WO2023112858A1 - 積層構造体およびその用途 - Google Patents

積層構造体およびその用途 Download PDF

Info

Publication number
WO2023112858A1
WO2023112858A1 PCT/JP2022/045494 JP2022045494W WO2023112858A1 WO 2023112858 A1 WO2023112858 A1 WO 2023112858A1 JP 2022045494 W JP2022045494 W JP 2022045494W WO 2023112858 A1 WO2023112858 A1 WO 2023112858A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
propylene
parts
ethylene
group
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2022/045494
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
雄介 福田
周一 高橋
裕一 松木
愛美 阿部
和樹 三浦
顕雄 池田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Prime Polymer Co Ltd
Sika Hamatite Co Ltd
Original Assignee
Prime Polymer Co Ltd
Sika Hamatite Co Ltd
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 Prime Polymer Co Ltd, Sika Hamatite Co Ltd filed Critical Prime Polymer Co Ltd
Priority to EP22907385.3A priority Critical patent/EP4450280A4/en
Priority to JP2023561244A priority patent/JP7522521B2/ja
Priority to US18/711,277 priority patent/US20250018693A1/en
Priority to MX2024007197A priority patent/MX2024007197A/es
Priority to CN202280081572.XA priority patent/CN118541264A/zh
Publication of WO2023112858A1 publication Critical patent/WO2023112858A1/ja
Anticipated expiration legal-status Critical
Priority to JP2024111004A priority patent/JP7575635B2/ja
Ceased legal-status Critical Current

Links

Images

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
    • B32B27/06—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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/542—Shear strength
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • 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
    • B32B2375/00—Polyureas; Polyurethanes
    • 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
    • B32B2605/08—Cars
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/14—Copolymers of propene
    • 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
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present invention relates to a laminate structure used, for example, as an automobile exterior member, and having a layer of a molded body made of a polypropylene-based resin composition.
  • the present invention provides a laminated structure of a molded article made of a polypropylene-based resin composition and a cured resin layer, which has a low coefficient of linear expansion, is primerless and has high adhesive strength with a cured resin layer such as an adhesive layer.
  • the challenge is to
  • the laminated structure with the cured resin layer has excellent dimensional stability and high adhesive strength between the specific molded article and the specific curable resin even at high temperatures at which adhesion tends to decrease.
  • the polypropylene-based resin composition is 5 to 47 parts by mass of a propylene-based polymer (A) having a melt flow rate (230°C, 2.16 kg load) of 50 to 150 g/10 minutes and a decane-soluble content of 6 to 15% by mass; 20 to 30 parts by mass of a propylene homopolymer (B) having a melt flow rate (230°C, 2.16 kg load) of 10 to 500 g/10 minutes; It is a random copolymer of ethylene and an ⁇ -olefin having 4 to 8 carbon atoms, and has a density of 0.850 to 0.880 g/cm 3 and a melt flow rate (230°C, 2.16 kg load) of 0.
  • a laminated structure comprising: [2] The laminated structure according to [1], which has a 90° C. hot shear test strength exceeding 1.5 MPa in a primerless adhesion test.
  • the propylene-based polymer (A) is a block copolymer of propylene and ethylene, and the intrinsic viscosity [ ⁇ ] of the decane-soluble portion of the copolymer is 2 to 9 dl/g. 1] or the laminated structure according to [2].
  • the cured resin layer containing the curable resin (E) having a urethane bond is obtained by curing a urethane-based adhesive containing a urethane prepolymer having a polyether skeleton and an aliphatic isocyanate derivative, [1 ] to [4].
  • the laminated structure according to any one of [1] to [6] which is used as an automobile exterior member.
  • An automobile exterior member comprising the laminated structure according to any one of [1] to [7].
  • the curable resin composition is a curable resin composition containing a urethane prepolymer having a polyether skeleton and an aliphatic isocyanate derivative.
  • R 37 and R 38 each independently represent a hydrocarbon group.
  • the curable resin composition according to [10] which contains an adduct of a compound represented by and a phenol compound.
  • the molded body and the cured resin layer made of a polypropylene resin composition are directly laminated without a primer, and the coefficient of linear expansion is low, the dimensional stability is excellent, and the adhesiveness tends to decrease. It is possible to provide a laminate structure that is primerless and has high adhesive strength between the specific molded article and the specific curable resin even at high temperatures.
  • FIG. 1 is a schematic diagram of hot shear test strength measurement of a laminated structure.
  • the laminated structure of the present invention is a laminated structure in which a resin-cured layer (ii) containing a curable resin having a urethane bond is directly laminated on a molded body (i) made of a polypropylene-based resin composition.
  • a molded body (i) made of a polypropylene-based resin composition and a curable resin layer (ii) formed of a urethane-based adhesive or the like are directly laminated without a primer. It is a struct.
  • the molded article (i) according to the present invention is a molded article made of a polypropylene-based resin composition.
  • Polypropylene-Based Resin Composition The polypropylene-based resin composition according to the present invention comprises a propylene-based polymer (A), a propylene homopolymer (B), an ethylene/ ⁇ -olefin copolymer (C), and an inorganic filler (D). and optionally other ingredients.
  • the propylene-based polymer (A) used in the present invention is a propylene-based polymer having a melt flow rate (230° C., 2.16 kg load) of 50 to 150 g/10 minutes and a decane-soluble portion amount of 6 to 15% by mass. is.
  • the propylene-based polymer (A) substantially contains 6-15% by mass of the decane-soluble portion (a1) and 85-94% by mass of the decane-insoluble portion (a2).
  • the decane-insoluble part (a2) is a component that is generally insoluble in an n-decane solvent at room temperature (23° C.), and is usually a propylene homopolymer part (propylene homopolymer component ) is equivalent to
  • the decane-soluble portion (a1) is equivalent to a portion other than the propylene homopolymer portion, and is preferably a copolymer portion of propylene and ethylene (ethylene/propylene copolymer component).
  • the propylene-based polymer (A) usually contains 6 to 15% by mass of decane-soluble portion (a1) and 85 to 94% by mass of decane-insoluble portion (a2), preferably 7 to 12% by mass of decane-soluble portion. It contains a soluble part (a1) and a decane-insoluble part (a2) of 88 to 93% by mass [wherein the sum of the content of (a1) and the content of (a2) is 100% by mass].
  • the propylene-based polymer (A) is preferably a propylene-based block copolymer obtained from propylene and ethylene.
  • the intrinsic viscosity [ ⁇ ] of the decane-soluble portion (a1) of the propylene-based block copolymer is preferably 2 to 9 dl/g, more preferably 3 to 8 dl/g.
  • the melt flow rate (230° C., 2.16 kg load) of the propylene-based polymer (A) is 50 to 150 g/10 minutes, preferably 50 to 130 g/10 minutes, more preferably 60 to 120 g/10 minutes, especially It is preferably 70 to 110 g/10 minutes.
  • the propylene-based polymer (A) can be produced by a known method. For example, propylene is polymerized using an olefin polymerization catalyst containing the solid titanium catalyst component (I) and the organometallic compound catalyst component (II) described below, and then propylene and ethylene are copolymerized to obtain propylene. A system block copolymer is obtained.
  • Solid titanium catalyst component (I) The solid titanium catalyst component (I) that constitutes the olefin polymerization catalyst contains, for example, titanium, magnesium, halogen and, if necessary, an electron donor. Known components can be used without limitation for the solid titanium catalyst component (I).
  • a magnesium compound and a titanium compound are often used in the preparation of the solid titanium catalyst component (I).
  • magnesium compounds include magnesium halides such as magnesium chloride and magnesium bromide; alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride and phenoxymagnesium chloride; ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, 2-ethyl alkoxymagnesium such as hexoxymagnesium; aryloxymagnesium such as phenoxymagnesium; carboxylate of magnesium such as magnesium stearate;
  • a magnesium compound may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the magnesium compound may also be a complex compound with other metals, a double compound, or a mixture with other metal compounds.
  • halogen-containing magnesium compounds are preferred, and magnesium halides, particularly magnesium chloride, are more preferred.
  • alkoxymagnesium such as ethoxymagnesium is also preferred.
  • Magnesium compounds may also be those derived from other substances, such as compounds obtained by contacting organomagnesium compounds such as Grignard reagents with titanium halides, silicon halides, halogenated alcohols, and the like.
  • titanium compounds examples include tetravalent titanium compounds represented by the following formula.
  • titanium compounds include titanium tetrahalides such as TiCl 4 and TiBr 4 ; Ti(OCH 3 )Cl 3 , Ti(OC 2 H 5 )Cl 3 , Ti(On-C 4 H 9 )Cl trihalogenated alkoxytitanium such as 3 , Ti( OC2H5 ) Br3 , Ti(Oi- C4H9 ) Br3 ; Ti( OCH3 ) 2Cl2 , Ti( OC2H5 ) 2 dihalogenated alkoxytitanium such as Cl2 ; monohalogenated alkoxytitanium such as Ti( OCH3 ) 3Cl , Ti(On - C4H9 ) 3Cl , Ti( OC2H5 ) 3Br ; Tetraalkoxytitanium
  • magnesium compound and titanium compound for example, compounds described in detail in JP-A-57-63310 and JP-A-5-170843 can also be used.
  • Specific examples of preferred methods for preparing the solid titanium catalyst component (I) used in the present invention include the following methods (P-1) to (P-4).
  • P-1) A solid adduct comprising an electron donor component (1) such as a magnesium compound and an alcohol, an electron donor component (2) described later, and a liquid titanium compound are combined in an inert hydrocarbon solvent.
  • P-2) A method of contacting in a suspended state under coexistence.
  • P-2 A method of contacting a solid adduct comprising a magnesium compound and an electron donor component (1), an electron donor component (2), and a liquid titanium compound in multiple steps.
  • a solid adduct comprising a magnesium compound and an electron donor component (1), an electron donor component (2), and a liquid titanium compound are suspended in the presence of an inert hydrocarbon solvent.
  • P-4) A method of contacting a liquid magnesium compound comprising a magnesium compound and an electron donor component (1), a liquid titanium compound, and an electron donor component (2).
  • the reaction temperature for preparing the solid titanium catalyst component (I) is preferably -30 to 150°C, more preferably -25 to 130°C, and particularly preferably -25 to 120°C.
  • the preparation of the solid titanium catalyst component (I) can also be carried out in the presence of a known medium, if necessary.
  • a known medium include slightly polar aromatic hydrocarbons such as toluene, and known aliphatic or alicyclic hydrocarbons such as heptane, octane, decane, and cyclohexane. Among them, aliphatic hydrocarbons are preferred.
  • the electron donor component (1) used for forming a solid adduct or a liquid magnesium compound a known compound capable of solubilizing the magnesium compound at a temperature range of room temperature to about 300° C. is preferred, such as alcohols and aldehydes. , amines, carboxylic acids and mixtures thereof are preferred. Examples of these compounds include compounds described in JP-A-57-63310 and JP-A-5-170843.
  • alcohols capable of solubilizing magnesium compounds include methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol. , decanol, and dodecanol; alicyclic alcohols such as cyclohexanol and methylcyclohexanol; aromatic alcohols such as benzyl alcohol and methylbenzyl alcohol; aliphatic alcohols having an alkoxy group such as n-butyl cellosolve; mentioned.
  • carboxylic acids include organic carboxylic acids having 7 or more carbon atoms, such as caprylic acid and 2-ethylhexanoic acid.
  • aldehydes include aldehydes having 7 or more carbon atoms such as capricaldehyde and 2-ethylhexylaldehyde.
  • amines include amines having 6 or more carbon atoms such as heptylamine, octylamine, nonylamine, laurylamine and 2-ethylhexylamine.
  • the electron donor component (1) the above alcohols are preferable, and ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, and decanol are particularly preferable.
  • the compositional ratio of magnesium in the obtained solid adduct or liquid magnesium compound to the electron donor component (1) varies depending on the type of compound used, and cannot be generally defined.
  • the electron donor component (1) is preferably 2 mol or more, more preferably 2.3 mol or more, and particularly preferably 2.7 mol or more and 5 mol or less.
  • electron donors optionally used in the solid titanium catalyst component (I) include aromatic carboxylic acid esters and/or compounds having two or more ether bonds via a plurality of carbon atoms ( Hereinafter referred to as "electron donor component (2)").
  • Examples of the electron donor component (2) include known aromatic carboxylic acid esters and polyether compounds that are preferably used in conventional olefin polymerization catalysts, such as JP-A-5-170843 and JP-A-2001-354714. etc. can be used without limitation.
  • aromatic carboxylic acid esters include aromatic carboxylic acid monoesters such as benzoic acid esters and toluic acid esters, as well as aromatic polyvalent carboxylic acid esters such as phthalic acid esters.
  • aromatic polyvalent carboxylic acid esters are preferable, and phthalates are more preferable.
  • phthalates phthalate alkyl esters such as ethyl phthalate, n-butyl phthalate, isobutyl phthalate, hexyl phthalate and heptyl phthalate are preferred, and diisobutyl phthalate is particularly preferred.
  • polyether compounds include compounds represented by the following chemical structural formula (1).
  • m is an integer of 1 ⁇ m ⁇ 10, more preferably an integer of 3 ⁇ m ⁇ 10, and R 11 to R 36 are each independently a hydrogen atom, or carbon, hydrogen, oxygen , fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron and silicon.
  • R 11 to R 36 are each independently a hydrogen atom, or carbon, hydrogen, oxygen , fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron and silicon.
  • m is 2 or more, a plurality of R 11 and R 12 may be the same or different. Any of R 11 to R 36 , preferably R 11 and R 12 may together form a ring other than a benzene ring.
  • Such compounds include monosubstituted dialkoxys such as 2-isopropyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, and 2-cumyl-1,3-dimethoxypropane.
  • 1,3-diethers are preferred, and particularly 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1 ,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane and 2,2-bis(cyclohexylmethyl)1,3-dimethoxypropane are preferred.
  • the halogen/titanium (atomic ratio) (that is, the number of moles of halogen atoms/the number of moles of titanium atoms) is 2 to 100, preferably 4 to 90, and the electron donor component (1)/titanium atom (molar ratio) is 0-100, preferably 0-10, and electron donor component (2)/titanium atom (molar ratio) is 0-100, preferably 0-10.
  • the magnesium/titanium (atomic ratio) ie moles of magnesium atoms/moles of titanium atoms) is 2-100, preferably 4-50.
  • the organometallic compound catalyst component (II) is a component containing a metal element selected from Groups 1, 2 and 13 of the periodic table.
  • compounds containing Group 13 metals organoaluminum compounds, etc.
  • complex alkylates of Group 1 metals and aluminum organometallic compounds of Group 2 metals, and the like can be used.
  • organoaluminum compounds are preferred.
  • organometallic compound catalyst component (II) the organometallic compound catalyst components described in known documents such as EP585869A1 can be suitably used.
  • a known electron donor component (3) may be used in combination with the electron donor component (1) and the electron donor component (2) described above as long as the object of the present invention is not impaired.
  • This organosilicon compound is, for example, a compound represented by the following formula.
  • RnSi (OR') 4-n (Wherein, R and R' are hydrocarbon groups, and n is an integer of 0 ⁇ n ⁇ 4.)
  • Specific examples of the organosilicon compound represented by the above formula include diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane.
  • cyclohexylmethyldiethoxysilane vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane , cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, cyclopentyldimethylethoxysilane and the like are used.
  • vinyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, and dicyclopentyldimethoxysilane are preferred.
  • silane compound represented by the following formula described in International Publication No. 2004/016662 is also a preferred example of the organosilicon compound.
  • R a is a hydrocarbon group having 1 to 6 carbon atoms.
  • it is an unsaturated or saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrocarbon group having 2 to 6 carbon atoms.
  • Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n -hexyl group, cyclohexyl group and the like.
  • an ethyl group is particularly preferred.
  • R b is a hydrocarbon group having 1 to 12 carbon atoms or hydrogen.
  • it is an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or hydrogen.
  • Specific examples include hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, octyl group and the like.
  • an ethyl group is particularly preferred.
  • R c is a hydrocarbon group having 1 to 12 carbon atoms.
  • it is an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms.
  • Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n -hexyl group, cyclohexyl group, octyl group and the like.
  • an ethyl group is particularly preferred.
  • organosilicon compound represented by the above formula examples include dimethylaminotriethoxysilane, diethylaminotriethoxysilane, diethylaminotrimethoxysilane, diethylaminotri-n-propoxysilane, di-n-propylaminotriethoxysilane, methyl-n- Propylaminotriethoxysilane, t-butylaminotriethoxysilane, ethyl n-propylaminotriethoxysilane, ethyliso-propylaminotriethoxysilane, methylethylaminotriethoxysilane and the like.
  • organosilicon compounds include compounds represented by the following formulas.
  • RN is a cyclic amino group.
  • Specific examples include a perhydroquinolino group, a perhydroisoquinolino group, a 1,2,3,4-tetrahydroquinolino group, a 1,2,3,4-tetrahydroisoquinolino group, an octamethyleneimino group, and the like. mentioned.
  • R a is the same as above.
  • organosilicon compound represented by the above formula examples include (perhydroquinolino)triethoxysilane, (perhydroisoquinolino)triethoxysilane, (1,2,3,4-tetrahydroquinolino)triethoxy silane, (1,2,3,4-tetrahydroisoquinolino)triethoxysilane, octamethyleneiminotriethoxysilane and the like.
  • organosilicon compounds described above Two or more of the organosilicon compounds described above may be used in combination.
  • a propylene/ethylene block copolymer which is a preferred embodiment of the propylene-based polymer (A), is obtained by polymerizing propylene in the presence of the above-described catalyst for olefin polymerization and then copolymerizing or prepolymerizing propylene and ethylene. It can be produced by polymerizing propylene in the presence of a prepolymerization catalyst obtained by the above method and then copolymerizing propylene and ethylene.
  • Prepolymerization is carried out by prepolymerizing olefin in an amount of usually 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g, per 1 g of olefin polymerization catalyst.
  • a catalyst with a concentration higher than that in the system in main polymerization can be used.
  • the concentration of the solid titanium catalyst component (I) in the prepolymerization is usually 0.001 to 200 millimoles, preferably 0.01 to 50 millimoles, more preferably 0.1 to 50 millimoles per liter of liquid medium in terms of titanium atoms. 20 millimoles.
  • the amount of the organometallic compound catalyst component (II) in the prepolymerization is usually 0.1 to 1000 g, preferably 0.3 to 500 g of polymer per 1 g of the solid titanium catalyst component (I).
  • the amount is usually 0.1 to 300 mol, preferably 0.5 to 100 mol, more preferably 1 to 50 mol, per 1 mol of titanium atom in the solid titanium catalyst component (I).
  • the above-mentioned electron donor components can be used if necessary. It is preferably 0.5 to 30 mol, more preferably 1 to 10 mol.
  • Prepolymerization can be carried out under mild conditions by adding the olefin and the above catalyst components to an inert hydrocarbon medium.
  • the prepolymerization is preferably carried out batchwise.
  • inert hydrocarbon media include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, methylcyclopentane, cyclohexane, cycloheptane, methylcycloheptane , alicyclic hydrocarbons such as cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; or mixtures thereof. Among them, aliphatic hydrocarbons are preferred.
  • Preliminary polymerization can also be performed using the olefin itself as a solvent. Prepolymerization can also be carried out in a substantially solvent-free state. In this case, it is preferable to carry out the preliminary polymerization continuously.
  • the olefin used in the preliminary polymerization may be the same as or different from the olefin used in the main polymerization described below. Propylene is particularly preferred as the olefin.
  • the temperature during the preliminary polymerization is usually -20 to 100°C, preferably -20 to 80°C, more preferably 0 to 40°C.
  • This polymerization is divided into a process for producing a propylene homopolymer component and a process for producing a propylene-ethylene copolymer component.
  • the main polymerization can be carried out by either liquid phase polymerization such as bulk polymerization, solution polymerization, suspension polymerization, or gas phase polymerization.
  • a liquid phase polymerization method such as bulk polymerization or suspension polymerization, or a gas phase polymerization method is preferable.
  • the process for producing the propylene-ethylene copolymer component is preferably a liquid phase polymerization method such as bulk polymerization or suspension polymerization, or a gas phase polymerization method, more preferably a gas phase polymerization method.
  • the reaction solvent may be the inert hydrocarbon used in the preliminary polymerization described above, or an olefin that is liquid at the reaction temperature and pressure.
  • the solid titanium catalyst component (I) is usually used in an amount of 0.0001 to 0.5 mmol, preferably 0.005 to 0.1 mmol in terms of titanium atoms per liter of polymerization volume. Used.
  • the organometallic compound catalyst component (II) is used in an amount of generally 1 to 2000 mol, preferably 5 to 500 mol, per 1 mol of titanium atoms in the preliminary polymerization catalyst component in the polymerization system.
  • an electron donor component it is usually 0.001 to 50 mol, preferably 0.01 to 30 mol, more preferably 0.05 to 20 mol, per 1 mol of the organometallic compound catalyst component (II). Used in molar amounts.
  • the molecular weight of the resulting polymer can be adjusted (lowered), and a polymer with a high melt flow rate (MFR) can be obtained.
  • MFR melt flow rate
  • the amount of hydrogen required to adjust the molecular weight varies depending on the type of production process used, polymerization temperature, and pressure, so it may be adjusted as appropriate.
  • the MFR can be adjusted by adjusting the polymerization temperature and the amount of hydrogen.
  • the intrinsic viscosity can be adjusted by adjusting the polymerization temperature, pressure and amount of hydrogen.
  • the olefin polymerization temperature is generally 0 to 200°C, preferably 30 to 100°C, more preferably 50 to 90°C.
  • the pressure gauge pressure
  • the pressure is usually normal pressure to 100 kgf/cm 2 (9.8 MPa), preferably 2 to 50 kgf/cm 2 (0.20 to 4.9 MPa).
  • the polymerization can be carried out by any of batch, semi-continuous and continuous methods.
  • the shape of the reactor can be either tubular or tank.
  • the polymerization can be carried out in two or more stages by changing the reaction conditions. In this case, the tubular type and the tank type can be combined.
  • the ethylene/(ethylene + propylene) gas ratio is adjusted to Control.
  • the ethylene/(ethylene+propylene) gas ratio is generally 5 to 80 mol %, preferably 10 to 70 mol %, more preferably 15 to 60 mol %.
  • the decane-insoluble portion (a2) of the propylene/ethylene block copolymer is mainly composed of the propylene homopolymer component.
  • the decane-soluble portion (a1) is mainly composed of an ethylene-propylene copolymer component, which is a rubber-like component.
  • a propylene/ethylene block copolymer which is a preferred embodiment of the propylene-based polymer (A)
  • Polymerization step 1 A step of polymerizing propylene in the presence of a solid titanium catalyst component to produce a propylene homopolymer component (propylene homopolymer production step).
  • Polymerization step 2) A step of copolymerizing propylene and ethylene in the presence of a solid titanium catalyst component to produce an ethylene/propylene copolymer component (copolymer rubber production step).
  • each polymerization step 1 and 2 can also be carried out using two or more polymerization tanks.
  • the content of the decane-soluble portion (a1) can be adjusted by the polymerization time (residence time) of the polymerization steps 1 and 2.
  • the former polymerization step 1 may be carried out in two or more stages of polymerization vessels connected in series. In that case, the ratio of propylene to hydrogen in each stage may be different for each polymerization vessel.
  • the propylene-based polymer (A) used in the present invention may contain one or more biomass-derived monomers.
  • the same kind of monomers constituting the polymer may be only biomass-derived monomers, or may contain both biomass-derived monomers and fossil fuel-derived monomers.
  • Biomass-derived monomers are monomers derived from any renewable natural raw materials and their residues, such as plant-derived or animal-derived, including fungi, yeast, algae and bacteria, and containing 14 C isotope as carbon .
  • the biomass carbon concentration (pMC) measured according to ASTM D 6866 is about 100 (pMC).
  • a biomass-derived monomer is obtained by a conventionally known method.
  • the propylene-based polymer (A) used in the present invention contains a biomass-derived monomer from the viewpoint of reducing the burden on the environment. If the polymer production conditions such as the polymerization catalyst and polymerization temperature are the same, even if the raw material olefin contains biomass-derived olefin, the molecular structure other than the 14 C isotope at a ratio of about 10 -12 is fossil fuel. It is equivalent to a propylene-based polymer consisting of derived monomers. Therefore, the performance is assumed to be unchanged.
  • the propylene-based polymer (A) according to the present invention may contain propylene derived from chemical recycling.
  • the propylene constituting the polymer may be only propylene derived from chemical recycling, or may contain propylene derived from chemical recycling and propylene derived from fossil fuel and/or propylene derived from biomass.
  • Propylene derived from chemical recycling can be obtained by a conventionally known method. It is preferable that the propylene-based polymer (A) according to the present invention contains propylene derived from chemical recycling from the viewpoint of reducing environmental load (mainly reducing waste).
  • the monomer derived from chemical recycling is a monomer obtained by depolymerizing or thermally decomposing a polymer such as waste plastic into a monomer unit such as propylene, or using the monomer as a raw material. Since it is a produced monomer, its molecular structure is equivalent to that of a propylene homopolymer composed of a fossil fuel-derived monomer if polymer production conditions such as a polymerization catalyst, polymerization process and polymerization temperature are the same. Therefore, the performance is assumed to be unchanged.
  • the propylene homopolymer (B) used in the present invention is a propylene homopolymer having a melt flow rate (230° C., 2.16 kg load) of 10 to 500 g/10 minutes.
  • the propylene homopolymer (B) may be a polymer obtained by polymerizing substantially only propylene.
  • a homopolymer obtained by polymerizing only propylene, or a crystalline polymer obtained by copolymerizing propylene with 6 mol % or less, preferably 3 mol % or less of another ⁇ -olefin can be used.
  • a homopolymer obtained by polymerizing only propylene is preferable.
  • the propylene homopolymer (B) can be produced by polymerizing monomers mainly composed of propylene by a known method.
  • an olefin polymerization catalyst containing the above-described solid titanium catalyst component (I) and an organometallic compound catalyst component (II), or titanium trichloride and an alkylaluminum compound commonly referred to as Ziegler-Natta catalysts It is obtained by polymerizing propylene-based monomers in the presence of a combined catalyst.
  • the polymerization reaction may be carried out continuously or batchwise. Further, for example, it can be suitably produced by performing only the polymerization step 1 described above.
  • the polymerization temperature is usually 0 to 200°C, preferably 30 to 100°C, more preferably 50 to 90°C.
  • the pressure gauge pressure
  • the pressure is usually normal pressure to 100 kgf/cm 2 (9.8 MPa), preferably 2 to 50 kgf/cm 2 (0.20 to 4.9 MPa).
  • the melt flow rate (230° C., 2.16 kg load) of the propylene homopolymer (B) is 10 to 500 g/10 minutes, preferably 10 to 300 g/10 minutes, more preferably 20 to 250 g/10 minutes. .
  • the propylene homopolymer (B) may be one type of polymer, or two or more types of propylene homopolymers may be arbitrarily combined within a range that satisfies the above melt flow rate as a whole.
  • the propylene homopolymer (B) used in the present invention may contain biomass-derived propylene.
  • the propylene constituting the polymer may be only biomass-derived propylene, or may contain both biomass-derived propylene and fossil fuel-derived propylene.
  • Biomass-derived propylene is a monomer derived from any renewable natural raw material and its residues, such as plant or animal origin, including fungi, yeast, algae and bacteria, and has 14C isotope as carbon.
  • the biomass carbon concentration (pMC) measured according to ASTM D 6866 is about 100 (pMC).
  • Biomass-derived propylene is obtained by a conventionally known method.
  • the propylene homopolymer (B) used in the present invention contains a biomass-derived monomer from the viewpoint of reducing the burden on the environment. If the polymer production conditions such as the polymerization catalyst and polymerization temperature are the same, even if the raw material propylene contains biomass-derived propylene, the molecular structure other than containing the 14C isotope at a ratio of about 10 -12 is derived from fossil fuels. It is equivalent to propylene homopolymer consisting of propylene. Therefore, the performance is assumed to be unchanged.
  • the propylene homopolymer (B) used in the present invention may contain propylene derived from chemical recycling as a monomer, like the propylene-based polymer (A) described above. That is, the propylene constituting the polymer may be only propylene derived from chemical recycling, or may contain propylene derived from chemical recycling and propylene derived from fossil fuel and/or propylene derived from biomass.
  • the ethylene/ ⁇ -olefin copolymer (C) used in the present invention is a random copolymer of ethylene and an ⁇ -olefin having 4 to 8 carbon atoms, and has a density of 0.850 to 0.880 g/cm. 3.
  • This ethylene/ ⁇ -olefin copolymer (C) contributes to improvement in dimensional stability (reduction in coefficient of linear expansion) of molded article (i) and laminated structure having the same through a synergistic effect with other components. In addition to contributing to the improvement of other physical properties, the molded product exhibits a high degree of physical property balance.
  • 1-butene, 1-hexene and 1-octene are preferable as the ⁇ -olefin having 4 to 8 carbon atoms constituting the ethylene/ ⁇ -olefin copolymer (C).
  • One type of ⁇ -olefin may be used alone, or two or more types may be used in combination.
  • the ethylene/ ⁇ -olefin copolymer (C) an ethylene-octene copolymer and an ethylene-butene copolymer are particularly preferred.
  • the melt flow rate (230°C, 2.16 kg load) of the ethylene/ ⁇ -olefin copolymer (C) is 0.5 to 30 g/10 minutes, preferably 1 to 25 g/10 minutes, more preferably 2. ⁇ 20 g/10 min.
  • melt flow rate (230° C., 2.16 kg load) of the ethylene/ ⁇ -olefin copolymer (C) is 0.5 g/10 minutes or more, the fluidity of the polypropylene resin composition will be reduced and during kneading Insufficient dispersion is less likely to occur, and physical properties such as impact resistance and the like tend to be less likely to deteriorate and the surface appearance of molded products to be less likely to occur. Also, when the melt flow rate (230° C., 2.16 kg load) is 30 g/10 minutes or less, the molded article (i) and the laminated structure having it tend to have sufficient impact resistance.
  • the ethylene/ ⁇ -olefin copolymer (C) has a density of 0.850 to 0.880 g/cm 3 , preferably 0.855 to 0.875 g/cm 3 .
  • the melting point peak of the ethylene/ ⁇ -olefin copolymer (C) is 110°C or higher, preferably 110 to 130°C.
  • Melting peak means the value determined by differential scanning calorimeter (DSC). Specifically, the temperature at the maximum peak position when the endothermic curve of a differential scanning calorimeter (DSC) is obtained can be obtained as the melting point peak (Tm).
  • Inorganic filler (D) As the inorganic filler (D) used in the present invention, known inorganic fillers can be used without particular limitation. Examples include talc, calcium carbonate, natural mica, synthetic mica, wollastonite, montmorillonite and the like. An inorganic filler (D) may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, talc is preferred. By using such an inorganic filler (D), the mechanical properties of the molded article (i) and the laminated structure having the molded article (i) are improved.
  • the inorganic filler (D) is not particularly limited as long as it is dispersed in the resin composition. It is 10.0 ⁇ m or less, preferably 3.0 ⁇ m to 8.0 ⁇ m, more preferably 3.0 ⁇ m to 7.0 ⁇ m.
  • This average particle size is a value measured by a laser diffraction method. Specifically, it is the particle size at an integrated value of 50% in the particle size distribution determined by a particle size distribution analyzer such as a laser diffraction scattering type particle size distribution analyzer. 920 type etc. are mentioned.
  • the aspect ratio of the inorganic filler (D) is not particularly limited, it is usually 3 or more and less than 15, preferably 4-13, more preferably 5-11.
  • the aspect ratio is a value that represents the ratio of the major diameter to the thickness of the filler, or the ratio of the long side to the short side. If this aspect ratio is 3 or more, the rigidity and dimensional stability of the molded product tend to be less likely to decrease. On the other hand, if it is less than 15, the balance of mechanical properties is less likely to deteriorate, and the impact strength tends to be less likely to decrease.
  • this aspect ratio is a value obtained by taking a photograph using an electron microscope, measuring the length and thickness of the powder, obtaining an average value, and calculating the average particle diameter/average thickness ratio.
  • the inorganic filler (D) contributes to improving the dimensional stability (reducing the linear expansion coefficient) of the molded article (i) and the laminated structure having the same, and improves mechanical properties such as rigidity and impact strength. contribute to When the inorganic filler (D) has the above-described average particle size (and aspect ratio), a synergistic effect with other components results in a high degree of excellent dimensional stability and excellent rigidity and impact resistance. It is suitable because a good balance of physical properties is likely to appear.
  • any shape of inorganic filler such as granular, plate-like, rod-like, fibrous, and whisker-like can be used.
  • Inorganic fillers commercially available as fillers for polymers can also be used.
  • chopped strands, compressed masses, pellets (granules), granules, and the like, which are more convenient to handle, can be used. Among them, powdery, compacted lumps, and granules are preferred.
  • the inorganic filler (D) may be a mixture of two or more types of inorganic fillers.
  • the method for producing the inorganic filler (D) is not particularly limited, and can be produced by various known methods.
  • talc for example, is used as the inorganic filler (D)
  • talc having a specific average particle size and aspect ratio can be produced by pulverization or granulation.
  • the aspect ratio and average particle size of talc can be appropriately adjusted by the pulverization device and the pulverization time, and talc with a controlled shape can be obtained by classification as necessary.
  • the inorganic filler (D) one obtained by pulverizing ore may be used directly, or one that has been surface-treated at least partially may be used.
  • various surface treatment agents such as organic titanate coupling agents, organic silane coupling agents, modified polyolefins grafted with unsaturated carboxylic acids or their anhydrides, fatty acids, fatty acid metal salts, and fatty acid esters are used. Available.
  • One surface treatment agent may be used alone, or two or more kinds may be used in combination.
  • the polypropylene-based resin composition according to the present invention may optionally contain a nucleating agent, a heat stabilizer, an antistatic agent, a weather stabilizer, a light stabilizer, an anti-aging agent, an antioxidant, a fatty acid metal salt, and a softening agent.
  • a nucleating agent e.g., sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium
  • the polypropylene-based resin composition according to the present invention comprises a propylene-based polymer (A) of 5 to 47 parts by mass, a propylene homopolymer (B) of 20 to 30 parts by mass, and an ethylene/ ⁇ -olefin copolymer (C) of 23 to 30 parts by mass, and 30 to 40 parts by mass of inorganic filler (D) [however, the total amount of components (A) to (D) shall be 100 parts by mass. ] contains.
  • the polypropylene-based resin composition according to the present invention preferably comprises a propylene-based polymer (A) of 7 to 35 parts by mass, a propylene homopolymer (B) of 20 to 30 parts by mass, and an ethylene/ ⁇ -olefin copolymer (C ) 23 to 28 parts by mass, and inorganic filler (D) 32 to 40 parts by mass [however, the total amount of components (A) to (D) is 100 parts by mass. ] contains.
  • the polypropylene-based resin composition according to the present invention includes a propylene-based polymer (A) of 8 to 28 parts by mass, a propylene homopolymer (B) of 23 to 30 parts by mass, and an ethylene/ ⁇ -olefin copolymer ( C) 24 to 28 parts by mass, and inorganic filler (D) 33 to 38 parts by mass [provided that the total amount of components (A) to (D) is 100 parts by mass. ] contains.
  • A propylene-based polymer
  • B propylene homopolymer
  • C ethylene/ ⁇ -olefin copolymer
  • D inorganic filler
  • the polypropylene resin composition according to the present invention is particularly preferably composed of a propylene polymer (A) of 10 to 22 parts by mass, a propylene homopolymer (B) of 25 to 30 parts by mass, and an ethylene/ ⁇ -olefin copolymer ( C) 24 to 27 parts by mass, and inorganic filler (D) 34 to 37 parts by mass [provided that the total amount of components (A) to (D) is 100 parts by mass. ] contains.
  • the polypropylene-based resin composition according to the present invention can be produced by blending the components (A) to (D) described above and, if necessary, optional components such as additives. Each component may be added successively in any order, or may be mixed at the same time. Also, a multi-stage mixing method may be employed in which some components are mixed and then other components are mixed. Specifically, for example, after first blending components (A) to (C), which are resin components (organic compound components) in the polypropylene resin composition, then component (D) and, if necessary, additives It can also be produced by adding and blending optional components such as
  • each component can be mixed or melt-kneaded simultaneously or sequentially. mentioned.
  • the melt flow rate (230°C, 2.16 kg load) of the polypropylene-based resin composition according to the present invention is usually 23 g/10 minutes or more, preferably more than 23 g/10 minutes and 50 g/10 minutes or less. By setting the melt flow rate within such a range, good moldability can be obtained, and deterioration of coating appearance after injection molding can be suppressed.
  • the molded article (i) according to the present invention is a molded article obtained from the above polypropylene-based resin composition according to the present invention. Molded article (i) can be obtained by appropriately molding the polypropylene-based resin composition according to the present invention.
  • the method for molding the polypropylene-based resin composition is not particularly limited, and various known methods for molding the resin composition can be used. Injection molding and press molding are particularly preferable as the method for molding the molded article (i).
  • the molded article (i) obtained from the polypropylene-based resin composition according to the present invention has small dimensional changes due to temperature changes and is excellent in dimensional stability. Excellent stability.
  • the cured resin layer (ii) is a layer of cured resin containing a curable resin (E) having a urethane bond.
  • the curable resin (E) used in the present invention is a curable resin having urethane bonds.
  • a curable resin (E) known curable resins having urethane bonds can be used without limitation, and specific examples thereof include polyurethane resins.
  • the curable resin (E) having a urethane bond may contain a urea bond, a burette bond, etc. in addition to the urethane bond. If necessary, a curing agent may be used in the production of the resin-cured layer (ii) containing the curable resin (E) having a urethane bond.
  • a known polyurethane resin can be used as the polyurethane resin used as the curable resin (E) having a urethane bond.
  • polymers obtained by reacting polyfunctional isocyanates or derivatives thereof with polyols or derivatives thereof and/or polyesters or derivatives thereof can be used.
  • Polyfunctional isocyanates or derivatives thereof used as raw materials for polyurethane resins include polyfunctional isocyanates such as tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), isophorone diisocyanate and norbornane diisocyanate. Examples thereof include isocyanates and derivatives such as block derivatives or isocyanurate derivatives thereof. These can be used individually by 1 type, and can also be used in combination of 2 or more types.
  • polyols or derivatives thereof used as raw materials for polyurethane resins include polypropylene glycols having a molecular weight of 500 to 100,000, polyethylene glycol-polypropylene glycol block copolymers, terminally aminated polypropylene glycols, and the like. These can be used individually by 1 type, and can also be used in combination of 2 or more types.
  • polyesters or derivatives thereof used as raw materials for polyurethane resins include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate and polybutylene isophthalate, and reaction products of these polyesters with polyethylene glycol or polypropylene glycol. These can be used individually by 1 type, and can also be used in combination of 2 or more types.
  • a polyurethane resin from a polyfunctional isocyanate and a polyol and/or polyester for example, the two can be mixed and stirred so that the polyfunctional isocyanate is in an equimolar to excess amount.
  • a polymerization accelerator such as an amine compound may be blended.
  • the cured resin layer (ii) according to the present invention may be produced by applying a composition such as an adhesive or a paint containing the raw material of the polyurethane resin described above onto the molded body (i) and curing it. It may be produced by coating it on another member to be attached to the body (i) and curing it.
  • a laminate comprising the molded body (i), the cured resin layer (ii), and other members is prepared by coating the molded body (i) with the composition containing the raw material for the polyurethane resin, and then attaching it to the molded body (i).
  • Other members to be combined are bonded together and cured before the composition is cured, or coated on a member other than the molded body (i), and the molded body (i) is combined with the molded body (i) when the composition is cured. It can be manufactured by pasting and curing before bonding.
  • the cured resin layer (ii) according to the present invention is, for example, a layer made of a composition obtained by mixing a first agent containing a curable resin (E) having a urethane bond and a second agent containing a curing agent, It may be obtained by curing, or may be obtained by forming a layer composed of a moisture-curable composition containing a curable resin (E) having a urethane bond and curing it, and urethane, which is a thermosetting resin It may be obtained by forming a layer containing a curable resin (E) having a bond and heat-curing it.
  • the cured resin layer (ii) according to the present invention is preferably a cured adhesive containing a polyurethane resin or an adhesive that forms a urethane bond.
  • the adhesive include a normal temperature two-component adhesive, a one-component moisture-curable adhesive, and a thermosetting adhesive.
  • a cured resin layer obtained by curing such an adhesive contains a curable resin having a urethane bond.
  • Known adhesives can be used as adhesives containing polyurethane resins or adhesives that form urethane bonds, but two-component or one-component moisture-curing adhesives and aqueous or aqueous emulsion adhesives are preferred.
  • two-component or one-component moisture-curing adhesives and water-based or water-based emulsion-based adhesives including polyurethane resins such as urethane resins, acrylic resins, urethane/acrylic resins, and epoxy resins.
  • polyurethane resins such as urethane resins, acrylic resins, urethane/acrylic resins, and epoxy resins.
  • the adhesive can be used in combination with a main agent (a composition containing an isocyanate compound) and a curing agent (a composition containing an active hydrogen-containing compound such as polyol).
  • a main agent a composition containing an isocyanate compound
  • a curing agent a composition containing an active hydrogen-containing compound such as polyol.
  • main agents include isocyanate-based, polyisocyanate-based, and the like
  • curing agents include polyol-based, polyamine-based, and the like.
  • the curing agent may be subjected to a latentizing treatment and blended with the adhesive, it is usually used by mixing with the adhesive at a specific ratio immediately before application.
  • isocyanate-based and polyisocyanate-based agents are preferable.
  • a commercially available polyurethane-based adhesive can also be used as the adhesive.
  • the cured resin layer containing the curable resin (E) having a urethane bond is preferably a cured urethane adhesive containing a urethane prepolymer having a polyether skeleton and an aliphatic isocyanate derivative.
  • Urethane prepolymer is produced by reacting a polyisocyanate compound having two or more isocyanate groups in one molecule with an active hydrogen compound having two or more active hydrogen atoms in one molecule that react with isocyanate groups. Obtainable.
  • Polyisocyanate compounds used in the preparation of urethane prepolymers include aliphatic polyisocyanates such as hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine methyl ester diisocyanate; ,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated tolylene diisocyanate, norbornene diisocyanate, hydrogenated m-xylylene diisocyanate, hydrogenated p-xylylene diisocyanate and other alicyclic polyisocyanates p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate
  • polyol compounds having two or more alcoholic hydroxyl groups in one molecule such as polyether polyols, polyester polyols or other polyols, may be used singly or in combination of two or more. Although they can be used, it is preferred to use polyether polyols.
  • a urethane prepolymer obtained by using a polyether polyol as an active hydrogen compound has a polyether skeleton, and the obtained adhesive has excellent adhesive performance with the molded article (i).
  • These polyol compounds preferably have a number average molecular weight of 100 to 50,000, particularly 300 to 10,000.
  • polyether polyols which are active hydrogen compounds that can be suitably used in the preparation of urethane prepolymers, include polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethyleneoxypropylene glycol, polyoxytetramethylene glycol, polyoxy In addition to hexamethylene glycol and the like, low-molecular-weight active hydrogen compounds having two or more active hydrogens, such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and diols such as 1,6-hexanediol; glycerin, trimethylolpropane , 1,2,6-hexanetriol and the like; propylene oxide and/or ethylene oxide ring-opening in the presence of one or more of amines such as ammonia, methylamine, ethylamine, propylamine and butylamine; A random copolymer obtained by polymerization can be mentioned.
  • active hydrogen compounds having two or more active hydrogens, such as bisphenol
  • the urethane prepolymer has a ratio of more than 1 mol of isocyanate groups contained in the polyisocyanate compound to 1 mol of hydroxyl groups contained in the polyol compound, that is, the chemical equivalent ratio (NCO/OH) exceeds 1.
  • NCO/OH chemical equivalent ratio
  • a compounding it can be obtained by reacting a polyol compound and a polyisocyanate compound by heating as necessary.
  • Such urethane prepolymers usually have isocyanate groups at both ends of the molecule.
  • a polyol compound and a polyisocyanate compound are reacted at a chemical equivalent ratio (NCO/OH) of 1.5 to 20 between the hydroxyl group contained in the polyol compound and the isocyanate group contained in the polyisocyanate compound. and exhibiting a liquid state at 23° C. is more preferable from the viewpoint of workability, physical properties of the cured product, and the like.
  • a urethane prepolymer obtained by reacting a polyether polyol and an aromatic polyisocyanate compound is preferable from the viewpoint of excellent adhesiveness and curability.
  • an isocyanate derivative that acts as a main agent can be used without particular limitation.
  • isocyanates, diisocyanates, polyisocyanates, and derivatives thereof can be used.
  • polyfunctional isocyanates described above or derivatives thereof can be used.
  • the isocyanate derivative is preferably a compound having an isocyanurate structure and an isocyanate group.
  • the isocyanate derivative when a compound having an isocyanurate structure and an isocyanate group, especially a compound having an isocyanurate structure and an isocyanate group, which is an aliphatic isocyanate derivative, is used, the adhesive strength with the molded article (i) is increased. This is preferable because it is expensive.
  • the isocyanurate structure is a structure represented by the following formula (B1).
  • the aliphatic isocyanate derivative can have at least one isocyanurate structure per molecule, and having one isocyanurate structure is one preferred embodiment.
  • the isocyanate derivative can have at least one isocyanate group per molecule, preferably a plurality of isocyanate groups, and more preferably three or more isocyanate groups.
  • the isocyanurate structure and the isocyanate group can be bonded directly or via a linking group, and bonding via a linking group is one preferred embodiment.
  • the isocyanurate structure and the isocyanate group can be bonded directly or via a linking group, and bonding via a linking group is one preferred embodiment.
  • Examples of the linking group include a hydrocarbon group that may have a heteroatom.
  • One preferred embodiment of the above hydrocarbon group is that it is composed only of carbon atoms and hydrogen atoms.
  • the hydrocarbon group is not particularly limited, but specific examples thereof include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. Among them, an aliphatic hydrocarbon group is preferred.
  • the above aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination thereof. Specific examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups.
  • the aliphatic hydrocarbon group is preferably a straight-chain aliphatic hydrocarbon group from the viewpoint of superior effects of the present invention.
  • the aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 4 to 5 carbon atoms, from the viewpoint of being superior in the effects of the present invention.
  • the aliphatic hydrocarbon group includes a methylene group, an ethylene group, a propylene group, a trimethylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, A decylene group is preferred, a butylene group and a pentylene group are more preferred, and a pentylene group is even more preferred.
  • the heteroatom which the hydrocarbon group may have is not particularly limited, and specific examples thereof include oxygen atom, nitrogen atom, sulfur atom, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.) and the like. be done.
  • the heteroatom may be combined with another heteroatom, carbon atom or hydrogen atom to form a functional group.
  • the isocyanate derivative is preferably a compound represented by the following formula (B2) from the viewpoint of being more excellent in the effects of the present invention.
  • R 141 , R 142 and R 143 each independently represent a hydrocarbon group which may have a heteroatom.
  • the hydrocarbon group optionally having a heteroatom as R 141 etc. is the same as described above.
  • the isocyanate derivative preferably contains an isocyanurate of an aliphatic polyisocyanate described later, and an isocyanurate of pentamethylene diisocyanate (represented by the following formula (B2-1) compound) and/or an isocyanurate of hexamethylene diisocyanate (a compound represented by the following formula (B2-2)), more preferably an isocyanurate of pentamethylene diisocyanate.
  • the isocyanate derivative may be composed of, for example, a polyisocyanate compound.
  • the polyisocyanate compound is not particularly limited as long as it is a compound in which a plurality of isocyanate groups are bonded to the linking group.
  • aliphatic polyisocyanates compounds in which a plurality of isocyanate groups are bonded to the above aliphatic hydrocarbon group are preferred.
  • isocyanate derivatives include aliphatic diisocyanates such as pentamethylene diisocyanate (PDI) and hexamethylene diisocyanate (HDI).
  • aliphatic diisocyanates such as pentamethylene diisocyanate (PDI) and hexamethylene diisocyanate (HDI).
  • the polyisocyanate compounds that can constitute the isocyanate compound (B) may be one or a combination of two or more.
  • the above isocyanate derivative is excellent in the effects of the present invention (initial adhesion and adhesion durability), and since it has a low viscosity and is easy to add to the composition, the compound represented by the above formula (B2-1) is preferable. .
  • the content of the isocyanate derivative is preferably 0.10 to 10.0% by mass with respect to the total amount of the composition of the present invention, from the viewpoint that the effect of the present invention (especially adhesion durability) is excellent. 0.50 to 5.0% by mass is more preferable.
  • An adhesive containing a polyurethane resin or an adhesive that forms a urethane bond is a compound represented by the following formula (X) (in formula (X), R 37 and R 38 are each independently a hydrocarbon group represents an adduct of a phenolic compound. This adduct can function as a tackifier in adhesives containing polyurethane resins or adhesives forming urethane bonds.
  • R 37 and R 38 each independently represent a hydrocarbon group.
  • the hydrocarbon groups for R 37 and R 38 are not particularly limited.
  • the hydrocarbon group may have a heteroatom.
  • One preferred mode is that it is composed only of carbon atoms and hydrogen atoms.
  • the hydrocarbon group is not particularly limited, but specific examples thereof include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. Among them, an aliphatic hydrocarbon group is preferred.
  • the above aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination thereof. Specific examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups.
  • the aliphatic hydrocarbon group is preferably a straight-chain aliphatic hydrocarbon group from the viewpoint of superior effects of the present invention.
  • the aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, from the standpoint of superior effects of the present invention.
  • the aliphatic hydrocarbon group is a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, or decyl group from the viewpoint that the effect of the present invention is superior. is preferred, and a methyl group is more preferred.
  • Examples of the aromatic hydrocarbon group include an aryl group and a naphthyl group.
  • Examples of the aryl group include aryl groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group.
  • the heteroatom which the hydrocarbon group may have is not particularly limited, and specific examples thereof include oxygen atom, nitrogen atom, sulfur atom, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.) and the like. be done.
  • the heteroatom may be combined with another heteroatom, carbon atom or hydrogen atom to form a functional group.
  • camphene is a compound represented by the following formula (X1).
  • the other compound forming the adduct is a phenolic compound.
  • the phenol compound is not particularly limited as long as it is a compound in which a hydroxy group is bonded to a benzene ring.
  • the above phenol compound can have one or more phenolic hydroxy groups (hydroxy groups directly bonded to a benzene ring) in one molecule, and preferably has one.
  • Examples of the phenol compound include compounds represented by the following formula (Y).
  • R 39 represents a substituent and n2 represents 0 or 1-4.
  • substituents for R 39 in formula (Y) include hydrocarbon groups and hydroxy groups.
  • n2 represents 0 or 1 to 4, and 0 is preferable from the viewpoint of superior effects of the present invention.
  • the phenol compound is preferably phenol from the viewpoint of being more excellent in the effects of the present invention.
  • the adduct is preferably a reaction product of one molecule of the compound represented by the formula (X) and one molecule of the phenol compound, from the viewpoint of being superior to the effects of the present invention and having little odor.
  • the adduct may have a phenolic hydroxy group or a phenoxy group (both of which may further have the above substituents on the benzene ring) of the phenol compound. preferable.
  • the adduct should at least contain the reaction product.
  • the above-mentioned adduct may further contain reaction by-products and unreacted substances in addition to the above-mentioned reaction products.
  • Examples of the adducts include compounds represented by the following formulas (Z1) to (Z3).
  • R 40 and R 41 each independently represent a hydrocarbon group
  • R 42 represents a substituent
  • n3 represents 0 or 1-4.
  • the hydrocarbon groups for R 40 and R 41 are the same as the hydrocarbon groups for R 37 and R 38 in formula (X).
  • the substituent for R 42 is the same as the substituent for R 39 in formula (Y).
  • n3 represents 0 or 1 to 4, with 0 being preferred.
  • R 43 and R 44 each independently represent a hydrocarbon group, R 45 represents a substituent, and n4 represents 0 or 1-4.
  • the hydrocarbon groups as R 43 and R 44 are the same as the hydrocarbon groups as R 37 and R 38 in formula (X).
  • the substituent as R 45 is the same as the substituent as R 39 in formula (Y).
  • n4 represents 0 or 1 to 4, with 0 being preferred.
  • R 51 and R 52 each independently represent a hydrocarbon group
  • R 53 represents a substituent
  • n5 represents 0 or 1-4.
  • the substituent for R 53 is the same as the substituent for R 39 in formula (Y).
  • n5 represents 0 or 1 to 4, with 0 being preferred.
  • the above adducts are compounds represented by the following formula (Z1-1), compounds represented by formula (Z1-2), and formula (Z2-1). It preferably contains at least one compound selected from the group consisting of the compound represented by the formula (Z2-2) and the compound represented by the formula (Z3-1).
  • the method for producing the adduct is not particularly limited as long as it is a method of reacting the compound represented by the formula (X) with the phenol compound.
  • the amounts of the compound represented by the formula (X) and the phenol compound used in the reaction are not particularly limited.
  • the amount (molar ratio) of the compound represented by the formula (X) and the phenol compound used (represented by (X) compound: phenolic compound) can be, for example, 1:0.5-2, preferably 1:0.8-1.2, more preferably 1:1.
  • the compound represented by the formula (X) and the phenol compound can be reacted in the presence of a catalyst.
  • the catalyst include boron trifluoride etherate.
  • the compound represented by formula (X) may be reacted with the phenol compound in a solvent.
  • the solvent include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as cyclohexane; and halogenated hydrocarbons such as carbon tetrachloride.
  • the reaction temperature for reacting the compound represented by the formula (X) with the phenol compound can be, for example, 0 to 100°C.
  • the content of the adduct is 0.05 to 10% by mass with respect to the total amount of the composition (adhesive) forming the curable resin (E) of the present invention, from the viewpoint of superior effects of the present invention. is preferred, and 0.1 to 1.0% by mass is more preferred.
  • the mass ratio of the content of the isocyanate derivative to the content of the adduct is 0.1:1 to 50:1 from the viewpoint that the effect of the present invention is superior. is preferred, and 10:1 to 2:1 is more preferred.
  • it can be appropriately selected whether the above-mentioned adduct is added to the main agent or the curing agent.
  • the adhesive containing the polyurethane resin or the adhesive forming the urethane bond may contain components other than those mentioned above.
  • other components include, for example, fillers (e.g., carbon black, calcium carbonate), catalysts (curing catalysts), plasticizers, antioxidants, antioxidants, silane coupling agents, pigments (dyes), Additives such as tackifiers, terpene compounds such as terpineol, thixotropic agents, UV absorbers, flame retardants, surfactants (including leveling agents), dispersants, dehydrating agents, antistatic agents, etc. can contain.
  • fillers e.g., carbon black, calcium carbonate
  • catalysts curing catalysts
  • plasticizers e.g., antioxidants, antioxidants, silane coupling agents, pigments (dyes)
  • Additives such as tackifiers, terpene compounds such as terpineol, thixotropic agents, UV absorbers, flame retardants, surfactants (including leveling agents
  • the filler may be surface-treated with, for example, at least one treating agent selected from the group consisting of fatty acids, resin acids, urethane compounds and fatty acid esters.
  • at least one treating agent selected from the group consisting of fatty acids, resin acids, urethane compounds and fatty acid esters.
  • the adhesive is of a two-component type, it can be appropriately selected whether the optional component is added to the main agent or the curing agent.
  • the cured resin layer (ii) may be a layer containing the above-described curable resin (E) having a urethane bond, and the method for forming the layer is not limited, but preferably an adhesive containing a polyurethane resin. Alternatively, it is obtained by curing an adhesive that forms a urethane bond.
  • the curable resin (E) having a urethane bond and the resin-cured layer (ii) containing it are manufactured using biomass-derived raw materials, at least in part, from the viewpoint of utilizing renewable resources and reducing CO emissions. It is also preferable that the That is, in the present invention, when forming a curable resin (E) having a urethane bond, such as a component constituting an adhesive containing a polyurethane resin or an adhesive that forms a urethane bond, or a cured resin layer (ii) containing the same It is preferable to use one or more biomass-derived raw materials as the raw materials used in the above.
  • biomass refers to “renewable, biologically derived organic resources excluding fossil resources.” It means a raw material containing a component derived from the generated organic matter. Whether or not the material is a biomass-derived material can also be determined by the ratio of biomass-derived carbon determined by the 14C method specified in ASTM D6866.
  • biomass-derived raw materials examples include raw materials with a biomass content of 50% or more as measured by ASTM D6866 Method B, raw materials with a vegetable content (ratio of plant-derived components) of 50% or more, and natural resources other than fossil resources.
  • Commercially available raw materials and the like that are clearly stated to be derived from the raw materials can be used without particular limitation.
  • the laminated structure of the present invention is obtained by directly laminating a resin-cured layer (ii) containing a curable resin (E) having a urethane bond on the molded body (i) made of the polypropylene-based resin composition described above. .
  • the polypropylene-based resin composition according to the present invention has excellent adhesion to the resin-cured layer (ii) containing the curable resin (E) having a urethane bond, and the molded article (i) and the resin-cured layer (ii) are primers. Although they are directly laminated without intervening, they are strongly adhered to each other, and the laminated structure maintains a high degree of adhesive strength even at high temperatures at which the adhesive strength usually decreases.
  • the molded article (i), the cured resin layer (ii), and the manufacturing method and shape of the laminated structure of the present invention in which these are laminated are not limited.
  • the laminated structure of the present invention may be a laminated structure consisting of only the molded body (i) and the cured resin layer (ii), and the molded body (i) and the layers other than the cured resin layer (ii) may further include It may be a laminated structure, for example, a laminated structure in which the molded body (i), the resin cured layer (ii), and another member are laminated in this order.
  • a laminated structure in which the molded article (i), the cured resin layer (ii), and another member are laminated is obtained, for example, by applying a curable composition that forms the cured resin layer (ii) on the molded article (i).
  • a curable composition that forms the resin cured layer (ii) is applied, the molded body (i) is attached before the composition is cured, and the composition is cured to form the molded body (i) and other members. It can be produced by a method of forming a cured resin layer (ii) therebetween.
  • the cured resin layer (ii) is obtained by curing an adhesive containing a polyurethane resin or an adhesive that forms a urethane bond
  • the cured resin layer (ii) is obtained by coating the adhesive on the molded article (i). It may be manufactured by applying and curing the adhesive, or the adhesive may be coated on the molded body (i) and cured in a state where it is attached to another member, and the adhesive may be coated on the molded body (i ) may be coated on another member to be bonded together with the molded article (i), and cured while being bonded to the molded body (i).
  • the molded body (i) is coated with an adhesive on a release film or the like.
  • the release film is peeled off to form an adhesive layer on the molded body (i), another member is bonded, and then the adhesive layer is cured to produce the cured resin layer (ii).
  • a release film or the like coated with an adhesive is attached to another member, the release film is peeled off to form an adhesive layer on the other member, the molded body (i) is attached, and then the adhesive layer may be cured to produce the cured resin layer (ii).
  • the adhesive is in contact with the molded article (i) during curing, and it is more preferable to apply the adhesive onto the molded article (i) and cure it. preferable.
  • the method for producing a laminated structure of the present invention includes a step of molding the above-described polypropylene-based resin composition by injection molding or press molding to produce a molded body (i); and a step of contacting or applying a curable resin (E) having a urethane bond or a raw material thereof to the molded body (i) and then curing the resin to form a cured resin layer (ii).
  • the surface of the molded body (i) obtained by injection molding or press molding the polypropylene resin composition described above is subjected to surface treatment such as flame treatment or plasma treatment as necessary.
  • a curable resin (E) having a urethane bond or an adhesive as a raw material thereof is directly applied and cured to form a cured resin layer (ii).
  • the curing conditions can be selected depending on the type of the curable resin (E) used or its raw material, the presence or absence and type of the curing agent. Can be cured at temperature.
  • the laminated structure of the present invention may have layers of members other than the molded body (i) and the cured resin layer (ii).
  • a preferred embodiment of the laminated structure of the present invention is a laminated structure in which the molded article (i), the resin-cured layer (ii), and another member layer are laminated in this order. In such a laminated structure, it is preferable that the molded body (i) and the layer of the other member are adhered via the cured resin layer (ii).
  • the other member constituting the layer of the other member is not particularly limited and may be any member, for example, resin members such as ABS resin, PVC sheet, polyolefin sheet, polyolefin sheet with foam layer, glass, cloth , fabrics, metals (iron (mild steel), cationic electrodeposited steel sheets, aluminum, etc.), wood, paper, and composites thereof.
  • resin members such as ABS resin, PVC sheet, polyolefin sheet, polyolefin sheet with foam layer, glass, cloth , fabrics, metals (iron (mild steel), cationic electrodeposited steel sheets, aluminum, etc.), wood, paper, and composites thereof.
  • a curable resin (E) having a urethane bond constituting the cured resin layer (ii) or a raw material thereof is applied to the surface of the molded body (i).
  • Such a laminate structure of the present invention is excellent in dimensional stability, and the molded article (i) and the cured resin layer (ii) are strongly bonded without a primer even at high temperatures at which adhesion tends to decrease. It will be For example, it maintains a high level of adhesive strength even in a high temperature environment of about 90°C, which is considered to be the most difficult to achieve in conventional adhesive tests, and exhibits sufficient adhesive strength even in a hot shear test at 90°C.
  • the interlayer shear between the molded body (i) and the resin cured layer (ii) is usually 1.2 MPa or more, preferably 1.5 MPa or more, more preferably 2.0 MPa or more, and further preferably 2.5 MPa or more, which is excellent adhesive strength.
  • the laminate structure of the present invention is used for automotive interior materials such as door trims, instrument panels, ceilings, console boxes, pillars, and glove boxes; and automotive exterior materials such as bumpers, side guards, air spoilers, side protectors, fenders, door panels, and back doors. It can be suitably used as industrial parts such as members, household appliance parts, building materials, etc., and can be particularly suitably used as automotive exterior parts such as back doors.
  • This mass was expressed as x 2 (g) in the following formula) was placed in a glass measuring container, 500 ml of n-decane, And a small amount of a heat stabilizer soluble in n-decane was charged, and the sample was dissolved by raising the temperature to 150 ° C. over 2 hours while stirring with a stirrer under a nitrogen atmosphere, holding at 150 ° C. for 2 hours, Slowly cooled to 23° C. over 8 hours. The resulting liquid containing precipitates was filtered under reduced pressure through a 25G-4 standard glass filter manufactured by Iwata Glass Co., Ltd.
  • melting point peak An endothermic curve of a differential scanning calorimeter (DSC) is determined, and the temperature at the maximum peak position is determined as the melting point peak (Tm). Pyris 1 manufactured by PerkinElmer was used as a measuring machine. The sample was packed in an aluminum pan, held at 30°C for 1 minute, then heated to 160°C at 500°C/min, held at 160°C for 5 minutes, and then cooled to -30°C at 10°C/min. Then, the melting point peak (Tm) was obtained from the endothermic curve obtained when the temperature was raised from -30°C to 160°C at 10°C/min.
  • the solid portion was collected by hot filtration, resuspended in 275 mL of titanium tetrachloride, and then heated again at 110°C for 2 hours. After completion of the reaction, the solid portion was collected again by hot filtration and thoroughly washed with 110° C. decane and hexane until no free titanium compound was detected in the solution.
  • this free titanium compound was confirmed by the following method. 10 mL of the supernatant liquid of the solid catalyst component was collected with a syringe and charged into a 100 mL branched Schlenk tube previously purged with nitrogen. Next, the solvent hexane was dried with a stream of nitrogen, followed by vacuum drying for 30 minutes. 40 mL of ion-exchanged water and 10 mL of (1+1) sulfuric acid were added thereto and stirred for 30 minutes.
  • This aqueous solution was transferred to a 100 mL volumetric flask through a filter paper, then 1 mL of concentrated H 3 PO 4 solution as a masking agent for iron (II) ions and 5 mL of 3% hydrogen peroxide aqueous solution as a coloring reagent for titanium were added, followed by addition of deionized water.
  • the volumetric flask filled up to 100 mL was shaken, and after 20 minutes, the absorbance at 420 nm was observed using UV, and free titanium was removed by washing until this absorption was no longer observed.
  • the solid titanium catalyst component prepared as described above was stored as a decane slurry, a portion of which was dried for the purpose of investigating the catalyst composition.
  • the composition of the solid titanium catalyst component thus obtained was 2.3% by weight of titanium, 61% by weight of chlorine, 19% by weight of magnesium and 12.5% by weight of DIBP.
  • (2) Preparation of prepolymerization catalyst 100 g of the solid titanium catalyst component, 131 mL of triethylaluminum, 37.3 mL of diethylaminotriethoxysilane, and 14.3 L of heptane are placed in an autoclave with an internal volume of 20 L and equipped with a stirrer, and the internal temperature is 15 to 20.
  • the resulting slurry was sent to a 100-L vessel polymerization reactor equipped with a stirrer, and polymerized further. 45 kg/hour of propylene and hydrogen were supplied to the polymerization vessel so that the hydrogen concentration in the gas phase was 8.8 mol %, and polymerization was carried out at a polymerization temperature of 68° C. and a pressure of 3.36 MPa/G.
  • the resulting slurry was transferred to a liquid transfer tube with an internal volume of 2.4 L, gasified, and gas-solid separation was performed.
  • the polypropylene homopolymer powder was sent to a gas phase polymerization reactor having an internal volume of 480 L, and ethylene/propylene block copolymerization was carried out.
  • Polymerization was carried out at a polymerization temperature of 70° C. and a pressure of 1.40 MPa/G.
  • the obtained propylene-based block copolymer was vacuum-dried at 80°C.
  • the MFR (230° C., 2.16 kg load) of the propylene/ethylene block copolymer (A-1) thus obtained was 80 g/10 min, and the decane soluble portion (propylene/ethylene copolymer component ) was 7% by mass, the amount of the decane-insoluble portion (propylene homopolymer component) was 93% by mass, and the intrinsic viscosity [ ⁇ ] of the decane-soluble portion was 7.5 dl/g.
  • the resulting slurry was sent to a 100-L vessel polymerization reactor equipped with a stirrer, and polymerized further. 45 kg/hour of propylene and hydrogen were supplied to the polymerization vessel so that the hydrogen concentration in the gas phase was 3.2 mol %, and polymerization was carried out at a polymerization temperature of 70° C. and a pressure of 3.28 MPa/G. Then, the obtained propylene homopolymer was vacuum-dried at 80°C. The MFR (230° C., 2.16 kg load) of the propylene homopolymer (B-1) thus obtained was 30 g/10 minutes.
  • the obtained slurry was sent to a vessel polymerization vessel with an internal capacity of 500 L and equipped with a stirrer, and was further polymerized. 30 kg/hour of propylene and hydrogen were supplied to the polymerization vessel so that the hydrogen concentration in the gas phase was 3.9 mol %, and polymerization was carried out at a polymerization temperature of 74.5° C. and a pressure of 3.4 MPa/G.
  • the obtained slurry was sent to a vessel polymerization vessel with an internal volume of 500 L equipped with a stirrer, and polymerized further. 20 kg/hour of propylene and hydrogen were supplied to the polymerization vessel so that the hydrogen concentration in the gas phase was 3.4 mol %, and polymerization was carried out at a polymerization temperature of 73° C. and a pressure of 3.4 MPa/G. Next, the obtained slurry was deactivated, vaporized, and then subjected to gas-solid separation. The obtained propylene homopolymer was vacuum-dried at 80°C. The MFR (230° C., 2.16 kg load) of the propylene homopolymer (B-2) thus obtained was 210 g/10 minutes.
  • Polymer 2 A modified silicone resin having a polyoxypropylene main chain and a methyldimethoxysilyl group as a hydrolyzable silyl group at the end.
  • Kaneka MS Polymer S203 manufactured by Kaneka Corporation
  • Epoxy resin 1 ADEKA RESIN EP-4100 (manufactured by ADEKA CORPORATION)
  • Epoxy resin 2 ADEKA RESIN EP-4006 (manufactured by ADEKA CORPORATION)
  • Compound 1 isocyanurate form of hexamethylene diisocyanate (Takenate D-170HN, manufactured by Mitsui Chemicals, Inc.)
  • Compound 2 A mixture of pentamethylene diisocyanate isocyanurate and allophanate (STABIO D-376N (low viscosity type), manufactured by Mitsui Chemicals, Inc.) (biomass-derived compound: vegetable content (ASTM D6866-04): 67% )
  • Compound 1 isocyanurate form
  • the adduct used as this compound 4 is a commercially available product, a compound represented by the following formula (Z1-1), a compound represented by the formula (Z1-2), and a compound represented by the formula (Z2-1) at least one compound selected from the group consisting of the compound represented by the formula (Z2-2) and the compound represented by the formula (Z3-1).
  • Z1-1 a compound represented by the following formula
  • Carbon black #200MP (manufactured by Shin Nikka Carbon Co., Ltd.)
  • Calcium carbonate 1 Super S (manufactured by Maruo Calcium Co., Ltd.)
  • Calcium carbonate 2 Kalfain 200 (manufactured by Maruo Calcium Co., Ltd.)
  • Plasticizer 1 Diisononyl phthalate (manufactured by J-Plus)
  • Plasticizer 2 Shellsol TM (manufactured by Japan Chemtech)
  • Catalyst 1 dimorpholinodiethyl ether (manufactured by San-Apro Co., Ltd.)
  • Catalyst 2 Tin-based catalyst Neostan U-303 (manufactured by Nitto Kasei Co., Ltd.)
  • Examples 1 to 3 Comparative Examples 1 to 3 ⁇ Preparation of molded product test piece and surface treatment 3, and using a twin-screw extruder (manufactured by Japan Steel Works, Ltd., TEX (registered trademark) 30 ⁇ ) under the conditions of a cylinder temperature of 180 ° C., a screw rotation of 750 rpm, and an extrusion rate of 60 kg / h. It was extruded to obtain a polypropylene resin composition.
  • Table 3 shows the melt flow rate (230° C., 2.16 kg load) of each of the obtained polypropylene resin compositions.
  • Each obtained polypropylene resin composition was injection molded at a resin temperature of 210°C and a mold temperature of 40°C using a mold cavity having a length of 350 mm, a width of 100 mm, and a thickness of 3 mm to obtain a flat plate.
  • a shape of 100 mm ⁇ 50 mm ⁇ 3 mm was cut out to obtain a molded body test piece (flat plate) for producing a laminated structure.
  • the flat plate obtained above was cut into a shape of 100 mm x 25 mm x 3 mm to obtain a test piece.
  • Surface treatment (frame treatment) was performed on the surface of the obtained test piece.
  • a flame treatment apparatus (FTS 201 manufactured by Arcogas) was used for the surface treatment.
  • the flame processor can regulate the flow rate of combustion gases and air.
  • the air flow rate was fixed at 100 L/min
  • the combustion gas (propane gas) flow rate was adjusted to 3.7 L/min
  • the distance between the flat plate and the flame irradiation head was 40 mm
  • the processing speed was 800 mm/sec.
  • a surface with a surface free energy of 42 dynes/cm (mN/m) was manufactured as (surface treatment state: low treatment).
  • a surface with a surface free energy of 52 dynes/cm (mN/m) was produced at a distance of 30 mm and 800 mm/sec (surface treatment state: medium treatment), and a surface free energy of 10 mm and 800 mm/sec was similarly produced.
  • the adhesives (E-1) and (E-3) are urethane-based adhesives, and the adhesive layers obtained using these are cured resin containing a curable resin having a urethane bond. form a layer.
  • the adhesive (E-2) is a non-urethane adhesive, and the adhesive layer obtained using this adhesive is cured to form a cured resin layer containing a curable resin having a non-urethane bond.
  • the laminated structure of the present invention is used for automotive interior materials such as door trims, instrument panels, ceilings, console boxes, pillars and glove boxes; automobiles such as bumpers, side guards, air spoilers, side protectors, fenders, door panels and back doors. It can be suitably used for applications such as exterior members, home appliance parts, and industrial parts such as building materials.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
PCT/JP2022/045494 2021-12-14 2022-12-09 積層構造体およびその用途 Ceased WO2023112858A1 (ja)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP22907385.3A EP4450280A4 (en) 2021-12-14 2022-12-09 LAYER STRUCTURE AND ITS USE
JP2023561244A JP7522521B2 (ja) 2021-12-14 2022-12-09 積層構造体およびその用途
US18/711,277 US20250018693A1 (en) 2021-12-14 2022-12-09 Layered structure and use thereof
MX2024007197A MX2024007197A (es) 2021-12-14 2022-12-09 Estructura en capas y el uso de la misma.
CN202280081572.XA CN118541264A (zh) 2021-12-14 2022-12-09 叠层结构体及其用途
JP2024111004A JP7575635B2 (ja) 2021-12-14 2024-07-10 積層構造体およびその用途

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-202932 2021-12-14
JP2021202932 2021-12-14

Publications (1)

Publication Number Publication Date
WO2023112858A1 true WO2023112858A1 (ja) 2023-06-22

Family

ID=86774685

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/045494 Ceased WO2023112858A1 (ja) 2021-12-14 2022-12-09 積層構造体およびその用途

Country Status (6)

Country Link
US (1) US20250018693A1 (https=)
EP (1) EP4450280A4 (https=)
JP (2) JP7522521B2 (https=)
CN (1) CN118541264A (https=)
MX (1) MX2024007197A (https=)
WO (1) WO2023112858A1 (https=)

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5763310A (en) 1980-08-13 1982-04-16 Montedison Spa Ingredient and catalyst for olefin polymerization
JPH0551498A (ja) 1991-02-15 1993-03-02 Sumitomo Chem Co Ltd 熱可塑性樹脂組成物およびその射出成形体
JPH05170843A (ja) 1991-12-20 1993-07-09 Mitsui Petrochem Ind Ltd プロピレン系ブロック共重合体の製造方法
EP0585869A1 (en) 1992-08-31 1994-03-09 Mitsui Petrochemical Industries, Ltd. Solid titanium catalyst component for olefin polymerization, process for preparing the same, catalyst for olefin polymerization and process for olefin polymerization
JP2000095919A (ja) 1998-09-22 2000-04-04 Chisso Corp 自動車サイドモール成形用樹脂組成物及び自動車サイドモール
JP2001354714A (ja) 1990-04-13 2001-12-25 Mitsui Chemicals Inc オレフィン重合用固体状チタン触媒成分、オレフィン重合用触媒およびオレフィンの重合方法
WO2004016662A1 (ja) 2002-08-19 2004-02-26 Ube Industries, Ltd. α−オレフィンの重合又は共重合に用いられるα−オレフィンの重合又は重合用触媒、その触媒成分及びその触媒を用いたα−オレフィン重合方法
JP2007091789A (ja) 2005-09-27 2007-04-12 Japan Polypropylene Corp 塗装外観に優れるポリプロピレン系樹脂組成物及び成形体
JP2010077396A (ja) 2008-08-28 2010-04-08 Japan Polypropylene Corp プロピレン系樹脂組成物およびその成形体
JP2013159709A (ja) 2012-02-06 2013-08-19 Japan Polypropylene Corp 自動車外装部材用ポリプロピレン系樹脂組成物及び自動車外装部材
JP2014058614A (ja) 2012-09-18 2014-04-03 Japan Polypropylene Corp 自動車外装部材用ポリプロピレン系樹脂組成物および自動車外装部材
JP2016084386A (ja) 2014-10-23 2016-05-19 株式会社プライムポリマー タルク含有ポリプロピレン系樹脂組成物
WO2017082358A1 (ja) 2015-11-11 2017-05-18 株式会社プライムポリマー ポリプロピレン系樹脂組成物
JP2020158554A (ja) * 2019-03-25 2020-10-01 株式会社プライムポリマー ポリプロピレン系樹脂組成物
WO2021124871A1 (ja) * 2019-12-17 2021-06-24 昭和電工マテリアルズ株式会社 車両用開閉体及び車両用開閉体の製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4314442B2 (ja) * 2001-04-06 2009-08-19 株式会社プライムポリマー 積層構造体およびその製造方法
US11667823B2 (en) * 2019-01-30 2023-06-06 Sika Hamatite Co., Ltd. Urethane adhesive composition
CN114026167A (zh) * 2019-09-13 2022-02-08 普瑞曼聚合物株式会社 聚丙烯系树脂组合物和包含其的成型体

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5763310A (en) 1980-08-13 1982-04-16 Montedison Spa Ingredient and catalyst for olefin polymerization
JP2001354714A (ja) 1990-04-13 2001-12-25 Mitsui Chemicals Inc オレフィン重合用固体状チタン触媒成分、オレフィン重合用触媒およびオレフィンの重合方法
JPH0551498A (ja) 1991-02-15 1993-03-02 Sumitomo Chem Co Ltd 熱可塑性樹脂組成物およびその射出成形体
JPH05170843A (ja) 1991-12-20 1993-07-09 Mitsui Petrochem Ind Ltd プロピレン系ブロック共重合体の製造方法
EP0585869A1 (en) 1992-08-31 1994-03-09 Mitsui Petrochemical Industries, Ltd. Solid titanium catalyst component for olefin polymerization, process for preparing the same, catalyst for olefin polymerization and process for olefin polymerization
JP2000095919A (ja) 1998-09-22 2000-04-04 Chisso Corp 自動車サイドモール成形用樹脂組成物及び自動車サイドモール
WO2004016662A1 (ja) 2002-08-19 2004-02-26 Ube Industries, Ltd. α−オレフィンの重合又は共重合に用いられるα−オレフィンの重合又は重合用触媒、その触媒成分及びその触媒を用いたα−オレフィン重合方法
JP2007091789A (ja) 2005-09-27 2007-04-12 Japan Polypropylene Corp 塗装外観に優れるポリプロピレン系樹脂組成物及び成形体
JP2010077396A (ja) 2008-08-28 2010-04-08 Japan Polypropylene Corp プロピレン系樹脂組成物およびその成形体
JP2013159709A (ja) 2012-02-06 2013-08-19 Japan Polypropylene Corp 自動車外装部材用ポリプロピレン系樹脂組成物及び自動車外装部材
JP2014058614A (ja) 2012-09-18 2014-04-03 Japan Polypropylene Corp 自動車外装部材用ポリプロピレン系樹脂組成物および自動車外装部材
JP2016084386A (ja) 2014-10-23 2016-05-19 株式会社プライムポリマー タルク含有ポリプロピレン系樹脂組成物
WO2017082358A1 (ja) 2015-11-11 2017-05-18 株式会社プライムポリマー ポリプロピレン系樹脂組成物
JP2017088742A (ja) * 2015-11-11 2017-05-25 株式会社プライムポリマー ポリプロピレン系樹脂組成物
JP2020158554A (ja) * 2019-03-25 2020-10-01 株式会社プライムポリマー ポリプロピレン系樹脂組成物
WO2021124871A1 (ja) * 2019-12-17 2021-06-24 昭和電工マテリアルズ株式会社 車両用開閉体及び車両用開閉体の製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ANONYMOUS: "ENGAGE™ Polyolefin Elastomers Product selection guide for transportation application", THE DOW CHEMICAL COMPANY, 1 January 2019 (2019-01-01), pages 1 - 4, XP093071017, Retrieved from the Internet <URL:https://www.dow.com/content/dam/dcc/documents/en-us/catalog-selguide/777/777-088-01-engage-polyolefin-elastomer-product-selection-guide.pdf> [retrieved on 20230806] *
See also references of EP4450280A4

Also Published As

Publication number Publication date
JP7575635B2 (ja) 2024-10-29
JP7522521B2 (ja) 2024-07-25
US20250018693A1 (en) 2025-01-16
JP2024138418A (ja) 2024-10-08
CN118541264A (zh) 2024-08-23
EP4450280A4 (en) 2025-11-12
EP4450280A1 (en) 2024-10-23
MX2024007197A (es) 2024-06-26
JPWO2023112858A1 (https=) 2023-06-22

Similar Documents

Publication Publication Date Title
EP1896539B1 (en) Filled tpo compositions, methods of making the same, and articles prepared from the same
JP6566842B2 (ja) ポリプロピレン系樹脂組成物
EP3901211A2 (en) Thermoplastic elastomer composition and molded body
EP3858941A1 (en) Fluidity modifier, composition containing same, and cured product of said composition
JP2016084386A (ja) タルク含有ポリプロピレン系樹脂組成物
JP2016506437A (ja) 臭気が改善された自動車用化合物
WO2019189486A1 (ja) プロピレン系樹脂組成物、それを用いたフィルムおよびその用途
JP7509329B2 (ja) 無機フィラー流動性改質剤、無機フィラー含有組成物および熱伝導性シリコーンシート
KR102771573B1 (ko) 무기 필러 분산안정화제, 무기 필러 함유 수지 조성물, 성형품 및 첨가제
JP7575635B2 (ja) 積層構造体およびその用途
JP2016506436A (ja) 低い表面タックを特徴とする自動車用化合物
KR930003891B1 (ko) 고급 α-올레핀계 공중합체, 그 제조방법 및 그 가황물 및 가황 가능한 고무조성물
JP7696446B2 (ja) ポリプロピレン系樹脂組成物およびその用途
JP7406922B2 (ja) ポリプロピレン系樹脂組成物
JP2012117005A (ja) ポリプロピレン系樹脂組成物
CN109923170B (zh) 母料组合物和包含该母料组合物的聚丙烯树脂组合物
JP6259751B2 (ja) ポリプロピレン系樹脂組成物およびその用途
JP2008260861A (ja) 自動車部品
JP2013147601A (ja) ポリプロピレン樹脂組成物、およびそれを含む成形体
JP2000319332A (ja) α−オレフィン／極性基含有ビニルモノマー共重合体およびその製造方法
JP2000319331A (ja) α−オレフィン／極性基含有ビニルモノマー／ポリエン共重合体およびその製造方法
JP2024126010A (ja) 樹脂組成物および成形体
TWI919063B (zh) 無機填料流動性改質劑、含有無機填料之組成物及熱傳導性聚矽氧薄片
JP2026068874A (ja) 重合体組成物
JP7186594B2 (ja) プロピレン系重合体の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22907385

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023561244

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 18711277

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 202280081572.X

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: MX/A/2024/007197

Country of ref document: MX

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112024011624

Country of ref document: BR

WWE Wipo information: entry into national phase

Ref document number: 202417050560

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 2022907385

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2022907385

Country of ref document: EP

Effective date: 20240715

ENP Entry into the national phase

Ref document number: 112024011624

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20240610