WO2024203664A1 - 変性ポリオレフィン樹脂組成物及び該樹脂組成物の用途 - Google Patents

変性ポリオレフィン樹脂組成物及び該樹脂組成物の用途 Download PDF

Info

Publication number
WO2024203664A1
WO2024203664A1 PCT/JP2024/010867 JP2024010867W WO2024203664A1 WO 2024203664 A1 WO2024203664 A1 WO 2024203664A1 JP 2024010867 W JP2024010867 W JP 2024010867W WO 2024203664 A1 WO2024203664 A1 WO 2024203664A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyolefin resin
modified polyolefin
resin composition
group
mass
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/JP2024/010867
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
北斗 山崎
健二 柏原
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.)
Toyobo MC Corp
Original Assignee
Toyobo MC Corp
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 Toyobo MC Corp filed Critical Toyobo MC Corp
Priority to JP2024557226A priority Critical patent/JPWO2024203664A1/ja
Priority to EP24779787.1A priority patent/EP4692215A1/en
Priority to CN202480023157.8A priority patent/CN121013884A/zh
Publication of WO2024203664A1 publication Critical patent/WO2024203664A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/108—Hydrocarbon resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds

Definitions

  • the present invention relates to a modified polyolefin resin composition and uses of the resin composition.
  • polyolefin resins such as polypropylene, polyethylene, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, polybutene, and poly(4-methyl-1-pentene) are used in fields such as automobile parts, electrical parts, construction materials, and packaging films because they are relatively inexpensive and have excellent properties such as chemical resistance, water resistance, and heat resistance.
  • polyolefin resins are crystalline and non-polar, making it difficult to apply coatings, adhesives, etc. to them.
  • chlorinated polyolefins which have strong adhesive power to polyolefin resins, are widely used as binder resins (for example, Patent Document 1 and Patent Document 2).
  • Japanese Patent Publication No. 59-75958 Japanese Patent Publication No. 60-99138 Japanese Patent Publication No. 6-16746 Japanese Patent Application Publication No. 8-12913 Japanese Patent Application Publication No. 2009-108259 Japanese Patent Application Publication No. 2020-33483
  • Patent Documents 3 and 4 are usually used in a dissolved state in an organic solvent such as toluene or xylene, and therefore a large amount of the organic solvent is released into the atmosphere during painting, which is undesirable from the standpoints of the environment, hygiene, etc.
  • mixtures and binder compositions described in Patent Documents 3 and 4 have problems of poor fluidity and poor adhesion to polyolefin-based substrates.
  • polyolefin-based base materials and plastic materials such as polyethylene terephthalate (PET) and ABS generally do not have good electrical conductivity, so there is a problem in that static electricity causes dust and dirt to adhere to the molded product, deteriorating its appearance.
  • the present invention has been made in consideration of the above, and aims to provide a modified polyolefin resin composition that has sufficient fluidity within a specific temperature range, sufficient adhesion to polyolefin substrates, excellent adhesion to plastic materials, and sufficient antistatic performance.
  • the inventors conducted extensive research into dispersing and/or dissolving an acid-modified polyolefin resin in a compound having a polymerizable unsaturated group, and discovered that a modified polyolefin resin composition containing an acid-modified polyolefin resin, a polyetheramine, a compound having a polymerizable unsaturated group, and an ionic liquid could solve the above problems, leading to the present invention.
  • a modified polyolefin resin composition comprising an acid-modified polyolefin resin (A), a polyetheramine (B), a compound having a polymerizable unsaturated group (C), and an ionic liquid (D).
  • the modified polyolefin resin composition of the present invention has sufficient fluidity within a specific temperature range, sufficient adhesion to polyolefin substrates, excellent adhesion to plastic materials, and sufficient antistatic performance. Since the modified polyolefin resin composition of the present invention exhibits sufficient fluidity within a specific temperature range, it can be suitably used for various applications as a liquid modified polyolefin resin composition.
  • the upper or lower limit of a certain numerical range can be arbitrarily combined with the upper or lower limit of a numerical range of another stage.
  • the upper or lower limit of the numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from an example.
  • a numerical value connected with " ⁇ " means a numerical range that includes the numerical values before and after " ⁇ " as the upper and lower limits.
  • a and/or B means “one of A and B” or “both A and B,” and specifically means “A,” “B,” or “A and B.”
  • n- means "normal”
  • i- means "iso”
  • tert- means "tiary.”
  • (meth)acrylic includes both acrylic and methacrylic
  • (meth)acrylate includes both acrylate and methacrylate.
  • an "acryloyl group” is represented by “CH 2 ⁇ CHC( ⁇ O)--"
  • a “methacryloyl group” is represented by “CH 2 ⁇ C(CH 3 )C( ⁇ O)--”
  • an acryloyloxy group is represented by “CH 2 ⁇ CHC( ⁇ O)O--”
  • a methacryloyloxy group is represented by "CH 2 ⁇ C(CH 3 )C( ⁇ O)O--”.
  • cation refers to a positively charged single atom or a group of atoms.
  • anion refers to a negatively charged single atom or a group of atoms.
  • the modified polyolefin resin composition of the present invention contains, as essential components, an acid-modified polyolefin resin (A), a polyetheramine (B), a compound having a polymerizable unsaturated group (C), and an ionic liquid (D).
  • A acid-modified polyolefin resin
  • B polyetheramine
  • C compound having a polymerizable unsaturated group
  • D ionic liquid
  • the modified polyolefin resin composition typically has sufficient fluidity within the range of 25°C to 80°C.
  • a resin composition having fluidity means, for example, a homogeneous liquid composition that does not contain coarse resin particles, aggregates, etc.
  • the modified polyolefin resin composition is a resin composition that flows when placed in a glass bottle and tilted, typically within the range of 25°C to 80°C.
  • the resin composition having flowability also includes a resin composition that flows when mechanical shear is applied, typically within the range of 25°C to 80°C.
  • the combined content of the acid-modified polyolefin resin (A), polyetheramine (B), compound having a polymerizable unsaturated group (C) and ionic liquid (D) relative to the total mass of the modified polyolefin resin composition is preferably in the following order: more than 50 mass%, 55 mass% or more, 60 mass% or more, 65 mass% or more, 70 mass% or more, 75 mass% or more, 80 mass% or more, 85 mass% or more, 90 mass% or more, 92.5 mass% or more, 95 mass% or more, 97.5 mass% or more, 99 mass% or more, 99.5 mass% or more, 99.9 mass% or more, 99.95 mass% or more and 99.99 mass% or more.
  • the present invention contains an acid-modified polyolefin resin (A).
  • the acid-modified polyolefin resin (A) is a polymer obtained by graft polymerizing an ⁇ , ⁇ -unsaturated carboxylic acid or an acid anhydride thereof onto a polyolefin resin.
  • the acid-modified polyolefin resin (A) is a graft polymer having a structure in which an ⁇ , ⁇ -unsaturated carboxylic acid or an acid anhydride thereof is grafted onto a polyolefin resin.
  • Polyolefin resins usually have structural units derived from ⁇ -olefins.
  • ⁇ -olefins include ⁇ -olefins having 2 to 20 carbon atoms (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20), such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
  • the polyolefin resin may be an olefin polymer containing a single type of structural unit derived from ⁇ -olefin, or it may be a copolymer of an olefin polymer containing two or more types of structural units derived from ⁇ -olefin.
  • the polyolefin resin is typically a petroleum-derived polyolefin resin.
  • a petroleum-derived polyolefin resin is a polyolefin-based resin synthesized from petroleum-derived olefins.
  • Petroleum-derived olefins are olefins produced by thermal cracking of petrochemical feedstocks such as naphtha, ethane, LPG (liquidized petroleum gas), NGL (natural gas liquid), and gas oil.
  • examples of petroleum-derived polyolefin resins include homopolypropylene (homopolymer of propylene), propylene- ⁇ -olefin copolymer, homopolyethylene (homopolymer of ethylene), ethylene- ⁇ -olefin copolymer, poly 1-butene, and 1-butene- ⁇ -olefin copolymer. These polyolefin resins can be used alone or in combination of two or more. In one embodiment, among these polyolefin resins, homopolypropylene and/or propylene- ⁇ -olefin copolymer are preferred.
  • the acid-modified polyolefin resin (A) is preferably a graft polymer having a structure in which an ⁇ , ⁇ -unsaturated carboxylic acid or its acid anhydride is grafted to a homopolypropylene or a propylene- ⁇ -olefin copolymer.
  • Propylene- ⁇ -olefin copolymer is a copolymer of propylene and ⁇ -olefin.
  • ⁇ -olefins include ethylene; ⁇ -olefins having 4 to 20 carbon atoms (4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20), such as 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
  • These ⁇ -olefins can be used alone or in combination of two or more.
  • the content of the propylene component in the propylene- ⁇ -olefin copolymer is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more. In one embodiment, when the content of the propylene component in the propylene- ⁇ -olefin copolymer is 50 mol% or more, the adhesion of the modified polyolefin resin composition to polyolefin substrates (particularly polypropylene substrates) and plastic materials (particularly PET and ABS) becomes even better.
  • Ethylene- ⁇ -olefin copolymers are copolymers of ethylene and ⁇ -olefins.
  • ⁇ -olefins include ⁇ -olefins having 3 to 20 carbon atoms (3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20), such as propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
  • These ⁇ -olefins can be used alone or in combination of two or more.
  • the content of the ethylene component in the ethylene- ⁇ -olefin copolymer is preferably 75 mol% or more.
  • the adhesion of the modified polyolefin resin composition to polyolefin substrates (particularly polyethylene substrates) and plastic materials (particularly PET and ABS) becomes even better.
  • the 1-butene- ⁇ -olefin copolymer is a copolymer of 1-butene and an ⁇ -olefin.
  • ⁇ -olefins include ethylene, propylene, and ⁇ -olefins having 5 to 20 carbon atoms (5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20), such as 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
  • These ⁇ -olefins can be used alone or in combination of two or more.
  • the content of the 1-butene component in the 1-butene- ⁇ -olefin copolymer is preferably 65 mol% or more.
  • the modified polyolefin resin composition of this embodiment has even better adhesion to polyolefin substrates (particularly polypropylene substrates or poly-1-butene substrates) and plastic materials (particularly PET and ABS).
  • the total content of ⁇ , ⁇ -unsaturated carboxylic acid and its anhydride components in the acid-modified polyolefin resin (A) is preferably 0.5 to 10 mass%, more preferably 0.7 to 6 mass%, even more preferably 0.8 to 3 mass%, and even more preferably 1 to 2 mass%. In one embodiment, when the total content of ⁇ , ⁇ -unsaturated carboxylic acid and its anhydride components in the acid-modified polyolefin resin (A) is within the range of 0.5 to 10 mass%, the fluidity of the modified polyolefin resin composition becomes even better.
  • a biologically derived polyolefin resin can be used as the polyolefin resin.
  • a biologically derived polyolefin resin means a polyolefin resin produced from biological resources (biomass). Biomass means a material formed from renewable organic resources derived from living organisms, excluding fossil resources.
  • the polyolefin resin contains a propylene structural unit.
  • the biomass degree of the polyolefin resin is usually 25% or more, preferably 27% or more, and more preferably 30% or more.
  • the upper limit of the biomass degree is not particularly limited as long as it is 100% or less.
  • the biomass degree of the polyolefin resin can be calculated, for example, from the carbon isotope content of mass number 14 measured in accordance with ASTM D6866.
  • Examples of ⁇ , ⁇ -unsaturated carboxylic acids or their anhydrides that can be graft polymerized onto polyolefins include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, himic anhydride, etc.
  • maleic acid, maleic anhydride, and itaconic anhydride are preferred, with maleic acid and maleic anhydride being more preferred.
  • the acid value of the ⁇ , ⁇ -unsaturated carboxylic acid and its anhydride component in the acid-modified polyolefin resin (A) is preferably 1 to 100 mgKOH/g, more preferably 5 to 50 mgKOH/g, even more preferably 10 to 40 mgKOH/g, and even more preferably 15 to 30.
  • the acid value of the ⁇ , ⁇ -unsaturated carboxylic acid and its anhydride component in the acid-modified polyolefin resin (A) is within the range of 1 to 100 mgKOH/g, the fluidity of the modified polyolefin resin composition becomes even better.
  • the acid value of the ⁇ , ⁇ -unsaturated carboxylic acid and its anhydride components in the acid-modified polyolefin resin (A) can be calculated using a Fourier transform infrared spectrophotometer (FT-IR) according to the following formula (i) using the coefficient (f) obtained from a calibration curve prepared using a chloroform solution of maleic anhydride and the absorbance (I) of the stretching peak (1780 cm ⁇ 1 ) of the carbonyl (C ⁇ O) bond of succinic anhydride in the acid-modified polyolefin solution.
  • FT-IR Fourier transform infrared spectrophotometer
  • Acid value (mg KOH/g) [absorbance (I) x coefficient (f) x 2 x molecular weight of potassium hydroxide x 1000 (mg) / molecular weight of succinic anhydride] ... formula (i)
  • the molecular weight of succinic anhydride is 100.07
  • the molecular weight of potassium hydroxide is 56.11.
  • a wide variety of known methods can be used to graft polymerize ⁇ , ⁇ -unsaturated carboxylic acids or their anhydrides onto polyolefins.
  • Examples of such methods include a method in which polyolefins are heated to above their melting point in the presence of a radical generator to melt them and react with ⁇ , ⁇ -unsaturated carboxylic acids or their anhydrides (melt method), and a method in which polyolefins are dissolved in an organic solvent and then heated and stirred in the presence of a radical generator to react with ⁇ , ⁇ -unsaturated carboxylic acids or their anhydrides (solution method).
  • the acid-modified polyolefin resin (A) may be an acid-modified chlorinated polyolefin resin that has been further chlorinated.
  • the chlorination method may include, for example, blowing chlorine gas into the acid-modified polyolefin resin to introduce chlorine atoms. More specifically, the acid-modified polyolefin resin may be dispersed or dissolved in a solvent as necessary, and then chlorination may be performed by blowing chlorine gas into the acid-modified polyolefin resin in the presence of a catalyst or under irradiation with ultraviolet light, under pressure or under normal pressure (atmospheric pressure), at a temperature range of 50 to 150°C.
  • Solvents used during chlorination include, for example, water and chlorine-based solvents (e.g., chloroform, methylene chloride, carbon tetrachloride, etc.), with chlorine-based solvents being preferred.
  • the chlorine-based solvent may be distilled off under reduced pressure or the like at the end of chlorination, or may be replaced with another organic solvent.
  • the catalyst used in the chlorination may be, for example, a radical initiator.
  • radical initiators include tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyoctoate, di-tert-butylperoxide, and dicumylperoxide.
  • the chlorine content in the acid-modified chlorinated polyolefin resin is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, particularly preferably 12% by mass or more, and most preferably 14% by mass or more.
  • the chlorine content in the acid-modified chlorinated polyolefin resin is 5% by mass or more, the stability in the solution is improved, and the acid-modified chlorinated polyolefin resin is more easily emulsified.
  • the chlorine content in the acid-modified chlorinated polyolefin resin is preferably 40% by mass or less, more preferably 38% by mass or less, even more preferably 35% by mass or less, particularly preferably 32% by mass or less, and most preferably 30% by mass or less.
  • the chlorine content in the acid-modified chlorinated polyolefin resin is 40% by mass or less, the crystallinity of the acid-modified chlorinated polyolefin resin is high, and the adhesion to polyolefin substrates (particularly polypropylene substrates) and plastic materials (particularly PET and ABS) is further improved.
  • the chlorine content in the acid-modified chlorinated polyolefin resin is preferably 5% by mass or more and 40% by mass or less, more preferably 8% by mass or more and 38% by mass or less, even more preferably 10% by mass or more and 35% by mass or less, even more preferably 12% by mass or more and 32% by mass or less, and particularly preferably 14% by mass or more and 30% by mass or less.
  • the chlorine content in acid-modified chlorinated polyolefin resin can be measured in accordance with JIS K-7229-1995. In other words, it can be measured using the "oxygen flask combustion method," in which acid-modified chlorinated polyolefin resin is burned in an oxygen atmosphere, the generated chlorine gas is absorbed with water, and the amount is quantified by titration.
  • the melting point of the acid-modified polyolefin resin (A) is preferably 90°C or less, more preferably 85°C or less, and particularly preferably 80°C or less.
  • the melting point of the acid-modified polyolefin resin (A) is 90°C or less, the adhesion to the polyolefin substrate (particularly the polypropylene substrate) is even better.
  • the melting point of the acid-modified polyolefin resin (A) is preferably 50°C or higher, more preferably 55°C or higher, and particularly preferably 60°C or higher.
  • the melting point of the acid-modified polyolefin resin (A) is 50°C or higher, the adhesion to the polyolefin substrate (particularly the polypropylene substrate) is further improved.
  • the melting point of the acid-modified polyolefin resin (A) can be measured by a differential scanning calorimeter (DSC) in accordance with JIS K7121-2012. Specifically, using a DSC measuring device, a sample of about 5 mg is heated and melted at 150°C for 10 minutes, cooled at a rate of 10°C/min, and held stable at -50°C, and then heated at a rate of 10°C/min to 150°C and melted, at which point the melting peak temperature is measured and the melting peak temperature is evaluated as the melting point.
  • DSC differential scanning calorimeter
  • the weight average molecular weight (Mw) of the acid-modified polyolefin resin (A) is preferably 3000 to 200,000, more preferably 10,000 to 150,000, even more preferably 20,000 to 120,000, even more preferably 30,000 to 100,000, and particularly preferably 40,000 to 90,000. If the weight average molecular weight (Mw) of the acid-modified polyolefin resin (A) is within the range of 3,000 to 200,000, it has good fluidity.
  • the weight average molecular weight (Mw) is within the range of 3,000 to 200,000, the cohesive force of the acid-modified polyolefin resin (A) is further improved, and the adhesion to polyolefin substrates (particularly polypropylene substrates) and to plastic materials (particularly PET and ABS) is further improved.
  • the weight average molecular weight (Mw) of the acid-modified polyolefin resin (A) can be measured by gel permeation chromatography (GPC). Specific measurement methods will be explained in the examples below.
  • the acid-modified polyolefin resin (A) may be further copolymerized with a radically polymerizable monomer, as long as the effect of the present invention is not impaired.
  • the content of the radically polymerizable monomer is usually 40 parts by mass or less, preferably 20 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of the acid-modified polyolefin resin (A).
  • the form in which the acid-modified polyolefin resin (A) is copolymerized with a radically polymerizable monomer is not limited, and examples of the copolymerization form include random copolymerization, block copolymerization, and graft copolymerization (graft modification).
  • Radically polymerizable monomers include, for example, (meth)acrylic compounds and vinyl compounds.
  • a (meth)acrylic compound is a compound that contains at least one (meth)acryloyl group (acryloyl group and/or methacryloyl group) in the molecule.
  • radical polymerizable monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, cyclohexyl (meth)acrylate, hydroxyethyl (meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, Examples of
  • methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, and lauryl (meth)acrylate are preferred, and these methacrylates, i.e., methyl methacrylate (methyl methacrylate), ethyl methacrylate (ethyl methacrylate), cyclohexyl methacrylate (cyclohexyl methacrylate), and lauryl methacrylate (lauryl methacrylate), are more preferred.
  • the above-mentioned radical polymerizable monomers can be used alone or in combination of two or more.
  • the content of the acid-modified polyolefin resin (A) is preferably 5 to 120 parts by mass, more preferably 10 to 90 parts by mass, more preferably 12.5 to 70 parts by mass, even more preferably 15 to 50 parts by mass, even more preferably 17.5 to 40 parts by mass, and particularly preferably 20 to 35 parts by mass, per 100 parts by mass of the compound (C) having a polymerizable unsaturated group.
  • the content of the acid-modified polyolefin resin (A) is preferably 1 to 60 mass %, more preferably 4 to 50 mass %, even more preferably 7 to 40 mass %, even more preferably 10 to 35 mass %, and particularly preferably 15 to 30 mass %, based on the total mass of the modified polyolefin resin composition, in order to maintain the fluidity of the modified polyolefin resin composition even better, and to further improve adhesion to polyolefin substrates (particularly polypropylene substrates) and to plastic materials (particularly PET and ABS).
  • the present invention contains a polyetheramine (B).
  • the polyetheramine (B) is usually a compound having a polyether chain and an amino group.
  • the polyetheramine (B) has a polyether chain, the polyether chain being A structure represented by formula 1: -(O-CH 2 CH 2 ) x - (wherein x is an integer of 2 to 120), Formula 2-1: A structure represented by -(O-CH 2 CH(CH 3 ))y 1 - (wherein y 1 is an integer of 2 to 90), Formula 2-2: A structure represented by -(O-CH 2 CH 2 CH 2 )y 2 - (wherein y 2 is an integer of 2 to 90), Formula 3-1: A structure represented by -(O-CH 2 CH 2 CH 2 CH 2 )z 1 - (in formula 3-1, z 1 is an integer of 2 to 80), Formula 3-2: a structure represented by -(O-CH(CH 3 )CH 2 CH 2 )z 2 - (in formula 3-2, z 2 is an integer of 2 to 80), It is preferable that the structure contains at least one selected from the group consisting of a structure represented by formula 3-3:
  • the polyetheramine (B) has a polyether chain, the polyether chain being A structure represented by formula 1: -(O-CH 2 CH 2 ) x - (wherein x is an integer of 2 to 120), It is more preferable that the structure contains at least one selected from the group consisting of a structure represented by formula 2-1: -(O-CH 2 CH(CH 3 ))y 1 - (in formula 2-1, y 1 is an integer of 2 to 90) and a structure represented by formula 3-1: -(O-CH 2 CH 2 CH 2 CH 2 )z 1 - (in formula 3-1, z 1 is an integer of 2 to 80).
  • the polyetheramine (B) has the following formula 1A: R 1 -(O-R 2 )a-R 3 Formula 1A (In Formula 1A: R 1 and R 3 each independently represent an amino group or a linear or branched alkyl group having 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms which may have an amino group. R2 represents a linear or branched alkylene group having 2 to 4 (2, 3, or 4) carbon atoms. a is an integer from 1 to 120. It is even more preferable that the compound is represented by the formula:
  • examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.
  • the linear or branched alkylene group having 2 to 4 carbon atoms (2, 3 or 4) is preferably an ethylene group (-CH 2 CH 2 -), a methylethylene group (-CH 2 CH(CH 3 -), an n-propylene group (-CH 2 CH 2 CH 2 -), a 1-methylpropylene group (-CH(CH 3 )CH 2 CH 2 -), a 2-methylpropylene group (-CH 2 CH(CH 3 )CH 2 -), a 3-methylpropylene group (-CH 2 CH 2 CH(CH 3 )-) or an n-butylene group (-CH 2 CH 2 CH 2 CH 2 -).
  • R 1 represents a linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10)
  • R 2 represents a linear or branched alkylene group having 2 to 4 carbon atoms (2, 3, or 4)
  • R 3 represents an amino group
  • a is an integer of 1 to 120.
  • the polyetheramine (B) has a primary amino group or a secondary amino group at one end, and that the weight average molecular weight (Mw) of the polyetheramine (B) is 200 to 50,000. In one embodiment, it is more preferable that the polyetheramine (B) has a primary amino group or a secondary amino group at one end, and that the weight average molecular weight (Mw) of the polyetheramine (B) is 300 to 10,000. In one embodiment, it is even more preferable that the polyetheramine (B) has a primary amino group at one end, and that the weight average molecular weight (Mw) of the polyetheramine (B) is 500 to 5,000.
  • the weight average molecular weight (Mw) of the polyetheramine (B) is usually 200 to 50,000, preferably 300 to 20,000, more preferably 350 to 10,000, even more preferably 450 to 7,000, and particularly preferably 500 to 5,000.
  • the weight average molecular weight (Mw) of the polyetheramine (B) can be measured by GPC and converted from a calibration curve for polystyrene.
  • the GPC measurement is performed by a conventional method using a commercially available device and a solvent such as THF.
  • the polyetheramine (B) preferably has an HLB value of 2 to 20, more preferably 5 to 19, and even more preferably 8 to 18.
  • HLB value is within the range of 2 to 20, the fluidity of the modified polyolefin resin composition can be maintained even better.
  • the HLB value means a value representing the degree of hydrophilicity or lipophilicity (hydrophobicity) of the polyetheramine (B).
  • the polyetheramine (B) can be bonded to the acid-modified polyolefin resin (A) through various reaction forms.
  • reaction forms include reaction forms that form covalent bonds and/or ionic bonds. More specifically, examples of such reaction forms include an amidation reaction between a carboxylic anhydride group and a primary or secondary amino group; an imidization reaction; and a neutralization reaction between a carboxylic acid group and a primary or secondary amino group.
  • the content of polyetheramine (B) is usually 6 to 100 parts by mass, preferably 10 to 90 parts by mass, more preferably 15 to 80 parts by mass, even more preferably 20 to 70 parts by mass, even more preferably 25 to 60 parts by mass, and particularly preferably 30 to 50 parts by mass, per 100 parts by mass of acid-modified polyolefin resin (A), in order to maintain the fluidity of the modified polyolefin resin composition even better, and to further improve adhesion to polyolefin substrates (particularly polypropylene substrates) and to plastic materials (particularly PET and ABS).
  • the content of polyetheramine (B) is usually 0.5 to 40% by mass, preferably 1 to 35% by mass, more preferably 2 to 30% by mass, even more preferably 3 to 25% by mass, even more preferably 4 to 20% by mass, and particularly preferably 5 to 17.5% by mass, based on the total mass of the modified polyolefin resin composition, in order to maintain the fluidity of the modified polyolefin resin composition even better, and to further improve adhesion to polyolefin substrates (particularly polypropylene substrates) and to plastic materials (particularly PET and ABS).
  • the present invention contains a compound (C) having a polymerizable unsaturated group.
  • the compound (C) having a polymerizable unsaturated group usually has one or more (for example, 1, 2, 3 or 4) polymerizable unsaturated groups.
  • the polymerizable unsaturated group means an unsaturated group capable of radical polymerization.
  • the number of polymerizable unsaturated groups in the compound (C) having a polymerizable unsaturated group is preferably 1 or 2.
  • the polymerizable unsaturated group in the compound (C) having a polymerizable unsaturated group is preferably at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a maleimide group, and a vinyl ether group.
  • the polymerizable unsaturated group in the compound (C) having a polymerizable unsaturated group is at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group.
  • the polymerizable unsaturated group in the compound (C) having a polymerizable unsaturated group is an acryloyloxy group and/or a methacryloyloxy group.
  • the compound (C) having a polymerizable unsaturated group preferably includes a compound having a hydroxyl group and one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups.
  • the number of hydroxyl groups is preferably 1 or 2, more preferably 1.
  • the compound (C) having a polymerizable unsaturated group includes a compound having a hydroxyl group and 1 to 3 (1, 2 or 3) polymerizable unsaturated groups.
  • the number of hydroxyl groups is preferably 1 or 2, more preferably 1.
  • the compound (C) having a polymerizable unsaturated group preferably contains an alkyleneoxy group and/or a linear or branched alkyl group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20), and a compound having one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups.
  • the number of polymerizable unsaturated groups is preferably 1 or 2, and more preferably 2.
  • the compound (C) having a polymerizable unsaturated group preferably includes a compound having a linear or branched alkyl group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20), and one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups.
  • the number of polymerizable unsaturated groups is preferably 1 or 2, more preferably 1.
  • the compound (C) having a polymerizable unsaturated group is It is preferable that the copolymer contains a compound having a hydroxyl group and one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups, and an alkyleneoxy group and/or a linear or branched alkyl group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20), and a compound having one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups.
  • the compound (C) having a polymerizable unsaturated group is it is more preferable that the copolymer contains a compound having a hydroxyl group and one or two polymerizable unsaturated groups, and an alkyleneoxy group and/or a linear or branched alkyl group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20), and a compound having one or two polymerizable unsaturated groups.
  • the alkyleneoxy group is typically represented by the following formula 5: -(Y 1 -O)m- Formula 5 [In formula 5: Y1 represents a linear or branched alkylene group having 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms. m represents an integer of 1 to 20. This is the structure represented by the following formula:
  • Y 1 is preferably a linear or branched alkylene group having 1 to 5 (1, 2, 3, 4 or 5) carbon atoms.
  • m is preferably an integer from 2 to 15.
  • the compound (C) having a polymerizable unsaturated group is represented by the following formula 6: R a -R b -R cFormula 6
  • R a represents a polymerizable unsaturated group.
  • Rc represents a polymerizable unsaturated group or a methyl group.
  • R b represents a group represented by -(Y 2 -O)n-, or a linear or branched alkylene group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20).
  • Y2 represents a linear or branched alkylene group having 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms.
  • n represents an integer of 1 to 20. It is preferable that the compound contains a compound represented by the following formula:
  • Y2 is preferably a linear or branched alkylene group having 1 to 5 carbon atoms (1, 2, 3, 4 or 5).
  • n is preferably an integer from 2 to 15.
  • the compound (C) having a polymerizable unsaturated group contains one or more compounds represented by the above formula 6.
  • the compound (C) having a polymerizable unsaturated group preferably includes a compound having a (meth)acryloyloxy group as the polymerizable unsaturated group.
  • compounds having a (meth)acryloyloxy group include compounds having one (meth)acryloyloxy group, compounds having two (meth)acryloyloxy groups, and compounds having three or more (meth)acryloyloxy groups. These compounds can be used alone or in combination of two or more.
  • Examples of the compound having one (meth)acryloyloxy group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol monoacrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, polyethylene glycol-polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, Alkyl (meth)acrylates such as phenoxydiethylene glycol (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)
  • Examples of the compound having two (meth)acryloyloxy groups include Alkanediol di(meth)acrylates such as 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and tricyclodecanedimethylol di(meth)acrylate; Bisphenol-modified di(meth)acrylates such as bisphenol A ethylene oxide-modified di(meth)acrylate and bisphenol F ethylene oxide-modified di(meth)acrylate; Examples of such compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate
  • Examples of the compound having three or more (meth)acryloyloxy groups include dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate; ethylene oxide-modified (meth)acrylates such as ethylene oxide-modified dipentaerythritol hexa(meth)acrylate and ethylene oxide-modified pentaerythritol tetra(meth)acrylate; Isocyanuric acid-modified tri(meth)acrylates such as ethylene oxide-modified isocyanuric acid and ⁇ -caprolactone-modified tris(acryloyloxyethyl)isocyanurate; Examples of the urethane methacrylate include pentaeryth
  • the compound (C) having a polymerizable unsaturated group includes a compound having two (meth)acryloyloxy groups.
  • the compound having two (meth)acryloyloxy groups is preferably at least one selected from the group consisting of neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate.
  • Specific examples of the compound (C) having a polymerizable unsaturated group include (meth)acrylamide, N-methoxymethyl-(meth)acrylamide, N-ethoxymethyl-(meth)acrylamide, N-propoxymethyl-(meth)acrylamide, N-butoxymethyl-(meth)acrylamide, N-pentoxymethyl-(meth)acrylamide, N,N-di(methoxymethyl)acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N,N-di(ethoxymethyl)acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N,N-di(propoxymethyl)acrylamide, N-butoxymethyl-N-(propoxymethyl)methacrylamide, N, Compounds having an amide group such as N-di(butoxymethyl)acrylamide, N-butoxymethyl-N-(methoxymethyl)methacrylamide, N,N-di(pentoxymethyl)acryl
  • the content of the compound (C) having a polymerizable unsaturated group is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, even more preferably 30 to 85% by mass, and even more preferably 40 to 80% by mass, based on the total mass of the modified polyolefin resin composition, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition even better and improving the adhesion to polyolefin substrates (particularly polypropylene substrates) and plastic materials (particularly PET and ABS).
  • the compound (C) having a polymerizable unsaturated group includes a compound having a hydroxyl group and one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups.
  • the content of the compound having a hydroxyl group and one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups is preferably 1 to 50 mass%, more preferably 3 to 45 mass%, even more preferably 6 to 40 mass%, and even more preferably 10 to 35 mass%, based on the total mass of the modified polyolefin resin composition.
  • compounds having a hydroxyl group and one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups include 2-hydroxy-1,3-dimethacryloxypropane, 2-hydroxy-3-methacrylpropyl acrylate, glycerin diacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, etc.
  • the compound (C) having a polymerizable unsaturated group may contain a biomass-derived (meth)acrylic monomer component.
  • the biomass-derived (meth)acrylic monomer component refers to a component composed of a biomass-derived (meth)acrylic acid or an ester of a biomass-derived alkanol and a biomass-derived or non-biomass-derived (meth)acrylic acid.
  • biomass-derived alkanols include biomass ethanol, and alkanols derived from plant materials such as palm oil, palm kernel oil, and coconut oil. When the biomass-derived alkanol has 3 or more carbon atoms, the alkanol may be linear or branched.
  • the weight average molecular weight (Mw) of the compound (C) having a polymerizable unsaturated group is preferably 5,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.
  • the weight average molecular weight (Mw) of the compound (C) having a polymerizable unsaturated group is preferably 100 or more, more preferably 120 or more, and even more preferably 140 or more.
  • the weight average molecular weight (Mw) of the compound (C) having a polymerizable unsaturated group is preferably 100 or more and 5,000 or less, more preferably 120 or more and 2,000 or less, and even more preferably 140 or more and 1,000 or less.
  • the modified polyolefin resin composition may contain a coating resin other than the compound (C) having a polymerizable unsaturated group.
  • coating resins include acrylic resins, polyester resins, alkyd resins, polyether resins, polyolefin resins, polyurethane resins, polycarbonate resins, melamine resins, epoxy resins, and carbodiimide resins. These resins may be used alone or in combination of two or more.
  • the content of the coating resin is preferably 10 to 30 parts by mass per 100 parts by mass of the modified polyolefin resin composition.
  • the ionic liquid (D) is composed of a cation and an anion.
  • the ionic liquid (D) generally means a salt that becomes liquid at 100° C. or less.
  • the ionic liquid (D) preferably means a salt that becomes liquid at 25° C.
  • the ionic liquid (D) can be an appropriate combination of cations and anions.
  • Examples of the cations constituting the ionic liquid (D) include cations having a positively charged nitrogen atom, cations having a positively charged phosphorus atom, cations having a positively charged sulfur atom, cations having positively charged nitrogen and sulfur atoms, cations having a positively charged metal element, etc.
  • the cations constituting the ionic liquid (D) are preferably cations having a positively charged nitrogen atom, cations having a positively charged phosphorus atom, or cations having a positively charged sulfur atom, and more preferably cations having a positively charged nitrogen atom.
  • Cations having a positively charged nitrogen atom include, for example, imidazolium cation, ammonium cation, pyridinium cation, quinolinium cation, pyrrolidinium cation, piperidinium cation, piperazinium cation, morpholinium cation, pyridazinium cation, pyrimidinium cation, pyrazinium cation, pyrazolium cation, thiazolium cation, oxazolium cation, triazolium cation, guanidium cation, 4-aza-1-azoniabicyclo[2,2,2]octanium cation, etc.
  • these cations may have one or more substituents at any position. Examples of the substituents include alkyl groups, etc.
  • ammonium cations include dialkylammonium cations such as dioctylammonium cation and bis(2-ethylhexyl)ammonium cation, trialkylammonium cations such as trioctylammonium cation, dimethylmyristylammonium cation, dimethylpalmitylammonium cation, dimethylstearylammonium cation, dimethylbehenylammonium cation, and dilaurylmethylammonium cation; Tetraalkylammonium cations such as methyltrioctylammonium cation, trihexyltetradecylammonium cation, (2-hydroxyethyl)trimethylammonium cation, (2-acryloyloxyethyl)trimethylammonium cation, (2-methacryloyloxyethyl)trimethylammonium cation, N,N-dieth
  • piperidinium cations include 1-methyl-1-propylpiperidinium cation, 1-butyl-1-methylpiperidinium cation, 1-(2-hydroxyethyl)-1-methylpiperidinium cation, and 1-ethyl-1-methylpiperidinium cation.
  • Cations having a positively charged phosphorus atom are generally called phosphonium cations.
  • Specific examples of cations having a positively charged phosphorus atom include tetrabutylphosphonium cation, tetrahexylphosphonium cation, trihexyltetradecylphosphonium cation, triphenylmethylphosphonium cation, (2-cyanoethyl)triethylphosphonium cation, (3-chloropropyl)trioctylphosphonium cation, tributyl(4-vinylbenzyl)phosphonium cation, triisobutylmethylphosphonium cation, triethylmethylphosphonium cation, tributylmethylphosphonium cation, tributylhexadecylphosphonium cation, 3-(triphenylphosphonio)propane-1-sulfonic acid cation, etc.
  • Cations that have a positively charged sulfur atom are generally called sulfonium cations.
  • Specific examples of cations that have a positively charged sulfur atom include the triethylsulfonium cation, tributylsulfonium cation, 1-ethyltetrahydrothiophenium cation, and 1-butyltetrahydrothiophenium cation.
  • the cation constituting the ionic liquid (D) is preferably at least one cation selected from the group consisting of tetraalkylammonium cations, imidazolium cations, pyridinium cations, pyrazolium cations, pyrrolium cations, pyrrolinium cations, pyrrolidinium cations, and piperidinium cations, from the viewpoints of better maintaining fluidity, improving adhesion to polyolefin substrates (particularly polypropylene substrates) and plastic materials (particularly PET and ABS), and improving antistatic performance, and more preferably a tetraalkylammonium cation.
  • the cation constituting the ionic liquid (D) is preferably a cation having a polymerizable unsaturated group from the viewpoints of maintaining the fluidity better, improving adhesion to polyolefin substrates (particularly polypropylene substrates) and plastic materials (particularly PET and ABS), and improving antistatic performance.
  • cations having a polymerizable unsaturated group include (2-acryloyloxyethyl)trimethylammonium cation, (2-methacryloyloxyethyl)trimethylammonium cation, etc.
  • the cations constituting the ionic liquid (D) are preferably tetraalkylammonium cations and tetraalkylammonium cations having one or two polymerizable unsaturated groups, and more preferably tetraalkylammonium cations and tetraalkylammonium cations having one polymerizable unsaturated group.
  • the polymerizable unsaturated group possessed by the cation constituting the ionic liquid (D) is preferably an acryloyl group, a methacryloyl group, an acryloyloxy group, or a methacryloyloxy group, more preferably an acryloyloxy group or a methacryloyloxy group, and even more preferably an acryloyloxy group.
  • the number of polymerizable unsaturated groups possessed by the cation is preferably 1 or 2, and more preferably 1.
  • the anion constituting the ionic liquid (D) is preferably a sulfonate anion, a carboxylate anion, a phosphate anion, a sulfonamide anion or a sulfonimide anion, and more preferably a sulfonimide anion.
  • sulfonimide anions include bis(fluorosulfonyl)imide anion, bis(trifluoromethanesulfonyl)imide anion, bis(pentafluoroethanesulfonyl)imide anion, bis(heptafluoropropanesulfonyl)imide anion, bis(nonafluorobutanesulfonyl)imide anion, and [(trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)]imide anion.
  • anions constituting the ionic liquid (D) include fluoride anion, chloride anion, bromide anion, iodide anion, dicyanamide anion, bis(fluorosulfonyl)imide anion, bis(trifluoromethylsulfonyl)imide anion, 2,2,2-trifluoro-N-(trifluoromethylsulfonyl)acetamide anion, bis(pentafluoroethylsulfonyl)imide anion, bis(nonafluorobutylsulfonyl)imide anion, tetrafluoroborate anion, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anion, methanesulfonate anion, butylsulfonate anion, trifluoromethanesulfonate anion, tetrafluoroethanesulfonate anion, nonafluoro
  • the ionic liquid (D) include: tetrahexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-butylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-heptylammonium bis(trifluoromethanesulfonyl)imide, N,N-ddi
  • the content of ionic liquid (D) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 0.8 to 12.5 parts by mass, per 100 parts by mass of the modified polyolefin resin composition.
  • the antistatic performance is further improved, adhesion to polyolefin substrates (particularly polypropylene substrates) and plastic materials (particularly PET and ABS) is further improved, and the flowability of the modified polyolefin resin composition tends to be further improved.
  • the modified polyolefin resin composition comprises an acid-modified polyolefin resin (A), a polyetheramine (B), two types of “compounds having a polymerizable unsaturated group (C)”, and an ionic liquid (D),
  • the compound (C) having two types of polymerizable unsaturated groups is one compound having an alkyleneoxy group or a linear or branched alkyl group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms) and one or two polymerizable unsaturated groups; and It is one type of compound having a hydroxyl group and one or two polymerizable unsaturated groups.
  • the alkyleneoxy group is preferably an alkyleneoxy group represented by the above-mentioned formula 5.
  • Y 1 in the above-mentioned formula 5 is preferably a linear or branched alkylene group having 1 to 5 (1, 2, 3, 4 or 5) carbon atoms, and m is preferably an integer of 2 to 15.
  • the number of carbon atoms in the linear or branched alkyl group is preferably 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).
  • the polymerizable unsaturated group is preferably at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group, and more preferably an acryloyloxy group and/or a methacryloyloxy group.
  • the modified polyolefin resin composition comprises an acid-modified polyolefin resin (A), a polyetheramine (B), a compound having a polymerizable unsaturated group (C), and an ionic liquid (D),
  • the compound (C) having a polymerizable unsaturated group is at least one compound selected from the group consisting of neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2-ethylhexyl acrylate, 4-hydroxybutyl acrylate, and 2-hydroxy-3-methacrylpropyl acrylate.
  • the amount of polymerization initiator used is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 5 parts by mass, per 100 parts by mass of the modified polyolefin resin composition, from the viewpoint of increasing the curing speed of the coating film obtained from the modified polyolefin resin composition.
  • a polymerization initiator capable of initiating a polymerization reaction of a polymerizable unsaturated group
  • a polymerization initiator capable of initiating a polymerization reaction of a polymerizable unsaturated group
  • a photopolymerization initiator that generates radicals by light
  • a thermal polymerization initiator that generates radicals by heat.
  • These polymerization initiators can be used alone or in combination of two or more kinds.
  • a photopolymerization initiator is a compound that generates radicals or acids when irradiated with ultraviolet or visible light, initiating a chain polymerization reaction.
  • photopolymerization initiators include acetophenone-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzophenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and titanocene-based photopolymerization initiators. These photopolymerization initiators can be used alone or in combination of two or more types.
  • acetophenone-based photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer. These can be used alone or in combination of two or more.
  • benzoin-based photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. These can be used alone or in combination of two or more.
  • benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, polyvinyl benzophenone, ⁇ -hydroxycyclohexyl phenyl ketone, etc. These can be used alone or in combination of two or more types.
  • thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, etc. These can be used alone or in combination of two or more types.
  • acylphosphine oxide photopolymerization initiators include bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide, ethoxyphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, etc. These can be used alone or in combination of two or more.
  • titanocene photopolymerization initiators include bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyr-1-yl)ethyl)phenyl]titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(3-(1-pyr-1-yl)propyl)phenyl]titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-((1-pyr-1-yl)methyl)phenyl]titanium, and bis(methylcyclopentadienyl)-bis[2,6-difluoro-3-((1-pyr-1-yl)methyl)phenyl]titanium.
  • Examples of such compounds include bis(cyclopentadienyl)-bis[2,6-difluoro-3-((2,5-dimethyl-1-pyr-1-yl)methyl)phenyl]titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-((2-isopropyl-5-methyl-1-pyr-1,6-yl)methyl)phenyl]titanium, and bis(cyclopentadienyl)-bis[2,6-difluoro-3-((2-(2-methoxyethyl)-5-methyl-1-pyr-1-yl)methyl)phenyl]titanium. These compounds can be used alone or in combination of two or more.
  • a thermal polymerization initiator is a compound that generates radicals by heating and initiates a chain polymerization reaction.
  • examples of the thermal polymerization initiator include organic peroxides; and inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide.
  • organic peroxides include ketone peroxide compounds such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, and acetylacetone peroxide; Peroxyketal compounds such as 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)octane, n-butyl-4,4-bis(t-butylperoxy)valerate, and 2,2-bis(t-butylperoxy)butane; Hydroperoxide compounds such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide
  • the modified polyolefin composition may contain an ultraviolet absorber as long as the effect of the present invention is not impaired.
  • the ultraviolet absorber include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and benzoxazine-based ultraviolet absorbers. These ultraviolet absorbers may be used alone or in combination of two or more.
  • the amount of ultraviolet absorber used is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the modified polyolefin resin composition.
  • the modified polyolefin composition may contain a light stabilizer within a range that does not impair the effects of the present invention.
  • the light stabilizer include hindered amine light stabilizers.
  • hindered amine light stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl sebacate, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, and decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester. These can be used alone or in combination of two or more.
  • the amount of light stabilizer used is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 1 part by mass, per 100 parts by mass of the modified polyolefin resin composition.
  • the modified polyolefin composition may contain a sensitizer within a range that does not impair the effects of the present invention.
  • the sensitizer include unsaturated ketone compounds such as chalcone and dibenzalacetone, 1,2-diketone compounds such as benzil and camphorquinone, polymethine dyes such as benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, and oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, and squarylium compounds.
  • Examples of the compounds include compounds such as porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxaliroporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphylline compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, Michler's ketone compounds, and biimidazole compounds. These compounds may be used alone or in combination of two or more.
  • the amount of sensitizer used is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the modified polyolefin resin composition.
  • the modified polyolefin resin composition may contain a surfactant within a range that does not impair the effects of the present invention.
  • the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. These surfactants can be used alone or in combination of two or more. Among these, from the viewpoint of improving the stability of the modified polyolefin resin composition, it is preferable to use a nonionic surfactant or anionic surfactant, and it is more preferable to use a nonionic surfactant.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxypropylene alkylphenyl ethers, polyoxyethylene styrenated phenyl ethers, polyoxypropylene styrenated phenyl ethers, polyoxyethylene fatty acid esters, polyoxypropylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxypropylene sorbitan fatty acid esters, polyoxyethylene alkylamides, polyoxypropylene alkylamides, polyoxyethylene lanolin alcohol ethers, polyoxypropylene lanolin alcohol ethers, polyoxyethylene lanolin fatty acid esters, polyoxypropylene lanolin fatty acid esters, (polyoxyethyleneoxypropylene) block copolymers, etc.
  • nonionic surfactants a wide variety of known commercially available products can be used, such as the Emulmin series (manufactured by Sanyo Chemical Industries Co., Ltd.), the Noigen series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the Brownon series (manufactured by Aoki Oil & Fat Industries Co., Ltd.).
  • anionic surfactants include higher alkyl sulfate ester salts, alkylaryl polyoxyethylene sulfate ester salts, higher fatty acid salts, alkylaryl sulfonates, and alkyl phosphate ester salts. These can be used alone or in combination of two or more.
  • a wide variety of known commercial products can be used as anionic surfactants, including, for example, the Neocol series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the Hitenol series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).
  • the amount of the surfactant used is preferably 1 to 60 parts by mass, more preferably 3 to 40 parts by mass, and even more preferably 5 to 30 parts by mass, per 100 parts by mass of the acid-modified polyolefin resin (A), from the viewpoint of improving the stability of the modified polyolefin resin composition.
  • the modified polyolefin resin composition may contain various additives as necessary, such as a tackifier, a film-forming assistant, an antifoaming agent, an anti-sagging agent, and a wetting agent.
  • tackifiers include rosin, dammar, polymerized rosin, hydrogenated rosin, ester rosin, rosin-modified maleic acid resin, polyterpene resin, petroleum resin, cyclopentadiene resin, phenol resin, xylene resin, coumarone-indene resin, etc. These can be used alone or in combination of two or more.
  • the amount of tackifier used is preferably 1 to 50 parts by mass, and more preferably 10 to 25 parts by mass, per 100 parts by mass of the modified polyolefin resin composition.
  • the modified polyolefin resin composition may or may not contain an organic solvent.
  • the modified polyolefin resin composition when the modified polyolefin resin composition contains an organic solvent, it is preferable that a small amount of organic solvent is contained from the viewpoint of the environment and hygiene.
  • the content of the organic solvent is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, per 100 parts by mass of the modified polyolefin resin composition.
  • the modified polyolefin resin composition when the modified polyolefin resin composition contains an organic solvent, the viscosity of the modified polyolefin resin composition is further reduced, which has the advantage of further improving the coatability.
  • the modified polyolefin resin composition when the modified polyolefin resin composition does not contain an organic solvent, the modified polyolefin resin composition can be suitably used as a base agent for a solventless radical curing binder.
  • solventless means that no organic solvent is intentionally added to the modified polyolefin resin composition, and the embodiment in which the organic solvent used in producing the acid-modified polyolefin resin (A) remains is included in the "solventless" category.
  • organic solvent examples include: Aromatic hydrocarbons such as benzene, toluene, and xylene; Aliphatic hydrocarbons such as hexane, heptane, octane, and decane; Alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane; Halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene, and chloroform; Alcohol-based solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, 1-hexanol, 2-ethylhexanol, 2-methylcyclohexanol, phenol, and 2-heptyl alcohol; Ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone,
  • Step (1) The acid-modified polyolefin resin (A) and the compound having a polymerizable unsaturated group (C) are charged into a stirrer equipped with a heating device and kneaded while being heated.
  • the heating temperature during kneading is usually 50 to 200°C, preferably 60 to 150°C, and more preferably 70 to 120°C.
  • the kneading time varies depending on the heating temperature, etc., but is usually 10 to 120 minutes, preferably 15 to 90 minutes, and more preferably 20 to 60 minutes.
  • the heating temperature during kneading is usually 50 to 200°C, preferably 60 to 150°C, and more preferably 70 to 120°C.
  • the kneading time varies depending on the heating temperature, etc., but is usually 10 to 120 minutes, preferably 15 to 90 minutes, and more preferably 20 to 75 minutes.
  • the heating temperature during kneading is usually 50 to 200°C, preferably 60 to 150°C, and more preferably 70 to 120°C.
  • the kneading time varies depending on the heating temperature, etc., but is usually 10 to 120 minutes, preferably 15 to 90 minutes, and more preferably 20 to 75 minutes.
  • the filtration can be carried out, for example, using a wire mesh with mesh size of 50 ⁇ m to 300 ⁇ m.
  • the cured product of the present embodiment is a cured product obtained by curing the modified polyolefin resin composition of the present embodiment.
  • the cured product of the present embodiment is a product obtained by curing the modified polyolefin resin composition of the present embodiment.
  • the above cured product will be simply referred to as the "cured product of the present embodiment.”
  • the modified polyolefin resin composition of this embodiment and the cured product of this embodiment can be suitably used for polyolefin substrates.
  • polyolefin substrates include polyolefin processed into lumps (plates, rods, spheres, etc.), sheets, films, threads, cloth (woven cloth, knitted cloth, nonwoven cloth, etc.), etc.
  • sheets and films are preferred from the viewpoint of production. Films having a thickness of 5 ⁇ m to 100 ⁇ m can be used.
  • polyolefins examples include polypropylene, polyethylene, ethylene propylene copolymers, ethylene propylene diene copolymers, polybutene, poly(4-methyl-1-pentene), etc.
  • the modified polyolefin resin composition of this embodiment and the cured product of this embodiment can be particularly suitably used for polypropylene substrates.
  • the modified polyolefin resin composition of this embodiment and the cured product of this embodiment can be suitably used in paints for molded bodies; inks; adhesives; sealants; primers: coating agents, paints for in-mold coating, etc.
  • the modified polyolefin resin composition of this embodiment and the cured product of this embodiment can be suitably used in inks for polyolefin substrates, adhesives for polyolefin substrates, primers for polyolefin substrates, paints for polyolefin substrates, and in-mold coating paints for polyolefin substrates.
  • a coating film can be obtained from the modified polyolefin resin composition of this embodiment.
  • the coating film can be particularly suitably used for metal products, electronic devices, packaging materials, automotive parts, etc.
  • the method of forming a coating film from the modified polyolefin resin composition of this embodiment includes, for example, a method of uniformly applying the modified polyolefin resin composition of this embodiment to the surface of various substrates and subjecting it to a heat treatment (e.g., baking treatment, etc.). This allows a uniform coating film to be formed on the surface of various substrates.
  • a heat treatment e.g., baking treatment, etc.
  • the coating method include gravure coating, curtain flow coating, Mayer bar method, dip coating, brush coating, roll coating, spray coating, etc.
  • the amount of the modified polyolefin resin composition applied to the substrate is not particularly limited and is appropriately selected depending on the application, and it is preferable that the dried coating film is within the range of 1 ⁇ m to 100 ⁇ m.
  • the heat treatment can be performed using a hot air circulation type oven, an infrared heater, etc.
  • a method of forming a coating film by molding a plastic substrate in a mold, injecting the modified polyolefin resin composition of this embodiment between the mold and the substrate, and applying heat and pressure can be used.
  • the heating temperature is usually 60 to 200°C.
  • the heating time is usually 15 seconds to 20 minutes.
  • a modified polyolefin resin composition comprising an acid-modified polyolefin resin (A), a polyetheramine (B), a compound having a polymerizable unsaturated group (C), and an ionic liquid (D).
  • a modified polyolefin resin composition comprising an acid-modified polyolefin resin (A), a polyetheramine (B), a compound having a polymerizable unsaturated group (C), and an ionic liquid (D).
  • the cation constituting the ionic liquid (D) is at least one ammonium cation selected from the group consisting of a tetraalkylammonium ion, an imidazolium ion, a pyridinium ion, a pyrazolium ion, a pyrrolium ion, a pyrrolinium ion, a pyrrolidinium ion, and
  • the content of the ionic liquid (D) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 0.8 to 12.5 parts by mass, relative to 100 parts by mass of the modified polyolefin resin composition.
  • Item 4. The modified polyolefin resin composition according to any one of Items 1 to 3, wherein a cation of the ionic liquid (D) has a polymerizable unsaturated group.
  • the modified polyolefin resin composition according to any one of Items 1 to 4, wherein the content of the acid-modified polyolefin resin (A) is preferably 5 to 120 parts by mass, more preferably 10 to 90 parts by mass, more preferably 12.5 to 70 parts by mass, even more preferably 15 to 50 parts by mass, still more preferably 17.5 to 40 parts by mass, and particularly preferably 20 to 35 parts by mass, relative to 100 parts by mass of the compound (C) having a polymerizable unsaturated group.
  • Item 6 The compound (C) having a polymerizable unsaturated group, Preferably, the compound contains a hydroxyl group and one or more polymerizable unsaturated groups.
  • the modified polyolefin resin composition according to any one of items 1 to 5 contains a compound having a hydroxyl group and one or two polymerizable unsaturated groups.
  • Item 7. The compound (C) having a polymerizable unsaturated group, Preferably, the compound includes an alkyleneoxy group and/or a linear or branched alkyl group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), and one or more polymerizable unsaturated groups.
  • the compound includes an alkyleneoxy group and/or a linear or branched alkyl group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20), and a compound having 1 to 4 (1, 2, 3, or 4) polymerizable unsaturated groups.
  • the modified polyolefin resin composition according to any one of items 1 to 6 contains an alkyleneoxy group and/or a linear or branched alkyl group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), and a compound having one or two polymerizable unsaturated groups. Item 8.
  • the modified polyolefin resin composition according to any one of Items 1 to 7, wherein the content of the polyetheramine (B) is usually 6 to 100 parts by mass, preferably 10 to 90 parts by mass, more preferably 15 to 80 parts by mass, even more preferably 20 to 70 parts by mass, still more preferably 25 to 60 parts by mass, and particularly preferably 30 to 50 parts by mass, relative to 100 parts by mass of the acid-modified polyolefin resin (A).
  • the content of the polyetheramine (B) is usually 6 to 100 parts by mass, preferably 10 to 90 parts by mass, more preferably 15 to 80 parts by mass, even more preferably 20 to 70 parts by mass, still more preferably 25 to 60 parts by mass, and particularly preferably 30 to 50 parts by mass, relative to 100 parts by mass of the acid-modified polyolefin resin (A).
  • Item 9 the content of the polyetheramine (B) is usually 6 to 100 parts by mass, preferably 10 to 90 parts by mass, more preferably 15 to 80 parts by mass, even more preferably 20
  • the polyetheramine (B) has a polyether chain,
  • the polyether chain is A structure represented by -(O-CH 2 CH 2 ) x- (x is an integer of 2 to 120), A structure represented by -(O- CH2CH ( CH3 )) y1- ( y1 is an integer of 2 to 90), A structure represented by -(O-CH 2 CH 2 CH 2 )y 2 - (y 2 is an integer of 2 to 90), A structure represented by -(O-CH 2 CH 2 CH 2 CH 2 )z 1 - (z 1 is an integer of 2 to 80), A structure represented by -(O-CH( CH3 ) CH2CH2 ) z2- ( z2 is an integer of 2 to 80),
  • the modified polyolefin resin composition according to any one of items 1 to 8, which is a structure containing at least one selected from the group consisting of a structure represented by -(O-CH 2 CH(CH 3 )CH 2 )z 3 - (z 3 is an integer
  • the polyetheramine (B) is Preferably, it has a primary amino group or a secondary amino group at one end and has a weight average molecular weight (Mw) of 200 to 50,000. More preferably, it has a primary amino group or a secondary amino group at one end and Mw is 300 to 10,000. More preferably, the modified polyolefin resin composition has a primary amino group at one end and Mw of 500 to 5000.
  • Item 11 The modified polyolefin resin composition according to any one of Items 1 to 10, wherein the HLB value of the polyetheramine (B) is preferably 2 to 20, more preferably 5 to 19, and even more preferably 8 to 18. Item 12.
  • Mw weight average molecular weight of the compound (C) having a polymerizable unsaturated group
  • the compound (C) having a polymerizable unsaturated group Preferably, a compound having a hydroxyl group and one or more polymerizable unsaturated groups, an alkyleneoxy group and/or a linear or branched alkyl group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20), and a compound having one or more polymerizable unsaturated groups; More preferably, a compound having a hydroxyl group and 1 to 4 (1, 2, 3, or 4) polymerizable unsaturated groups; and a compound having an alkyleneoxy group and/or a linear or branched alkyl group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20), and 1 to 4 (1, 2, 3, or 4) polymerizable unsaturated groups, More preferably, a compound having a hydroxyl group and one or two polymerizable unsaturated groups, Item 13.
  • Item 14 The modified polyolefin resin composition according to any one of Items 1 to 13, wherein the acid-modified polyolefin resin (A) is a graft polymer having a structure in which an ⁇ , ⁇ -unsaturated carboxylic acid or an acid anhydride thereof is grafted to a polyolefin resin.
  • the acid-modified polyolefin resin (A) is a graft polymer having a structure in which an ⁇ , ⁇ -unsaturated carboxylic acid or an acid anhydride thereof is grafted to a polyolefin resin.
  • the polyolefin resin is at least one copolymer selected from the group consisting of homopolypropylene, propylene- ⁇ -olefin copolymer, homopolyethylene, ethylene- ⁇ -olefin copolymer, poly 1-butene, and 1-butene- ⁇ -olefin copolymer, More preferably, it is homopolypropylene and/or propylene- ⁇ -olefin copolymer.
  • the modified polyolefin resin composition according to any one of Items 1 to 15, wherein the content of the acid-modified polyolefin resin (A) is preferably 1 to 60 mass%, more preferably 4 to 50 mass%, even more preferably 7 to 40 mass%, still more preferably 10 to 35 mass%, and particularly preferably 15 to 30 mass%, relative to the total mass of the modified polyolefin resin composition.
  • the polyetheramine (B) has a polyether chain, The polyether chain is A structure represented by formula 1: -(O-CH 2 CH 2 ) x - (wherein x is an integer of 2 to 120), Item 17.
  • the modified polyolefin resin composition according to any one of items 1 to 16, which is a structure containing at least one selected from the group consisting of a structure represented by formula 2-1: -(O- CH 2 CH ( CH 3 ))y 1 - (in formula 2-1, y 1 is an integer of 2 to 90) and a structure represented by formula 3-1: -(O-CH 2 CH 2 CH 2 CH 2 )z 1 - (in formula 3-1, z 1 is an integer of 2 to 80).
  • Item 18 is a structure containing at least one selected from the group consisting of a structure represented by formula 2-1: -(O- CH 2 CH ( CH 3 ))y 1 - (in formula 2-1, y 1 is an integer of 2 to 90) and a structure represented by formula 3-1: -(O-CH 2 CH 2 CH 2 CH 2 )z 1 - (in formula 3-1, z 1 is an integer of 2 to 80).
  • the polyetheramine (B) is represented by the following formula 1A: R 1 -(O-R 2 )a-R 3 Formula 1A (In Formula 1A: R 1 and R 3 each independently represent an amino group or a linear or branched alkyl group having 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms which may have an amino group. R2 represents a linear or branched alkylene group having 2 to 4 (2, 3, or 4) carbon atoms. a is an integer from 1 to 120.
  • Item 18 The modified polyolefin resin composition according to any one of items 1 to 17, wherein the compound is represented by the formula: Item 19.
  • R 1 represents a linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10)
  • R 2 represents a linear or branched alkylene group having 2 to 4 carbon atoms (2, 3, or 4)
  • R 3 represents an amino group
  • a is an integer of 1 to 120.
  • the content ratio of the polyetheramine (B) is usually 0.5 to 40 mass%, preferably 1 to 30 mass%, more preferably 2 to 20 mass%, still more preferably 3 to 15 mass%, still more preferably 4 to 12.5 mass%, particularly preferably 5 to 10 mass%, based on the total mass of the modified polyolefin resin composition.
  • the weight average molecular weight (Mw) of the compound (C) having a polymerizable unsaturated group is preferably 100 or more and 5000 or less, more preferably 120 or more and 2000 or less, and even more preferably 140 or more and 1000 or less.
  • the content ratio of the compound (C) having a polymerizable unsaturated group is preferably 10 to 95 mass%, more preferably 20 to 90 mass%, still more preferably 30 to 85 mass%, and even more preferably 40 to 80 mass%, based on the total mass of the modified polyolefin resin composition.
  • the polymerizable unsaturated group in the compound (C) having a polymerizable unsaturated group is Preferably, it is at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a maleimide group, and a vinyl ether group. More preferably, it is at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group. Item 25.
  • the polymerizable unsaturated group in the cation of the ionic liquid (D) is Preferably, it is at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group.
  • Item 28 The modified polyolefin resin composition according to any one of Items 4 to 27, wherein the group is an acryloyloxy group.
  • Item 29. The modified polyolefin resin composition according to any one of Items 4 to 28, wherein the number of polymerizable unsaturated groups in the cation of the ionic liquid (D) is 1 or 2.
  • the total content ratio of the acid-modified polyolefin resin (A), the polyetheramine (B), the compound having a polymerizable unsaturated group (C) and the ionic liquid (D) relative to the total mass of the modified polyolefin resin composition is more than 50 mass%, 55 mass% or more, 60 mass% or more, 65 mass% or more, 70 mass% or more, 75 mass% or more, 80 mass% or more, 85 mass% or more, 90 mass% or more, 92.5 mass% or more, 95 mass% or more, 97.5 mass% or more, 99 mass% or more, 99.5 mass% or more, 99.9 mass% or more, 99.95 mass% or more, and 99.99 mass% or more are preferable in this order.
  • Item 31. Item 31. A cured product obtained by curing the modified polyolefin resin composition according to any one of items 1 to 30.
  • Item 32. Item 32.
  • An ink comprising the modified polyolefin resin composition according to any one of items 1 to 30 or the cured product according to item 31.
  • Item 33. Item 32.
  • An adhesive comprising the modified polyolefin resin composition according to any one of items 1 to 30 or the cured product according to item 31.
  • Item 34. Item 32.
  • a primer comprising the modified polyolefin resin composition according to any one of items 1 to 30 or the cured product according to item 31.
  • Item 35. Item 32.
  • a coating material comprising the modified polyolefin resin composition according to any one of items 1 to 30 or the cured product according to item 31.
  • Item 31. A coating material for in-mold coating, comprising the modified polyolefin resin composition according to any one of items 1 to 30 or the cured product according to item 31.
  • room temperature means a temperature within the range of 20°C to 25°C.
  • DSC differential scanning calorimeter
  • MPO-1 solid acid-modified polyolefin resin
  • MPO-2 solid acid-modified polyolefin resin
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of CPO-1 measured by high-temperature GPC was 80,000, and the melting point of CPO-1 measured by DSC was 75° C.
  • the content of maleic anhydride component in CPO-1 was 1.0% by mass, the chlorine content was 21% by mass, and the acid value of the maleic anhydride component was 11.2 mgKOH/g.
  • Example 1 In a 200-milliliter four-neck flask equipped with a cooler, a thermometer, and a stirrer, 20 g of MPO-1 was charged as an acid-modified polyolefin resin (A), 50 g of neopentyl glycol diacrylate and 30 g of 2-hydroxy-3-methacrylpropyl acrylate were charged as a compound (C) having a polymerizable unsaturated group, and the internal temperature was heated to 90 ° C. and dissolved by heating for 30 minutes. Then, 8 g of "JEFFAMINE M-2070" was added as a polyetheramine (B) and stirred at 90 ° C. for 1 hour.
  • A acid-modified polyolefin resin
  • C 2-hydroxy-3-methacrylpropyl acrylate
  • B polyetheramine
  • Examples 2 to 18 The modified polyolefin resin compositions (b) to (r) were obtained in the same manner as in Example 1, except that the types and amounts of the acid-modified polyolefin resin (A), the polyetheramine (B), the compound having a polymerizable unsaturated group (C), and the ionic liquid (D) were changed as shown in Tables 1 and 2 below.
  • the mixture obtained by stirring was applied at room temperature to a PP (polypropylene) bumper substrate washed with isopropyl alcohol, an ABS substrate washed with isopropyl alcohol, and a PET substrate washed with isopropyl alcohol so that the coating thickness after drying was about 10 ⁇ m for each, using a No. 16 bar coater.
  • After baking at 110 ° C for 10 minutes it was left in an atmosphere of 25 ° C x 60% relative humidity for 72 hours to prepare a test plate.
  • 100 squares were made at 1 mm intervals, reaching the base material, and cellophane tape was pressed onto the squares and peeled off three times at an angle of 90 degrees to the coating surface. If no peeling occurred after three peeling attempts, the result was rated as ⁇ , if peeling occurred after the third peeling attempt, it was rated as ⁇ , and if peeling occurred after the first or second peeling attempt, it was rated as ⁇ .
  • the modified polyolefin resin (A) was not used, so the PP adhesion was significantly inferior.
  • the polyetheramine (B) was not used, so the resin precipitated and the resin composition itself could not be produced.
  • the compound (C) having a polymerizable unsaturated group was not used, so the adhesion to the ABS substrate and the PET substrate was significantly inferior.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2024/010867 2023-03-30 2024-03-19 変性ポリオレフィン樹脂組成物及び該樹脂組成物の用途 Ceased WO2024203664A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2024557226A JPWO2024203664A1 (https=) 2023-03-30 2024-03-19
EP24779787.1A EP4692215A1 (en) 2023-03-30 2024-03-19 Modified polyolefin resin composition and use for said resin composition
CN202480023157.8A CN121013884A (zh) 2023-03-30 2024-03-19 改性聚烯烃树脂组合物及该树脂组合物的用途

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023055922 2023-03-30
JP2023-055922 2023-03-30

Publications (1)

Publication Number Publication Date
WO2024203664A1 true WO2024203664A1 (ja) 2024-10-03

Family

ID=92904950

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/010867 Ceased WO2024203664A1 (ja) 2023-03-30 2024-03-19 変性ポリオレフィン樹脂組成物及び該樹脂組成物の用途

Country Status (5)

Country Link
EP (1) EP4692215A1 (https=)
JP (1) JPWO2024203664A1 (https=)
CN (1) CN121013884A (https=)
TW (1) TW202449055A (https=)
WO (1) WO2024203664A1 (https=)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5975958A (ja) 1982-10-26 1984-04-28 Sanyo Kokusaku Pulp Co Ltd ポリプロピレン系樹脂用塗料組成物
JPS6099138A (ja) 1983-11-02 1985-06-03 Mitsui Petrochem Ind Ltd ポリオレフイン成形品の塗装用下塗剤
JPH0616746A (ja) 1992-07-01 1994-01-25 Mitsubishi Rayon Co Ltd 塗料用樹脂
JPH0812913A (ja) 1994-06-29 1996-01-16 Sanyo Chem Ind Ltd 印刷インキ用バインダー
JP2005097596A (ja) * 2003-08-29 2005-04-14 Sanyo Chem Ind Ltd ポリオレフィン樹脂組成物
JP2007070370A (ja) * 2004-09-03 2007-03-22 Kansai Paint Co Ltd 塗料組成物
JP2009108259A (ja) 2007-10-31 2009-05-21 Sanyo Chem Ind Ltd 帯電防止剤
JP2010001334A (ja) * 2008-06-18 2010-01-07 Mitsubishi Chemicals Corp ポリオレフィン水分散体の製造方法
JP2011094047A (ja) * 2009-10-30 2011-05-12 Nippon Paper Chemicals Co Ltd 変性ポリオレフィン樹脂水分散組成物及びその製造方法
JP2018199788A (ja) * 2017-05-29 2018-12-20 三菱ケミカル株式会社 水性樹脂分散体及び水性樹脂分散体の製造方法
JP2020033483A (ja) 2018-08-31 2020-03-05 松本油脂製薬株式会社 帯電防止剤とその利用

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5975958A (ja) 1982-10-26 1984-04-28 Sanyo Kokusaku Pulp Co Ltd ポリプロピレン系樹脂用塗料組成物
JPS6099138A (ja) 1983-11-02 1985-06-03 Mitsui Petrochem Ind Ltd ポリオレフイン成形品の塗装用下塗剤
JPH0616746A (ja) 1992-07-01 1994-01-25 Mitsubishi Rayon Co Ltd 塗料用樹脂
JPH0812913A (ja) 1994-06-29 1996-01-16 Sanyo Chem Ind Ltd 印刷インキ用バインダー
JP2005097596A (ja) * 2003-08-29 2005-04-14 Sanyo Chem Ind Ltd ポリオレフィン樹脂組成物
JP2007070370A (ja) * 2004-09-03 2007-03-22 Kansai Paint Co Ltd 塗料組成物
JP2009108259A (ja) 2007-10-31 2009-05-21 Sanyo Chem Ind Ltd 帯電防止剤
JP2010001334A (ja) * 2008-06-18 2010-01-07 Mitsubishi Chemicals Corp ポリオレフィン水分散体の製造方法
JP2011094047A (ja) * 2009-10-30 2011-05-12 Nippon Paper Chemicals Co Ltd 変性ポリオレフィン樹脂水分散組成物及びその製造方法
JP2018199788A (ja) * 2017-05-29 2018-12-20 三菱ケミカル株式会社 水性樹脂分散体及び水性樹脂分散体の製造方法
JP2020033483A (ja) 2018-08-31 2020-03-05 松本油脂製薬株式会社 帯電防止剤とその利用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4692215A1

Also Published As

Publication number Publication date
TW202449055A (zh) 2024-12-16
EP4692215A1 (en) 2026-02-11
JPWO2024203664A1 (https=) 2024-10-03
CN121013884A (zh) 2025-11-25

Similar Documents

Publication Publication Date Title
US9255211B2 (en) Adhesion to plastic with block copolymers obtained using RAFT
KR101989008B1 (ko) 좁은 몰 질량 분포를 지니는 비-착색된 폴리아크릴레이트 접착제 화합물을 생산하는 방법
JP6055833B2 (ja) 高官能化樹脂ブレンド
TW201529777A (zh) （甲基）丙烯酸系共聚合體、含有其的黏著劑組成物及黏著片
CN117043210A (zh) 嵌段共聚物、分散剂和着色组合物
US5587410A (en) Aqueous resin composition
EP1544267B1 (en) Primer composition for coating
WO2024203664A1 (ja) 変性ポリオレフィン樹脂組成物及び該樹脂組成物の用途
JP2013249426A (ja) 塗料組成物及び塗装物品
US11421101B2 (en) Aqueous resin dispersion, method for producing aqueous resin dispersion, aqueous coating material, and adhesive
JP2019210308A (ja) 水性塗料組成物
WO2017213250A1 (ja) 水性樹脂分散体の製造方法
WO2024166764A1 (ja) 変性ポリオレフィン樹脂組成物及び該樹脂組成物の用途
EP4737493A1 (en) Modified polyolefin resin composition and use for said resin composition
EP4621020A1 (en) Polyolefin-based paint composition and primer paint
JP6643581B2 (ja) 樹脂化合物及び樹脂組成物
WO2025205039A1 (ja) 変性ポリオレフィン樹脂組成物及び該樹脂組成物の用途
JP2008069297A (ja) ブロック樹脂およびその製造方法
WO2024106431A1 (ja) ポリオレフィン系塗料組成物及びプライマー塗料
JP2017057309A (ja) 樹脂付着アルミニウム顔料、塗料、及びインキ
JP2024086158A (ja) 塗料用樹脂エマルション
WO2021182021A1 (ja) 活性エネルギー線硬化性樹脂組成物及びその硬化物
JP2016222841A (ja) アンダーコート材用樹脂組成物およびアンダーコート材

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2024557226

Country of ref document: JP

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

Ref document number: 24779787

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 202517092571

Country of ref document: IN

WWP Wipo information: published in national office

Ref document number: 202517092571

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 2024779787

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: 2024779787

Country of ref document: EP

Effective date: 20251030

ENP Entry into the national phase

Ref document number: 2024779787

Country of ref document: EP

Effective date: 20251030

ENP Entry into the national phase

Ref document number: 2024779787

Country of ref document: EP

Effective date: 20251030

ENP Entry into the national phase

Ref document number: 2024779787

Country of ref document: EP

Effective date: 20251030

ENP Entry into the national phase

Ref document number: 2024779787

Country of ref document: EP

Effective date: 20251030

ENP Entry into the national phase

Ref document number: 2024779787

Country of ref document: EP

Effective date: 20251030

ENP Entry into the national phase

Ref document number: 2024779787

Country of ref document: EP

Effective date: 20251030

ENP Entry into the national phase

Ref document number: 2024779787

Country of ref document: EP

Effective date: 20251030

WWP Wipo information: published in national office

Ref document number: 2024779787

Country of ref document: EP