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  • 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
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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  • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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  • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/106—Esters of polycondensation macromers
  • C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
• • 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
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
• • 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
  • C08F8/18—Introducing halogen atoms or halogen-containing groups
  • C08F8/20—Halogenation
• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
  • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • 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
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • 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
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  • 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
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  • 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
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  • 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
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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  • 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
• • 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
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  • 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
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  • 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
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00

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 polyolefin resins which have strong adhesive power to polyolefin resins, are widely used as binder resins (for example, Patent Document 1 and Patent Document 2).
• mixtures and binder compositions are usually used in a dissolved state in an organic solvent such as toluene or xylene, which means that a large amount of organic solvent is released into the atmosphere during application, which is undesirable from the standpoints of the environment, hygiene, etc.
• organic solvent such as toluene or xylene
• these mixtures and binder compositions have problems such as poor fluidity at low temperatures (e.g., -5°C) and poor adhesion to polyolefin substrates.
• the present invention has been made in consideration of the above, and aims to provide a modified polyolefin resin composition that has sufficient water resistance, sufficient fluidity within a specific temperature range, and sufficient adhesion to polyolefin substrates.
• 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, and a compound having a polymerizable unsaturated group 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), and a compound having a polymerizable unsaturated group (C).
• the modified polyolefin resin composition of the present invention has sufficient water resistance and sufficient fluidity within a specific temperature range, and has sufficient adhesion to polyolefin substrates. 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--”.
• the modified polyolefin resin composition of the present invention contains, as essential components, an acid-modified polyolefin resin (A), a polyetheramine (B), and a compound having a polymerizable unsaturated group (C).
• the modified polyolefin resin composition of the present invention usually has sufficient fluidity within the range of -5°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 of the present invention is a resin composition that flows when placed in a glass bottle and tilted, typically within the range of -5°C to 80°C.
• a resin composition having flowability also includes a resin composition that flows when mechanical shear is applied, typically within the range of -5°C to 80°C.
• the modified polyolefin resin composition includes: (a) a hydrolyzable silyl group-containing polyether resin having a number average molecular weight of 18,000, a viscosity at 25°C of 12,000 mPa ⁇ s, and an average number of hydrolyzable silyl groups per molecule of 1.4, and/or It is preferred that the composition does not contain (b) a hydrolyzable silyl group-containing acrylic polymer having a number average molecular weight of 9,000, a viscosity at 25° C. of 7,000 mPa ⁇ s, and an average number of hydrolyzable silyl groups per molecule of 1.0.
• the content ratio of the hydrolyzable silyl group-containing polyether resin and/or the hydrolyzable silyl group-containing acrylic polymer is preferably 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 7.5% by mass or less, 5% by mass or less, 2.5% by mass or less, 1% by mass or less, 0.5% by mass or less, and 0.1% by mass or less, based on the total mass of the modified polyolefin resin composition.
• the "content ratio of the hydrolyzable silyl group-containing polyether resin and the hydrolyzable silyl group-containing acrylic polymer” means the total content ratio (mass%) of the hydrolyzable silyl group-containing polyether resin and the hydrolyzable silyl group-containing acrylic polymer based on the total mass of the modified polyolefin resin composition.
• the modified polyolefin resin composition does not contain the hydrolyzable silyl group-containing polyether resin and/or the hydrolyzable silyl group-containing acrylic polymer.
• the combined content ratio of the acid-modified polyolefin resin (A), the polyetheramine (B) and the compound having a polymerizable unsaturated group (C) relative to the total mass of the modified polyolefin resin composition is preferably in the following order: 45% by mass, 50% by mass, more than 50% by mass, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, 92.5% by mass or more, 95% by mass or more, 97.5% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.9% by mass or more, 99.95% by mass or more and 99.99% by 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 and/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 and/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 usually 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 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.
• homopolypropylene and/or propylene- ⁇ -olefin copolymer are preferred.
• the acid-modified polyolefin resin (A) is preferably a graft polymer having a structure in which ⁇ , ⁇ -unsaturated carboxylic acid and/or its acid anhydride are grafted to homopolypropylene or 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 55 mol% or more, even more preferably 60 mol% or more, even more preferably 65 mol% or more, and particularly preferably 70 mol% or more.
• the content of the propylene component in the propylene- ⁇ -olefin copolymer is 50 mol% or more, the water resistance and adhesion to polyolefin substrates (particularly polypropylene substrates) of the modified polyolefin resin composition of the present invention become even better.
• the isotacticity of the ⁇ -olefin portion in the propylene- ⁇ -olefin copolymer is preferably 30 to 100%, more preferably 50 to 100%, and even more preferably 70 to 100%, in order to maintain fluidity 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 content of the ethylene component in the ethylene- ⁇ -olefin copolymer is 75 mol% or more, the water resistance and adhesion to polyolefin substrates (particularly polyethylene substrates) of the modified polyolefin resin composition of the present invention are further improved.
• the isotacticity of the ⁇ -olefin portion in the ethylene- ⁇ -olefin copolymer is preferably 30 to 100%, more preferably 50 to 100%, and even more preferably 70 to 100%, in order to maintain fluidity 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 content of the 1-butene component in the 1-butene- ⁇ -olefin copolymer is 65 mol% or more, the water resistance and adhesion to polyolefin substrates (particularly polypropylene substrates or poly-1-butene substrates) of the modified polyolefin resin composition of the present invention are further improved.
• 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%.
• 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 of the present invention becomes even better.
• 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 the ⁇ , ⁇ -unsaturated carboxylic acid or its acid anhydride that is graft polymerized onto the polyolefin resin 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 of the present invention 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 polyolefin resins.
• Examples of such methods include a method in which polyolefin is heated to above its melting point in the presence of a radical generator to melt it and react with ⁇ , ⁇ -unsaturated carboxylic acids or their anhydrides (melt method), and a method in which polyolefin is 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 involve blowing chlorine gas into the acid-modified polyolefin resin to introduce chlorine atoms.
• the acid-modified polyolefin resin may be dispersed or dissolved in a solvent as necessary, and then chlorination may be carried out 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 is increased, and the adhesion to the polyolefin substrate 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. When the melting point of the acid-modified polyolefin resin (A) is 90°C or less, the adhesion to the polyolefin 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. When the melting point of the acid-modified polyolefin resin (A) is 50°C or higher, the adhesion to the polyolefin substrate is even better.
• 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 until melted. The peak melting 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 3,000 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. Also, if the 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 is further improved.
• the weight average molecular weight (Mw) of the acid-modified polyolefin resin (A) can be measured by gel permeation chromatography (GPC). A specific measurement method will be described in the examples described later.
• the tensile modulus of the acid-modified polyolefin resin (A) is preferably 10 MPa or more, more preferably 50 MPa or more, and even more preferably 100 MPa or more.
• the tensile modulus is 10 MPa or more, the adhesion of the coating film obtained from the modified polyolefin resin composition tends to be further improved.
• 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 examples 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, hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N,N-dimethyl ...
• ethylaminoethyl(meth)acrylate acetoacetoxyethyl(meth)acrylate, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-isobutyl(meth)acrylamide, N-t-butyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-methylene-bis(meth)acrylamide, N-methylol(meth)acrylamide, hydroxyethyl(meth)acrylamide, (meth)acryloylmorpholine, n-butyl vinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl ether, and the like.
• 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 usually 5 to 120 parts by mass, 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, 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 the water resistance and adhesion to the polyolefin substrate.
• 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, and 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), 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
• the polyetheramine (B) has a polyether chain, and 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), 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) 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 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
• 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 the present invention, 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 the present invention, 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 polyetheramine (B) is usually a polymeric compound having a weight average molecular weight (Mw) in the range of 200 to 50,000. If the Mw of the polyetheramine (B) is within this range, the steric repulsion of the polyetheramine (B) in the compound (C) having a polymerizable unsaturated group tends to become large, and the acid-modified polyolefin resin (A) can be stably dispersed and/or dissolved in the compound (C) having a polymerizable unsaturated group.
• Mw weight average molecular weight
• 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) in the present invention can be measured by GPC and converted from the polystyrene calibration curve.
• the GPC measurement is performed by a conventional method using a commercially available device with THF as a solvent.
• 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 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 the polyolefin substrate.
• the content of polyetheramine (B) is usually 0.5 to 40 mass%, preferably 1 to 30 mass%, more preferably 2 to 20 mass%, even more preferably 3 to 15 mass%, even more preferably 4 to 12.5 mass%, and particularly preferably 5 to 10 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 the polyolefin substrate.
• 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, one, two, three or four) 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 one or two.
• 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 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. In this case, 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 A compound having a hydroxyl group and one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups; It is preferable that the copolymer 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 compound (C) having a polymerizable unsaturated group is a compound having a hydroxyl group and one or two polymerizable unsaturated groups; It is more preferable that the compound 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 one or two polymerizable unsaturated groups.
• the alkyleneoxy group is usually represented by the following formula 4: -(Y 1 -O)m- Formula 4 [In formula 4: 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 5: R a -R b -R cFormula 5
• R a represents a polymerizable unsaturated group
• R c 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 5.
• the compound (C) having a polymerizable unsaturated group preferably includes a compound having a (meth)acryloyloxy group as the polymerizable unsaturated group.
• the compound having a (meth)acryloyloxy group include a compound having one (meth)acryloyloxy group, a compound having two (meth)acryloyloxy groups, and a compound 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.
• the content of the compound (C) having a polymerizable unsaturated group in the present invention is usually 10 to 90% by mass, preferably 20 to 85% by mass, more preferably 30 to 80% by mass, even more preferably 40 to 77% by mass, and particularly preferably 50 to 75% by mass, based on the total mass of the modified polyolefin resin composition, from the viewpoints of maintaining the fluidity of the modified polyolefin resin composition even better and improving the water resistance and adhesion to the polyolefin substrate.
• 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 2 to 45 mass%, and even more preferably 3 to 40 mass%, based on the total mass of the modified polyolefin resin composition.
• the compound (C) having a polymerizable unsaturated group includes a compound having a hydroxyl group and one or two polymerizable unsaturated groups.
• 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 preferably contains a compound having a unit having a carbonyl group and one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups.
• the compound (C) having a polymerizable unsaturated group includes a compound having a unit having a carbonyl group represented by the following formula (1) or the following formula (2) and one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups.
• R 1 represents a hydrogen atom or a methyl group. * indicates a bond.
• the bond is bonded to an oxygen atom.
• R 1 is preferably a methyl group.
• R 1 is a methyl group and the bond is bonded to an oxygen atom.
• R2 represents a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom (F, Cl, Br, or I), an alkoxyl group, or another substituent.
• R3 represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms containing a substituent such as an aldehyde group, an acetyl group, a halogen atom (F, Cl, Br, or I), or an alkoxyl group.
• * represents a bond.
• the hydrocarbon group may contain a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl.
• the bond is bonded to an oxygen atom.
• the compound having a unit with a carbonyl group and one or more polymerizable unsaturated groups preferably contains one or more of the units with a carbonyl group represented by the above formula (1) or formula (2) and compounds having one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups.
• the compound (C) having a polymerizable unsaturated group includes a compound having a unit having a carbonyl group represented by the above formula (1) and one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups.
• the compound (C) having a polymerizable unsaturated group includes a compound having a unit having a carbonyl group represented by the above formula (1) and one polymerizable unsaturated group.
• Examples of the compound having a unit having a group represented by the above formula (1) or formula (2) and one or more (for example, 1, 2, 3, or 4) polymerizable unsaturated groups include acrylic acid acetoacetate esters such as acetoacetoxy(meth)acrylate, acetoacetoxyethyl(meth)acrylate, acetoacetoxypropyl(meth)acrylate, allyl acetoacetate, acetoacetoxybutyl(meth)acrylate, and 2,3-di(acetoacetoxy)propyl(meth)acrylate; Crotonic acid acetoacetate esters such as 2-acetoacetoxyethyl crotonate and 2-acetoacetoxypropyl crotonate; Acetoacetate esters of N-alkylol(meth)acrylamides such as acetoacetoxy(meth)acrylamide, N-(acetoacetoxymethyl)(meth)acrylamide, and N-(acetoacet
• 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 raw materials such as palm oil, palm kernel oil, and coconut oil.
• 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 150 or more, and even more preferably 160 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 150 or more and 2,000 or less, and even more preferably 160 or more and 1,000 or less.
• the present invention it is preferable to include a compound having a polymerizable unsaturated group with an SP value of 9 or more.
• a compound having a polymerizable unsaturated group with an SP value of 9 or more By including a compound having a polymerizable unsaturated group with an SP value of 9 or more, the viscosity thickening during long-term storage can be suppressed, and the fluidity of the modified polyolefin resin composition can be further improved.
• the SP value is defined by the Fedors method, and the unit of the SP value is cal/cm 3.
• the upper limit of the SP value is not particularly limited, but from the viewpoint of the water resistance of the cured coating film, for example, the upper limit of the SP value of the compound (C) having a polymerizable unsaturated group is 15 or less.
• the compound (C) having a polymerizable unsaturated group with an SP value of 9 or more may be used alone or in combination of two or more. It may also be used in combination with a compound having a polymerizable unsaturated group with an SP value of 9 or less.
• the modified polyolefin resin composition of the present invention 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 modified polyolefin resin composition comprises an acid-modified polyolefin resin (A), a polyetheramine (B), and two or three types of “compounds having a polymerizable unsaturated group (C)”, (a) When two types of compound (C) having a polymerizable unsaturated group are contained, (a1) the compound (C) having two kinds of polymerizable unsaturated groups is one kind of compound having one polymerizable unsaturated group and one kind of compound having two polymerizable unsaturated groups; or (a2) the compound (C) having two kinds of polymerizable unsaturated groups is two kinds of compounds having two polymerizable unsaturated groups, (b) When three types of compound (C) having a polymerizable unsaturated group are contained, the compound (C) having three types of polymerizable unsaturated groups is one type of compound having
• the compound having one polymerizable unsaturated group is Compounds having a hydroxyl group and one polymerizable unsaturated group; 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 polymerizable unsaturated group; or a compound having a unit having a carbonyl group represented by the above formula (1) or (2) and one polymerizable unsaturated group.
• the compound having one polymerizable unsaturated group is Compounds having a hydroxyl group and one polymerizable unsaturated group; It is more preferable that the compound is a compound having a linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) and one polymerizable unsaturated group; or a compound having a unit having a carbonyl group represented by the above formula (1) and one polymerizable unsaturated group.
• the compound having two polymerizable unsaturated groups is A compound having an alkyleneoxy group and two polymerizable unsaturated groups, as represented by the above formula 4; or a compound having a hydroxyl group and two polymerizable unsaturated groups; It is preferable that:
• 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), and a compound (C) having a polymerizable unsaturated group
• the compound (C) having a polymerizable unsaturated group is at least one compound selected from the group consisting of neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2-ethylhexyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-methacrylpropyl acrylate, and acetoacetoxyethyl methacrylate.
• the modified polyolefin resin composition of the present invention may contain a polymerization initiator as long as the effect of the present invention is not impaired.
• a polymerization initiator By containing the polymerization initiator, the polymerization reaction of the polymerizable unsaturated group of the compound (C) proceeds, and a resin for forming a coating film can be formed.
• the corrosion resistance and durability of the coating film are further improved.
• 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, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer, etc. 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, Bis(methylcyclopentadienyl)-bis[2,6-difluoro-3-((1-pyr-1-yl)methyl)phenyl]titanium, Bis(cyclopentadienyl)-bis[2,6-difluoro-3-((2,5-dimethyl-1-pyr-1-yl)methyl)phenyl]titan
• 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 of the present invention may contain an ultraviolet absorber as long as the effect of the present invention is not impaired.
• ultraviolet absorbers 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 of the present invention 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, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, etc. These may 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 of the present invention 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 of the present invention 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 them, from the viewpoint of further improving the stability of the modified polyolefin resin composition and the water resistance of the coating film obtained from 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 alkylamine ethers, polyoxypropylene alkylamine ethers, 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 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 further improving the stability of the modified polyolefin resin composition and the water resistance of the coating film obtained from the modified polyolefin resin composition.
• the modified polyolefin resin composition of the present invention may contain various additives as necessary, such as a tackifier, a film-forming assistant, an antifoaming agent, an anti-sagging agent, a wetting agent, etc.
• 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 of the present invention may or may not contain an organic solvent.
• the present invention contains an organic solvent
• the present invention contains a small amount of organic solvent from the viewpoint of the environment and hygiene.
• the amount of organic solvent used 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 viscosity of the modified polyolefin resin composition is further reduced, which has the advantage of further improving the coatability.
• the present invention when the present invention does not contain an organic solvent, the present invention can be suitably used as a base agent for a solventless two-component curing polyurethane binder.
• solventless means that no organic solvent is intentionally added to the modified polyolefin resin composition of the present invention, 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 filtration can be carried out, for example, using a wire mesh with mesh size of 50 ⁇ m to 300 ⁇ m.
• the present invention is a cured product obtained by curing a modified polyolefin resin composition.
• the cured product is a product in which the modified polyolefin resin composition of the present invention has been cured.
• the above cured product will be referred to simply as the "cured product of the present invention.”
• the modified polyolefin resin composition of the present invention and the cured product of the present invention 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 the present invention and the cured product of the present invention can be particularly suitably used for polypropylene substrates.
• the modified polyolefin resin composition of the present invention and the cured product of the present invention 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 the present invention and the cured product of the present invention 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 the present invention.
• 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 the present invention includes, for example, a method of uniformly applying the modified polyolefin resin composition of the present invention 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 the present invention between the mold and the substrate, and applying heat and pressure can be included.
• the heating temperature is usually 60 to 200°C.
• the heating time is usually 15 seconds to 20 minutes.
• Item 1 A modified polyolefin resin composition comprising an acid-modified polyolefin resin (A), a polyetheramine (B), and a compound having a polymerizable unsaturated group (C).
• Item 2. The modified polyolefin resin composition according to Item 1, wherein the content of the acid-modified polyolefin resin (A) is usually 5 to 120 parts by mass, 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, based on 100 parts by mass of the compound (C) having a polymerizable unsaturated group.
• the compound (C) having a polymerizable unsaturated group Preferably, the compound contains a hydroxyl group and one or more polymerizable unsaturated groups. More preferably, it contains a compound having a hydroxyl group and 1 to 4 (1, 2, 3, or 4) polymerizable unsaturated groups. 3.
• 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. More 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), 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 3 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 5.
• the modified polyolefin resin composition according to any one of Items 1 to 4, 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).
• 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 ), 6.
• the modified polyolefin resin composition according to any one of items 1 to 5, which has at least one structure 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 of 2 to 80) and a structure represented by -(O-CH 2 CH 2 CH(CH 3 )) z 4 - (z 4 is an integer of 2 to 80).
• the polyetheramine (B) is Preferably, it has a primary amino group or a secondary amino group at one end and a weight average molecular weight (Mw) of 200 to 50,000.
• the modified polyolefin resin composition has a primary amino group or a secondary amino group at one end and a weight average molecular weight (Mw) of 300 to 10,000. More preferably, the modified polyolefin resin composition has a primary amino group at one end and a weight average molecular weight (Mw) of 500 to 5000.
• Item 8 The modified polyolefin resin composition according to any one of Items 1 to 7, 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 9 The modified polyolefin resin composition according to any one of Items 1 to 8, wherein the compound (C) having a polymerizable unsaturated group has a weight average molecular weight (Mw) of 5,000 or less.
• Item 10 The compound (C) having a polymerizable unsaturated group, A compound having a hydroxyl group and one or more polymerizable unsaturated groups, a compound having an alkyleneoxy group and/or a linear or branched alkyl group having 1 to 20 carbon atoms, and one or more polymerizable unsaturated groups;
• the modified polyolefin resin composition according to any one of Items 1 to 10, wherein the acid-modified polyolefin resin (A) is a graft polymer having a structure in which an ⁇ , ⁇ -unsaturated carboxylic acid and/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 and/or an acid anhydride thereof is grafted to a polyolefin resin.
• the polyolefin resin - preferably 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, Item 12.
• the modified polyolefin resin composition according to any one of Items 1 to 12, 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 14.
• the modified polyolefin resin composition according to any one of Items 1 to 13, 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).
• Items 1 to 13 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 carbon atoms. a is an integer from 1 to 120.
• Item 15 The modified polyolefin resin composition according to any one of items 1 to 14, wherein the compound is represented by the formula: Item 16. Item 16.
• 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
• 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 modified polyolefin resin composition according to any one of items 1 to 16. Item 18.
• 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 150 or more and 2000 or less, and even more preferably 160 or more and 1000 or less.
• the modified polyolefin resin composition according to Item 19 wherein when the compound (C) having a polymerizable unsaturated group (b) is contained in a mixture of three kinds, the compound (C) having three kinds of polymerizable unsaturated groups is one kind of compound having one polymerizable unsaturated group and two kinds of compounds having two polymerizable unsaturated groups.
• Item 21 The modified polyolefin resin composition according to any one of items 3 to 20, wherein the number of hydroxyl groups is preferably 1 or 2, more preferably 1.
• the content ratio of the compound (C) having a polymerizable unsaturated group is usually 10 to 90 mass%, preferably 20 to 85 mass%, more preferably 30 to 80 mass%, still more preferably 40 to 77 mass%, particularly preferably 50 to 75 mass%, based on the total mass of the modified polyolefin resin composition.
• the modified polyolefin resin composition according to any one of items 1 to 21. Item 23.
• the 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, 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.
• the modified polyolefin resin composition is an acryloyloxy group and/or a methacryloyloxy group.
• the total content ratio of the acid-modified polyolefin resin (A), the polyetheramine (B) and the compound having a polymerizable unsaturated group (C) relative to the total mass of the modified polyolefin resin composition is preferably in the order of 45 mass%, 50 mass%, 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.
• Item 25 A cured product obtained by curing the modified polyolefin resin composition according to any one of items 1 to 24.
• Item 26 An ink comprising the modified polyolefin resin composition according to any one of items 1 to 24 or the cured product according to item 11.
• Item 27 An adhesive comprising the modified polyolefin resin composition according to any one of items 1 to 24 or the cured product according to item 11.
• a primer comprising the modified polyolefin resin composition according to any one of items 1 to 24 or the cured product according to item 11.
• Item 29 A coating material comprising the modified polyolefin resin composition according to any one of items 1 to 24 or the cured product according to item 11.
• Item 30 A coating material for in-mold coating, comprising the modified polyolefin resin composition according to any one of items 1 to 24 or the cured product according to item 11.
• room temperature means a temperature within the range of 20°C to 25°C.
• DSC differential scanning calorimeter
• the modified polyolefin resin composition shown in the following Production Example was dissolved in toluene to obtain a solution.
• the obtained solution was applied to a Teflon (registered trademark) sheet to a film thickness of about 50 ⁇ m, and the toluene was dried to obtain a dry coating film.
• the coating film was cut to a width of 10 mm and a length of 70 mm to obtain a test piece.
• the tensile modulus of the obtained test piece was measured using a tensile tester (Tensilon RTM-100, manufactured by Orientec Corporation) under the condition of a chuck distance of 50 mm.
• the obtained resin was dried under reduced pressure to obtain a solid acid-modified polyolefin resin (MPO-1).
• MPO-1 solid acid-modified polyolefin resin
• the acid value of the maleic anhydride component and the maleic acid component in MPO-1 was 22.4 mg KOH/g.
• the weight average molecular weight (Mw) of MPO-1 measured by high-temperature GPC was 70,000, and the melting point by DSC was 70° C.
• the tensile modulus of MPO-1 was 190 MPa.
• the obtained resin was dried under reduced pressure to obtain a solid acid-modified polyolefin resin (MPO-2).
• MPO-2 solid acid-modified polyolefin resin
• the acid value of the maleic anhydride component and the maleic acid component in MPO-2 was 20.2 mg KOH / g.
• the weight average molecular weight (Mw) of MPO-2 measured by high-temperature GPC was 40,000
• the melting point measured by DSC was 75 ° C.
• the tensile modulus of MPO-2 was 130 MPa.
• 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 chlorine content in CPO-1 was 21% by mass, and the acid value of the maleic anhydride component was 16.8 mg KOH/g.
• the tensile modulus of CPO-1 was 18 MPa.
• Example 1 In a 200-milliliter four-neck flask equipped with a cooler, a thermometer, and a stirrer, 20 g of MPO-1 as an acid-modified polyolefin resin (A), 50 g of neopentyl glycol diacrylate as a compound (C) having a polymerizable unsaturated group, and 30 g of 2-hydroxy-3-methacrylpropyl acrylate were charged, and the internal temperature was heated to 90°C, and the mixture was dissolved by heating for 30 minutes. Then, 8 g of "JEFFAMINE M-2070" as a polyetheramine (B) was added, and the mixture was stirred at 90°C for 1 hour. Then, the mixture was cooled to room temperature and filtered through a wire mesh with an opening of 149 ⁇ m to obtain a modified polyolefin resin composition (a).
• Example 2 to 16 The amounts of the acid-modified polyolefin resin (A), the polyetheramine (B) and the compound having a polymerizable unsaturated group (C) used were changed as shown in Table 1 below, and the same method as in Example 1 was used to obtain modified polyolefin resin compositions (b) to (p).
• test plate was immersed in 40 ° C warm water for 10 days (240 hours). After immersion, 100 squares were made on the test plate at 1 mm intervals, reaching the base material, and cellophane tape was pressed onto the squares and peeled off at an angle of 90 degrees to the coating surface three times. The case where no peeling occurred even after three repeated peeling attempts was evaluated as ⁇ , the case where peeling occurred after the third peeling attempt was evaluated as ⁇ , and the case where peeling occurred after the first or second peeling attempt was evaluated as ⁇ .

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