Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
  • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
• • 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
  • C08F8/44—Preparation of metal salts or ammonium salts
• • 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
• • 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
  • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
  • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B21/08—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
  • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
• • 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
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
  • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
• • 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
  • B32B2605/00—Vehicles
  • B32B2605/003—Interior finishings
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S525/919—Ionomer resins, carboxylate salt-containing copolymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/298—Physical dimension
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31645—Next to addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31678—Of metal
  • Y10T428/31692—Next to addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/3188—Next to cellulosic
  • Y10T428/31895—Paper or wood

Definitions

• the present invention relates to an oriented thermoplastic elastomer sheet and a method for producing the same, and a laminate having a surface layer formed of the sheet. More specifically, the present invention has excellent rubber elasticity, softness, mechanical properties, scratch resistance, and moldability.
• the present invention relates to an olefin-based thermoplastic elastomer sheet, a method for producing the same, and a laminate.
• thermoplastic thermoplastic elastomer sheet has excellent heat resistance, weather resistance, and cold resistance, can be molded by the same method as thermoplastic resin, can be recycled, and can be compared. For example, it can be used as a substitute for polychlorinated vinyl sheet, which is widely used as an interior skin material for automobiles, and vulcanized rubber sheet, which is used in various fields. Attention has been paid.
• a material of the olefin-based thermoplastic elastomer a material obtained by mixing an olefin-based resin and an olefin-based copolymer rubber, or an olefin-based resin and an olefin-based copolymer rubber are partially mixed with a crosslinking agent.
• Crosslinks and the like are known (for example, see the following Reference 1).
• Prior document 1 Japanese Patent Application Laid-Open No. 2000-2666-68
• the present invention has been made in view of the above circumstances, and an object thereof is to have rubber elasticity, flexibility and moldability similar to those of a conventional olefin-based thermoplastic elastomer sheet.
• Another object of the present invention is to provide an olefin thermoplastic elastomer sheet having good mechanical properties and particularly excellent scratch resistance, a method for producing the same, and a laminate having a surface layer made of the sheet.
• the olefin-based thermoplastic elastomer sheet of the present invention is an olefin containing a copolymer of ethylene, a-olefin having 3 to 10 carbon atoms, an unsaturated monomer having a functional group, and, if necessary, a non-conjugated diene. It is characterized by comprising an elastomer material containing a random copolymer and a metal ion for cross-linking the random copolymer.
• the unsaturated monomer having a functional group is preferably a functional cyclic compound represented by the following general formula (1).
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
• Y 1 , Y 2 and Y 3 each independently represent a hydrogen atom, a carbon number of 1 to 1 0 hydrocarbon group or one COOH
• at least one of Y 1 , Y 2 and Y 3 is one COOH
• two or more of Y 1 , Y 2 and Y 3 are one COH
• they may be acid anhydrides (1-CO— (O) —CO—) formed by linking each other.
• o is an integer from 0 to 2 and p is an integer from 0 ⁇ 5.
• the elastomer material is selected from a thermoplastic resin, a thermoplastic elastomer, and a rubber. And further containing Z or a softener. Further, the thickness is preferably 10 ⁇ to 2 cm.
• the method for producing an oriented thermoplastic elastomer sheet according to the present invention comprises the steps of: extruding the above-mentioned elastomer material by an extrusion method, a calendar molding method, a solvent casting method, an injection molding method, a vacuum molding method, a padder slush molding method or a hot press It is characterized by forming by a method.
• the laminate of the present invention is characterized by having a surface layer made of the above-mentioned olefin thermoplastic elastomer sheet.
• the lower layer is preferably made of a material selected from the group consisting of rubber, plastic, thermoplastic elastomer, glass, metal, cloth and wood.
• the olefin-based thermoplastic elastomer sheet of the present invention has the same rubber elasticity and flexibility as the conventional olefin-based thermoplastic elastomer sheet, and has good mechanical properties and is particularly scratch-resistant. It can be easily obtained by melt molding methods such as injection molding, extrusion molding, hollow molding, compression molding, vacuum molding, powder slush molding, lamination molding, force render molding, and solvent casting. Things.
• the olefin thermoplastic sheet of the present invention has good adhesiveness to other materials, so that it can be easily formed into a laminate integrally laminated on the surface of a lower layer made of other materials. It is.
• the olefin-based thermoplastic elastomer sheet of the present invention and the laminate having a surface layer made of the sheet are a bumper of an automobile using a conventional olefin-based thermoplastic elastomer, an exterior molding, a gasket for a wind seal, Gaskets for door seals, gaskets for trunk seals, roof side rails, emblems, interior and exterior skins for panels, door trims, console boxes, etc., weather strips, etc.
• the above-mentioned olefin-based thermoplastic elastomer sheet can be advantageously produced.
• the olefin-based thermoplastic elastomer sheet of the present invention comprises an olefin-type random copolymer (hereinafter, referred to as “specified”) obtained by copolymerizing at least ethylene, a olefin having 3 to 10 carbon atoms, and a compound having a functional group. And a metal ion for cross-linking the specific functional group-containing copolymer.
• specified olefin-type random copolymer
• sheet is a term that includes not only what is generally called “sheet” but also what is called “film”.
• ethylene is used as an essential monomer component.
• the ratio of ethylene, 3 5 9 4 of the entire monomer components. 9 9 moles is preferably 0/0, more preferably 4 0-8 9. 9 9 mol%, particularly preferably 4 5 8 is 4. 9 9 mol 0/0.
• an a-olefin having 3 to 10 carbon atoms (hereinafter referred to as “specific ⁇ _olefin”) is used as an essential monomer.
• ⁇ -olefin having 10 or less carbon atoms the copolymerizability of the ⁇ -olefin with other monomers is improved.
• Specific examples of the specific ⁇ -olefin include propylene, 1-butene, 1-pentene, 4-methyl-pentene-11,1-hexene, 1-heptene, 11-otaten, 1-decene, and the like. Among these, propylene, 1-butene, 1-hexene and 1-otaten are preferred, and propylene and 1-butene are more preferred.
• Specific alpha - proportion of Orefin is preferably 5-5 0 mol% of the total monomer component, more preferably 1 0-4 5 mol%, particularly preferably 1 5-4 0 mole 0 / It is 0 .
• the proportion of the specific ⁇ -olefin used is less than 5 mol%, it may be difficult to obtain the rubber elasticity required for a thermoplastic elastomer sheet.
• the use ratio of the specific ⁇ -olefin exceeds 50 mol%, the obtained thermoplastic elastomer sheet may have low durability.
• an unsaturated monomer having a functional group capable of crosslinking with metal ions (hereinafter, referred to as “functional group-containing unsaturated monomer”) is an essential monomer component.
• the unsaturated monomer having a functional group preferably has a functional group such as a hydroxyl group, a hydroxyl group, an epoxy group or a sulfonic acid group.
• a functional group-containing unsaturated monomer it is preferable to use a functional cyclic compound represented by the above general formula (1) (hereinafter, referred to as “specific functional cyclic compound”).
• R 1 is a hydrogen atom or W
• Y 1 , Y 2 and Y 3 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or one COOH, and Y 1 , Y 1 At least one of 2 and Y 3 is one COOH.
• Y 1 , Y 2, and Y 3 are acid anhydrides (one CO— (O) one CO—) formed by being connected to each other. There may be.
• hydrocarbon group having 1 to 10 carbon atoms examples include a methyl group and an ethyl group.
• the number of repetitions o is an integer of 0 to 2. When the number of repetitions o is 3 or more, it may be difficult to copolymerize the cyclic compound with another monomer.
• the number of repetitions! Is an integer from 0 to 5.
• Such a specific functional cyclic compound can be produced by condensing a cyclopentene and a functional group-containing unsaturated compound by a Diels-Alder reaction.
• the proportion of the functional group-containing unsaturated monomer is preferably from 0.01 to 5 mol% of the total monomer component, more preferably from 0.01 to 4 mol 0/0.
• the obtained thermoplastic elastomer sheet When the content of the unsaturated monomer having a functional group is less than 0.01 mol%, the obtained thermoplastic elastomer sheet has a low cross-linking density and a high mechanical strength. Is likely to be low. On the other hand, when the use ratio of the functional group-containing unsaturated monomer exceeds 5 mol%, the obtained olefin thermoplastic elastomer sheet may have too high a cross-linking density and a decrease in fluidity. Is not preferred.
• a non-conjugated diene can be used as an arbitrary monomer component in addition to the above-mentioned essential monomer component.
• non-conjugated gen examples include linear non-cyclic gens such as 1,4-hexadiene, 1,6-hexadiene, 1,5-hexadiene, 5-methyl_1,41-hexadiene, 3,7-Dimethyl 1,6-octadiene, 5,7-Dimethylta_1,6-diene, 3,7-Dimethyl-1,7-octadiene, 7_Methylocta-1,6-diene, dihydromyrcene, etc.
• linear non-cyclic gens such as 1,4-hexadiene, 1,6-hexadiene, 1,5-hexadiene, 5-methyl_1,41-hexadiene, 3,7-Dimethyl 1,6-octadiene, 5,7-Dimethylta_1,6-diene, 3,7-Dimethyl-1,7-octadiene, 7_Methylocta-1,6-diene, dihydromyrcene, etc.
• Branched-chain acyclic gen tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo [2.2.1] 1 hepter 2, ⁇ -gen, 5-methylene-1 2-norporne Alicyclics such as styrene, 5-ethylidene-1-norpolene, 5-propenyl-2-norpolene, 5-isopropylidene-2-norbornene, 5-cyclohexylidene-2-norpolene, 5-vinyl-2-norporene Jen and others. These compounds can be used alone or in combination of two or more.
• non-conjugated diene examples include 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and the like.
• the proportion of non-conjugated gen used is preferably 0 to 10 mol% of the total monomer components.
• the use ratio of this conjugated gen is more than 10 mol%, the obtained thermoplastic elastomer sheet may have low durability.
• the specific functional group-containing copolymer has a weight average molecular weight Mw in terms of polystyrene measured by gel permeation chromatography (GPC) of usually from 1,000 to 3,000,000, preferably from 3,000 to 1,000. ,, 000,000, more preferably from 5,000 to 700,000.
• GPC gel permeation chromatography
• the specific functional group-containing copolymer preferably has a melt flow rate (MFR) force of 0.01 to 100 gZl Omin measured at a temperature of 230 ° C. and a load of 10 kg, More preferably 0.05 to 50 g / 1 Omin. Also, the specific functional group-containing copolymer has a glass transition temperature of 90 to 50 ° C, preferably — 70 to 10 ° C. .
• MFR melt flow rate
• the specific functional group-containing copolymer may be an oil-extended polymer in which a softener is added during polymerization.
• the metal ion used in the present invention forms a crosslinked structure between molecules of the specific functional group-containing copolymer by ionic bonding to a functional group in the specific functional group-containing copolymer.
• Such metal ions include lithium, potassium, sodium, anolemmium, magnesium, potassium, barium, Examples include ions of metals of Groups I to VIII of the periodic table such as shim, strontium, rubidium, titanium, zinc, copper, iron, tin, lead, and zirconium. Of these, metal ions of potassium, sodium, aluminum, magnesium, barium, zinc, iron, zirconium, calcium, titanium, and lead are preferred.
• the elastomer material for forming the olefin-based thermoplastic sheet of the present invention may contain a polymer compound selected from a thermoplastic resin, a thermoplastic elastomer and rubber.
• the polymer compound is not particularly limited as long as it is other than a specific functional group-containing copolymer, and various compounds can be used. Specific examples thereof include ionomers and aminoacrylamide polymers. , Polyethylene and its maleic anhydride graft polymer, polyisobutylene, ethylene vinyl chloride polymer, ethylene vinyl alcohol polymer, ethylene acetate butyl copolymer, polyethylene oxide, ethylene acrylate copolymer, polypropylene Its maleic anhydride graft polymer, polyisobutylene and its maleic anhydride graft polymer, chlorinated polypropylene, 4-methylpentene-11 resin, polystyrene, ABS resin, ACS resin, AS resin, AES resin, ASA resin, MBS Resin, acrylic resin, methacrylic resin, PVC Resin, vinylidene chloride resin, polyamide resin, polycarbonate resin, acrylic resin, methacrylic resin, vinyl chloride resin, vinylidene chloride resin, butyl
• the proportion of the polymer compound used is 300 parts by weight or less, preferably 1 to 200 parts by weight, per 100 parts by weight of the specific functional group-containing copolymer.
• the elastomer material may contain a softener.
• This softening agent may be added to a monomer solution for obtaining a specific functional group-containing copolymer, and may be added when preparing an elastomer material or when manufacturing a sheet. May be done.
• the softening agent is not particularly limited as long as it is a commonly used rubber softening agent.
• examples thereof include paraffinic, naphthenic, aromatic mineral oil-based hydrocarbons, and low molecular weight polymers such as polybutene and polybutadiene. And the like.
• mineral oil-based hydrocarbons are preferred, and those having a weight-average molecular weight of 300 to 20,000, particularly 500 to 1,500, are preferred.
• Rubber softeners composed of mineral oil-based hydrocarbons are generally a mixture of aromatic hydrocarbons, naphthenic hydrocarbons, and paraffinic hydrocarbons. Those that account for 50% or more of the total number are paraffinic oils, those whose naphthenic hydrocarbons have 30 to 45% of the total carbon number are those of naphthenic oils and aromatic hydrocarbons. Is aromatic if more than 30% of the total carbon number Each is classified as a system oil. In the present invention, paraffinic ones are preferred, and hydrogenated paraffinic ones are particularly preferred.
• the mineral oil-based hydrocarbon preferably has a kinematic viscosity at 40 ° C of 20 to 800 cSt, particularly 50 to 600 cSt, and a pour point of _40 to 0 ° C, particularly Is preferably from 30 to 0 ° C.
• the softener is used in an amount of 100 parts by weight or less, preferably 1 to 67 parts by weight, based on 100 parts by weight of the specific functional group-containing copolymer.
• additives may be added to the elastomer material as required, such as lubricants, anti-aging agents, heat stabilizers, weathering agents, metal deactivators, ultraviolet absorbers, light stabilizers, and copper inhibitor.
• the elastomer material constituting the olefin-based thermoplastic elastomer sheet of the present invention can be produced as follows.
• component (A) a specific functional group-containing copolymer
• component (B) a metal compound that supplies a metal ion for crosslinking the copolymer
• a metal oxide, a metal hydroxide, a metal salt, an organometallic compound and a metal salt of a monovalent carboxylic acid can be used.
• organometallic compound used as the component (B) include organic aluminum compounds, organic titanium compounds, organic phosphorus compounds, organic boron compounds, organic zirconium compounds, organic gallium compounds, organic tin compounds, and organic magnesium compounds.
• the carboxylic acid preferably has 3 to 23 carbon atoms.
• carboxylic acids include propionic acid, acrylic acid, butyric acid, methacrylic acid, valeric acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, palmitic acid, myristic acid, lauric acid, Examples include stearic acid, oleic acid, behenic acid, naphthenic acid, and benzoic acid.
• These metal compounds are treated with a silane coupling agent or a higher fatty acid in order to enhance the dispersibility of the specific functional group-containing copolymer (A). There may be.
• These metal compounds can be used alone or in combination of two or more.
• the proportion of the metal compound used as the component (B) is usually 0.1 to 20 parts by weight, preferably 0.1 to 100 parts by weight for the specific functional group-containing copolymer as the component (A). It is 2 to 15 parts by weight, especially 0.5 to 10 parts by weight. When this proportion is less than 0.1 part by weight, the obtained thermoplastic elastomer sheet tends to have a low crosslinking density and low mechanical strength and scratch resistance. On the other hand, when this proportion exceeds 20 parts by weight, the obtained thermoplastic elastomer sheet is too high in crosslink density and may decrease the fluidity.
• the above components (A) and (B) are mixed with other components that are used as required.
• a method of crosslinking a solution or dispersion of each component is prepared and mixed.
• Various methods such as a method using a commonly used melt kneading apparatus can be used, but a method of mixing under heating is preferable because an elastomer material having stable characteristics can be obtained. Examples of the method include the following methods (I) and (II).
• component (I) a solution in which the specific functional group-containing copolymer as the component (A) is dissolved in an appropriate solvent, and a solution in which the metal compound as the component (B) is dissolved or dispersed in an appropriate solvent. Is a dispersion, a polymer compound (hereinafter also referred to as “component (C)”), and a softener.
• component (D) A solution or dispersion obtained by dissolving or dispersing other components used as necessary is cross-linked by heating or cross-linked. Dissolve component (A) in solvent, and mix components (B) and (C)
• (D) A method of heating while dissolving or dispersing components and other components used as necessary, such as components, or after dissolving or dispersing.
• the solvent used in the above method (I) is not particularly limited. However, in view of easily dissolving the specific functional group-containing copolymer, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, etc. Preferably, aromatic hydrocarbons and their halides are used.
• a dispersion in which the component (B) is dispersed in a solvent in a suspended state may be prepared.
• Other solvents and additives may be added for dissolution.
• solubility of the components (C) and (D) used in the above solvent is low, even if a dispersion in which the components (C) and (D) are dispersed in a solvent in a suspended state is prepared.
• Other solvents and additives may be added to dissolve the components (C) and (D), or after the solvent is removed, the components (C) and (D) are added. These may be subjected to dynamic heat treatment.
• the proportion of the specific functional group-containing copolymer in the solution is preferably from 0.1 to 60% by weight, and more preferably from 0.2 to 50% by weight.
• the ratio of the component (B) and the activator in the solution or dispersion is preferably from 0.01 to 60% by weight in total, more preferably from 0.05 to 50% by weight. is there.
• the mixing of the solution or dispersion can be carried out by a commonly used solution stirring device, and the temperature at the time of mixing is preferably at least 20 ° C, more preferably at 30 ° C. That is all.
• an appropriate catalyst may be added to promote the crosslinking reaction.
• the “dynamic heat treatment” refers to a treatment for applying a shearing force or a heating treatment.
• a dynamic heat treatment can be performed using, for example, a melt kneading apparatus.
• This melt kneading device is of the patch type, May also be of a continuous type.
• Specific examples of the melt-kneading apparatus include an open-type mixing roll, a non-open-type Banbury mixer, a patch-type melt-kneading apparatus such as an ader, a single-screw extruder, a co-rotating continuous twin-screw extruder, and a different direction.
• a continuous melt kneading device such as a rotary continuous twin screw extruder can be used.
• Specific methods include the following methods (II-1) and (II-2).
• (II-1) A specific functional group-containing copolymer as the component (A), a metal compound as the component (B), and other components used as necessary, such as the components (C) and (D).
• a method for preparing an elastomer material by subjecting a mixture containing the components (1) to (2) to a continuous heat treatment by shearing heat generation by a twin-screw extruder to crosslink the mixture.
• a method for preparing an elastomer material by subjecting a mixture containing the components (a) and (b) to a dynamic heat treatment using shear heat generation by a batch kneader to crosslink the mixture.
• the processing conditions in the dynamic heat treatment include the melting point of the specific functional group-containing copolymer used as the component (A), the type of the metal compound used as the component (B), and the type of the polymer compound used as the component (C).
• the processing temperature is 120 to 350 ° C, preferably 150 to 290 ° C, and the processing time is 20 to 320 minutes, preferably 30 to 25 minutes.
• the shear force applied to the mixture is 10 to 20,000 O / sec, preferably 100 to 100,000 OOZsec in shear rate.
• the elastomer material obtained in this way has a melt flow rate (MFR) measured at a temperature of 230 ° C and a load of 10 kg of 0.5 g / l 0 min or more, especially 1 g / 1 It is preferably at least Omin, the permanent elongation is at most 30%, particularly preferably at most 25%, and the durometer A hardness is at most 96, especially at most 90.
• MFR melt flow rate
• the olefin-based thermoplastic elastomer sheet of the present invention is characterized in that: The component (A), component (B), and other components used as necessary can be crosslinked with component (A) and component (B) to form a crosslinked structure. By mixing under appropriate conditions that can be formed, it can also be produced by performing the step of preparing an elastomer material and the step of molding in a single step.
• the molding method is not particularly limited.
• various methods used as a method for molding a thermoplastic resin sheet can be employed. Examples include an extrusion molding method, a calendar molding method, a solvent casting method, and an injection method.
• a molding method, a vacuum molding method, a powder slush molding method and a hot pressing method can be suitably used, and among these, the extrusion molding method, the injection molding method, and the solvent casting method are particularly preferable.
• the molding temperature depends on the specific functional group-containing copolymer and the melting point of the high-molecular compound constituting the elastomer material, the type of molding machine used, etc.
• the temperature is appropriately set according to the temperature, but is usually 120 to 350 ° C.
• the solvent is not particularly limited as long as it can dissolve the elastomer material.
• examples thereof include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halides thereof.
• butane for example, butane, pentane, hexane, heptane, 2-butane, 2-methynole-12-butane, cyclopentane, methinolecyclopentane, cyclohexane, isooctane, Benzene, tonolen, xylene, benzene, dichloromethane, dichloroethane and the like can be mentioned.
• the solvent casting method involves dissolving or dispersing the respective components in an appropriate solvent, casting the resulting liquid to remove the solvent, and then subjecting the solvent to crosslinking by heating.
• removing and cross-linking simultaneously or a solution in which the specific functional group-containing copolymer as the component (A) is dissolved in an appropriate solvent, and the solution of the component (B) in an appropriate solvent
• Cast and melt A method in which the solvent is removed followed by heat crosslinking, or a method in which the solvent is removed and the crosslinking is performed simultaneously by heating after casting.
• the thus obtained olefin thermoplastic sheet preferably has a thickness of 10 12 cm, more preferably 20 ⁇ ! ⁇ 1 cm.
• the laminate of the present invention has a surface layer composed of the above-mentioned thermoplastic thermoplastic elastomer sheet.
• the lower layer on which the surface layer is formed can be made of a material selected from rubber, plastic, thermoplastic elastomer, glass, metal, and cloth and wood.
• the rubber includes ethylene ' ⁇ -olefin copolymer rubber and its anhydrous maleic acid graft polymer, ethylene' ⁇ -olefin 'non-conjugated gen copolymer rubber, styrene' butadiene rubber, butadiene, rubber, isoprene Rubber, nitrile rubber and its hydrogenated products, acrylic rubber, silicone rubber, fluoro rubber, butyl rubber, natural rubber, etc.
• Plastics include ionomer, aminoacrylamide polymer, polyethylene and its maleic anhydride graft polymer, polyisobutylene, ethylene butyl chloride polymer, ethylene butyl alcohol polymer, ethylene vinyl acetate copolymer, polyethylene oxide, ethylene acrylic acid Copolymer, polypropylene and its maleic anhydride graft polymer, polyisobutylene and its maleic anhydride graft polymer, chlorinated polypropylene, 4-methylpentene-11 resin, polystyrene, ABS resin, ACS resin, AS resin, AE S resin, ASA resin, MBS resin, acrylic resin, methacrylic resin, vinyl chloride resin, vinylidene chloride resin, polyamide resin, polycarbonate, acrylic resin, methacrylic resin, shiridani butyl resin Vinylidene chloride resin, Bulle alcohol resin, Bieruaseta Le resins, methyl methacrylate Atari rates resins, fluorocarbon resins, polyether resins
• Syndiotactic 1,2-polybutadiene simple blend type olefin-based thermoplastic elastomer, implant type olefin-based thermoplastic elastomer, dynamic cross-linked olefin-based thermoplastic elastomer, polyvinyl chloride-based thermoplastic elastomer, polyurethane-based Maleic anhydride graft of hydrogenated thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, fluorine-based thermoplastic elastomer, styrene-butadiene rubber hydrogenated product, styrene-butadiene rubber hydrogenated product Polymer, hydrogenated butadiene rubber, maleic anhydride grafted polymer of hydrogenated butadiene rubber, hydrogenated maleic anhydride of isoprene rubber, grafted maleic anhydride of hydrogenated isoprene rubber, styrene / isopren
• Metals include stainless steel, aluminum, iron, copper, nickel, zinc, lead, tin, and alloys such as nickel-zinc alloy, iron-zinc alloy, lead-tin alloy used in automobiles, ships, home appliances, etc. And the like.
• thermoplastic thermoplastic elastomer sheet As a method for forming the surface layer, the above-described molding method for obtaining the above-mentioned thermoplastic thermoplastic elastomer sheet can be used.
• the surface layer is formed by extruding the elastomer material on the surface of the base material prepared in advance.
• two or more extruders are connected to one die, and one extruder is supplied with a thermoplastic resin and the other extruder is supplied with an elastomer material.
• the lower substrate and the surface layer may be simultaneously formed inside the die.
• the base material as the lower layer is made of a thermoplastic resin or a thermoplastic elastomer
• the base material prepared in advance is placed in a mold, and the elastomer base material is formed.
• the surface layer may be formed by injection molding the material, but using two injection molding machines and one mold, one elastomer is supplied to one injection molding machine and the other is used. By supplying the thermoplastic resin to the injection molding machine and operating the two injection molding machines continuously, the lower substrate and the surface layer may be continuously molded in the mold.
• the base material as the lower layer is made of glass, plastic or metal
• a solution or dispersion in which the elastomer material is dissolved or dispersed is cast to form a solvent.
• the laminate may be manufactured by removing the solvent and then performing heating and crosslinking, or by heating after casting to simultaneously remove and crosslink the solvent.
• the olefin-based thermoplastic elastomer sheet of the present invention has rubber elasticity, flexibility and moldability similar to conventional olefin-based thermoplastic elastomer sheets, and has good gripping force, mechanical properties, and especially scratch resistance. Since it is excellent in adhesiveness and has good adhesiveness to other materials, it is easy to form a laminate integrally laminated on the surface of a lower layer made of another material.
• the olefin thermoplastic elastomer sheet of the present invention and the laminate having a surface layer made of the sheet have the above-mentioned characteristics, and therefore, the automobile of the conventional olefin thermoplastic elastomer sheet is used.
• the content of structural units derived from ethylene is 86.1 mol%
• the content of structural units derived from propylene is 10.6 mol%
• the content of structural units derived from 5-ethylidene-2-norporene is 2.6 mol% %
• the structural unit derived from the 12-heptene content is 0.7 mol%
• the weight average molecular weight (Mw) is 16.5 ⁇ 10 4 .
• Magnesium stearate Magnesium stearate.
• Polyethylene resin (C-1) High-density polyethylene resin with a MFR (temperature of 190 ° C, load of 2.16 kg) of 20 g_ / l Omin (Novatec HDPE HJ490, manufactured by Nippon Polychem Co., Ltd.).
• Polypropylene resin with MFR (temperature 230 ° C, load 2.16 kg) of 20 g / 10 min (manufactured by Chisso Corporation, product name “XF 9520”).
• Anti-aging agent (D-1) isobutyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl):
• Carbon black masterbatch (polypropylene resin base, carbon black content 30% by weight, manufactured by Dainichi Seika Kogyo Co., Ltd., product name "PPM-77255").
• Specific functional group-containing copolymer (A-1) 100 parts by weight, metal compound (B-1) 1.0 parts by weight, metal compound (B-2) 4.5 parts by weight, antioxidant (D-1 ) 0.3 parts by weight and 1.7 parts by weight of the colorant (E-1) were put into a 10-L double-arm press kneader (Moriyama) heated to 230 ° C, and then at 40 rpm. The mixture was kneaded for 20 minutes (shear speed 200 s- 1 ). Thereafter, the obtained molten kneaded mass was granulated by a feeder-ruder (manufactured by Moriyama) set at 180 ° C. and 40 rpm to obtain a pelletized elastomer material.
• a feeder-ruder manufactured by Moriyama
• the resulting pellets of the elastomer material are pressed by an electrothermal press forming machine (manufactured by Kansai Roll Co., Ltd.) under the conditions of a mold temperature of 180 ° C, a pressurization heating time of 10 minutes, and a pressurization cooling time of 5 minutes. Press molding was performed to obtain a thermoplastic thermoplastic elastomer sheet having a thickness of 2 mm, a length of 120 mm, and a width of 12 Omm.
• melt flow rate (MFR) was measured under the condition of a weight of 10 kg. The results are shown in Table 1 below. '
• thermoplastic elastomer sheet durometer A hardness as an index of flexibility, permanent elongation as an index of rubber elasticity, tensile strength at break and tensile elongation at break as mechanical strength, and specific gravity were measured.
• scratch resistance test 1 and scratch resistance test 2 were performed. The results are shown in Table 1.
• Durometer A hardness Measured according to JIS-K6253 and used as an index of flexibility.
• Scratch resistance test 1 Using a taper scratch tester manufactured by Toyo Seiki Seisaku-sho, a metal claw (material: tungsten carpide) with a load of 10 g was run on the sheet surface. This operation was repeated while increasing the load in increments of 10 g until the surface of the molded sheet was damaged, and the value of the load when the surface of the molded sheet was damaged was recorded. In this test, the higher the value of the recorded load, the better the scratch resistance.
• Specific functional group-containing copolymer (A-1) 100 parts by weight, metal compound (B-1) 1 5 parts by weight, 6.0 parts by weight of metal compound (B-2), 20 parts by weight of polyethylene resin (C-1), 7 parts by weight of polypropylene resin (C-1), and antioxidant (D-1) 0. 3 parts by weight and 1.7 parts by weight of the coloring agent (E-1) are put into a 10 L double-arm pressurized kneader (Moriyama) heated to 230 ° C, and mixed at 40 rpm for 20 minutes. Kneaded (shear speed 200 s- 1 ). Thereafter, the obtained molten kneaded mass was granulated by a feeder-ruder (manufactured by Moriyama) set at 180 ° C and 40 rpm to obtain a pelletized elastomer material.
• a feeder-ruder manufactured by Moriyama
• thermoplastic thermoplastic elastomer sheet having a thickness of 2 mm, a width of 120 mm and a width of 120 mm was obtained.
• the evaluation of this thermoplastic thermoplastic elastomer sheet was performed in the same manner as in Example 1. Table 1 shows the results.
• a pellet of the obtained elastomer material is injected into an injection molding machine (Nippon Steel Works,
• thermoplastic thermoplastic elastomer sheet having a thickness of 2 mm, a vertical width of 12 Omm and a horizontal width of 12 Omm was obtained by injection molding.
• the evaluation of this thermoplastic thermoplastic elastomer sheet was performed in the same manner as in Example 1. Table 1 shows the results.
• ⁇ Comparative Example 1 100 parts by weight of a specific functional group-containing copolymer (A-1), 0.3 parts by weight of an antioxidant (D-1), and 1.7 parts by weight of a coloring agent (E-1) at 230 ° C
• A-1 specific functional group-containing copolymer
• D-1 an antioxidant
• E-1 coloring agent
• E-1 coloring agent
• the mixture was charged into a 10-liter double-arm pressurized eader (Moriyama Co., Ltd.) and kneaded at 40 rpm for 20 minutes (shear speed 200 s- 1 ). Thereafter, the obtained molten kneaded mass was granulated by a feeder-ruder (manufactured by Moriyama Co., Ltd.) set at 180 ° C and 40 rpm to obtain a pelletized elastomer material.
• the resulting pellets of the elastomer material are pressed by an electrothermal press forming machine (manufactured by Kansai Roll Co., Ltd.) under the conditions of a mold temperature of 180 ° C, a pressurization heating time of 10 minutes, and a pressurization cooling time of 5 minutes.
• a olefin-based thermoplastic elastomer sheet having a thickness of 2 mm, a width of 120 mm, and a width of 12 Omm was obtained.
• the evaluation of this thermoplastic thermoplastic elastomer sheet was performed in the same manner as in Example 1. Table 1 shows the results.
• Comparative Example 1 since the copolymer was not crosslinked by metal ions, the mechanical strength and rubber elasticity and scratch resistance were low.
• Specific functional group-containing copolymer 100 parts by weight, metal compound (B-1) 1 • 5 parts by weight, metal compound (B-2) 6.0 parts by weight, polyethylene resin (C-1) 20 parts by weight, 7 parts by weight of polypropylene resin (C-1), 0.3 parts by weight of antioxidant (D-1), and 1.7 parts by weight of colorant (E-1), each heated to 230 ° C Into a 10 L double-arm pressure kneader (Moriyama) and kneaded at 40 rpm for 20 minutes (shear speed 200 s- 1 ). Thereafter, the obtained molten kneaded mass was granulated by a feeder-ruder (manufactured by Moriyama) set at 180 ° C and 40 rpm to obtain a pelletized elastomer material.
• a feeder-ruder manufactured by Moriyama
• the obtained pellets of the elastomer material were extruded with a 50 OmmT die (Model: MG427, manufactured by Hattori Gear Mfg. Co., Ltd.).
• the screw was a single-shaft unimelt screw.
• the ratio of the screw diameter D to the screw diameter LZD is 26, the T-die lip thickness is 0.5 mm), and the thickness is extruded under the conditions that the temperature inside the cylinder is 210 ° C and the screw rotation speed is 30 rpm.
• One sheet of a thermoplastic thermoplastic elastomer having a thickness of 0.05 mm and a width of 500 mm was obtained.
• melt flow rate of the obtained elastomer material was measured under the same conditions as in Example 1, it was 13 gZl Omin.
• thermoplastic elastomer sheet The specific gravity of the obtained thermoplastic elastomer sheet was measured by performing a scratch resistance test 1 and a scratch resistance test 2 in the same manner as in Example 1. The result was 0.9, the evaluation result of scratch resistance test 1 was 120 g, and the evaluation result of scratch resistance test 2 was 1.
• the tensile breaking strength and tensile breaking elongation of this olefin thermoplastic elastomer sheet were measured in accordance with JIS S-K7127, and the measurement result of tensile breaking strength was 29. The measurement result was 510%.
• the resulting mixed solution is cast on a glass plate at room temperature and air-dried for 12 hours. Crosslinked by heating under vacuum at 80 ° C for 4 hours. Thereafter, the film formed on the glass plate was peeled off to obtain a 210- ⁇ m thick olefin thermoplastic elastomer sheet.
• the obtained olefin-based thermoplastic elastomer sheet was subjected to a scratch resistance test 1 and a scratch resistance test 2 in the same manner as in Example 1, and the evaluation result of the scratch resistance test 1 was 130 g, indicating that the sheet was scratch-resistant.
• the evaluation result of sex test 2 was 1.
• the total haze of the obtained olefin-based thermoplastic elastomer sheet was measured according to JIS-K6782, and it was 2%.
• Specific functional group-containing copolymer (A-1) 100 parts by weight, metal compound (B-1) 1.5 parts by weight, metal compound (B-2) 6.0 parts by weight, polyethylene resin (C-1) 20 parts by weight, 7 parts by weight of polypropylene resin (C-1), 0.3 parts by weight of antioxidant (D-1), and 1.7 parts by weight of colorant (E-1), each heated to 230 ° C Into a 10-liter double-arm pressurized eder (Moriyama) and kneaded at 40 rpm for 20 minutes (shear speed 200 s- 1 ).
• the obtained mass kneaded material in a molten state was granulated by a feeder-ruder (manufactured by Moriyama Co., Ltd.) at 180 rpm at 180 to obtain a pelletized elastomer material.
• a hollow cylindrical base material having a thickness of 20 mm and a diameter of 53 mm was prepared by injection molding a polypropylene resin (C-2) at a mold temperature of 50 ° C.
• C-2 polypropylene resin
• the surface layer of the obtained laminate was subjected to a scratch resistance test 1 and a scratch resistance test 2 in the same manner as in Example 1.
• the evaluation result of the scratch resistance test 1 was 100 g.
• the evaluation result of 2 was 1.
• the surface layer of the laminate is to be peeled from the substrate, the surface layer does not peel at the interface with the substrate and breaks down, and the laminate has good adhesion between the surface layer and the substrate. was confirmed.

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