WO2019188858A1 - Résine de polyoléfine modifiée et utilisation de celle-ci - Google Patents

Résine de polyoléfine modifiée et utilisation de celle-ci Download PDF

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Publication number
WO2019188858A1
WO2019188858A1 PCT/JP2019/012276 JP2019012276W WO2019188858A1 WO 2019188858 A1 WO2019188858 A1 WO 2019188858A1 JP 2019012276 W JP2019012276 W JP 2019012276W WO 2019188858 A1 WO2019188858 A1 WO 2019188858A1
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Prior art keywords
copolymer
polyolefin resin
modified polyolefin
modified
mol
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PCT/JP2019/012276
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English (en)
Japanese (ja)
Inventor
小野　勇
木村　浩司
恵太 迫
関口　俊司
高本　直輔
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日本製紙株式会社
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Priority to JP2020510004A priority Critical patent/JP7297736B2/ja
Publication of WO2019188858A1 publication Critical patent/WO2019188858A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • 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
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
    • 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
    • C09D131/00—Coating compositions based on homopolymers or 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/06—Homopolymers or copolymers of esters of polycarboxylic acids
    • 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
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • 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
    • C09J131/00—Adhesives based on homopolymers or 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/06—Homopolymers or copolymers of esters of polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention relates to a modified polyolefin resin and its use.
  • Aluminum laminate films are widely used as packaging materials in various fields such as food, toiletries, pharmaceuticals, and electronic equipment parts because of their excellent light-shielding properties and oxygen / water vapor barrier properties.
  • a polyolefin resin is generally used for the innermost layer in order to seal the contents by adhering the end portions by heat sealing.
  • polyethylene specifically linear low density polyethylene (hereinafter abbreviated as “LLDPE”)
  • LLDPE linear low density polyethylene
  • the surface is subjected to surface treatment such as corona discharge treatment or plasma treatment and then aluminum is added via a polyester or polyurethane adhesive. Need to laminate with foil.
  • the surface treatment such as corona discharge treatment has a problem that the number of steps increases and the effect decreases with time, so that stable adhesive strength cannot be obtained.
  • a primer for a polyolefin substrate a modified polyolefin such as a chlorinated polyolefin or an acid-modified polyolefin is generally used because of its excellent adhesion to the substrate (for example, see Patent Documents 1 and 2). .
  • the modified polyolefin resin mainly composed of polypropylene resin is inferior in adhesion to a polyethylene base material among polyolefin base materials, and an improvement is desired.
  • a composition using an ethylene copolymer and a polyolefin resin in combination has been proposed (see, for example, Patent Document 3).
  • composition described in Patent Document 3 has improved adhesion to a polyethylene substrate.
  • use of the composition described in Patent Document 3 is limited as a heat seal composition, and there is a problem in solution stability and the like for use as a paint or primer.
  • An object of the present invention is to provide a modified polyolefin resin having excellent solution stability and good adhesion to a polyolefin substrate including a metal such as aluminum or a polyethylene substrate.
  • the present inventors have found that a copolymer a having an ethylene structural unit content of 50 mol% or more, a copolymer b having an ethylene structural unit content of less than 50 mol%,
  • the present inventors have found that the above-mentioned problems can be solved by modifying a polyolefin resin containing at least the above-mentioned compounds, and have completed the present invention. That is, the present inventors provide the following [1] to [13].
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrocarbon group represented by C n H 2n + 1 , where n is an integer of 8 to 18
  • a composition comprising the modified polyolefin resin according to any one of [1] to [7].
  • a primer comprising the modified polyolefin resin according to any one of [1] to [7] or the composition according to [8] or [9].
  • An ink binder comprising the modified polyolefin resin according to any one of [1] to [7] or the composition according to [8] or [9].
  • a laminate having a modified polyolefin resin according to any one of [1] to [7] or a layer containing the composition according to [8] or [9], a metal layer, and a resin layer.
  • a modified polyolefin resin having excellent solution stability and good adhesion to a polyolefin substrate including a metal such as aluminum or a polyethylene substrate.
  • (meth) acrylic acid refers to methacrylic acid and / or acrylic acid.
  • the modified polyolefin resin of the present invention is a graft modified product obtained by modifying a predetermined polyolefin resin with an ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof, and a modified product further modified with a predetermined (meth) acrylic acid ester. It is preferable.
  • the modified polyolefin resin is used for applications such as primer, paint, ink, etc., it is required to apply uniformly to eliminate coating unevenness. Therefore, the modified polyolefin resin is required to have a solution stability such that it is uniformly dissolved in a solvent and the resin does not precipitate over time, in addition to the property of adhering to the substrate.
  • the modified polyolefin resin of the present invention is a graft-modified product obtained by modifying a predetermined polyolefin resin described later, it adheres to a nonpolar substrate such as a polyethylene substrate and has excellent solution stability. It has been found out that it can be used for applications.
  • the polyolefin resin contains at least a copolymer a having an ethylene structural unit content of less than 50 mol% and a copolymer b having an ethylene structural unit content of 50 mol% or more.
  • Copolymer a is a copolymer having an ethylene structural unit content of less than 50 mol%. Since the copolymer a having an upper limit of ethylene structural unit content of less than 50 mol% is used, a modified polyolefin resin excellent in solution stability can be obtained by imparting polarity by a modification treatment described later.
  • Examples of the copolymer a include a copolymer obtained by copolymerizing an olefin or the like using a Ziegler-Natta catalyst or a metallocene catalyst as a polymerization catalyst.
  • Examples of the olefin include ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, ⁇ -olefins such as 1-decene and 1-octadecene; 2-butene; isobutylene; conjugated dienes such as butadiene, isoprene and cyclopentadiene; vinylcyclohexane; ⁇ -pinene.
  • ethylene or ⁇ -olefin is preferable, and ethylene or ⁇ -olefin having 3 to 6 carbon atoms (ethylene, propylene, 1-butene, 1-pentene, 1-hexene) is more preferable.
  • examples of the copolymer a include a copolymer of ethylene and propylene, and a copolymer of ethylene and one or more other olefins.
  • a copolymer of ethylene and propylene, and a copolymer of ethylene and an ⁇ -olefin having 3 to 6 carbon atoms are preferable, an ethylene-propylene copolymer, an ethylene-propylene-1-butene copolymer. Is more preferable.
  • the copolymer a may be a random copolymer or a block copolymer. Further, the copolymer a may be a single type or a combination of two or more types.
  • the upper limit of the ethylene structural unit content of the copolymer a is less than 50 mol%, preferably 30 mol% or less, and more preferably 20 mol% or less.
  • the upper limit value of the ethylene structural unit content of the copolymer a is less than 50 mol%, a modified polyolefin resin excellent in solution stability can be obtained by imparting polarity by a modification treatment described later.
  • the lower limit is usually 1 mol% or more.
  • the lower limit value of the ethylene structural unit content of the copolymer a is 1 mol% or more, the crystallinity of the copolymer a is lowered, so that the adhesion to a substrate at low temperatures and the solution stability are further improved. obtain.
  • the ethylene structural unit content of the copolymer a is 1 to less than 50 mol%, preferably 1 to 30 mol%, more preferably 1 to 20 mol%.
  • each structural unit such as an ethylene structural unit of the copolymer a can be calculated from the amount of the monomer used for the preparation of the copolymer a and the analysis result of the copolymer a using an instrument such as NMR. Moreover, in the case of a commercial item, you may judge based on product information.
  • the melting point of the copolymer a is 40 ° C. or more, when the modified polyolefin resin is used for applications such as inks and paints, sufficient coating strength can be exhibited and the adhesion to the substrate is sufficiently exhibited. Can be done. Further, when used as an ink, blocking during printing can be suppressed.
  • the upper limit is preferably 90 ° C. or less, and more preferably 70 ° C. or less. When the melting point of the copolymer a is 90 ° C.
  • the melting point of the copolymer a is preferably 40 to 90 ° C, more preferably 50 to 70 ° C.
  • the melting point was measured by using a DSC measuring device (Seiko Denshi Kogyo Co., Ltd.), and about 5 mg of sample was melted at 200 ° C. for 10 minutes, and then cooled to ⁇ 50 ° C. at a rate of 10 ° C./min for crystallization. Later, it can be obtained as the melting peak temperature when it is further heated to 200 ° C. and melted at 10 ° C./min.
  • the lower limit of the weight average molecular weight of the copolymer a is preferably 30,000 or more, and more preferably 50,000 or more.
  • the resin has a cohesive force and can exhibit adhesion to a substrate.
  • the upper limit is preferably 300,000 or less, and more preferably 250,000 or less.
  • the weight average molecular weight is 300,000 or less, it has compatibility with other resins and solubility in solvents, and can be applied to paints and inks.
  • the weight average molecular weight of the copolymer a is preferably 30,000 to 300,000, more preferably 50,000 to 250,000.
  • the weight average molecular weight can be obtained from a standard polystyrene calibration curve by gel permeation chromatography (GPC).
  • the copolymer b is a copolymer having an ethylene structural unit content of 50 mol% or more. Since the copolymer b having a lower limit of ethylene structural unit content of 50 mol% or more is used, a modified polyolefin resin having good adhesion to a polyolefin substrate, particularly a polyethylene substrate, can be obtained.
  • Examples of the copolymer b include a copolymer obtained by copolymerizing an olefin or the like using a Ziegler-Natta catalyst or a metallocene catalyst as a polymerization catalyst.
  • Examples of the olefin include ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, ⁇ -olefins such as 1-decene and 1-octadecene; 2-butene; isobutylene; conjugated dienes such as butadiene, isoprene and cyclopentadiene; vinylcyclohexane; ⁇ -pinene.
  • ethylene and ⁇ -olefin are preferable, and ethylene and ⁇ -olefin having 3 to 6 carbon atoms (propylene, 1-butene, 1-pentene, 1-hexene
  • examples of the copolymer b include a copolymer of ethylene and propylene, and a copolymer of ethylene and one or more other olefins.
  • a copolymer of ethylene and propylene, and a copolymer of ethylene and an ⁇ -olefin having 3 to 6 carbon atoms are preferable.
  • An ethylene-propylene copolymer and an ethylene-1-butene copolymer are preferable. Is more preferable.
  • the copolymer b may be a random copolymer or a block copolymer. Further, the copolymer b may be a single type or a combination of two or more types.
  • the lower limit of the ethylene structural unit content of the copolymer b is 50 mol% or more, and preferably 60 mol% or more.
  • a modified polyolefin resin having good adhesion to a polyolefin substrate, particularly a polyethylene substrate can be obtained.
  • the upper limit is usually 90 mol% or less.
  • the upper limit value of the ethylene structural unit content of the copolymer b is 90 mol% or less, a modified polyolefin resin having excellent solution stability can be obtained.
  • the ethylene structural unit content of the copolymer b is 50 mol% or more, preferably 60 to 90 mol%.
  • each structural unit such as an ethylene structural unit of the copolymer b can be calculated from the amount of the monomer used for the preparation of the copolymer b and the analysis result of the copolymer b using an instrument such as NMR. Moreover, in the case of a commercial item, you may judge based on product information.
  • the lower limit of the melting point of the copolymer b is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, and further preferably 50 ° C. or higher.
  • the upper limit is preferably 150 ° C. or lower, more preferably 100 ° C. or lower, and further preferably 95 ° C. or lower.
  • the melting point of the copolymer b is preferably 20 to 150 ° C, more preferably 30 to 150 ° C, further preferably 35 to 150 ° C, still more preferably 50 to 100 ° C, and particularly preferably 50 to 95 ° C.
  • the melting point was measured by using a DSC measuring device (Seiko Denshi Kogyo Co., Ltd.), and about 5 mg of sample was melted at 200 ° C. for 10 minutes, and then cooled to ⁇ 50 ° C. at a rate of 10 ° C./min for crystallization. Later, it can be obtained as the melting peak temperature when it is further heated to 200 ° C. and melted at 10 ° C./min.
  • the lower limit of the weight average molecular weight of the copolymer b is preferably 1,000 or more, and more preferably 2,500 or more. When the weight average molecular weight is 1,000 or more, the resin has a cohesive force and can exhibit adhesion to a substrate. Moreover, the upper limit is preferably 200,000 or less, and more preferably 150,000 or less. When the weight average molecular weight is 200,000 or less, it has compatibility with other resins and solubility in solvents, and can be applied to paints and inks.
  • the weight average molecular weight of the copolymer b is preferably 1,000 to 200,000, more preferably 2,500 to 150,000. The weight average molecular weight can be obtained from a standard polystyrene calibration curve by gel permeation chromatography (GPC).
  • the graft modified product is a modified product obtained by modifying the polyolefin resin described in “1-1. Polyolefin resin” with an ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof, and further modified with a predetermined (meth) acrylic ester.
  • the modified product is preferably used.
  • the graft modified product can be a modified polyolefin resin that adheres to a nonpolar substrate such as a polyethylene substrate and is excellent in solution stability.
  • ⁇ , ⁇ -unsaturated carboxylic acid or derivative thereof examples include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, Examples include hymic anhydride and (meth) acrylic acid. Of these, maleic anhydride is preferred.
  • the ⁇ , ⁇ -unsaturated carboxylic acid or derivative thereof may be one or more compounds selected from ⁇ , ⁇ -unsaturated carboxylic acid and derivatives thereof, and one or more ⁇ , ⁇ -unsaturated carboxylic acid may be used. And combinations of one or more derivatives thereof, combinations of two or more ⁇ , ⁇ -unsaturated carboxylic acids, and combinations of two or more derivatives of ⁇ , ⁇ -unsaturated carboxylic acids.
  • the introduction amount (graft weight) of the ⁇ , ⁇ -unsaturated carboxylic acid or derivative thereof is preferably 0.1 to 10% by weight, and 0.5 to 4% by weight when the modified polyolefin resin is 100% by weight. More preferred. When the graft weight is 0.1% by weight or more, the adhesion of the resulting modified polyolefin resin to a material such as a metal adherend can be maintained. When the graft weight is 10% by weight or less, generation of unreacted grafts can be prevented, and sufficient adhesion to the resin adherend can be obtained.
  • the introduction amount (graft weight) of the ⁇ , ⁇ -unsaturated carboxylic acid or derivative thereof can be measured by an alkali titration method.
  • ((Meth) acrylic acid ester) (Meth) acrylic acid ester is a compound represented by general formula (I).
  • the (meth) acrylic acid ester represented by the general formula (I) may be used alone, or a plurality of them may be mixed and used in an arbitrary ratio.
  • R 1 represents H or CH 3 , preferably CH 3 .
  • R 2 represents C n H 2n + 1 .
  • n represents an integer of 8 to 18, preferably 8 to 15, more preferably 8 to 14, and still more preferably 8 to 13.
  • lauryl (meth) acrylate and octyl (meth) acrylate are preferable, and lauryl methacrylate and octyl methacrylate are more preferable.
  • the introduction amount (graft weight) of the (meth) acrylic acid ester is preferably 0.1 to 10% by weight, more preferably 0.4 to 4% by weight when the modified polyolefin resin is taken as 100% by weight.
  • the graft weight is 0.1% by weight or more, the molecular weight distribution of the modified polyolefin resin can be kept in a sufficiently narrow range. That is, the adverse effect of the high molecular weight portion can be prevented, and the solvent solubility, the low temperature stability of the solution, and the compatibility with other resins can be maintained well. Moreover, the bad influence of a low molecular weight part can be prevented and adhesive force can be improved.
  • the introduction amount (graft weight) of (meth) acrylic acid ester can be obtained by 1 H-NMR.
  • the graft-modified product can be used in combination with other modifying agents other than ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof and (meth) acrylic acid ester.
  • other modifiers include (meth) acrylic acid derivatives (for example, N-methyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, (meth) acryloylmorpholine).
  • Other modifiers other than ⁇ , ⁇ -unsaturated carboxylic acid or its derivative and (meth) acrylic acid ester in the modified polyolefin resin may be used alone or in combination of two or more. Good.
  • the total graft weight of the other modifiers does not exceed the total graft weight of the ⁇ , ⁇ -unsaturated carboxylic acid or its derivative and (meth) acrylic acid ester.
  • the method for modifying the polyolefin resin to obtain the modified polyolefin resin is not particularly limited, and may be performed by a known method.
  • a solution method in which a mixture of a polyolefin resin, an ⁇ , ⁇ -unsaturated carboxylic acid or derivative thereof, and a (meth) acrylic acid ester is dissolved in a solvent such as toluene and a radical generator is added, a Banbury mixer, Modified polyolefin resin by a melt kneading method or the like using a kneader, an extruder or the like to add and knead polyolefin resin, ⁇ , ⁇ -unsaturated carboxylic acid or derivative thereof, (meth) acrylic acid ester, and radical generator
  • the method of obtaining is mentioned.
  • ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof and (meth) acrylic ester are used, these may be added all at once or sequentially
  • the radical generator can be appropriately selected from known radical generators.
  • organic peroxide compounds are preferred.
  • the addition amount of the radical generator in the graft polymerization reaction is 1 to 100% by weight with respect to the total amount (weight) of the addition amount of ⁇ , ⁇ -unsaturated carboxylic acid or its derivative and the addition amount of (meth) acrylic acid ester.
  • 1% by weight or more sufficient graft efficiency can be maintained.
  • 100 weight% or less the fall of the weight average molecular weight of modified polyolefin resin can be prevented.
  • the lower limit value of the weight average molecular weight of the modified polyolefin resin is preferably 30,000 or more, more preferably 50,000 or more, further preferably 80,000 or more, still more preferably 100,000 or more, particularly more than 150,000. preferable. When it is 30,000 or more, there is a cohesive force of the resin, and adhesion to the substrate can be expressed.
  • the upper limit is preferably 300,000 or less, more preferably 250,000 or less, and even more preferably 200,000 or less. If it is 300,000 or less, it has compatibility with other resins and solubility in solvents, and can be applied to paints and inks.
  • the weight average molecular weight of the modified polyolefin resin is preferably 30,000 to 300,000, more preferably 50,000 to 250,000, further preferably 80,000 to 200,000, and more preferably 100,000 to 200,000. More preferably, it is more preferably more than 150,000 to 200,000 or less.
  • the weight average molecular weight can be obtained from a standard polystyrene calibration curve by gel permeation chromatography (GPC).
  • the modified polyolefin resin of the present invention has low adhesion (adhesiveness) and is also useful as an intermediate medium for substrates that are difficult to apply, such as paints.
  • polypropylene having poor adhesion (adhesiveness) It can be used as an adhesive between polyolefin-based substrates such as polyethylene. In this case, it can be used regardless of whether the substrate is surface-treated with plasma, corona or the like.
  • the adhesion stability of the paint can be improved by laminating the modified polyolefin resin of the present invention on the surface of the polyolefin base material by a hot melt system and further coating the paint on the polyolefin resin.
  • the modified polyolefin resin of the present invention can also exhibit excellent adhesion between a metal and a resin.
  • the metal include aluminum, aluminum alloy, nickel, and stainless steel.
  • the resin include nonpolar resins such as polyethylene, polyurethane resins, polyamide resins, acrylic resins, and polyester resins. Therefore, the modified polyolefin resin of the present invention can be used as an adhesive, a primer, a paint binder and an ink binder or as these components.
  • composition of this invention contains said modified polyolefin resin.
  • the composition preferably further includes at least one component selected from the group consisting of a solution, a curing agent, and an adhesive component as another component.
  • composition of the present invention is a resin composition comprising the modified polyolefin resin and a solution.
  • An organic solvent is mentioned as a solution.
  • organic solvents include aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone, methyl butyl ketone and ethyl cyclohexane; fats such as cyclohexane, methyl cyclohexane, nonane and decane And aliphatic or alicyclic hydrocarbon solvents.
  • organic solvents may be used individually by 1 type, and may be contained in the resin composition as 2 or more types of mixed solvents. From the viewpoint of environmental problems, it is preferable to use a solvent other than the aromatic solvent as the organic solvent, and it is more preferable to use a mixed solvent of an alicyclic hydrocarbon solvent and an ester solvent or a ketone solvent.
  • alcohol eg, methanol, ethanol, propanol, isopropyl alcohol, butanol
  • propylene glycol ether eg, propylene glycol methyl ether
  • Propylene glycol ethyl ether propylene glycol-t-butyl ether
  • composition of the present invention is a composition comprising the modified polyolefin resin and a curing agent.
  • the curing agent include a polyisocyanate compound, an epoxy compound, a polyamine compound, a polyol compound, or a crosslinking agent whose functional group is blocked with a protective group.
  • One type of curing agent may be used, or a combination of a plurality of types may be used.
  • the blending amount of the curing agent can be appropriately selected depending on the content of the modified polyolefin resin of the present invention. Moreover, when mix
  • composition of the present invention is a composition comprising the modified polyolefin resin and an adhesive component.
  • adhesive component known adhesive components such as a polyester-based adhesive, a polyurethane-based adhesive, and an acrylic-based adhesive can be used as long as the desired effects are not impaired.
  • composition of the present invention is excellent in adhesion between nonpolar resins such as polyolefin-based substrates or between nonpolar resins and metals, it can be used as an adhesive, a primer, a binder for paints, and a binder for ink. It is useful as an adhesive in a laminate film such as a laminate film.
  • the primer, paint binder or ink binder of the present invention comprises the modified polyolefin resin or the composition described above. Therefore, it is excellent in adhesiveness, solution stability, and heat resistance, and should be suitably used as a primer for top coating on polyolefin substrates such as automobile bumpers, and a binder for coatings that have excellent adhesion to top coating and clear. Can do.
  • Primers, paint binders, or ink binders of the present invention can be used in the form of a solution, powder, sheet, or the like depending on the application. At that time, additives such as antioxidants, light stabilizers, ultraviolet absorbers, pigments, dyes, inorganic fillers and the like can be blended as necessary.
  • the laminated body of this invention has a layer containing said modified polyolefin resin or said composition, a metal layer, and a resin layer.
  • the arrangement of the layers in the laminate is not particularly limited, but the mode in which the metal layer and the resin layer are positioned with the layer containing the modified polyolefin resin or composition interposed therebetween, the first resin layer and the second resin layer with the metal layer interposed therebetween And a layer containing a modified polyolefin resin or a composition is sandwiched between the metal layer and each resin layer.
  • the laminate of the present invention may be used as a pouch for refilling toiletries.
  • melt flow rate 130 ° C / 10 min
  • ASTM D12308 melt flow index tester (manufactured by Yasuda Seiki Seisakusho) under the conditions of a measurement temperature of 130 ° C. and a measurement load of 2.16 kg.
  • the coated aluminum foil is each of linear low density polyethylene (hereinafter referred to as “LLDPE”), low density polyethylene (hereinafter referred to as “LDPE”), or high density polyethylene (hereinafter referred to as “HDPE”).
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • a test piece cut out to a width of 15 mm was prepared by laminating with a film and thermocompression bonding under conditions of 200 kPa at 90 ° C. for 10 seconds. After the test piece was stored at 23 ° C. and 50% relative humidity for 24 hours at constant temperature and humidity, the laminate adhesive strength was measured under the conditions of 180-degree direction peeling and peeling speed of 100 mm / min.
  • Example 1 Production of modified polyolefin resin (Example-1))
  • 10 parts in 400 g of toluene was heated and dissolved, and then the temperature in the system was kept at 110 ° C while stirring, while 4.0 parts of maleic anhydride, 3.0 parts of lauryl methacrylate, di-t- 1.5 parts of butyl peroxide was added dropwise over 3 hours, and the mixture
  • the reaction mixture was cooled to room temperature and purified by putting the reaction product into a large excess of acetone.
  • the MFR was 9.0 g / 10 min (130 ° C.), the weight average molecular weight was 190,000, maleic anhydride A modified polyolefin resin (Execution-1) having a graft weight of 2.6% by weight and a lauryl methacrylate graft weight of 2.0% by weight was obtained.
  • Example 2 Production of modified polyolefin resin (Example-2)
  • 10 parts in toluene 400 g After dissolution, while stirring while maintaining the temperature in the system at 110 ° C., 4.0 parts of maleic anhydride, 3.0 parts of lauryl methacrylate, and 1 part of di-t-butyl peroxide were respectively added over 3 hours.
  • the solution was added dropwise and allowed to react for an additional hour. After completion of the reaction, the reaction mixture was cooled to room temperature and purified by putting the reaction product into a large excess of acetone.
  • the MFR was 5.0 g / 10 min (130 ° C.), the weight average molecular weight was 180,000, maleic anhydride A modified polyolefin resin (Example-2) having a graft weight of 2.6% by weight and a lauryl methacrylate graft weight of 1.9% by weight was obtained.
  • Vacuum degassing is performed in the extruder to remove the remaining unreacted material, the MFR is 5.0 g / 10 min (130 ° C.), the weight average molecular weight is 180,000, and the graft weight of maleic anhydride is 0.5 wt. %, And a modified polyolefin resin (Execution-3) having a graft weight of 0.4% by weight of lauryl methacrylate was obtained.
  • Example 4 Production of modified polyolefin resin (Example 4)
  • the reaction was carried out by kneading 0 part and 0.5 part of di-t-butyl peroxide using a twin screw extruder set at 200 ° C.
  • Vacuum degassing is performed in the extruder to remove the remaining unreacted material, the MFR is 20.0 g / 10 min (130 ° C.), the weight average molecular weight is 100,000, and the maleic anhydride graft weight is 0.5 weight. %, A modified polyolefin resin (Execution-4) having a graft weight of 0.4% by weight of lauryl methacrylate was obtained.
  • Example 1 Production of modified polyolefin resin (Comparative-1)
  • the modification was performed in the same manner as in Example 1.
  • the resulting modified polyolefin resin (Comparative-1) had an MFR of 250 g / 10 min (130 ° C.), a weight average molecular weight of 70,000, a maleic anhydride graft weight of 3.5% by weight, and a lauryl methacrylate graft weight. It was 2.0% by weight.
  • the modification was performed in the same manner as in Example 2.
  • the resulting modified polyolefin resin (Comparative-2) has an MFR of 20 g / 10 min (130 ° C.), a weight average molecular weight of 130,000, a maleic anhydride graft weight of 3.1% by weight, and a lauryl methacrylate graft weight. It was 1.9% by weight.
  • the resulting modified polyolefin resin (Comparative-3) had an MFR of 10 g / 10 min (130 ° C.), a weight average molecular weight of 150,000, a maleic anhydride graft weight of 2.6 wt%, and a lauryl methacrylate graft weight. It was 2.0% by weight.
  • Table 2 shows a list of physical property values of the modified polyolefin resins prepared in Examples 1 to 4 and Comparative Examples 1 to 3.
  • Table 3 shows the heat seal strength test results of the modified polyolefin resin aluminum foils prepared in Examples 1 to 4 and Comparative Examples 1 to 3 and various polyethylene films and the low-temperature storage stability test results of the solutions.
  • the modified polyolefin resin provided by the present invention is excellent in adhesiveness between the aluminum foil and various polyethylene films, and at the same time has low-temperature storage stability of the solution (Examples 1 to 4).
  • the conventional modified polyolefin resin has insufficient adhesion between the aluminum foil and various polyethylene films (Comparative-1 and Comparative-2).
  • polyethylene itself was used instead of the ethylene high content copolymer b, the low-temperature storage stability of the solution was inferior even if the adhesiveness between the aluminum foil and various polyethylene films was sufficient (Comparative-3). ).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention a pour objet une résine de polyoléfine modifiée qui a une excellente stabilité en solution, tout en présentant une bonne adhérence à un métal tel que l'aluminium et à un matériau de base en polyoléfine, notamment un matériau de base en polyéthylène. À cet effet la présente invention concerne une résine de polyoléfine modifiée qui est un produit modifié par greffage qui est obtenu par modification d'un composant (A), qui est composé d'une résine de polyoléfine qui contient au moins un copolymère (a) ayant une teneur en motifs de structure dérivés d'éthylène inférieure à 50% en moles et un copolymère (b) ayant une teneur en motifs de structure dérivés d'éthylène supérieure ou égale à 50% en moles, par un composant (B), qui est composé d'un ester d'acide (méth)acrylique et d'un acide carboxylique à insaturation α, β ou d'un dérivé de celui-ci.
PCT/JP2019/012276 2018-03-26 2019-03-22 Résine de polyoléfine modifiée et utilisation de celle-ci WO2019188858A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022024476A1 (fr) 2020-07-27 2022-02-03 日本製紙株式会社 Résine de polyoléfine modifiée et son utilisation
WO2024203662A1 (fr) * 2023-03-30 2024-10-03 東洋紡エムシー株式会社 Composition de résine, composition de résine à base d'eau, adhésif à base d'eau et stratifié

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56122816A (en) * 1980-03-01 1981-09-26 Tokuyama Soda Co Ltd Production of modified polypropylene composition
JPS59193175A (ja) * 1983-04-19 1984-11-01 Toa Nenryo Kogyo Kk 積層物
WO2008013085A1 (fr) * 2006-07-25 2008-01-31 Nippon Paper Chemicals Co., Ltd. Résine de polyoléfine modifiée et ses utilisations
JP2014101415A (ja) * 2012-11-16 2014-06-05 Mitsui Chemicals Inc プロピレン系共重合体組成物に極性基含有化合物を付加する方法、該方法を用いて得られた極性基含有プロピレン系共重合体組成物、該共重合体組成物を含む組成物および該方法を含む極性基含有プロピレン系共重合体組成物の製造方法
JP2016184500A (ja) * 2015-03-26 2016-10-20 株式会社カネカ タブリード用積層フィルム
WO2018016460A1 (fr) * 2016-07-21 2018-01-25 三井化学株式会社 Composition de résine de polypropylène et film monocouche et multicouche
WO2018037849A1 (fr) * 2016-08-24 2018-03-01 日本製紙株式会社 Résine à base de polyoléfine modifiée

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56122816A (en) * 1980-03-01 1981-09-26 Tokuyama Soda Co Ltd Production of modified polypropylene composition
JPS59193175A (ja) * 1983-04-19 1984-11-01 Toa Nenryo Kogyo Kk 積層物
WO2008013085A1 (fr) * 2006-07-25 2008-01-31 Nippon Paper Chemicals Co., Ltd. Résine de polyoléfine modifiée et ses utilisations
JP2014101415A (ja) * 2012-11-16 2014-06-05 Mitsui Chemicals Inc プロピレン系共重合体組成物に極性基含有化合物を付加する方法、該方法を用いて得られた極性基含有プロピレン系共重合体組成物、該共重合体組成物を含む組成物および該方法を含む極性基含有プロピレン系共重合体組成物の製造方法
JP2016184500A (ja) * 2015-03-26 2016-10-20 株式会社カネカ タブリード用積層フィルム
WO2018016460A1 (fr) * 2016-07-21 2018-01-25 三井化学株式会社 Composition de résine de polypropylène et film monocouche et multicouche
WO2018037849A1 (fr) * 2016-08-24 2018-03-01 日本製紙株式会社 Résine à base de polyoléfine modifiée

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022024476A1 (fr) 2020-07-27 2022-02-03 日本製紙株式会社 Résine de polyoléfine modifiée et son utilisation
KR20230044212A (ko) 2020-07-27 2023-04-03 닛뽄세이시가부시끼가이샤 변성 폴리올레핀 수지 및 이의 용도
EP4190559A4 (fr) * 2020-07-27 2024-08-21 Jujo Paper Co Ltd Résine de polyoléfine modifiée et son utilisation
WO2024203662A1 (fr) * 2023-03-30 2024-10-03 東洋紡エムシー株式会社 Composition de résine, composition de résine à base d'eau, adhésif à base d'eau et stratifié

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