WO2012090646A1 - 接着剤組成物及びそれを用いた熱融着性部材 - Google Patents
接着剤組成物及びそれを用いた熱融着性部材 Download PDFInfo
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- WO2012090646A1 WO2012090646A1 PCT/JP2011/077929 JP2011077929W WO2012090646A1 WO 2012090646 A1 WO2012090646 A1 WO 2012090646A1 JP 2011077929 W JP2011077929 W JP 2011077929W WO 2012090646 A1 WO2012090646 A1 WO 2012090646A1
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- polyolefin resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
- B32B15/085—Layered products comprising a layer of metal comprising metal 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 comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09J123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
Definitions
- the present invention relates to an adhesive composition and a heat-fusible member using the adhesive composition. More specifically, an adhesive composition that provides excellent adhesion, heat resistance at the bonded portion, and the like, and is useful for bonding a polyolefin resin molded body such as a polyolefin resin film and other members, and an aluminum foil using the adhesive composition
- the present invention relates to a heat-fusible member obtained by bonding a metal foil such as a heat-fusible resin film.
- Patent Document 1 discloses an adhesive composition for polyolefin sheets containing an acid-modified chlorinated polyolefin resin having a softening point of 70 ° C. to 100 ° C., a specific amount of blocked isocyanate, and an organic solvent.
- Patent Document 2 discloses an adhesive composition in which a component comprising a carboxylic acid-containing polyolefin resin, a carboxylic acid-containing epoxy resin, a polyisocyanate compound, and, if necessary, an epoxy resin is dissolved and dispersed in an organic solvent. Things are disclosed.
- the adhesive composition forms a composite as a result of being used to bond a plurality of members. And this composite is applied to uses, such as a sealing container which accommodates foodstuffs, a medicine, etc., a household miscellaneous goods.
- a sealing container which accommodates foodstuffs, a medicine, etc., a household miscellaneous goods.
- shape stability can be obtained.
- the composite is left in an automobile in a hot season, and so on. When the temperature becomes high, shape stability is not always obtained.
- An object of this invention is to provide the adhesive composition from which sufficient adhesive strength is acquired when it uses for adhesion
- Another object of the present invention is to provide an adhesive composition excellent in heat resistance (heat resistant adhesiveness) and the like in an adhesive part in a joined body of a polyolefin resin molded body and another member. Furthermore, the present invention aims to provide these with an adhesive composition, the heat-welding member and heat-fusible resin film such as a metal foil and a polyolefin resin film such as an aluminum foil, which are joined To do.
- the present inventors have obtained excellent adhesiveness by using a composition containing a carboxyl group-containing polyolefin resin having specific physical properties and a polyfunctional isocyanate compound.
- a polyolefin resin having two types of carboxyl groups different from each other and a polyfunctional isocyanate compound it has been found that excellent adhesiveness and heat resistance (heat-resistant adhesiveness) at the bonded portion can be obtained. It came to complete. That is, the present invention is as follows. 1. Containing an organic solvent, a polyolefin resin (A) having a carboxyl group dissolved in the organic solvent and having a melt flow rate measured at 130 ° C.
- the mass ratio of the polyolefin resin (A) and the polyolefin resin (B) is 1 to 70 mass% when the total of the polyolefin resin (A) and the polyolefin resin (B) is 100 mass%, and 6.
- An adhesive layer adhesive composition obtained by curing according to any one of the above 1 to 6, and a metal layer bonded to one side of the adhesive layer is bonded to the other surface side of the adhesive layer And a heat-fusible resin layer.
- the adhesive composition of the present invention is suitable for adhesion between a polyolefin resin molded body and other members (metal member, resin member, etc.), and not only polyolefin resin molded bodies such as polyolefin resin films but also polyolefins. It can also be used for adhesion between a resin film and a metal foil made of aluminum or the like, adhesion between a polyolefin resin film and a metal layer in a composite film including a resin layer and a metal layer, and the like.
- the adhesive layer exhibits high adhesive strength at room temperature (25 ° C.).
- the adhesive layer is bonded at a temperature of about 60 ° C. to 80 ° C. Excellent heat resistance (heat resistant adhesiveness) and the like in the part can be obtained.
- the heat-fusible member using the adhesive composition of the present invention is suitable for forming a heat-fusible composite product having excellent heat resistance (heat-resistant adhesiveness), it is hermetically sealed to contain food, medicine, etc. When the container is used as a heat fusion composite product, the contents can be prevented from being altered while the structure is maintained.
- the adhesive composition of the present invention is an organic solvent, dissolved in the organic solvent, and having a melt flow rate (hereinafter referred to as “MFR”) measured at 130 ° C. of 5 to 40 g / 10 min. It contains a polyolefin resin (A) having a carboxyl group and a polyfunctional isocyanate compound.
- the adhesive composition of the present invention can further contain a polyolefin resin (B) having a carboxyl group having a melting point of 120 ° C. to 170 ° C., which is dispersed in an organic solvent.
- the carboxyl group content in the polyolefin resin is obtained as a value per gram of resin by dividing the acid content in the polyolefin resin calculated from the calibration curve created using the infrared spectrum by the formula amount (45) of the carboxyl group. Can do.
- the melting point of the polyolefin resin was measured according to JIS K 7121-1987 “Method for measuring transition temperature of plastic”.
- the adhesive composition containing no polyolefin resin (B) and containing the polyolefin resin (A) is referred to as “adhesive composition of the first embodiment”, and the polyolefin resin (A) and the polyolefin resin.
- the adhesive composition containing both (B) is referred to as “the adhesive composition of the second aspect”.
- the adhesive composition according to the first aspect is a composition containing the polyolefin resin (A) dissolved in an organic solvent.
- the adhesive composition of the second aspect includes at least the polyolefin resin (A) dissolved in an organic solvent, and the polyolefin resin (B) may or may not be dissolved in the organic solvent. A good composition.
- the polyolefin resin (A) is not particularly limited as long as it has a carboxyl group and a melt flow rate (MFR) measured at 130 ° C. of 5 to 40 g / 10 min.
- a modified polyolefin resin (A1) obtained by graft polymerization of an ethylenically unsaturated carboxylic acid or an anhydride thereof to an unmodified polyolefin resin, and an olefin monomer and an ethylenically unsaturated carboxylic acid are polymerized.
- Such a polyolefin resin (A) can be produced by a known method, and for example, can be produced by a method described in International Publication WO2005 / 82963 and International Publication WO2008 / 13085.
- Examples of the unmodified polyolefin resin for forming the modified polyolefin resin (A1) include homopolymers or copolymers of olefin monomers such as ethylene, propylene, and 1-butene, these olefin monomers, dicyclopentadiene, 4 -A copolymer with methylpentene-1, vinyl acetate or the like can be used.
- Preferred unmodified polyolefin resins are propylene homopolymers, copolymers of propylene and ethylene, and copolymers of propylene and 1-butene.
- the content of propylene monomer units when the total amount of all the monomer units constituting the copolymer is 100 wt%, preferably 50 to 90 mass% is there.
- the ethylenically unsaturated carboxylic acid for forming the modified polyolefin resin (A1) or copolymer resin (A2) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, and citraconic acid. , 5-norbornene-2,3-dicarboxylic acid and the like. These ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more.
- the polyolefin resin (A) is preferably a modified polyolefin resin (A1), more preferably a resin obtained by modifying a propylene homopolymer or a copolymer of propylene and ethylene, particularly preferably a propylene homopolymer. Resin.
- the MFR of the polyolefin resin (A) is 5 to 40 g / 10 min, preferably 5 to 30 g / 10 min, from the viewpoint of adhesiveness.
- the MFR of the polyolefin resin (A) is obtained by using an unmodified propylene copolymer resin body prepared by copolymerizing propylene, ethylene, 1-butene, etc. at an appropriate ratio to adjust the MFR as an acid-modified raw material. Can be adjusted.
- the carboxyl group content in the polyolefin resin (A) is preferably from 0.10 to 2.0 mmol, particularly preferably from 0.15 to 1.0 mmol, per 1 g of the polyolefin resin (A), from the viewpoint of adhesiveness. It is.
- the content of the carboxyl group is less than 0.10 mmol, for example, the adhesion to an adherend containing a highly polar substance such as aluminum on the surface may be lowered.
- the carboxyl group content exceeds 2.0 mmol, the adhesion to an adherend containing a low-polarity substance such as polyolefin on its surface may be lowered.
- the adherend contains aluminum or the like, the adhesive composition may corrode the adherend.
- the melting point of the polyolefin resin (A) is preferably 50 ° C. to 90 ° C., more preferably 60 ° C. to 85 ° C. If the melting point is less than 50 ° C., the adhesive strength of the bonded portion at a temperature of 80 ° C. or higher may be reduced. On the other hand, when the melting point exceeds 90 ° C., the viscosity of the adhesive composition increases, and the storage stability may decrease.
- the polyolefin resin (A) having a preferred melting point can be obtained, for example, by adjusting the production conditions of the unmodified polyolefin resin or the copolymer resin (A2) before producing the modified polyolefin resin (A1). it can.
- the polyolefin resin (A) is dissolved in an organic solvent. That is, this organic solvent is a substance that dissolves the polyolefin resin (A).
- the organic solvent that dissolves the polyolefin resin (A) is preferably an organic solvent that is easily volatilized and removed by heating the adhesive composition. Examples of such organic solvents include aromatic organic solvents such as toluene and xylene, aliphatic organic solvents such as n-hexane, alicyclic organic solvents such as cyclohexane and methylcyclohexane, and ketone organic solvents such as methyl ethyl ketone. Etc. can be used. These organic solvents may be used alone or in combination of two or more.
- the mass ratio of the organic solvent and the polyolefin resin (A) is not particularly limited. This mass ratio can be set according to the type of organic solvent and polyolefin resin.
- the content of the polyolefin resin (A), when the sum of the organic solvent and the polyolefin resin (A) is 100 mass%, preferably 5 to 25 mass%, particularly preferably 10 to 20 mass%. If it is such content, it will be easy to apply
- a film such as polyethylene terephthalate with a bar coater.
- Engineering to form a coating film having a thickness of 0.99 ⁇ 200 [mu] m the surface roughness of the film obtained after drying (thickness becomes 30 ⁇ 40 [mu] m) can be determined by at 50 ⁇ m or less.
- the surface roughness of the film can be measured by a stylus type surface roughness meter defined in JIS B0651.
- the polyfunctional isocyanate compound has an action of reacting with a carboxyl group of a polyolefin resin and curing to form an adhesive.
- This polyfunctional isocyanate compound is not particularly limited as long as it has two or more isocyanate groups in one molecule, and various aromatic, aliphatic, and alicyclic isocyanate compounds, A modified product of the isocyanate compound can be used.
- diisocyanate compounds such as toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, and modified products obtained by adduct modification of these compounds with isocyanurate-modified, burette-modified, trimethylolpropane, and the like, isocyanates
- isocyanates Are blocked isocyanates which are stabilized by masking with a blocking agent.
- These polyfunctional isocyanate compounds may be used alone or in combination of two or more. In the present invention, a compound having 3 or more isocyanate groups in one molecule is preferable. In the adhesive composition of the present invention, this polyfunctional isocyanate compound is usually dissolved in an organic solvent.
- the mass ratio of the polyolefin resin (A) and the polyfunctional isocyanate compound in the adhesive composition of the first embodiment is not particularly limited, but the isocyanate group (NCO) and the polyolefin resin (A) of the polyfunctional isocyanate compound are
- the equivalent ratio (NCO / OH) with the hydroxyl group (OH) constituting the carboxyl group having is preferably 0.01 to 12.0, more preferably 0.04 to 12.0, still more preferably 0.1 to Both are contained so as to be 12.0, particularly preferably 0.1 to 9.0.
- the equivalent ratio is 0.01 to 12.0, it is possible to obtain an adhesive composition particularly excellent in initial adhesiveness, and has a sufficient crosslinking density and a cured product excellent in flexibility and the like. (Adhesive) can be formed.
- the adhesive composition of the present invention may further contain a polyolefin resin (B) having a carboxyl group and a melting point of 120 ° C. to 170 ° C. (adhesive composition of the second embodiment).
- a polyolefin resin (B) having a carboxyl group and a melting point of 120 ° C. to 170 ° C.
- the polyolefin resin (B) the resins exemplified in the description of the polyolefin resin (A) can be used, and a modified polyolefin resin obtained by graft-polymerizing an ethylenically unsaturated carboxylic acid or its anhydride to an unmodified polyolefin resin.
- a copolymer resin obtained by polymerizing an olefin monomer and an ethylenically unsaturated carboxylic acid.
- unmodified polyolefin resin and the ethylenically unsaturated carboxylic acid when producing these polyolefin resins (B) the same materials as those exemplified as the raw materials for producing the polyolefin resin (A) can be used.
- Preferred unmodified polyolefin resins are a homopolymer of propylene, a copolymer of propylene and ethylene, and a copolymer of propylene and 1-butene.
- the unmodified polyolefin resin is a copolymer
- the content of propylene monomer units when the total amount of all the monomer units constituting the copolymer is 100 wt%, preferably 50 to 90 mass% is there.
- polyolefin resin (B) since the high heat-resistant adhesiveness in the junction part of two members is obtained at the high temperature to about 80 degreeC, and the adhesiveness with respect to a low polarity adherend is improved, propylene is independent.
- a polymer a resin obtained by modifying a copolymer of propylene and ethylene or a copolymer of propylene and 1-butene is preferable.
- the melting point of the polyolefin resin (B) is preferably 120 ° C. to 170 ° C., more preferably 130 ° C. to 160 ° C.
- the adhesive strength at the bonding portion between the two members can be improved at a high temperature of about 80 ° C.
- the melting point of the polyolefin resin (B) is more than 170 ° C., there are cases where bonding of the two members defect occurs, also, it is necessary to increase the bonding temperature during bonding, may workability is lowered is there.
- Polyolefin resin having a preferable melting point (B) for example, it can be obtained by adjusting the previous production conditions unmodified polyolefin resin, or the production conditions of the copolymer resin to produce a modified polyolefin resin.
- the carboxyl group content in the polyolefin resin (B) is preferably 0.01 to 2.0 mmol, particularly preferably 0.1 to 1.mol per 1 g of the polyolefin resin (B) from the viewpoint of heat-resistant adhesion. 0 mmol.
- the content of the carboxyl group is less than 0.01 mmol, for example, the adhesion to an adherend containing a highly polar substance such as aluminum on the surface may decrease.
- the carboxyl group content exceeds 2.0 mmol, the adhesion to an adherend containing a low-polarity substance such as polyolefin on its surface may be lowered.
- the adherend contains aluminum or the like, the adhesive composition may corrode the adherend.
- the polyolefin resin (B) in the adhesive composition of the second aspect may be dissolved in an organic solvent or insoluble, like the polyolefin resin (A).
- the polyolefin resin (B) may or may not dissolve in the organic solvent depending on the temperature of the organic solvent or the production method of the polyolefin resin (B).
- the polyolefin resin (B) is preferably dispersed without being dissolved in an organic solvent.
- the shape of the polyolefin resin (B) is not particularly limited, and may be a spherical shape, a spindle shape, a dish shape, a linear shape, a tuft shape, an indefinite shape, or the like.
- the average particle diameter (D50) of the polyolefin resin (B) is preferably 1 to 50 ⁇ m, more preferably 5 to 20 ⁇ m, from the viewpoint of heat-resistant adhesion.
- the average particle size (D50) of is a volume-based average particle size and means, for example, the particle size at an integrated value of 50% in the particle size distribution obtained by “Coulter Counter” manufactured by Beckman Coulter.
- the mass ratio of the polyolefin resin (A) and the polyolefin resin (B) is preferably 1 to 70% by mass and 100% by mass, respectively, 99 to 30% by mass, more preferably 3 to 50% by mass and 97 to 50% by mass, still more preferably 5 to 40% by mass and 95 to 60% by mass.
- the mass ratio of the polyolefin resin (A) is less than 1% by mass, the adhesive strength at room temperature (25 ° C.) may be insufficient.
- the mass ratio of the polyolefin resin (A) exceeds 70% by mass, the hot adhesive strength may decrease, and the heat resistant adhesiveness may decrease.
- the mass ratio between the total amount of the polyolefin resin (A) and the polyolefin resin (B) and the polyfunctional isocyanate compound in the adhesive composition of the second aspect is not particularly limited, but the isocyanate group (NCO) of the polyfunctional isocyanate compound is not limited.
- the hydroxyl groups (OH) constituting the carboxyl groups of the polyolefin resins (A) and (B) are preferably 0.01 to 12.0, more preferably 0.00. Both are contained so as to be 04 to 12.0, more preferably 0.1 to 12.0, particularly preferably 0.1 to 9.0.
- the equivalent ratio is 0.01 to 12.0, it is possible to obtain an adhesive composition particularly excellent in initial adhesiveness, and has a sufficient crosslinking density and a cured product excellent in flexibility and the like. (Adhesive) can be formed.
- the mass ratio of the organic solvent to the polyolefin resin (A) and the polyolefin resin (B) is not particularly limited. This mass ratio can be set according to the type of organic solvent and polyolefin resin.
- the total amount of the polyolefin resin (A) and the polyolefin resin (B) is preferably 5 to 25% by mass when the total of the organic solvent, the polyolefin resin (A) and the polyolefin resin (B) is 100% by mass, Particularly preferred is 10 to 20% by mass. If it is such content, it will be easy to apply
- the polyolefin resin (B) is dissolved, the solution of the polyolefin resin (A) and the polyolefin resin (B) is applied with a bar coater and can be determined in the same manner as described above.
- the adhesive composition of the present invention includes, in addition to polyolefin resins and polyfunctional isocyanate compounds, reaction accelerators, tackifier resins, non-acid-modified thermoplastic elastomers, non-acid-modified thermoplastic resins, plasticizers, etc. Can also be included.
- the reaction accelerator has an action of promoting the reaction between the polyolefin resin and the polyfunctional isocyanate compound.
- the reaction accelerator include organotin compounds and tertiary amines.
- the organotin compound include dioctyltin fatty acids having 3 to 10 carbon atoms in the alkyl group such as dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, and dioctyltin dimaleate. These compounds may be used alone or in combination of two or more.
- Tertiary amines include tetraalkylethylenediamines such as tetramethylethylenediamine; N, N′-dialkylbenzylamines such as dimethylbenzylamine; triethylenediamine, pentamethyldiethylenetriamine, N-ethylmorphine, N-methylmorphylline. 1-methyl-4-dimethylamine ethyl piperazine and the like. These compounds may be used alone or in combination of two or more.
- an organotin compound and a tertiary amine can be used in combination.
- the content of the reaction accelerator is preferably 0.01 to 1% by mass with respect to the entire resin component.
- tackifier examples include polyterpene resins, rosin resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, and hydrogenated petroleum resins. These tackifiers may be used alone or in combination of two or more.
- examples of the polyterpene resin include ⁇ -pinene polymers, ⁇ -pinene polymers, and copolymers of these with phenol or bisphenol A.
- the rosin resin include natural rosin, polymerized rosin, and ester derivatives thereof.
- Aliphatic petroleum resins, also referred to as C 5 resins are generally resin synthesized from C 5 fraction of oil.
- An alicyclic petroleum resin is also referred to as a C 9 resin, and is generally a resin synthesized from a C 9 fraction of petroleum.
- the copolymerized petroleum resin is also referred to as a C 5 / C 9 copolymer resin.
- the hydrogenated hydrocarbon resin is generally produced by hydrogenation of the various petroleum resins described above.
- thermoplastic elastomer examples include SEBS and SEPS.
- the thermoplastic resin not modified with acid is preferably an ethylene-vinyl acetate copolymer resin, an ethylene-ethyl acrylate copolymer resin, a wax, or the like.
- the plasticizer is preferably a liquid rubber such as polyisoprene or polybutene, or process oil.
- the contents of the tackifier, the thermoplastic elastomer and the like are preferably 70% by mass or less, more preferably 60 to 10% by mass, when the adhesive composition of the present invention containing them is 100% by mass. %, More preferably 50 to 20% by mass. Thereby, it can be set as the adhesive composition which has sufficient adhesiveness, heat-resistant adhesiveness, etc.
- the method for producing the adhesive composition of the first aspect preferably comprises mixing a solution obtained by dissolving the polyolefin resin (A) in an organic solvent and other components excluding the polyfunctional isocyanate compound. Then, it is the method of mixing the obtained mixture and a polyfunctional isocyanate compound.
- the temperature at the time of mixing is usually 40 ° C. or lower, preferably 10 ° C. to 30 ° C.
- polyfunctional isocyanate compound a commercially available product can be used.
- a commercially available product modified with isocyanurate “Coronate HX” (trade name) manufactured by Nippon Polyurethane Industry Co., Ltd., “Duranate TPA-100” manufactured by Asahi Kasei Chemicals Corporation ( Product name), “Takenate D-170N” (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd., and the like.
- Examples of commercially available burette-modified products include “Takenate D-165NN” (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.
- the method for producing the adhesive composition of the second aspect preferably comprises a solution obtained by dissolving the polyolefin resin (A) in the organic solvent (S-1) and the polyolefin resin (B) as the organic solvent.
- This is a method of mixing a solution obtained by dissolving or dispersing in (S-2) with other components excluding the polyfunctional isocyanate compound, and then mixing the resulting mixture with the polyfunctional isocyanate compound.
- the temperature at the time of mixing is usually 40 ° C. or lower, preferably 10 ° C. to 30 ° C.
- the types of organic solvent (S-1) and organic solvent (S-2) may be the same or different.
- a method for preparing a dispersion of the polyolefin resin (B) a method in which the polyolefin resin (B) insoluble in the organic solvent (S-2) is physically pulverized and dispersed in the organic solvent (S-2); The polyolefin resin (B) dissolved in the organic solvent (S-2) is dissolved in the organic solvent (S-2) when heated, and then cooled to cool the polyolefin resin (B) in the organic solvent (S-2). And a method of precipitating the polyolefin resin (B) by adding a poor solvent to the solution of the polyolefin resin (B) using a good solvent.
- the polyolefin resin (B) is usually an organic solvent ((S-1) and (S-2)). Without being dissolved in the mixture).
- the coating film is dried and the organic solvent is volatilized to produce a dried coating film, that is, a cured product.
- the drying temperature of the coating film is not particularly limited, and is preferably 30 ° C. to 100 ° C. from the viewpoint of workability.
- the dried coating film is a reaction product of the polyolefin resin (A) or the polyolefin resins (A) and (B) and the polyfunctional isocyanate, that is, the carboxyl group in the polyolefin resin and the isocyanate group in the polyfunctional isocyanate.
- the reaction product containing the compound obtained by the reaction acts as an adhesive for bonding the two members. In order to obtain strong adhesion between the two members, a method such as pressure bonding at a temperature of 80 ° C. or higher can be applied.
- the heat-fusible member of the present invention is bonded to the adhesive layer formed by curing the adhesive composition of the present invention, the metal layer bonded to one side of the adhesive layer, and the other side of the adhesive layer.
- a heat-fusible resin layer A schematic view of the heat-fusible member of the present invention is shown in FIGS. That is, the heat-fusible member 1 of FIG. 1 is provided with the heat-fusible resin layer 11, the adhesive bond layer 12, and the metal layer 13 in order. Moreover, the heat-fusible member 1 of FIG. 2 is equipped with the heat-fusible resin layer 11, the adhesive bond layer 12, the metal layer 13, and the other layer 14 in order.
- the shape of the heat-fusible member of the present invention is appropriately selected depending on the application and the like, and as shown in FIGS. 1 and 2, it may be a sheet shape, a linear shape, a dot shape, a lattice shape. Or a checkered pattern.
- the “heat-fusible resin layer” is a layer containing a resin that is melted by heat and can fuse the material constituting the layer on one side and the material constituting the layer on the other side.
- the heat-fusible resin layer is preferably a layer containing a resin that melts at a temperature of 50 ° C. to 200 ° C.
- the resin having such properties include polyolefin resins, polyamide resins, and polyester resins. Among these, polyolefin resin is preferable because it can be heat-sealed with sufficient strength. Furthermore, polypropylene is preferable as the polyolefin resin.
- the above heat-fusible resin layer is made of a lubricant, a filler, a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a colorant, a dispersant, an adhesion-imparting agent, etc., if necessary. It may be a layer containing an additive.
- the thickness of the heat-fusible resin layer is not particularly limited depending on the resin material and the like, but is usually 10 to 200 ⁇ m.
- the thickness is preferably 10 to 200 ⁇ m, more preferably 20 to 100 ⁇ m, and still more preferably 60 to 100 ⁇ m.
- the thickness of the layer containing unstretched polypropylene is 10 to 200 ⁇ m, it is not easily damaged, and a highly heat-sealed composite product such as a sealed container having high durability can be obtained.
- the “adhesive layer” is a layer formed by curing the adhesive composition described above, that is, a reaction product of a polyolefin resin (A) and a polyfunctional isocyanate compound; a polyolefin resin ( A), a reaction product of a polyfunctional isocyanate compound, and a mixture of a polyolefin resin (B) and a reaction product of a polyfunctional isocyanate compound; or a polyolefin resin (A) and a polyolefin resin (B) It is a layer formed of a cured product containing both and a reaction product of a polyfunctional isocyanate compound.
- the thickness of the adhesive layer is not particularly limited depending on the material, use of the heat-fusible member, etc., but is preferably 1 to 20 ⁇ m, particularly preferably 2 to 10 ⁇ m. If the thickness of the adhesive layer is 1 to 20 ⁇ m, the heat-fusible member can be easily processed, for example, when it is in the form of a sheet.
- the “metal layer” is a layer containing a metal (including an alloy).
- the metal or alloy is not particularly limited, but aluminum is usually used because of excellent workability.
- the thickness of the metal layer is not particularly limited depending on the material and the use of the heat-fusible member.
- the metal layer is made of, for example, aluminum, it is preferably 20 to 100 ⁇ m, particularly preferably 20 to 80 ⁇ m, and further preferably 30 to 60 ⁇ m.
- the heat-fusible member of the present invention includes a metal layer
- another layer 14 can be provided on the surface of the metal layer 13 as shown in FIG.
- the material constituting the other layer preferably contains a resin from the viewpoint of protecting the metal layer. That is, the other layer is preferably a resin layer.
- This resin is not particularly limited, and may be a polyamide resin, a polyester resin, or the like.
- the transparency of the resin layer is not particularly limited, but when this resin layer is transparent or translucent, an excellent appearance can be obtained when a heat-sealed composite product is used as a sealed container or the like.
- the thickness of the other layer is not particularly limited, and is preferably 30 to 60 ⁇ m, particularly preferably 30 to 50 ⁇ m.
- the manufacturing method of the heat-fusible member shown in FIG. 1 is as follows. (1) The adhesive composition is applied to the surface of a metal foil or metal film for forming the metal layer 13, and then the organic solvent in the composition is removed to form the adhesive layer 12. A method in which a heat-fusible resin layer 11-forming resin film (heat-fusible resin film) is brought into contact with the surface on which the adhesive layer 12 is formed, and is bonded while heating. (2) The adhesive composition is applied to the surface of the resin film for forming the heat-fusible resin layer 11 (heat-fusible resin film), and then the organic solvent in the composition is removed to remove the adhesive layer 12. Then, a metal foil or the like for forming the metal layer 13 is brought into contact with the surface on which the adhesive layer 12 has been formed, and is subjected to pressure bonding while heating.
- the manufacturing method of the heat-fusible member shown by FIG. 2 is as follows. (3) the adhesive composition, and a resin layer constituting the other layers 14, this on one side of the resin layer, coated on the surface of the metal layer 13 in the composite film having a metal layer 13 formed by vapor deposition or the like Thereafter, the organic solvent in the composition is removed to form the adhesive layer 12, and then the surface on which the adhesive layer 12 is formed and the resin film for forming the heat-fusible resin layer 11 (heat-sealing) A pressure-sensitive adhesive film is heated and brought into contact.
- the adhesive composition is applied to the surface of the resin film for forming the heat-fusible resin layer 11 (heat-fusible resin film), and then the organic solvent in the composition is removed to remove the adhesive layer 12. It is formed and then the composite film having a surface on which the adhesive layer 12 is formed, and a resin layer constituting the other layers 14, on one side of the resin layer, a metal layer 13 formed by vapor deposition or the like A method in which the surface on which the metal layer 13 is formed is brought into contact with the metal layer 13 and heated and heated. (5) A method of extruding another layer 14 forming film on the surface of the metal layer 13 in the laminate obtained by the method (1) or (2).
- Adhesive composition the metal layer forming material such as a metal foil, or, is often applied to the surface of the metal layer in the composite film comprising a metal layer and other layers (the resin layer) is not particularly limited.
- a metal foil it is preferable to use an aluminum foil having a thickness of 20 to 100 ⁇ m. Thereby, the heat-fusible member in which damage is suppressed can be easily formed.
- a metal layer contains aluminum and another layer (resin layer) contains a polyamide resin, a polyester resin, etc. Further, when the heat-fusible member shown in FIG.
- a film containing As a heat-fusible resin film, a polyolefin resin film, a polyamide resin film, a polyester resin film, or the like can be used. These resin films can be films obtained by film forming methods such as an extrusion method, a cast molding method, a T-die method, and an inflation method.
- the thickness of the heat-fusible resin film is usually 10 to 200 ⁇ m.
- a polyolefin resin film is preferable because non-stretching is preferable because heat fusion for completing a heat-fusible member and heat fusion when producing a heat-fusion composite product can be easily performed.
- Polypropylene film is particularly preferred. When this unstretched polypropylene film is used, the preferred thickness is 10 to 200 ⁇ m, more preferably 20 to 100 ⁇ m, and still more preferably 60 to 100 ⁇ m.
- the adhesive composition can be conventionally applied by a known method, for example, using a bar coater, a gravure coater or the like.
- the thickness of the coating film and its drying temperature are not particularly limited.
- the drying temperature of the coating film is preferably 30 ° C. to 100 ° C.
- the dried coating film since the dried coating film generally has adhesiveness and adhesiveness, it is possible to bond two members without heating, but when producing the heat-fusible member of the present invention. Is subjected to pressure bonding or the like while being heated to a temperature in consideration of the melting point and melt viscosity of the resin component based on the polyolefin resin (A) or the polyolefin resins (A) and (B).
- the heating conditions and pressure bonding conditions for completing the heat-fusible member are not particularly limited, and are set according to the material of the metal foil, the material of the heat-fusible resin film, the melting temperature, the composition of the adhesive layer, and the like. It is preferable.
- heat-fusible member of the present invention when the heat-fusible resin layer contains unstretched polypropylene, a heat-fusible composite product such as a sealing container that is not easily damaged and has excellent durability can be obtained. .
- Viscosity Viscosity was measured using a Tokimec type B rotational viscometer at a temperature of 25 ° C. ⁇ 0.5 ° C. 1-5. Peeling adhesive strength (1) Preparation of test piece The adhesive composition was applied to a 40 ⁇ m thick aluminum foil (100 mm ⁇ 200 mm) whose surface was subjected to chemical conversion treatment with a bar coater, and then at 80 ° C. for 60 seconds and further for 180 seconds. The organic solvent contained in the adhesive composition was removed by drying at 20 ° C. for 20 seconds to form an adhesive layer having a thickness of 4 ⁇ m.
- an 80 ⁇ m-thick unstretched polypropylene film (hereinafter abbreviated as “CPP”) is bonded to the surface of the adhesive layer as a heat-fusible resin film, and the surface of the aluminum foil using a thermal inclination tester. From which pressure was applied.
- the bonding conditions at this time were a temperature of 180 ° C., a pressure of 0.3 MPa, and a pressure bonding time of 2 seconds.
- this integrated product was housed in a hot-air circulating oven adjusted to 40 ° C. for 3 days to obtain a test piece.
- the T peel strength measurement test piece was cut into a 15mm width were measured T peel strength between the aluminum foil and the CPP to (N / 15mm).
- the measurement conditions are a temperature of 25 ° C. and 80 ° C., and a tensile speed of 100 mm / min.
- the polyolefin resin (a1) had an MFR of 12 g / 10 min, a melting point of 85 ° C., an acid value of 20 mg KOH / g, and a carboxyl group content of 0.4 mmol per 1 g of resin.
- a stirrer, a thermometer, and a condenser were attached to a 1 L three-necked flask, charged with 680 g of toluene and 170 g of methyl ethyl ketone (hereinafter referred to as “MEK”), and heated to 60 ° C. while stirring.
- 150 g of the polyolefin resin (a1) was supplied to this and stirred for about 1 hour. After dissolving the resin, it was cooled to room temperature to obtain a solution having a solid content of 15%. This solution is designated as “PP solution a1”.
- Synthesis Example 1-2 A polyolefin resin (a2) was synthesized in the same manner as in Synthesis Example 1-1 using a propylene random copolymer having an MFR of 20 g / 10 min.
- the polyolefin resin (a2) had an MFR of 23 g / 10 min, a melting point of 85 ° C., an acid value of 20 mg KOH / g, and a carboxyl group content of 0.4 mmol per 1 g of resin. Thereafter, the resin was dissolved in the same manner as in Synthesis Example 1-1 to obtain “PP solution a2”.
- Synthesis Example 1-3 A polyolefin resin (a3) was synthesized in the same manner as in Synthesis Example 1-1, using a propylene random copolymer having an MFR of 25 g / 10 min.
- the polyolefin resin (a3) had an MFR of 28 g / 10 min, a melting point of 84 ° C., an acid value of 20 mg KOH / g, and a carboxyl group content of 0.4 mmol per 1 g of resin. Thereafter, the resin was dissolved in the same manner as in Synthesis Example 1-1 to obtain “PP solution a3”.
- Synthesis Example 1-4 A polyolefin resin (x1) was synthesized in the same manner as in Synthesis Example 1-1, using a propylene random copolymer having an MFR of 44 g / 10 min.
- the polyolefin resin (x1) had an MFR of 47 g / 10 min, a melting point of 84 ° C., an acid value of 20 mg KOH / g, and a carboxyl group content of 0.4 mmol per 1 g of resin. Thereafter, the resin was dissolved in the same manner as in Synthesis Example 1-1 to obtain “PP solution x1”.
- Synthesis Example 1-5 A polyolefin resin (x2) was synthesized in the same manner as in Synthesis Example 1-1 using a propylene random copolymer having an MFR of 90 g / 10 min.
- the polyolefin resin (x2) had an MFR of 94 g / 10 min, a melting point of 83 ° C., an acid value of 20 mg KOH / g, and a carboxyl group content of 0.4 mmol per 1 g of resin. Thereafter, the resin was dissolved in the same manner as in Synthesis Example 1-1 to obtain “PP solution x2”.
- the modified polymer had a maleic anhydride grafting amount of 2.8% by mass, a melting point of 156 ° C., an acid value of 32 mgKOH / g, and a carboxyl group content of 0.6 mmol per 1 g of resin.
- 15 parts by mass of this modified copolymer and 85 parts by mass of toluene were placed in an autoclave equipped with a stirrer and heated to 130 ° C. to completely dissolve the resin.
- the temperature was lowered to 90 ° C. at a cooling rate of 25 ° C./hour with stirring, and then cooled to 60 ° C. at a cooling rate of 5 ° C./hour.
- the temperature was lowered to 30 ° C. at a cooling rate of 20 ° C./hour to obtain a milky white uniform dispersion having a solid content of 15%.
- D50 average particle diameter of the dispersion (resin particles) was measured, it was 11.0 ⁇ m. This dispersion is designated as “PP dispersion b1”.
- Synthesis Example 2-2 Of propylene units 95.7 mol% of ethylene units 4.3 mol% propylene - ethylene copolymer (melting point: 140 ° C.) 100 parts by mass of toluene 435 parts by mass, the internal volume 1.5L equipped with a stirrer was attached In an autoclave and heated to 140 ° C. with stirring to dissolve completely. While maintaining this solution at 140 ° C., 16 parts by mass of maleic anhydride and 1.5 parts by mass of dicumyl peroxide were added dropwise over 4 hours with stirring, and after completion of the addition, further at 140 ° C. for 1 hour. Stirring and post-reaction were performed to obtain a modified polymer.
- the modified copolymer had a maleic anhydride grafting amount of 2.6% by mass, a melting point of 136 ° C., an acid value of 30 mgKOH / g, and a carboxyl group content of 0.5 mmol per 1 g of resin.
- 15 parts by mass of this modified copolymer, 70 parts by mass of toluene and 15 parts by mass of MEK were placed in an autoclave equipped with a stirrer and heated to 130 ° C. to completely dissolve the resin.
- the temperature was lowered to 90 ° C. at a cooling rate of 25 ° C./hour with stirring, and then cooled to 60 ° C. at a cooling rate of 5 ° C./hour.
- the temperature was lowered to 30 ° C. at a cooling rate of 20 ° C./hour to obtain a milky white uniform dispersion having a solid content of 15%. It was 10.3 micrometer when the average particle diameter (D50) of the dispersion (resin particle) was measured. This dispersion is designated as “PP dispersion b2”.
- Synthesis Example 2-3 100 parts by mass of a propylene-butene copolymer (melting point: 117 ° C.) composed of 82 mol% of propylene units and 18 mol% of butene units and 435 parts by mass of toluene are placed in an autoclave having an internal volume of 1.5 L equipped with a stirrer. While stirring, the temperature was raised to 140 ° C. to completely dissolve. While maintaining this solution at 140 ° C., 16 parts by mass of maleic anhydride and 1.5 parts by mass of dicumyl peroxide were added dropwise over 4 hours with stirring, and after completion of the addition, further at 140 ° C. for 1 hour. Stirring and post-reaction were performed to obtain a modified polymer.
- a propylene-butene copolymer melting point: 117 ° C.
- the solution was cooled to room temperature, and acetone was added to the solution to precipitate a modified copolymer.
- the precipitated modified copolymer was repeatedly washed with acetone and then dried to recover the modified polymer.
- the graft amount of maleic anhydride of this modified copolymer was 2.4% by mass, the melting point was 113 ° C., the acid value was 27 mgKOH / g, and the carboxyl group content was 0.5 mmol per 1 g of resin.
- 15 parts by mass of this modified copolymer, 17 parts by mass of toluene and 68 parts by mass of MEK were placed in an autoclave equipped with a stirrer and heated to 130 ° C. to completely dissolve the resin.
- the temperature was lowered to 90 ° C. at a cooling rate of 25 ° C./hour with stirring, and then cooled to 60 ° C. at a cooling rate of 5 ° C./hour.
- the temperature was lowered to 30 ° C. at a cooling rate of 20 ° C./hour to obtain a milky white uniform dispersion having a solid content of 15%. It was 11.2 micrometers when the average particle diameter (D50) of the dispersion (resin particle) was measured. This dispersion is designated as “PP dispersion y1”.
- Synthesis Example 2-4 100 parts by mass of a propylene-butene copolymer (melting point: 110 ° C.) composed of 74 mol% of propylene units and 26 mol% of butene units and 435 parts by mass of toluene are placed in an autoclave having an internal volume of 1.5 L equipped with a stirrer. While stirring, the temperature was raised to 140 ° C. to completely dissolve. While maintaining this solution at 140 ° C., 16 parts by mass of maleic anhydride and 1.5 parts by mass of dicumyl peroxide were added dropwise over 4 hours with stirring, and after completion of the addition, further at 140 ° C. for 1 hour. Stirring and post-reaction were performed to obtain a modified polymer.
- a propylene-butene copolymer melting point: 110 ° C.
- the modified copolymer had a maleic anhydride grafting amount of 2.6% by mass, a melting point of 107 ° C., an acid value of 30 mgKOH / g, and a carboxyl group content of 0.5 mmol per 1 g of resin.
- 15 parts by mass of this modified copolymer, 17 parts by mass of toluene and 68 parts by mass of MEK were placed in an autoclave equipped with a stirrer and heated to 130 ° C.
- Example 1 Production and Evaluation of Adhesive Composition 10 g of “PP solution a1” and 190 g of “PP dispersion b1” were charged into a 300-ml flask equipped with a condenser and a stirrer, and stirred at room temperature for 10 minutes to obtain a mixed solution. Thereafter, 0.15 mg of dibutyltin dilaurate (hereinafter referred to as “DBTL”) is added to the mixed solution and further mixed, and the viscosity at 25 ° C. is 43 mPa ⁇ s, and the resin concentration is 15% by mass. A cloudy liquid resin composition was obtained.
- DBTL dibutyltin dilaurate
- this resin composition is used as a main ingredient, and a polyfunctional isocyanate compound (trade name “Duranate TPA-100” manufactured by Asahi Kasei Chemicals Corporation) is blended with this main ingredient so that the equivalent ratio (NCO / OH) is 1.5. And mixed to obtain an adhesive composition.
- a polyfunctional isocyanate compound trade name “Duranate TPA-100” manufactured by Asahi Kasei Chemicals Corporation
- NCO / OH equivalent ratio
- Examples 2 to 9 An adhesive composition was obtained in the same manner as in Example 1 except that the blending amounts of the PP solution, PP dispersion, reaction accelerator and polyfunctional isocyanate compound were as shown in Table 1. And it used for said adhesiveness test. The composition and the evaluation results are shown in Table 1. In Example 8, the viscosity (25 ° C.) of the resin composition before blending the polyfunctional isocyanate compound was 68 mPa ⁇ s.
- Comparative Example 1 The “PP dispersion b1” was directly used as an adhesive composition and subjected to the above-described adhesion test. The composition and the evaluation results are shown in Table 1. In addition, the viscosity (25 degreeC) of the resin composition before mix
- Comparative Examples 2 and 3 An adhesive composition was obtained in the same manner as in Example 1 except that the blending amounts of the PP solution, PP dispersion, reaction accelerator and polyfunctional isocyanate compound were as shown in Table 1. And it used for said adhesiveness test. The composition and the evaluation results are shown in Table 1.
- the adhesive compositions of Examples 1 to 9 have a high adhesive strength at 25 ° C. of 13 N or more, and in particular, the adhesive compositions of Examples 1 to 7 have an adhesive strength at 80 ° C. Is 9N or more, and it is understood that the heat resistance is excellent.
- Comparative Example 1 was an example in which only the PP dispersion (b1) was used as the adhesive composition, and the adhesive strength at 25 ° C. was low.
- the adhesive composition (Comparative Examples 2 and 3) containing the PP solution and PP dispersion (b1) that are out of the scope of the present invention are insufficient in both the adhesive strength at 25 ° C. and the adhesive strength at 80 ° C. Met.
- the adhesive composition of the present invention is suitable for adhesion between a polyolefin resin molded body and other members (metal member, resin member, etc.), and not only polyolefin resin molded bodies such as polyolefin resin films but also polyolefins. It can also be used for adhesion between a resin film and a metal layer in a composite film including a resin layer and a metal layer. Since the heat-fusible member obtained by using the adhesive composition containing the polyolefin resin (A) and the polyolefin resin (B) according to the present invention is excellent in heat resistance (heat-resistant adhesiveness), food, medicine, etc. It can be used for forming packaging materials.
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Abstract
Description
接着剤組成物は、複数の部材どうしの接着に用いられた結果、複合物を形成する。そして、この複合物は、食品、薬品等を収容する密封用容器、生活雑貨等の用途に適用されている。一般に、このような複合物は、生活環境の中で用いられると、形状安定性を得ることができるが、例えば、複合物が、暑い季節における自動車の中で放置される等により、80℃程度の高い温度になると、必ずしも、形状安定性が得られるわけではない。
本発明は、本来、他部材との接着性に劣るポリオレフィン樹脂成形体の接着に用いたときに、十分な接着強度が得られる接着剤組成物を提供することを目的とする。また、本発明は、ポリオレフィン樹脂成形体と他部材との接合体において、接着部における耐熱性(耐熱接着性)等に優れた接着剤組成物を提供することを目的とする。更に、本発明は、これらの接着剤組成物により、アルミニウム箔等の金属箔とポリオレフィン樹脂フィルム等の熱融着性樹脂フィルムとが接合されてなる熱融着性部材を提供することを目的とする。
即ち、本発明は、以下の通りである。
1.有機溶剤と、該有機溶剤に溶解されており、且つ、130℃で測定したメルトフローレートが5~40g/10minのカルボキシル基を有するポリオレフィン樹脂(A)と、多官能イソシアネート化合物とを含有することを特徴とする接着剤組成物。
2.上記ポリオレフィン樹脂(A)に含まれるカルボキシル基の含有量が、該ポリオレフィン樹脂(A)1gあたり0.01~2.0mmolである上記1に記載の接着剤組成物。
3.更に、融点が120℃~170℃のカルボキシル基を有するポリオレフィン樹脂(B)を含む上記1又は2に記載の接着剤組成物。
4.上記ポリオレフィン樹脂(B)に含まれるカルボキシル基の含有量が、該ポリオレフィン樹脂(B)1gあたり0.01~2.0mmolである上記3に記載の接着剤組成物。
5.上記ポリオレフィン樹脂(B)の平均粒子径が、1~50μmである上記3又は4に記載の接着剤組成物。
6.上記ポリオレフィン樹脂(A)及び上記ポリオレフィン樹脂(B)の質量割合が、上記ポリオレフィン樹脂(A)及び上記ポリオレフィン樹脂(B)の合計を100質量%とした場合に、それぞれ、1~70質量%及び99~30質量%である上記3~5のいずれかに記載の接着剤組成物。
7.上記1~6のいずれかに記載の接着剤組成物が硬化してなる接着剤層と、該接着剤層の一面側に接合された金属層と、該接着剤層の他面側に接合された熱融着性樹脂層とを備えることを特徴とする熱融着性部材。
1.接着剤組成物
本発明の接着剤組成物は、有機溶剤と、この有機溶剤に溶解されており、且つ、130℃で測定したメルトフローレート(以下「MFR」という)が5~40g/10minのカルボキシル基を有するポリオレフィン樹脂(A)と、多官能イソシアネート化合物とを含有する。また、本発明の接着剤組成物は、更に、有機溶剤に分散されており、且つ、融点が120℃~170℃のカルボキシル基を有するポリオレフィン樹脂(B)を含むことができる。
ポリオレフィン樹脂におけるカルボキシル基の含有量は、赤外線スペクトルを用いて作成した検量線より算出したポリオレフィン樹脂中の酸含量を、カルボキシル基の式量(45)で除し、樹脂1g当たりの値として求めることができる。
また、ポリオレフィン樹脂の融点は、JIS K 7121-1987「プラスチックの転移温度測定方法」に準じて、測定されたものである。
本明細書において、ポリオレフィン樹脂(B)を含有せず、ポリオレフィン樹脂(A)を含有する接着剤組成物を、「第1態様の接着剤組成物」といい、ポリオレフィン樹脂(A)及びポリオレフィン樹脂(B)の両方を含有する接着剤組成物を、「第2態様の接着剤組成物」という。
第1態様の接着剤組成物は、ポリオレフィン樹脂(A)が有機溶剤に溶解されて含まれる組成物である。
一方、第2態様の接着剤組成物は、少なくともポリオレフィン樹脂(A)が有機溶剤に溶解されて含まれており、ポリオレフィン樹脂(B)が有機溶剤に溶解していても溶解していなくてもよい組成物である。
また、上記変性ポリオレフィン樹脂(A1)又は共重合樹脂(A2)を形成するためのエチレン性不飽和カルボン酸としては、アクリル酸、メタクリル酸、マレイン酸、フマル酸、クロトン酸、イタコン酸、シトラコン酸、5-ノルボルネン-2,3-ジカルボン酸等が挙げられる。これらのエチレン性不飽和カルボン酸は、1種のみを用いてもよいし、2種以上を併用してもよい。
ポリオレフィン樹脂(A)のMFRは、プロピレンと、エチレン、1-ブテン等とを、適当な割合で共重合してMFRを調整した未変性プロピレン共重合樹脂体を、酸変性の原料とすることで調整することができる。
好ましい融点を有するポリオレフィン樹脂(A)は、例えば、変性ポリオレフィン樹脂(A1)を製造する前の未変性ポリオレフィン樹脂の製造条件、又は共重合樹脂(A2)の製造条件を調整することにより得ることができる。
上記ポリオレフィン樹脂(A)を溶解する有機溶剤は、接着剤組成物の加熱等により揮発させ、除去することが容易な有機溶剤であることが好ましい。このような有機溶剤としては、トルエン、キシレン等の芳香族系有機溶剤、n-ヘキサン等の脂肪族系有機溶剤、シクロヘキサン、メチルシクロヘキサン等の脂環族系有機溶剤、メチルエチルケトン等のケトン系有機溶剤等を用いることができる。これらの有機溶剤は、1種のみ用いてもよいし、2種以上を併用してもよい。
尚、ポリオレフィン樹脂(A)が溶解したことは、ポリエチレンテレフタレート等のフィルム上に、濃度20質量%のポリオレフィン樹脂(A)の溶液(有機溶剤:トルエン/メチルエチルケトン=8/2)をバーコーターで塗工して厚さ150~200μmの塗膜を形成し、乾燥した後に得られる皮膜(厚さは30~40μmになる)の表面粗さが50μm以下であることにより判定することができる。皮膜の表面粗さは、JIS B0651に規定される触針式表面粗さ計により測定することができる。
また、ポリオレフィン樹脂(B)としては、80℃程度までの高い温度において2つの部材の接着部における高い耐熱接着性が得られ、低極性の被着体に対する接着性を高められることから、プロピレン単独重合体、プロピレンとエチレンとの共重合体又はプロピレンと1-ブテンとの共重合体を変性した樹脂が好ましい。
好ましい融点を有するポリオレフィン樹脂(B)は、例えば、変性ポリオレフィン樹脂を製造する前の未変性ポリオレフィン樹脂の製造条件、又は共重合樹脂の製造条件を調整することにより得ることができる。
尚、平均粒子径(D50)は、体積基準の平均粒子径であり、例えば、ベックマン・コールター社製「コールターカウンター」等により得られた粒度分布における積算値50%における粒子径を意味する。
尚、ポリオレフィン樹脂(B)が溶解している場合には、ポリオレフィン樹脂(A)及びポリオレフィン樹脂(B)の溶液をバーコーターで塗工し、上記と同様にして、判定することができる。
有機スズ化合物としては、ジブチルスズジラウレート、ジブチルスズジマレエート、ジオクチルスズジラウレート、ジオクチルスズジマレエート等のアルキル基の炭素原子数が3~10のジオクチルスズ脂肪酸等が挙げられる。これらの化合物は、1種のみ用いてもよいし、2種以上を併用してもよい。
また、第3級アミンとしては、テトラメチルエチレンジアミン等のテトラアルキルエチレンジアミン;ジメチルベンジルアミン等のN,N’-ジアルキルベンジルアミン;トリエチレンジアミン、ペンタメチルジエチレントリアミン、N-エチルモルフィリン、N-メチルモルフィリン、1-メチル-4-ジメチルアミンエチルピペラジン等が挙げられる。これらの化合物は、1種のみ用いてもよいし、2種以上を併用してもよい。
上記反応促進剤において、有機スズ化合物と第3級アミンとを併用することもできる。上記反応促進剤の含有量は、樹脂成分の全体に対して、0.01~1質量%であることが好ましい。
ポリテルペン系樹脂としては、α-ピネン重合体、β-ピネン重合体、及びこれらとフェノール又はビスフェノールA等との共重合体が挙げられる。ロジン系樹脂としては、天然ロジン、重合ロジン及びこれらのエステル誘導体等が挙げられる。脂肪族系石油樹脂は、C5系樹脂ともいわれ、一般に、石油のC5留分より合成される樹脂である。脂環族系石油樹脂は、C9系樹脂ともいわれ、一般に、石油のC9留分より合成される樹脂である。共重合石油樹脂は、C5/C9共重合樹脂ともいわれる。水添炭化水素樹脂は、一般に、上記の各種の石油樹脂の水素添加により製造されたものである。
本発明の熱融着性部材の概略図は、図1及び図2に示される。即ち、図1の熱融着性部材1は、熱融着性樹脂層11と、接着剤層12と、金属層13と、を、順次、備える。また、図2の熱融着性部材1は、熱融着性樹脂層11と、接着剤層12と、金属層13と、他の層14と、を、順次、備える。
本発明の熱融着性部材の形状は、用途等に応じて、適宜、選択され、図1及び図2に示されるように、シート状であってよいし、線状、点状、格子状、市松模様状等であってもよい。
上記熱融着性樹脂層は、必要に応じて、滑剤、充填剤、熱安定剤、酸化防止剤、紫外線吸収剤、帯電防止剤、難燃剤、着色剤、分散剤、密着性付与剤等の添加剤を含む層であってもよい。
他の層の厚さは、特に限定されず、好ましくは30~60μm、特に好ましくは30~50μmである。
(1)接着剤組成物を、金属層13形成用の金属箔、金属製フィルム等の表面に塗布し、その後、組成物中の有機溶剤を除去して接着剤層12を形成し、次いで、接着剤層12が形成された面に、熱融着性樹脂層11形成用樹脂フィルム(熱融着性樹脂フィルム)を接触させて、加熱しながら、圧着する方法。
(2)接着剤組成物を、熱融着性樹脂層11形成用樹脂フィルム(熱融着性樹脂フィルム)の表面に塗布し、その後、組成物中の有機溶剤を除去して接着剤層12を形成し、次いで、接着剤層12が形成された面に、金属層13形成用の金属箔等を接触させて、加熱しながら、圧着する方法。
(3)接着剤組成物を、他の層14を構成する樹脂層と、この樹脂層の一面側に、蒸着等により形成された金属層13とを有する複合フィルムにおける金属層13の表面に塗布し、その後、組成物中の有機溶剤を除去して接着剤層12を形成し、次いで、接着剤層12が形成された面と、熱融着性樹脂層11形成用樹脂フィルム(熱融着性樹脂フィルム)を接触させて、加熱しながら、圧着する方法。
(4)接着剤組成物を、熱融着性樹脂層11形成用樹脂フィルム(熱融着性樹脂フィルム)の表面に塗布し、その後、組成物中の有機溶剤を除去して接着剤層12を形成し、次いで、接着剤層12が形成された面に、他の層14を構成する樹脂層と、この樹脂層の一面側に、蒸着等により形成された金属層13とを有する複合フィルムにおける金属層13が形成された面を接触させて、加熱しながら、圧着する方法。
(5)上記(1)又は(2)の方法により得られた積層体における金属層13の表面に、他の層14形成用フィルムを押出成形する方法。
また、熱融着性樹脂フィルムとしては、ポリオレフィン樹脂フィルム、ポリアミド樹脂フィルム、ポリエステル樹脂フィルム等を用いることができる。これらの樹脂フィルムは、押出法、キャスト成形法、Tダイ法、インフレーション法等の製膜化法により得られたフィルムとすることができる。熱融着性樹脂フィルムの厚さは、通常、10~200μmである。本発明においては、熱融着性部材を完成させる熱融着、及び、熱融着複合製品を製造する際の熱融着、を容易に行うことができることから、ポリオレフィン樹脂フィルムが好ましく、無延伸ポリプロピレンフィルムが特に好ましい。この無延伸ポリプロピレンフィルムを用いる場合、好ましい厚さは10~200μmであり、より好ましくは20~100μm、更に好ましくは60~100μmである。
1.評価方法
MFR、融点、平均粒子径、粘度及びはく離接着強さの測定方法を以下に示す。
1-1.MFR
JIS K7210に規定された方法で測定した。測定温度は、130℃とした。
1-2.融点
JIS K 7121-1987に規定された方法で、示差走査型熱量計(DSC)により測定した。昇温速度は、10℃/minとした。
1-3.平均粒子径(D50)
ベックマン・コールター社製「コールターカウンター」を使用して測定した。
1-4.粘度
トキメック製B型回転粘度計を用いて、温度25℃±0.5℃の条件で測定した。
1-5.はく離接着強さ
(1)試験片の作製
表面を化成処理した厚さ40μmのアルミニウム箔(100mm×200mm)に、接着剤組成物をバーコーターで塗布し、その後、80℃で60秒間、更に180℃で20秒間乾燥させ、接着剤組成物に含有されていた有機溶剤を除去して膜厚4μmの接着剤層を形成した。次いで、接着剤層の表面に、熱融着性樹脂フィルムとして厚さ80μmの無延伸ポリプロピレンフィルム(以下「CPP」と略記する)を貼合し、熱傾斜試験機を用いて、アルミニウム箔の面から加圧して圧着させた。このときの接着条件は、温度180℃、圧力0.3MPa、圧着時間2秒とした。その後、この一体化物を40℃に調温された熱風循環式オーブンに3日間収容し、試験片を得た。
(2)Tはく離接着強さの測定
試験片を15mm幅に裁断し、アルミニウム箔とCPPとの間のTはく離接着強さ(N/15mm)を測定した。測定条件は、温度が25℃及び80℃であり、引張速度は100mm/分である。
合成例1-1
メタロセン触媒を重合触媒として製造した、プロピレン単位97モル%及びエチレン単位3モル%からなるプロピレン-エチレンランダム共重合体(MFR:10g/10min、融点:85℃、以下、「プロピレン系ランダム共重合体」という)100質量部、無水マレイン酸2質量部、ラウリルメタクリレート1質量部及びジ-t-ブチルパーオキサイド1.5質量部を、シリンダー部の最高温度を170℃に設定した二軸押出機を用いて混練反応した。その後、押出機内にて減圧脱気を行い、残留する未反応物を除去して、ポリオレフィン樹脂(a1)を合成した。ポリオレフィン樹脂(a1)は、MFRが12g/10min、融点が85℃、酸価が20mgKOH/gであり、カルボキシル基の含有量は、樹脂1gあたり0.4mmolであった。
次に、内容積1Lの三つ口フラスコに撹拌機、温度計及びコンデンサーを取り付け、トルエン680g及びメチルエチルケトン(以下「MEK」という)170gを仕込み、撹拌しながら60℃に昇温した。これに上記ポリオレフィン樹脂(a1)150gを供給し、1時間程度撹拌した。樹脂を溶解した後、室温まで冷却して固形分15%の溶液を得た。この溶液を「PP溶液a1」とする。
MFRが20g/10minであるプロピレン系ランダム共重合体を用い、合成例1-1と同様にして、ポリオレフィン樹脂(a2)を合成した。ポリオレフィン樹脂(a2)は、MFRが23g/10min、融点が85℃、酸価が20mgKOH/gであり、カルボキシル基の含有量は、樹脂1gあたり0.4mmolであった。その後、樹脂の溶解を合成例1-1と同様にして行い、「PP溶液a2」を得た。
MFRが25g/10minであるプロピレン系ランダム共重合体を用い、合成例1-1と同様にして、ポリオレフィン樹脂(a3)を合成した。ポリオレフィン樹脂(a3)は、MFRが28g/10min、融点が84℃、酸価が20mgKOH/gであり、カルボキシル基の含有量は、樹脂1gあたり0.4mmolであった。その後、樹脂の溶解を合成例1-1と同様にして行い、「PP溶液a3」を得た。
MFRが44g/10minであるプロピレン系ランダム共重合体を用い、合成例1-1と同様にして、ポリオレフィン樹脂(x1)を合成した。ポリオレフィン樹脂(x1)は、MFRが47g/10min、融点が84℃、酸価が20mgKOH/gであり、カルボキシル基の含有量は、樹脂1gあたり0.4mmolであった。その後、樹脂の溶解を合成例1-1と同様にして行い、「PP溶液x1」を得た。
MFRが90g/10minであるプロピレン系ランダム共重合体を用い、合成例1-1と同様にして、ポリオレフィン樹脂(x2)を合成した。ポリオレフィン樹脂(x2)は、MFRが94g/10min、融点が83℃、酸価が20mgKOH/gであり、カルボキシル基の含有量は、樹脂1gあたり0.4mmolであった。その後、樹脂の溶解を合成例1-1と同様にして行い、「PP溶液x2」を得た。
合成例2-1
プロピレン重合体(融点:163℃)100質量部及びトルエン435質量部を撹拌機が付設された内容積1.5Lのオートクレーブに入れ、攪拌下、140℃に昇温し、完全に溶解した。この溶液を140℃に保ったまま、攪拌下、無水マレイン酸16質量部及びジクミルパーオキサイド1.5質量部を、それぞれ、4時間かけて滴下し、滴下終了後、更に140℃で1時間撹拌し、後反応を行い、変性重合体を得た。反応終了後、溶液を室温まで冷却し、溶液にアセトンを加えて変性重合体を析出させた。析出した変性重合体を繰り返しアセトンで洗浄した後、乾燥し、変性重合体を回収した。この変性重合体の無水マレイン酸のグラフト量は2.8質量%であり、融点が156℃、酸価が32mgKOH/g、カルボキシル基の含有量は、樹脂1gあたり0.6mmolであった。
次に、この変性共重合体15質量部及びトルエン85質量部を、撹拌機付きオートクレーブに入れ、130℃に加熱して樹脂を完全に溶解した。その後、撹拌しながら25℃/時間の冷却速度で90℃まで降温した後、5℃/時間の冷却速度で60℃まで冷却した。次いで、20℃/時間の冷却速度で、30℃まで降温したさせて、固形分15%の乳白色の均一な分散液を得た。分散物(樹脂粒子)の平均粒子径(D50)を測定したところ、11.0μmであった。この分散液を、「PP分散液b1」とする。
プロピレン単位95.7モル%及びエチレン単位4.3モル%からなるプロピレン-エチレン共重合体(融点:140℃)100質量部及びトルエン435質量部を、撹拌機が付設された内容積1.5Lのオートクレーブに入れ、攪拌下、140℃に昇温し、完全に溶解した。この溶液を140℃に保ったまま、攪拌下、無水マレイン酸16質量部及びジクミルパーオキサイド1.5質量部を、それぞれ、4時間かけて滴下し、滴下終了後、更に140℃で1時間撹拌し、後反応を行い、変性重合体を得た。反応終了後、溶液を室温まで冷却し、溶液にアセトンを加えて変性共重合体を析出させた。析出した変性共重合体を繰り返しアセトンで洗浄した後、乾燥し、変性重合体を回収し得た。この変性共重合体の無水マレイン酸のグラフト量は2.6質量%であり、融点が136℃、酸価が30mgKOH/g、カルボキシル基の含有量は、樹脂1gあたり0.5mmolであった。
次に、この変性共重合体15質量部、トルエン70質量部及びMEK15質量部を、撹拌機付きオートクレーブに入れ、130℃に加熱して樹脂を完全に溶解した。その後、撹拌しながら25℃/時間の冷却速度で90℃まで降温した後、5℃/時間の冷却速度で60℃まで冷却した。次いで、20℃/時間の冷却速度で、30℃まで降温させて、固形分15%の乳白色の均一な分散液を得た。分散物(樹脂粒子)の平均粒子径(D50)を測定したところ、10.3μmであった。この分散液を、「PP分散液b2」とする。
プロピレン単位82モル%及びブテン単位18モル%からなるプロピレン-ブテン共重合体(融点:117℃)100質量部及びトルエン435質量部を、撹拌機が付設された内容積1.5Lのオートクレーブに入れ、攪拌下、140℃に昇温し、完全に溶解した。この溶液を140℃に保ったまま、攪拌下、無水マレイン酸16質量部及びジクミルパーオキサイド1.5質量部を、それぞれ、4時間かけて滴下し、滴下終了後、更に140℃で1時間撹拌し、後反応を行い、変性重合体を得た。反応終了後、溶液を室温まで冷却し、溶液にアセトンを加えて変性共重合体を析出させた。析出した変性共重合体を繰り返しアセトンで洗浄した後、乾燥し、変性重合体を回収し得た。この変性共重合体の無水マレイン酸のグラフト量は2.4質量%であり、融点が113℃、酸価が27mgKOH/g、カルボキシル基の含有量は、樹脂1gあたり0.5mmolであった。
次に、この変性共重合体15質量部、トルエン17質量部及びMEK68質量部を、撹拌機付きオートクレーブに入れ、130℃に加熱して樹脂を完全に溶解した。その後、撹拌しながら25℃/時間の冷却速度で90℃まで降温した後、5℃/時間の冷却速度で60℃まで冷却した。次いで、20℃/時間の冷却速度で、30℃まで降温させて、固形分15%の乳白色の均一な分散液を得た。分散物(樹脂粒子)の平均粒子径(D50)を測定したところ、11.2μmであった。この分散液を、「PP分散液y1」とする。
プロピレン単位74モル%及びブテン単位26モル%からなるプロピレン-ブテン共重合体(融点:110℃)100質量部及びトルエン435質量部を、撹拌機が付設された内容積1.5Lのオートクレーブに入れ、攪拌下、140℃に昇温し、完全に溶解した。この溶液を140℃に保ったまま、攪拌下、無水マレイン酸16質量部及びジクミルパーオキサイド1.5質量部を、それぞれ、4時間かけて滴下し、滴下終了後、更に140℃で1時間撹拌し、後反応を行い、変性重合体を得た。反応終了後、溶液を室温まで冷却し、溶液にアセトンを加えて変性共重合体を析出させた。析出した変性共重合体を繰り返しアセトンで洗浄した後、乾燥し、変性重合体を回収し得た。この変性共重合体の無水マレイン酸のグラフト量は2.6質量%であり、融点が107℃、酸価が30mgKOH/g、カルボキシル基の含有量は、樹脂1gあたり0.5mmolであった。
次に、この変性共重合体15質量部、トルエン17質量部及びMEK68質量部を、撹拌機付きオートクレーブに入れ、130℃に加熱して樹脂を完全に溶解した。その後、撹拌しながら25℃/時間の冷却速度で90℃まで降温した後、5℃/時間の冷却速度で60℃まで冷却した。次いで、20℃/時間の冷却速度で、30℃まで降温させて、固形分15%の乳白色の均一な分散液を得た。分散物(樹脂粒子)の平均粒子径(D50)を測定したところ、10.0μmであった。この分散液を、「PP分散液y2」とする。
実施例1
コンデンサー及び攪拌機が付設された内容積300mlのフラスコに、10gの「PP溶液a1」及び190gの「PP分散液b1」を仕込み、室温で10分間撹拌し、混合液を得た。その後、この混合液に、反応促進剤としてジブチルスズジラウレート(以下「DBTL」という)0.15mgを添加して更に混合し、25℃における粘度が43mPa・sであり、樹脂濃度が15質量%である、白濁した液状の樹脂組成物を得た。
次いで、この樹脂組成物を主剤とし、この主剤に多官能イソシアネート化合物(旭化成ケミカルズ社製、商品名「デュラネートTPA-100」)を、当量比(NCO/OH)が1.5になるように配合して混合し、接着剤組成物を得た。この接着剤組成物を用いて、上記の接着性試験に供した。尚、試験片の作製に際して、多官能イソシアネート化合物を配合後、1時間以内に、接着剤組成物を使用した。配合組成及び評価結果を表1に示す。
PP溶液、PP分散液、反応促進剤及び多官能イソシアネート化合物の配合量を表1の通りとした以外は、実施例1と同様にして接着剤組成物を得た。そして、上記の接着性試験に供した。配合組成及び評価結果を表1に示す。
尚、実施例8において、多官能イソシアネート化合物を配合する前の樹脂組成物の粘度(25℃)は、68mPa・sであった。
「PP分散液b1」をそのまま接着剤組成物として、上記の接着性試験に供した。配合組成及び評価結果を表1に示す。
尚、多官能イソシアネート化合物を配合する前の樹脂組成物の粘度(25℃)は、40mPa・sであった。
PP溶液、PP分散液、反応促進剤及び多官能イソシアネート化合物の配合量を表1の通りとした以外は、実施例1と同様にして接着剤組成物を得た。そして、上記の接着性試験に供した。配合組成及び評価結果を表1に示す。
Claims (9)
- 有機溶剤と、該有機溶剤に溶解されており、且つ、130℃で測定したメルトフローレートが5~40g/10minのカルボキシル基を有するポリオレフィン樹脂(A)と、多官能イソシアネート化合物とを含有することを特徴とする接着剤組成物。
- 上記ポリオレフィン樹脂(A)に含まれるカルボキシル基の含有量が、該ポリオレフィン樹脂(A)1gあたり0.01~2.0mmolであることを特徴とする請求項1に記載の接着剤組成物。
- 更に、融点が120℃~170℃のカルボキシル基を有するポリオレフィン樹脂(B)を含むことを特徴とする請求項1又は2に記載の接着剤組成物。
- 上記ポリオレフィン樹脂(B)に含まれるカルボキシル基の含有量が、該ポリオレフィン樹脂(B)1gあたり0.01~2.0mmolであることを特徴とする請求項3に記載の接着剤組成物。
- 更に、融点が120℃~170℃のカルボキシル基を有するポリオレフィン樹脂(B)を含むことを特徴とする請求項3又は4に記載の接着剤組成物。
- 上記ポリオレフィン樹脂(B)に含まれるカルボキシル基の含有量が、該ポリオレフィン樹脂(B)1gあたり0.01~2.0mmolであることを特徴とする請求項3~5のいずれか1項に記載の接着剤組成物。
- 上記ポリオレフィン樹脂(B)の平均粒子径が、1~50μmであることを特徴とする請求項3~6のいずれか1項に記載の接着剤組成物。
- 上記ポリオレフィン樹脂(A)及び上記ポリオレフィン樹脂(B)の質量割合が、上記ポリオレフィン樹脂(A)及び上記ポリオレフィン樹脂(B)の合計を100質量%とした場合に、それぞれ、1~70質量%及び99~30質量%であることを特徴とする請求項3~7のいずれか1項に記載の接着剤組成物。
- 請求項1~8のいずれか1項に記載の接着剤組成物が硬化してなる接着剤層と、該接着剤層の一面側に接合された金属層と、該接着剤層の他面側に接合された熱融着性樹脂層とを備えることを特徴とする熱融着性部材。
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Also Published As
Publication number | Publication date |
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EP2660296A1 (en) | 2013-11-06 |
ES2750317T3 (es) | 2020-03-25 |
US20130338284A1 (en) | 2013-12-19 |
EP2660296A4 (en) | 2014-03-05 |
KR20130131325A (ko) | 2013-12-03 |
KR101864909B1 (ko) | 2018-06-05 |
JPWO2012090646A1 (ja) | 2014-06-05 |
JP5370597B2 (ja) | 2013-12-18 |
TW201237132A (en) | 2012-09-16 |
US9309373B2 (en) | 2016-04-12 |
CN103189462B (zh) | 2015-08-05 |
TWI507494B (zh) | 2015-11-11 |
CN103189462A (zh) | 2013-07-03 |
EP2660296B1 (en) | 2019-09-11 |
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