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WO2001068785A1 - Adhesif, procede de production de stratifie avec l'adhesif, et stratifie - Google Patents

Adhesif, procede de production de stratifie avec l'adhesif, et stratifie Download PDF

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Publication number
WO2001068785A1
WO2001068785A1 PCT/JP2001/001926 JP0101926W WO0168785A1 WO 2001068785 A1 WO2001068785 A1 WO 2001068785A1 JP 0101926 W JP0101926 W JP 0101926W WO 0168785 A1 WO0168785 A1 WO 0168785A1
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WO
WIPO (PCT)
Prior art keywords
styrene
adhesive
resin
block copolymer
modified block
Prior art date
Application number
PCT/JP2001/001926
Other languages
English (en)
Japanese (ja)
Inventor
Toru Fujiki
Toshiki Mori
Hironobu Iyama
Shigeki Naitoh
Original Assignee
Sumitomo Chemical Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Priority to AU2001241107A priority Critical patent/AU2001241107A1/en
Publication of WO2001068785A1 publication Critical patent/WO2001068785A1/fr

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Classifications

    • 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
    • C08L51/006—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 block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • 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
    • C09J151/006—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 block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof

Definitions

  • the present invention relates to an adhesive, a method for producing a laminate using the adhesive, and the laminate.
  • a modified block copolymer obtained by graft-polymerizing water-free maleic acid to a hydrogenated product of a styrene-conjugated-gen-styrene-based block copolymer, and / or water of a styrene-conjugated-gen-styrene-based block copolymer The present invention relates to a resin composition containing an additive, an adhesive containing the resin composition as an active ingredient, a method for producing a laminate using the adhesive, and a laminate obtained using the adhesive.
  • Laminates made of a resin such as olefin resin such as polypropylene and a polar group-containing resin such as urethane-based resin and acryl-based resin with a design property are laminated or coated to form a housing for home appliances, Used in automotive exterior products, etc.Uses a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of styrene, conjugated gen, and styrene-based block copolymer as an adhesive for both base materials. It is known to
  • Japanese Patent Publication No. 4-45532 discloses a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of a styrene 'conjugated gen' styrene block copolymer and a solvent. Adhesives have been proposed. However, when a laminate was trial-produced using this adhesive, when a film of a polar group-containing resin or the like was laminated, streaks were formed on the surface of the film, and the appearance properties were impaired
  • a method for improving the adhesiveness in the case of bonding a base material of a polar group-containing resin to a base material such as an olefin resin, or bonding a base material such as an olefin resin to a metal such as aluminum, a method for improving the adhesiveness.
  • An adhesive containing a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of styrene, conjugated gen, and styrene-based block copolymer, an organic peroxide and a solvent is used as a material of 130 tx 1
  • a method of thermosetting under the condition of 0 minutes has also been proposed (Japanese Patent Publication No. 63-65116).
  • the present inventors have intensively studied a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of a styrene-conjugated gen-styrene block copolymer in order to solve such a problem.
  • a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of a styrene-conjugated-gen-styrene-based block copolymer the viscosity in a 20% by weight toluene solution was 10 to 10%.
  • the present inventors have also conducted intensive studies on a resin composition comprising a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of a styrene-conjugated gen-styrene block copolymer.
  • Two types of the modified block copolymers having different flow rates (hereinafter referred to as MFRs) are mixed at a specific MFR ratio. By squeezing, it was found that the obtained resin composition had high adhesiveness.
  • thermosetting method under specific conditions has shown that a laminate made of a polyolefin-based resin and a polar resin has significantly improved solvent resistance. Found to give.
  • the present inventors further carried out graft polymerization of maleic anhydride onto a hydrogenated product of styrene ⁇ conjugated gen, styrene-based block copolymer and / or a hydrogenated product of styrene ⁇ conjugated gen ⁇ styrene-based block copolymer. It has been found that a modified block copolymer and a resin composition containing a styrene resin have excellent adhesiveness. The present invention has been completed based on these findings.
  • the present invention provides an adhesive comprising a solvent and a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of a styrene-conjugated gen-styrene block copolymer, and a solvent.
  • the present invention provides a practically excellent adhesive (hereinafter referred to as "adhesive M"), characterized in that the viscosity in a 20% by weight toluene solution is 10 to 200 mPa's. .
  • the present invention also relates to a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated styrene-conjugated-gen-styrene block copolymer, wherein the two types of modified block copolymers having different MFRs are provided.
  • a resin composition N an adhesive containing the resin composition as an active ingredient
  • a laminate N obtained by laminating a base material via the adhesive N.
  • the present invention further provides an adhesive containing a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated styrene-conjugated-gen-styrene-based block copolymer, an organic peroxide and a solvent (hereinafter referred to as “adhesive”).
  • An adhesive O. is a thermosetting method characterized in that C represented by the following general formula (1) is thermoset under the conditions of 2.5 to 12; It is characterized by attaching a kimono (Hereinafter referred to as a laminate O).
  • A represents the heating temperature (° C) during thermosetting
  • B represents the heating time (minutes) during thermosetting.
  • the present invention further provides a resin composition characterized by containing the following resin (I) and resin (II) (hereinafter referred to as “resin composition P”), and the resin composition P as an active ingredient. It provides an adhesive (hereinafter referred to as adhesive P).
  • a modified block copolymer is a modified block copolymer obtained by graft polymerizing maleic anhydride to a hydrogenated product of styrene, conjugated gen, and styrene block copolymer. Refers to union.
  • the styrene-conjugated-gen-styrene-based block copolymer used in the present invention or the styrene-conjugated-gen-styrene-based block copolymer used in the production of the modified block copolymer used in the present invention are: It is a copolymer containing at least one, preferably at least two, polymer blocks mainly composed of styrene units and one or more polymer blocks mainly composed of conjugated gen units.
  • the polymer block mainly composed of styrene units usually contains a styrene unit and a conjugated gen unit.
  • the styrene unit in the polymer block is preferably at least about 60 mol%, more preferably at least 80 mol%.
  • the polymer block mainly composed of a conjugated gen unit usually contains a styrene unit and a conjugated gen unit, and the conjugated gen unit in the polymer block is preferably about 60 mol% or more, more preferably 8% or more. 0 mol% or more.
  • Examples of the monomer that will be the styrene unit of the styrene / conjugated / styrene-based block copolymer include styrene, ⁇ -methylstyrene, vinyltoluene, p-tert-butylstyrene, and among others, styrene Is preferred.
  • Examples of the monomer which is a conjugated diene unit include 1,3-butadiene, isoprene, 1,3-pentene diene, and 2,3-dimethyl-1,3-butadiene. , 3-butadiene and isoprene are preferred.
  • the molar ratio of the styrene unit to the conjugated unit in the styrene / conjugated / styrene-based block copolymer as a monomer is usually about ⁇ ⁇ ⁇ ⁇ ⁇ , preferably about 8/92 to 34-66. is there.
  • the hydrogenated product of styrene-conjugated gen-styrene block copolymer is obtained by hydrogenating the unsaturated bond in the main chain olefin bond of the styrene-conjugated gen-styrene block copolymer. It is. It is preferable that the hydrogenated product is generally hydrogenated with about 80% or more of main chain olefin bonds. If the degree of hydrogenation does not reach 80%, the adhesion to an adherend such as an olefin resin and the thermal stability tend to decrease, which is not preferable.
  • Examples of the method for producing a hydrogenated product of styrene, conjugated gen, and styrene-based block copolymer include, for example, JP-B-36-19286, JP-B-40-23798, JP-B-49_36957, and The block copolymers obtained by the methods described in JP-B-48-2423, JP-B-48-4106 and the like can be obtained by combining JP-B-42-8704, JP-A-59-133203 and JP-A-59-133203.
  • a method of hydrogenating by the method described in 0-79005 and the like can be mentioned.
  • hydrogenated styrene, conjugated gen, and styrene block copolymers include, for example, “Septon 8007”, “Septon 2007”, “Septon 1001”,
  • the modified block copolymer obtained by graft polymerizing maleic anhydride to the hydrogenated styrene-conjugated-styrene-based block copolymer thus obtained is the modified block copolymer used in the present invention.
  • the grafting amount of maleic anhydride in the modified block copolymer is usually about 0.1 to 5 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the hydrogenated product of the block copolymer. It is about 3 parts by weight.
  • the grafting amount of maleic anhydride is less than 0.1 part by weight, the adhesion to an adherend such as a polar group-containing resin tends to decrease, which is not preferable. This is not preferable because the brittleness of the steel tends to increase to cause cohesive separation.
  • Examples of the method for producing the modified block copolymer of the present invention include the methods described in JP-B-62-79211, JP-B-3-12087, and JP-B-63-44784. Specifically, a hydrogenated product of the block copolymer, maleic anhydride and a radical initiator are dry-blended, then put into an extruder, mixed while being heated and melted, and unreacted maleic anhydride is heated and depressurized. A method obtained by distilling off is exemplified.
  • the MFR in the present invention is a value obtained by measuring at 230 ° C. under a load of 2160 g according to JISK-7210. It is.
  • the viscosity of a 20% by weight toluene solution of the modified block copolymer constituting the adhesive M is 10 to 200 OmPa ⁇ s (B-type viscometer, 25 ° C.).
  • an organic solvent or the like that dissolves the modified block copolymer is usually used, and among them, aromatic hydrocarbon solvents are preferable, and toluene and xylene are particularly preferable.
  • a modified block copolymer dispersed in water or the like may be used.
  • the content of the modified block copolymer contained in the adhesive M is usually about 5 to 40% by weight, preferably 10 to 30% by weight.
  • the adhesive M in the present invention may be, if necessary, a transition metal compound such as titanium oxide (rutile type) or zinc oxide, a pigment such as carbon black, a thixotropic agent, a thickener, a defoaming agent, and a surface conditioner.
  • a transition metal compound such as titanium oxide (rutile type) or zinc oxide
  • a pigment such as carbon black
  • a thixotropic agent such as a thickener
  • a defoaming agent such as anti-settling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, and antistatic agents may be added.
  • laminate M (Hereinafter, this laminate is referred to as a laminate M.)
  • the resin composition N of the present invention which is obtained by mixing two types of modified block copolymers having different MFRs at an MFR ratio of 3 to 2,000, is a modified block having a higher MFR than the other.
  • the copolymer (III) and the other modified block copolymer (IV) having a low MFR are obtained by mixing two kinds of MFRs in a specific ratio.
  • the MFR ratio of the modified block copolymer (II I) having a high MFR and the modified block copolymer (IV) having a low MFR in the resin composition N of the present invention is 3 to 2,000, and the above ratio is preferably about 5 to 1,000, and particularly preferably about 10 to 500.
  • modified block copolymer (III) having a high MFR for example, a modified block copolymer having an MFR of about 30 to 200 (gZlO content) is mentioned, and among them, the MFR is 40 to 150 (gZlO content).
  • degree of modified block copolymer It is suitable.
  • modified block copolymer (IV) having a low MFR for example, a modified block copolymer having an MFR of about 0.1 to 20 (g / 10 minutes) is exemplified.
  • a modified block copolymer having a viscosity of about 5 to 10 (g / 10 minutes) is preferable.
  • Examples of the method for producing the resin composition N of the present invention include a method of dissolving or dispersing two types of modified block copolymers in a solvent and mixing the resulting solutions, and a method of producing two types of modified block copolymers. Simultaneously dissolving or dispersing in a solvent, dry blending two types of modified block copolymers, melting and mixing two types of modified block copolymers, and roll mixing two types of modified block copolymers And other methods.
  • the resin composition N can be used for, for example, an adhesive N.
  • the adhesive N may be, for example, a solution obtained by dissolving or dispersing the resin composition N in a solvent, a sheet or film obtained by hot pressing, extrusion molding, injection molding, or the like of the resin composition N. Having.
  • an organic solvent or the like that dissolves the resin composition is usually used, and among them, an aromatic hydrocarbon solvent is preferable, and toluene and xylene are particularly preferable. It is. Further, the resin composition may be dispersed in a solvent such as water.
  • the content of the solvent contained in the adhesive N is usually about 60 to 95% by weight, preferably 70 to 90% by weight.
  • the adhesive N of the present invention includes, for example, a olefin resin such as a hydrogenated product of styrene, conjugated gen, and styrene block copolymer, a polyester resin, and a polyamide resin, as long as the adhesiveness is not impaired.
  • a thermoplastic resin or the like may be mixed.
  • the adhesive N of the present invention may include a transition metal compound such as titanium oxide (rutile type) and zinc oxide, a pigment such as carbon black, a thixotropic agent, a thickener, a defoaming agent, and a surface, if necessary.
  • a transition metal compound such as titanium oxide (rutile type) and zinc oxide
  • a pigment such as carbon black
  • a thixotropic agent such as a thickener
  • a defoaming agent such as a surface, if necessary.
  • Coating additives such as conditioners, antisettling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, and antistatic agents may be added.
  • a laminate of the present invention having excellent adhesiveness can be obtained. That is, as the laminate of the present invention, a laminate N such as (a) a Z adhesive layer (a), (a) an adhesive layer (b), (b) an adhesive layer Z (b) is exemplified. .
  • the polar group-containing resin used in the production of the laminate M or the laminate N is a resin containing a polar group such as a hydroxyl group, an ester group, an amide group, an ether group, a nitrile group, a carbonyl group, and a carboxyl group.
  • hydroxyl group-containing resins such as polyvinyl alcohol and saponified ethylene-vinyl acetate copolymer; saturated polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyamides — Polyamide resins such as 6, polyamide-6,6 and polyamide-6,10; urethane resins; melamine resins; polycarbonate resins; polyphenylene ether resins; (meth) acrylic acid, (meth) acrylic acid Acrylic ester, (meth) acrylamide, (meth) acrylo nitrile
  • the base resin (a) include a composition comprising the above resin and a (meth) acrylic acid / methyl (meth) acrylate copolymer. And a copolymer of a monomer containing a polar group.
  • the shape of the substrate (a) is not particularly limited, and examples thereof include shapes of paints, films, sheets and the like.
  • Paints are usually acrylic resin, melamine resin and urethane resin
  • a polar group-containing resin such as a urethane-based resin
  • An acrylic resin or the like is usually used as the film and sheet.
  • the olefin resin (b) include homopolyolefins such as polyethylene and homopolypropylene, block polypropylene such as ethylene-propylene block copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, propylene- Olefin copolymers such as butene copolymer, ethylene propylene butene copolymer, styrene block copolymer, styrene block copolymer, styrene block copolymer, styrene block copolymer, styrene block copolymer such as SBR, etc.
  • hydrogenated products of the aforementioned homopolyolefins and copolymers
  • the base material (b) a composition comprising two or more types of the olefin resin may be used.
  • the base material (b) contains additives that are added to the olefin resin as required, for example, inorganic fillers such as talc, silica, myriki, clay, and glass fiber, pigments, antioxidants, and processing stability. Agents, weathering agents, heat stabilizers, light stabilizers, nucleating agents, lubricants, release agents, flame retardants, antistatic agents and the like.
  • inorganic fillers such as talc, silica, myriki, clay, and glass fiber, pigments, antioxidants, and processing stability.
  • a laminate composed of (a) a Z adhesive layer / (b) is as follows:
  • the adhesive is spray-coated by air spray, air atomization electrostatic, electrostatic atomization electrostatic coating, etc., or by a coating method such as bar coater, doctor blade, wire coater, etc. for (a) and Z or (b).
  • a sheet or film adhesive is prepared, and then (a) and (b) are laminated via the adhesive to form a heat sealer.
  • a method of thermocompression bonding at about 100 to 220 ° C. using a press machine, an extruder or the like can be used.
  • the obtained laminate may be further subjected to pressing, pressing, heating, and the like.
  • the thickness of the adhesive layer is usually about l to 20 / m, preferably about 5 to 15 mm. If the thickness of the adhesive layer does not reach 1 m, the adhesive strength is When the thickness is more than 20 / m, cohesive separation tends to occur, which is not preferable.
  • the adhesive N has a sheet or film shape
  • its thickness is usually 10 to 100 mm.
  • the thickness of the adhesive layer does not reach 100 m or is larger than 100 m, the adhesiveness tends to decrease, which is not preferable.
  • a laminate M obtained by laminating an olefin resin such as polypropylene and a polar group-containing resin such as a decorative film or a paint via the adhesive M of the present invention has excellent appearance properties, It can be used for packaging materials, building materials, housing for home appliances, pampers, door moldings, door mirrors, polypropylene resin laminates for automobile exteriors such as door undercovers, etc.
  • a laminate N obtained by laminating an olefin resin such as polypropylene and a polar group-containing resin such as a decorative film or a paint via the adhesive N of the present invention has excellent adhesive properties, Materials, building materials, household electrical appliance housings, bumpers, door moldings, door mirrors, door under covers, and other automotive exterior polypropylene resin laminates.
  • a modified block copolymer obtained by graft polymerization of maleic anhydride to a hydrogenated product of styrene, conjugated gen, and styrene block copolymer, an adhesive O containing an organic peroxide and a solvent are heated under specific conditions.
  • the organic peroxide contained in the adhesive O includes, for example, methyl ethyl ketone peroxide, black hexanone peroxide, methyl black hexanone peroxide, methyl oxalate.
  • Ketone peroxides such as acetoacetate peroxide and acetylacetone peroxide, 1,1-bis (t-hexylperoxy) _3,3,5-trimethylcyclohexane, 1,1-bis (t_ Hexylpropoxy) cyclohexane, 1,1-bis (t-butylperoxy) -1,3,3,5-trimethylcyclyl Hexane, 1,1-bis (t-butylperoxy) -12-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2, 2-bis ( t-butylperoxy) butane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane , P-menthane hydride peroxide
  • an organic peroxide having a one-hour half-life temperature of about 80 to 160 is preferable.
  • Specific examples are oxyperoxide, lauroylperoxide, stearoyl peroxide, 1,1,3,3_tetramethylbutylperoxy-12-ethylhexanoate, succinic peroxide, 2,5- Dimethyl 2,5-bis (2-ethylhexanoylperoxy) hexane, 1 _ cyclohexyl 1-methylethylbenzoyl 2-ethylhexanoate, t-hexylpropoxy-1-ethylhexanoe Tert-butylperoxy-1-ethylhexanoate, m-toluoyl peroxide, benzoylperoxide, tert-butylperoxyisobutyrate, 1,1-bis (t-hexylpa) —3,3,5-trimethylcyclohexane, 1,1
  • the organic peroxide two or more kinds of organic peroxides may be used.
  • the content of the organic peroxide in the adhesive O of the present invention is usually about 0.05 to 0.1 mol based on 1 kg of the modified block copolymer.
  • the content of the organic peroxide per 1 kg of the modified block copolymer is less than 0.05 mol, the solvent resistance of the obtained laminate 0 tends to decrease, and when it exceeds 0.1 mol.
  • the intermolecular crosslinking reaction of the modified block copolymer tends to proceed excessively, and the adhesiveness between the adhesive layer and the adherend tends to decrease.
  • a crosslinking accelerator such as a compound having a redox effect or a crosslinking aid such as a compound having a reducing property such as an amine compound may be contained.
  • a solvent used for the adhesive O an organic solvent or the like that dissolves the modified block copolymer is usually used, and among them, aromatic hydrocarbon solvents are preferable, and toluene and xylene are particularly preferable. Further, water or the like may be used as a solvent, and the modified block copolymer may be dispersed in water.
  • the content of the solvent in the adhesive ⁇ is usually about 150 to 200 parts by weight, preferably 200 to 100 parts by weight, based on 100 parts by weight of the modified block copolymer. It is moderate.
  • Adhesive ⁇ is a mixture of modified block copolymer, organic peroxide and solvent Things.
  • Adhesives ⁇ include transition metal compounds such as titanium oxide (rutile type) and zinc oxide, pigments such as carbon black, etc. as necessary; thixotropic agents, thickeners, defoamers, surface conditioners
  • paint additives such as anti-settling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, and antistatic agents.
  • A represents the heating temperature () during thermosetting
  • B represents the heating time (minutes) during thermosetting.
  • C is preferably 3 to 12, and particularly preferably C is 5 to 11.
  • the heating temperature (A) is a heating temperature for the laminate ⁇ , such as an oven temperature in an oven, a press temperature in a hot press, etc., and is usually about 60 to 250 t: about, preferably about 80 to 200 t. It is.
  • the heating time (B) is the heating time for the laminate ⁇ such as the residence time in an oven and the press time in a hot press, and is usually about 10 to 180 minutes, preferably about 15 to 160 minutes. Yes, particularly preferably about 30 to 140 minutes.
  • the laminate O of the present invention is obtained by bonding an adherend using an adhesive ⁇ ⁇ ⁇ by a thermosetting method under the above conditions.
  • the laminate of the present invention is excellent in solvent resistance, it is used for a building material, a housing for home electric appliances, a bumper, a door molding, a door mirror, a door under cover, a polypropylene resin laminate for an automobile exterior, and the like. I can do it.
  • the resin ( ⁇ ) constituting the resin composition P is, for example, a homopolymer of styrene units, It is a styrene resin such as a copolymer of a styrene unit, an ⁇ , i3-unsaturated carboxylic acid unit, an acrylonitrile unit, and the like.
  • examples of the monomer of ⁇ ,] 3-unsaturated carboxylic acid unit include (meth) acrylic acid esters such as (meth) acrylic acid and (meth) methyl acrylate, maleic acid, and maleic anhydride. And so on.
  • the resin ( ⁇ ) include polystyrene, acrylonitrile-styrene copolymer, styrene- ⁇ -methylstyrene copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and styrene. ⁇ Methyl (meth) acrylate copolymer and the like. Among them, polystyrene and styrene / maleic anhydride copolymer are preferred.
  • the styrene unit content in the styrene resin (II) is usually about 50% by weight or more.
  • the resin composition ⁇ of the present invention is a resin composition containing the resin (I) and the resin ( ⁇ ).
  • the content of the resin ( ⁇ ) in the resin composition ⁇ is usually about 1 to 30 parts by weight based on 100 parts by weight of the resin (I). If the resin (I) is out of the above range, the adhesiveness tends to decrease, which is not preferable.
  • the resin (I) when the resin (I) is a hydrogenated product of a block copolymer, it is preferably about 5 to 20 parts by weight based on 100 parts by weight of the resin (I).
  • I) when I) is a modified block copolymer, it is preferably about 5 to 25 parts by weight based on 100 parts by weight of the resin (I).
  • a method for producing the resin composition ⁇ for example, a method of dissolving or dispersing the resin (I) and the resin (II) in a solvent and then mixing the obtained solution or dispersion, the method of resin (I) and the method of resin A method of dissolving or dispersing (II) in a solvent, a method of dry-blending resin (I) and resin (II), a method of melt-mixing resin (I) and resin (II), a method of melting and mixing resin (I) and resin ( )), And the like.
  • the resin composition ⁇ thus obtained is, for example, an active ingredient such as an adhesive or a molding material, and is particularly suitable as an active ingredient of the adhesive.
  • the adhesive has a shape such as a sheet or film obtained by, for example, a solution obtained by dissolving or dispersing a resin composition in a solvent, hot pressing, extrusion molding, injection molding, or the like.
  • a solvent used for the adhesive P an organic solvent or the like that dissolves the resin composition of the present invention is usually used, and among them, an aromatic hydrocarbon solvent is preferable, and particularly, toluene and xylene are preferable.
  • water or the like may be used as a solvent, and the resin composition may be dispersed in water.
  • Adhesive P may include, if necessary, transition metal compounds such as titanium oxide (rutile type) and zinc oxide; pigments such as carbon black; thixotropic agents, thickeners, defoamers, surface conditioners, anti-settling agents It may contain additives for paints, such as agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, and antistatic agents.
  • transition metal compounds such as titanium oxide (rutile type) and zinc oxide
  • pigments such as carbon black
  • paints such as agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, and antistatic agents.
  • the laminated body of the present invention can be obtained by laminating and bonding the adherends via the adhesive P thus obtained.
  • the adherend laminated via the adhesive O or the adhesive P is, for example, an olefin resin, a hydrogenated product obtained by hydrogenating the olefin bond of the main chain of the olefin resin, a cell-based polymer material, Materials that can be bonded to adhesives, such as metals and polar group-containing resins. Further, two or more different types of adherends may be used as a mixture.
  • the adherend may be a liquid such as a solution. In this case, the liquid adherend is applied on the adhesive and cured.
  • examples of the olefin-based resin include homopolyolefins such as polyethylene and homopolypropylene, block polypropylene such as ethylene-propylene block copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, and the like.
  • Olefin-based copolymers such as propylene-butene copolymer, ethylene-propylene-butene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-based copolymer such as SBR Polymers.
  • examples of the metal include aluminum, iron, and copper
  • examples of the cellulosic polymer material include paper and wood.
  • the polar group-containing resin may be a melamine resin, an acrylic / urethane resin, a urethane resin, a (meth) acrylic resin, when laminated via an adhesive O.
  • examples include styrene / acrylonitrile copolymer, polycarbonate resin, phenol resin, alkyd resin, and epoxy resin.
  • the adhesive P When laminated via the adhesive P, it is a resin containing polar groups such as a hydroxyl group, an ester group, an amide group, an ether group, a nitrile group, a carbonyl group, and a carboxyl group.
  • polar groups such as a hydroxyl group, an ester group, an amide group, an ether group, a nitrile group, a carbonyl group, and a carboxyl group.
  • Hydroxyl-containing resins such as alcohols and saponified ethylene-vinyl acetate copolymers; saturated polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyamide-6, polyamide-6,6 and polyamide- Polyamide resins such as 6, 10; urethane resins; melamine resins; polycarbonate resins; polyphenylene ether resins; (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamide, ( Meta) Vinyl-based compounds such as acrylonitrile as monomers And an acryl resin.
  • a copolymer of a monomer containing a polar group such as a composition comprising the above resin or a methyl (meth) acrylate (meth) acrylate copolymer, may also be used.
  • a olefin resin, a hydrogenated product obtained by hydrogenating the olefin bond of the main chain of the olefin resin, and a polar group-containing resin are preferable. is there.
  • the adherends laminated via the adhesive O or the adhesive P include, for example, inorganic fillers such as talc, silica, myriki, clay, and glass fiber, antioxidants, heat stabilizers, and weathering agents. , Heat stabilizers, light stabilizers, nucleating agents, lubricants, release agents, flame retardants, antistatic agents, etc .; inorganic pigments such as titanium oxide (rutile type), zinc oxide, carbon black, and organic pigments Pigments such as water; aromatic hydrocarbons such as water, toluene and xylene; aliphatic hydrocarbons such as hexane; esters such as ethyl acetate and butyl acetate; methylethyl ketone; methyl isobutyl ketone; Solvents such as ketones, alcohols such as methanol, isopropyl alcohol, ethylene glycol and propylene glycol.
  • inorganic fillers such as talc, silica, myriki,
  • Examples of the shape of the adherend laminated via the adhesive O or the adhesive P include, for example, a solution containing a pigment, a solvent, etc. in a polar group-containing resin, a film such as a decorative film, a sheet, etc. Shape.
  • polar group-containing resin, pigment, solvent The adherend in the form of a solution containing, for example, is preferable because it can be handled as a coating material.Also, a sheet or film such as an olefin resin and a hydrogenated product obtained by hydrogenating the olefin bond of the main chain of the resin may be used. It is suitable.
  • two or more kinds of polar group-containing resins may be used as a mixture, and furthermore, the same or different kinds of paints may be applied a plurality of times.
  • the laminate is usually a laminate obtained by laminating at least one or more types of adherends and thermosetting.
  • the specific lamination order of the laminates ⁇ or P is as follows: olefin resin Z adhesive Z olefin -Based resin, Orefin-based resin Adhesive Hydrogenated product obtained by hydrogenating the main-chain Orefin bond of the Norefin-based resin, Hydrogenated product obtained by hydrogenating the main-chain Orefin-bond of Orefin-based resin and / or Orefin-based resin Z Adhesive Z Metals, olefinic resins and / or hydrogenated hydrogenated olefin bonds in the main chain of olefinic resins Z adhesives Non-polar group-containing resins, metal adhesives Z-polar group-containing resins, polar group-containing resins Adhesives
  • the resin include a polar group-containing resin, and particularly, an olefin resin and / or a hydrogenated product obtained by hydrogenating the
  • the thickness of the adhesive layer after heat curing in the laminates ⁇ and P is usually about 1 to 20 m, preferably 5 to 15 m. When the thickness of the adhesive layer does not reach 1 zm, the adhesiveness tends to decrease, and when the thickness is more than 20 m, the adhesiveness tends to decrease, which is not preferable.
  • a method for producing the laminate 0 or P of the present invention for example, a method for producing a laminate in which a sheet-like adherend Z solution liquid adhesive Z solution adherend (paint) is sequentially laminated and adhered
  • the adhesive is applied to a sheet-like material by spraying methods such as air spray, air atomization electrostatic, electrostatic atomization electrostatic coating, etc., Barco overnight, doctor blade, wireco overnight, etc. Apply to the surface of the body, then apply paint.
  • a method of bonding by heating at about 80 to 250 may be used.
  • a method of manufacturing a laminated body P composed of a sheet-like adherend Z sheet-like adhesive Z and a sheet-like adherend using the adhesive P will be described.
  • a method of crimping at 110 to 220 is exemplified.
  • the obtained laminate O or P may be further subjected to pressing, pressing, heating, or the like.
  • the resin composition P of the present invention has high adhesiveness to an olefin resin, a hydrogenated hydrogenated main chain olefin bond of the olefin resin, a polar group-containing resin, and the like, the resin composition P can be used for building materials, It can be used as an adhesive for polypropylene-based resin laminates for automobile exteriors such as home appliance housings, bumpers, door moldings, door mirrors, and door undercovers.
  • the solution of the resin composition P is also suitable as a paint.
  • the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Examples 1 to 5 and Comparative Examples 1 and 2
  • the mixture was stirred and dissolved for 1 hour while keeping the temperature at 80 to obtain an adhesive in the form of a toluene solution containing 20% by weight of the modified block copolymer.
  • Viscosity The above adhesive was measured under the conditions of 25 using a B-type viscometer.
  • Example of production of laminate M The adhesive obtained in (1) was applied to the following corona-treated surface of the olefin resin using “Aprike Ichiichi” manufactured by Toyo Seiki Seisakusho Co., Ltd. 50 m was applied and dried in an oven at 80 for 20 minutes to obtain a laminate of the adhesive layer / olefin resin.
  • the polar group-containing resin shown in Table 1 was heat-sealed at a heat seal bar temperature of 1 using “Hyster-Lites Yuichi TP-701_B” manufactured by Tester Sangyo Co., Ltd. 60: A laminate comprising a polar group-containing resin Z adhesive layer and a olefin-based resin was obtained by thermocompression bonding at a pressure of 0.294 MPa for 3 seconds.
  • Peel strength A test piece having a length of 100 and a width of 1 Omm was cut out from a laminate composed of a olefin resin containing a polar group-containing resin adhesive layer obtained in (3). Using AGS-20 kNG, the peel strength was measured at 180 ° peeling at a peeling speed of 100 t / min. Polar group-containing resin
  • the modified block copolymer used is shown below.
  • Heat bonding is performed for 3 seconds at a heat seal bar temperature of 120 and a pressure of 0.294MPa for (A-1) Z adhesive layer Z ( B-1) was obtained.
  • Polar group-containing resin (A-4) is replaced by olefin resin (B-2), Sumitomo Chemical
  • a laminate comprising (B-2) was obtained.
  • Modified block copolymer "Tuftec Ml 9 13" made by graft polymerization of maleic anhydride to hydrogenated styrene / butadiene / styrene block copolymer Asahi Kasei Kogyo Co., Ltd.
  • 1-4 Styrene, butadiene, styrene block copolymer "Clearylene 530 L” manufactured by Denki Kagaku Kogyo Co., Ltd.
  • PET film ⁇ Lumirror M351 '', film thickness 5 ⁇ ) on the Teflon sheet, place the resin composition obtained in the previous section on it, and glue it with a press set at 230mm. Hot pressing was performed so that the agent layer became 5 ⁇ .
  • a laminate comprising a PET film Z adhesive layer Z polar group-containing resin sheet (A-4) was obtained by thermocompression bonding at a compression temperature of 180 ° C and a pressure of 0.294 MPa for 3 seconds.
  • the obtained laminate was cut into test pieces 100 length in length and 1 Omm in width, and peeled at 180 ° peeling rate at a peeling rate of 10 Omm / min using “Autograph AGS-20 kNG” manufactured by Shimadzu Corporation. When the strength was measured, it was 14.5N / 10IM. Examples 17-35, Comparative Examples 12 and 13)
  • Example 16 Except that the resin composition of the adhesive, the adherend, and the compression temperature are set to the conditions shown in Table 4, the same procedure as in Example 16 was carried out to obtain a PET film Z adhesive layer. A laminated body was obtained.
  • MFR 2. Og / 10min (230 ⁇ , 3800g according to JISK 7210)
  • A-1 Biaxially stretched PVA film manufactured by Toseguchi Co., Ltd.
  • MFR 15g / 10min (230 ⁇ , 2160g according to JISK 7210) was obtained by injection molding using a 5.5 ⁇ injection molding machine at a cylinder set temperature of 230 ⁇ and a mold temperature of 50 ⁇ 10.
  • Ommxl 50 Flat plate having a thickness of 2 mm Table 4 shows the peel strengths of the laminates obtained in Example 16 35, Comparative Example 12 and Comparative Example 13. The peel strength was measured in the same manner as in Example 16.
  • the PET film did not peel between the adhesive layers, but did peel between the adhesive layer Z-polar group-containing resin sheet or the adhesive layer or the olefin resin film.
  • Adhesive Compression peeling Resin (I) Resin (II) Temperature strength Kouichi 1 Kouichi 2 Kouichi 3 ⁇ 4 ⁇ 1 1 ⁇ _1 body ( ⁇ ) (N / 10mm) Example 16 100 5.3 ⁇ - ⁇ 1 ⁇ o onU
  • Example 17 100 11.1 ⁇ -4 1 ⁇ ⁇ A ⁇
  • Example 18 100 11.1 ⁇ — 4 1 on ⁇ A ⁇
  • Example 19 100 11.1 A-4 oj 1 A 1
  • Example 20 100 5.3 1 ⁇
  • Example 22 100 17.6 A-1 1 OA I ICD.DC Example 23 100 5.3 ⁇ — 1 ⁇ 1 ⁇ 7 ⁇ , 1 ⁇ Example 24 100 11.1 ⁇ -1 1 n I C Q
  • Example 31 100 11.1 A-- 51 o QA 1 A
  • Example 32 100 17.6 A- 5 180 13.1
  • Example 33 100 5.3 A- 5 180 15.4
  • Example 34 100 11.1 A-5 180 14.3
  • Comparative Example 12 100 5.3 A-1 120 ⁇ 0.1 Comparative Example 13 100 A-5 180 ⁇ 0.1

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

Abstract

L'invention concerne une composition de résine caractérisée en ce qu'elle est obtenue par mélange de deux copolymères blocs modifiés qui sont obtenus par polymérisation avec greffage d'anhydride maléique avec un copolymère bloc styrène/diène conjugué/styrène hydrogéné, et qui différent en vitesse d'écoulement à l'état fondu (MFR) d'une telle façon que le rapport de la MFR de l'un des copolymères modifiés à celle de l'autre est de 3 à 2000. L'invention concerne aussi un adhésif comprenant la composition de résine comme constituant actif. Elle concerne encore un procédé de durcissement à chaud de l'adhésif sous des conditions telles que la valeur de C représentée par la formule générale suivante (I) C = (AxB)/1000 est comprise entre 2,5 et 12. Elle concerne enfin un produit stratifié caractérisé en ce qu'il est obtenu par l'assemblage d'éléments par le procédé de durcissement à chaud (avec A représentant la température (°C) de durcissement à chaud et B représentant la durée de chauffage (min)).
PCT/JP2001/001926 2000-03-13 2001-03-12 Adhesif, procede de production de stratifie avec l'adhesif, et stratifie WO2001068785A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP2005146177A (ja) * 2003-11-18 2005-06-09 Mitsui Chemicals Inc 接着剤組成物及び容器蓋材
JP2005239812A (ja) * 2004-02-25 2005-09-08 Mitsui Chemicals Inc ポリエステル用接着剤組成物
JP2005272545A (ja) * 2004-03-23 2005-10-06 Mitsui Chemicals Inc ラミネート鋼板用接着剤組成物
JP2006323340A (ja) * 2005-04-20 2006-11-30 Gunze Ltd シュリンクラベル
JP2006323339A (ja) * 2005-04-20 2006-11-30 Gunze Ltd シュリンクラベル
JP2007063509A (ja) * 2005-09-02 2007-03-15 Kuraray Co Ltd 粘着剤
EP1862505A2 (fr) * 2006-05-30 2007-12-05 Nof Corporation Composition de résine pour film de carte à circuit imprimé et son utilisation
US20090280341A1 (en) * 2005-04-20 2009-11-12 Naoyuki Maruichi Shrink labels
JP2011170379A (ja) * 2005-04-20 2011-09-01 Gunze Ltd シュリンクラベル
JP2011203741A (ja) * 2005-04-20 2011-10-13 Gunze Ltd シュリンクラベル
WO2013164976A1 (fr) 2012-05-01 2013-11-07 三井化学株式会社 Agent de revêtement, film décoratif et corps moulé
WO2014119547A1 (fr) * 2013-01-30 2014-08-07 デクセリアルズ株式会社 Film adhésif et procédé de fabrication de composant électronique
JP2015006771A (ja) * 2013-06-26 2015-01-15 三菱樹脂株式会社 ヒートシール性フィルムおよび易開封性医療用包装体
CN104293255A (zh) * 2013-07-19 2015-01-21 北京东方雨虹防水技术股份有限公司 一种高胶强hdpe自粘卷材用热熔压敏胶及其制备方法
WO2021054030A1 (fr) * 2019-09-19 2021-03-25 東レフィルム加工株式会社 Film stratifié et son procédé de production
WO2022163284A1 (fr) * 2021-01-29 2022-08-04 信越ポリマー株式会社 Composition adhésive
WO2022244879A1 (fr) 2021-05-20 2022-11-24 三井化学株式会社 Composition de résine, son utilisation et procédé pour sa production

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05237932A (ja) * 1992-02-26 1993-09-17 Sekisui Chem Co Ltd 合成樹脂ライニング管の製造方法
JPH06299089A (ja) * 1993-04-19 1994-10-25 Mitsui Toatsu Chem Inc プライマー組成物および難接着プラスチック素材の加工方法
JPH0741580A (ja) * 1993-07-29 1995-02-10 Sekisui Chem Co Ltd 好感触シートの製造方法
JPH07214734A (ja) * 1994-02-01 1995-08-15 Sekisui Chem Co Ltd 多層成形体
JPH07292243A (ja) * 1994-04-25 1995-11-07 Asahi Chem Ind Co Ltd 耐衝撃性ポリアミド樹脂組成物
JPH0820088A (ja) * 1994-07-06 1996-01-23 Sekisui Chem Co Ltd シート状積層体
JPH0841435A (ja) * 1994-08-03 1996-02-13 Sekisui Chem Co Ltd ホットメルト型接着剤組成物
JPH08218057A (ja) * 1995-02-09 1996-08-27 Bridgestone Corp パッキング材
JPH08259849A (ja) * 1995-03-24 1996-10-08 Daicel Chem Ind Ltd プライマー組成物、および難接着プラスチック素材の加工方法
JPH09150473A (ja) * 1995-11-30 1997-06-10 Sekisui Chem Co Ltd 架橋ポリオレフィン発泡体
JPH09286962A (ja) * 1996-04-24 1997-11-04 Sekisui Chem Co Ltd ホットメルト接着剤組成物
JPH09314767A (ja) * 1996-05-27 1997-12-09 Fukuvi Chem Ind Co Ltd 耐候性に優れた共押出成形体
JPH1017780A (ja) * 1996-07-08 1998-01-20 Sekisui Chem Co Ltd 樹脂組成物、硬化型接着剤及び硬化型粘接着剤
JPH11279521A (ja) * 1997-05-08 1999-10-12 Sekisui Chem Co Ltd 接着剤組成物

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05237932A (ja) * 1992-02-26 1993-09-17 Sekisui Chem Co Ltd 合成樹脂ライニング管の製造方法
JPH06299089A (ja) * 1993-04-19 1994-10-25 Mitsui Toatsu Chem Inc プライマー組成物および難接着プラスチック素材の加工方法
JPH0741580A (ja) * 1993-07-29 1995-02-10 Sekisui Chem Co Ltd 好感触シートの製造方法
JPH07214734A (ja) * 1994-02-01 1995-08-15 Sekisui Chem Co Ltd 多層成形体
JPH07292243A (ja) * 1994-04-25 1995-11-07 Asahi Chem Ind Co Ltd 耐衝撃性ポリアミド樹脂組成物
JPH0820088A (ja) * 1994-07-06 1996-01-23 Sekisui Chem Co Ltd シート状積層体
JPH0841435A (ja) * 1994-08-03 1996-02-13 Sekisui Chem Co Ltd ホットメルト型接着剤組成物
JPH08218057A (ja) * 1995-02-09 1996-08-27 Bridgestone Corp パッキング材
JPH08259849A (ja) * 1995-03-24 1996-10-08 Daicel Chem Ind Ltd プライマー組成物、および難接着プラスチック素材の加工方法
JPH09150473A (ja) * 1995-11-30 1997-06-10 Sekisui Chem Co Ltd 架橋ポリオレフィン発泡体
JPH09286962A (ja) * 1996-04-24 1997-11-04 Sekisui Chem Co Ltd ホットメルト接着剤組成物
JPH09314767A (ja) * 1996-05-27 1997-12-09 Fukuvi Chem Ind Co Ltd 耐候性に優れた共押出成形体
JPH1017780A (ja) * 1996-07-08 1998-01-20 Sekisui Chem Co Ltd 樹脂組成物、硬化型接着剤及び硬化型粘接着剤
JPH11279521A (ja) * 1997-05-08 1999-10-12 Sekisui Chem Co Ltd 接着剤組成物

Cited By (23)

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Publication number Priority date Publication date Assignee Title
JP2005146177A (ja) * 2003-11-18 2005-06-09 Mitsui Chemicals Inc 接着剤組成物及び容器蓋材
JP2005239812A (ja) * 2004-02-25 2005-09-08 Mitsui Chemicals Inc ポリエステル用接着剤組成物
JP2005272545A (ja) * 2004-03-23 2005-10-06 Mitsui Chemicals Inc ラミネート鋼板用接着剤組成物
JP2011170379A (ja) * 2005-04-20 2011-09-01 Gunze Ltd シュリンクラベル
JP2006323340A (ja) * 2005-04-20 2006-11-30 Gunze Ltd シュリンクラベル
JP2006323339A (ja) * 2005-04-20 2006-11-30 Gunze Ltd シュリンクラベル
US9028933B2 (en) 2005-04-20 2015-05-12 Gunze Limited Shrink labels
JP2011203741A (ja) * 2005-04-20 2011-10-13 Gunze Ltd シュリンクラベル
US20090280341A1 (en) * 2005-04-20 2009-11-12 Naoyuki Maruichi Shrink labels
JP2007063509A (ja) * 2005-09-02 2007-03-15 Kuraray Co Ltd 粘着剤
EP1862505A3 (fr) * 2006-05-30 2008-02-13 Nof Corporation Composition de résine pour film de carte à circuit imprimé et son utilisation
EP1862505A2 (fr) * 2006-05-30 2007-12-05 Nof Corporation Composition de résine pour film de carte à circuit imprimé et son utilisation
US9365737B2 (en) 2012-05-01 2016-06-14 Mitsui Chemicals, Inc. Coating agent, decorative film and article
WO2013164976A1 (fr) 2012-05-01 2013-11-07 三井化学株式会社 Agent de revêtement, film décoratif et corps moulé
KR20140146659A (ko) 2012-05-01 2014-12-26 미쓰이 가가쿠 가부시키가이샤 코팅제, 장식 필름 및 성형체
WO2014119547A1 (fr) * 2013-01-30 2014-08-07 デクセリアルズ株式会社 Film adhésif et procédé de fabrication de composant électronique
JP2014145055A (ja) * 2013-01-30 2014-08-14 Dexerials Corp 接着フィルム、及び電子部品の製造方法
JP2015006771A (ja) * 2013-06-26 2015-01-15 三菱樹脂株式会社 ヒートシール性フィルムおよび易開封性医療用包装体
CN104293255A (zh) * 2013-07-19 2015-01-21 北京东方雨虹防水技术股份有限公司 一种高胶强hdpe自粘卷材用热熔压敏胶及其制备方法
WO2021054030A1 (fr) * 2019-09-19 2021-03-25 東レフィルム加工株式会社 Film stratifié et son procédé de production
WO2022163284A1 (fr) * 2021-01-29 2022-08-04 信越ポリマー株式会社 Composition adhésive
WO2022244879A1 (fr) 2021-05-20 2022-11-24 三井化学株式会社 Composition de résine, son utilisation et procédé pour sa production
KR20230160903A (ko) 2021-05-20 2023-11-24 미쓰이 가가쿠 가부시키가이샤 수지 조성물, 및 그 용도 및 제조 방법

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