substrate is preferable.
The rubber base material used in the present invention is not particularly limited, but includes natural rubber, nitrile rubber, styrene-butadiene rubber, and the like, and may contain antioxidants, plasticizers, pigments, inorganic particles, and the like.
　本発明の接着剤組成物により得られる接着剤層を含有する積層体は、例えば本発明の接着剤組成物を基材の表面に塗布し、形成された塗膜を接着剤層として他の材料と接着することにより、得ることができる。また、本発明の接着剤組成物を基材の表面に塗布し、形成された塗膜をプライマー層とし、この上にさらに従来公知の接着剤を塗布して接着剤層を形成して他の材料と接着することにより積層体を得ることもできる。
　従来公知の接着剤としては、たとえば、エチレン・酢酸ビニル共重合体樹脂系接着剤、変性エチレン・酢酸ビニル共重合体樹脂系接着剤、アクリル樹脂系接着剤、ウレタン樹脂系接着剤、ポリオレフィン樹脂系接着剤、変性ポリオレフィン系接着剤、ポリクロロプレンなどの合成ゴム系接着剤、ロジン樹脂系接着剤が挙げられる。これらの接着剤は、溶剤系、水系、ホットメルト系などのいずれの接着剤も用いることができるが、引火の危険性や環境衛生上、水系接着剤が好適に使用される。 A laminate containing an adhesive layer obtained by the adhesive composition of the present invention can be obtained, for example, by coating the adhesive composition of the present invention on the surface of a base material, and using the formed coating film as an adhesive layer for other materials. can be obtained by bonding with Alternatively, the adhesive composition of the present invention may be applied to the surface of a base material, the resulting coating film may be used as a primer layer, and a conventionally known adhesive may be applied thereon to form an adhesive layer. Laminates can also be obtained by bonding materials.
Conventionally known adhesives include, for example, ethylene/vinyl acetate copolymer resin adhesives, modified ethylene/vinyl acetate copolymer resin adhesives, acrylic resin adhesives, urethane resin adhesives, and polyolefin resin adhesives. Examples include adhesives, modified polyolefin adhesives, synthetic rubber adhesives such as polychloroprene, and rosin resin adhesives. These adhesives may be solvent-based, water-based, or hot-melt-based, but water-based adhesives are preferably used in view of the risk of fire and environmental hygiene.
　以下、実施例を挙げて本発明を更に詳細に説明する。但し、本発明は実施例に限定されない。
＜製造例＞
製造例１ （塩素化変性ポリオレフィン樹脂の製造）
　プロピレン・エチレン・ブテンターコポリマー（ ＰＯ－１、エチレン成分含有量＝３．４モル％、ブテン成分含有量＝２．７モル％） ５００ｇ 、無水マレイン酸２５ｇ、ジｔｅｒｔ－ブチルパーオキシド２０ｇ、およびトルエン７６０ｇ を、攪拌器を取り付けたオートクレーブ中に入れ、窒素置換を約５分行った後、加熱攪拌しながら１４０℃ で５時間反応を行った。反応終了後、アセトンにより再沈殿を３回繰り返し、未反応の無水マレイン酸を除去した。減圧乾燥後、得られた無水マレイン酸変性ポリオレフィン樹脂を５００ｇ およびクロロホルム５０４５ｇ を、攪拌器を取り付けたオートクレーブ中に入れ、窒素置換を約５分間行った後、１１０℃ に加熱して樹脂を充分に溶解させた。次いで、ｔｅｒｔ-ブチルパーオキシ－２－エチルヘキサノエート　５．０ｇを加え、塩素ガスを１４０ｇ吹き込んだ。反応溶媒であるクロロホルムを減圧留去して乾燥させることにより、塩素含有率が１０質量％ 、重量平均分子量が１２万、無水マレイン酸の含有量が１．０質量％ の塩素化変性ポリオレフィン樹脂（A-１）の固形物を得た。 EXAMPLES The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the examples.
<Manufacturing example>
Production Example 1 (Production of chlorinated modified polyolefin resin)
500 g of propylene-ethylene-butene tercopolymer (PO-1, ethylene component content = 3.4 mol%, butene component content = 2.7 mol%), 25 g maleic anhydride, 20 g di-tert-butyl peroxide, and 760 g of toluene was placed in an autoclave equipped with a stirrer, and after purging with nitrogen for about 5 minutes, a reaction was carried out at 140° C. for 5 hours while heating and stirring. After completion of the reaction, reprecipitation with acetone was repeated three times to remove unreacted maleic anhydride. After drying under reduced pressure, 500 g of the resulting maleic anhydride-modified polyolefin resin and 5,045 g of chloroform were placed in an autoclave equipped with a stirrer, and after purging with nitrogen for about 5 minutes, the resin was sufficiently hardened by heating to 110°C. Dissolved. Then, 5.0 g of tert-butylperoxy-2-ethylhexanoate was added, and 140 g of chlorine gas was blown thereinto. Chloroform, which is the reaction solvent, is distilled off under reduced pressure and dried to obtain a chlorinated modified polyolefin resin ( A-1) solid matter was obtained.
製造例２～製造例９
　表１に示す質量部のポリオレフィン樹脂、無水マレイン酸、ジｔｅｒｔ－ブチルパーオキシドおよび塩素を使用し、製造例１と同様にして塩素化変性ポリオレフィン（A－２）～（A－９）を得た。 Production Example 2 to Production Example 9
Using the polyolefin resin, maleic anhydride, di-tert-butyl peroxide and chlorine in the parts by mass shown in Table 1, chlorinated modified polyolefins (A-2) to (A-9) were obtained in the same manner as in Production Example 1. rice field.
実施例１　（接着剤組成物の作製）
　製造例１で得られた塩素化変性ポリオレフィン樹脂（Ａ－１） １００ｇとギ酸　３０ｇをエチルシクロヘキサン/酢酸ブチル混合溶剤　２０００ｇに加え、６０℃で２時間撹拌し塩素化変性ポリオレフィン樹脂溶液を得た。さらに、イオン交換水　２０００ｇ中に乳化剤（ノイゲンEA－１７７D、第一工業製薬株式会社製、ノニオン系界面活性剤）を２０ｇ加え６０℃で２時間撹拌し、乳化剤水溶液を得た。得られた塩素化変性ポリオレフィン樹脂溶液と乳化剤水溶液を１Ｌトールビーカー中に加え、高速撹拌機（クレアミックスＣＬＭ－０．８Ｓ：エムテクニック社製）を用いて室温下、回転数８０００ｒｐｍで５分間撹拌し、接着剤組成物１を得た。 Example 1 (Preparation of adhesive composition)
100 g of the chlorinated modified polyolefin resin (A-1) obtained in Production Example 1 and 30 g of formic acid were added to 2000 g of an ethylcyclohexane/butyl acetate mixed solvent and stirred at 60° C. for 2 hours to obtain a chlorinated modified polyolefin resin solution. Further, 20 g of an emulsifier (Noigen EA-177D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., a nonionic surfactant) was added to 2000 g of ion-exchanged water, and the mixture was stirred at 60° C. for 2 hours to obtain an aqueous emulsifier solution. The resulting chlorinated modified polyolefin resin solution and emulsifier aqueous solution were added to a 1 L tall beaker and stirred at room temperature at 8,000 rpm for 5 minutes using a high-speed stirrer (CLEARMIX CLM-0.8S: manufactured by M-Technic Co., Ltd.). and an adhesive composition 1 was obtained.
実施例２～実施例１６および比較例１～４
　表２、表３に示す通りに変更して実施例１と同様に接着剤組成物を作製し、各評価を実施した。 Examples 2 to 16 and Comparative Examples 1 to 4
An adhesive composition was prepared in the same manner as in Example 1 with changes shown in Tables 2 and 3, and each evaluation was carried out.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　上記のようにして得られた各塩素化変性ポリオレフィンおよび接着剤組成物に対して下記方法に基づいて分析測定および評価を行った。
＜無水マレイン酸含有量の測定＞
　本発明における無水マレイン酸含量（質量％）はＦＴ－ＩＲにより求めることができる。具体的にはが挙げられる。具体的な測定条件としては、まず無水マレイン酸を任意の濃度で溶解して検量線溶液を作製した。ＦＴ―ＩＲ８２００ＰＣ（島津製作所社製）を用いて、検量線溶液のＦＴ―ＩＲ測定を行い、無水マレイン酸のカルボニル（Ｃ＝Ｏ）基の伸縮ピーク（１７８０ｃｍ-1）の吸光度より検量線を作成した。変性ポリオレフィン樹脂をクロロホルムに溶解させてＦＴーＩＲ測定を行い、前記検量線をもとに無水マレイン酸のカルボニル結合の伸縮ピーク（１７８０ｃｍ-1）の吸光度より無水マレイン酸による酸変性量を求めた。 Each chlorinated modified polyolefin and adhesive composition obtained as described above were analyzed, measured and evaluated according to the following methods.
<Measurement of maleic anhydride content>
The maleic anhydride content (% by mass) in the present invention can be determined by FT-IR. Specifically. As a specific measurement condition, first, maleic anhydride was dissolved at an arbitrary concentration to prepare a calibration curve solution. Using FT-IR8200PC (manufactured by Shimadzu Corporation), FT-IR measurement of the calibration curve solution is performed, and a calibration curve is created from the absorbance of the stretching peak (1780 cm -1 ) of the carbonyl (C=O) group of maleic anhydride. did. The modified polyolefin resin was dissolved in chloroform and subjected to FT-IR measurement, and based on the calibration curve, the amount of acid modification by maleic anhydride was determined from the absorbance of the stretching peak (1780 cm -1 ) of the carbonyl bond of maleic anhydride. .
＜数平均分子量（Ｍｎ）および重量平均分子量（Ｍｗ）の測定＞
　本発明における重量平均分子量は日本ウォーターズ社製ゲルパーミエーションクロマトグラフＡｌｌｉａｎｃｅ ｅ２６９５（以下、ＧＰＣ、標準物質：ポリスチレン樹脂、移動相：テトラヒドロフラン、カラム：ｓｈｏｄｅｘ ＫＦ-８０６ + ＫＦ-８０３、カラム温度：４０℃、流速：１．０ｍｌ/分、検出器：フォトダイオードアレイ検出器（波長２５４ｎｍ = 紫外線））によって測定した値である。 <Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw)>
The weight-average molecular weight in the present invention is determined by gel permeation chromatograph Alliance e2695 (GPC manufactured by Nippon Waters Co., Ltd., hereinafter referred to as GPC, standard substance: polystyrene resin, mobile phase: tetrahydrofuran, column: shodex KF-806 + KF-803, column temperature: 40°C. , flow rate: 1.0 ml/min, detector: photodiode array detector (wavelength 254 nm = ultraviolet light)).
　評価用試験片の作製
・EVA/熱可塑性エラストマーの試験片の作製
EVA基材には発泡ＥＶＡシート〔エチレン／酢酸ビニル共重合体の発泡体、サイズ１００ｍｍ×３０ｍｍ×１０ｍｍの立方体）を使用し、熱可塑性エラストマー基材としては、TPU基材（ウレタン系熱可塑性エラストマーのシート　サイズ１００ｍｍ×１０ｍｍ×２ｍｍ）を使用した。
　ＥＶＡ基材はあらかじめＭＥＫにて脱脂、温風乾燥機を用いて６０℃×３分乾燥させる。乾燥後、ＥＶＡ基材を温風乾燥機に入れ６０℃×５分プレヒートし、取り出した直後に、接着剤組成物をＥＶＡ基材に塗布した。この際、接着剤組成物は脱脂綿に染み込ませたものを基材の表面全体に塗布した。接着剤組成物塗布後、塗布面を温風乾燥機を用いて６０℃×３分乾燥させ、接着剤層が積層されたＥＶＡ基材を得た。得られたＥＶＡ基材およびＴＰＵ基材それぞれの表面にポリウレタン系接着剤（ディスパコールＵ５４、コベストロ社製）を乾燥後の膜厚が２００μｍになるようにブラシで塗布し、温風乾燥機で５分間乾燥した。乾燥直後にＥＶＡ基材およびＴＰＵ基材を貼り合わせ、２０kgf/ｃｍ２の圧力のプレス機で１５秒間圧着した。このようにして、接着性評価用の試験片を得た。この試験片を２４時間、室温下で静置した後、下記のＴ型剥離試験において引張試験機により接着性を評価した。 Production of test pieces for evaluation ・Production of EVA/thermoplastic elastomer test pieces
Foamed EVA sheet [ethylene/vinyl acetate copolymer foam, size 100mm x 30mm x 10mm cube] is used as the EVA base material, and TPU base material (urethane thermoplastic elastomer) is used as the thermoplastic elastomer base material. sheet size 100 mm x 10 mm x 2 mm) was used.
The EVA base material is previously degreased with MEK and dried at 60° C. for 3 minutes using a warm air dryer. After drying, the EVA substrate was placed in a hot air dryer and preheated at 60° C. for 5 minutes, and immediately after taking out, the adhesive composition was applied to the EVA substrate. At this time, the adhesive composition soaked in absorbent cotton was applied to the entire surface of the substrate. After applying the adhesive composition, the coated surface was dried at 60° C. for 3 minutes using a hot air dryer to obtain an EVA base material laminated with an adhesive layer. A polyurethane adhesive (DISPERCOL U54, manufactured by Covestro) was applied to the surface of each of the EVA and TPU substrates with a brush so that the film thickness after drying was 200 μm, followed by drying with a hot air dryer. dried for a minute. Immediately after drying, the EVA base material and the TPU base material were laminated together and pressed for 15 seconds with a press at a pressure of 20 kgf/cm 2 . Thus, a test piece for adhesion evaluation was obtained. After this test piece was allowed to stand at room temperature for 24 hours, adhesion was evaluated by a tensile tester in the following T-type peel test.
＜Ｔ型剥離試験＞
　前記試験片を１００ｍｍ×１０ｍｍの大きさに切断し、Ｔ型剥離試験により接着性を以下の基準により評価した。
　ＡＳＴＭ－Ｄ１８７６－６１の試験法に準拠し、オリエンテックコーポレーション社製のテンシロンＲＴＭ－１００を用いて、２５℃環境下で、引張速度５０ｍｍ／分における剥離強度を測定した。ＥＶＡ基材／ＴＰＵ基材間の剥離強度（ｋｇｆ／ｃｍ）は５回の試験値の平均値とした。
＜接着性　評価基準＞
　◎（実用上特に優れる）：５．０ｋｇｆ／ｃｍ以上またはＥＶＡが材破する。材破とは、EVA基材／TPUの界面で剥離が生じず、ＥＶＡ基材が破壊されることをいう。
　○（実用可能）：３．０ｋｇｆ／ｃｍ以上５．０ｋｇｆ／ｃｍ未満
　×（実用不可能）：３．０ｋｇｆ／ｃｍ未満 <T-type peel test>
The test piece was cut into a size of 100 mm×10 mm, and the adhesion was evaluated by the T-type peel test according to the following criteria.
Based on the test method of ASTM-D1876-61, using Tensilon RTM-100 manufactured by Orientec Corporation, the peel strength was measured at a tensile speed of 50 mm/min under an environment of 25°C. The peel strength between the EVA substrate and the TPU substrate (kgf/cm) was the average value of five test values.
<Adhesion Evaluation Criteria>
⊚ (particularly excellent in practical use): 5.0 kgf/cm or more or EVA breaks. Material failure means that the EVA substrate is destroyed without peeling at the EVA substrate/TPU interface.
○ (Practical): 3.0 kgf/cm or more and less than 5.0 kgf/cm × (Impossible): Less than 3.0 kgf/cm
　本発明にかかる接着剤は、塩素含量が１０～４０％の塩素化変性ポリオレフィン（A）、乳化剤、水、及び酸を含有し、ポットライフ性が良好であり、紫外線照射を行わなくても高い接着強度を発現できる。そのため、本発明の接着剤から形成されるポリオレフィン基材と熱可塑性エラストマーまたはゴムとの積層体は、自動車内装部品、家具用素材、建築内装用部材などの分野のみならず履物やスポーツシューズの靴底に用いられる接着剤およびプライマーとしても幅広く利用し得るものである。 The adhesive according to the present invention contains a chlorinated modified polyolefin (A) having a chlorine content of 10 to 40%, an emulsifier, water, and an acid, has good pot life, and is high even without ultraviolet irradiation. Adhesive strength can be expressed. Therefore, a laminate of a polyolefin base material and a thermoplastic elastomer or rubber formed from the adhesive of the present invention can be used not only in fields such as automobile interior parts, furniture materials, and building interior materials, but also footwear and sports shoes. It is also widely available as a bottom adhesive and primer.

Claims (7)

  1. 塩素含量が１０～４０質量％の塩素化変性ポリオレフィン（A）、水（B）、及び酸（C）を含有する接着剤組成物。 An adhesive composition containing chlorinated modified polyolefin (A) having a chlorine content of 10 to 40% by mass, water (B) and acid (C).
  2. 塩素化変性ポリオレフィン（A）がα，β-不飽和カルボン酸及び/又はその酸無水物を合計０．０１～２０質量％の割合で含有することを特徴とする、請求項１に記載の接着剤組成物。 The adhesion according to claim 1, wherein the chlorinated modified polyolefin (A) contains α,β-unsaturated carboxylic acid and/or its acid anhydride in a total proportion of 0.01 to 20% by mass. agent composition.
  3. さらに乳化剤（D）を含有する請求項1または２に記載の接着剤組成物。 3. The adhesive composition according to claim 1, further comprising an emulsifier (D).
  4. さらに有機溶剤（E）を含有する請求項１～３のいずれかに記載の接着剤組成物。 4. The adhesive composition according to any one of claims 1 to 3, further comprising an organic solvent (E).
  5. 硬化剤の含有量が塩素化変性ポリオレフィン（A）に対して５質量%以下である請求項１～４のいずれかに記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 4, wherein the content of the curing agent is 5% by mass or less relative to the chlorinated modified polyolefin (A).
  6. エチレン-酢酸ビニル共重合体（EVA）基材と熱可塑性エラストマーまたはゴムからなる基材との接着に用いられる請求項１～５のいずれかに記載の接着剤組成物。 6. The adhesive composition according to any one of claims 1 to 5, which is used for bonding an ethylene-vinyl acetate copolymer (EVA) substrate and a thermoplastic elastomer or rubber substrate.
  7. エチレン-酢酸ビニル共重合体（EVA）基材、請求項１～６のいずれかに記載の接着剤組成物から得られる接着剤層及び、熱可塑性エラストマーまたはゴムからなる基材、の3層がこの順で積層された構造を有する積層体。 Three layers of an ethylene-vinyl acetate copolymer (EVA) substrate, an adhesive layer obtained from the adhesive composition according to any one of claims 1 to 6, and a substrate made of a thermoplastic elastomer or rubber A laminate having a structure laminated in this order.
PCT/JP2022/012057 2021-03-29 2022-03-16 Polyolefin adhesive composition and multilayer body WO2022209918A1 (en)

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JPS49116145A (en) * 1973-03-12 1974-11-06
JPH05214308A (en) * 1992-01-31 1993-08-24 Mitsui Petrochem Ind Ltd Water-dispersible adhesive
JPH10231402A (en) * 1997-02-20 1998-09-02 Nippon Paper Ind Co Ltd Aqueous dispersion and its production
WO2015079918A1 (en) * 2013-11-26 2015-06-04 東洋紡株式会社 Aqueous dispersion composition containing modified polyolefin
WO2020138117A1 (en) * 2018-12-27 2020-07-02 日本製紙株式会社 Chlorinated polyolefin resin composition and use thereof

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JP4774189B2 (en) 2003-06-04 2011-09-14 電気化学工業株式会社 Chloroprene-based graft adhesive composition and method for producing the same
JP2005290313A (en) 2004-04-05 2005-10-20 Mitsui Chemicals Inc Primer for bonding footwear part
JP2020122166A (en) 2020-05-14 2020-08-13 住友化学株式会社 Aqueous emulsion and coating film, cured product and laminate

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Publication number Priority date Publication date Assignee Title
JPS49116145A (en) * 1973-03-12 1974-11-06
JPH05214308A (en) * 1992-01-31 1993-08-24 Mitsui Petrochem Ind Ltd Water-dispersible adhesive
JPH10231402A (en) * 1997-02-20 1998-09-02 Nippon Paper Ind Co Ltd Aqueous dispersion and its production
WO2015079918A1 (en) * 2013-11-26 2015-06-04 東洋紡株式会社 Aqueous dispersion composition containing modified polyolefin
WO2020138117A1 (en) * 2018-12-27 2020-07-02 日本製紙株式会社 Chlorinated polyolefin resin composition and use thereof

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