Classifications

• • 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
  • 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
  • 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
• • 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
  • C09D5/002—Priming paints
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• the present invention relates to a resin composition containing a modified polyolefin obtained by modification with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof.
• Polyolefin resins have many excellent properties, including excellent mechanical properties such as tensile strength, tear strength, and impact strength, as well as excellent water resistance and chemical resistance, and are lightweight, inexpensive, and easy to mold, so they are used in a variety of applications such as sheets, films, and molded products.
• polyolefin resins unlike polar base materials such as polyurethane resins, polyamide resins, acrylic resins, and polyester resins, polyolefin resins are non-polar and crystalline, which can make painting and bonding difficult.
• modified polyolefin resins modified with highly adhesive ⁇ , ⁇ -unsaturated carboxylic acids or derivatives thereof are used as adhesion promoters for adhering poorly adhesive paints to polyolefin resins (in the automotive industry, paints that are applied directly to substrates and consist mainly of adhesion promoters are called primer paints) (Patent Document 1).
• modified polyolefin resins obtained by modifying polyolefin resins with relatively high melting points can achieve excellent heat-resistant adhesion to poorly adhesive substrates such as polyolefins.
• such resins have the problem of poor solution stability and poor handling.
• the object of the present invention is to provide a resin composition that has excellent heat resistance to adhesion to poorly adhesive substrates and excellent solution stability.
• the present invention provides the following: [1] A modified product obtained by modifying a polyolefin resin (A) having a melting point of 100°C or less, as measured in accordance with JIS K7121-1987 using a differential scanning calorimeter at a heating rate of 10°C/min, with one or more compounds selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acids and derivatives thereof; and a modified product obtained by modifying a polyolefin resin (B) having an extrapolated melting onset temperature (Tim) of 120°C or more, as measured in accordance with JIS K7121-1987 using a differential scanning calorimeter at a heating rate of 10°C/min, with one or more compounds selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acids and derivatives thereof,
• the modified resin (B) is dispersed in the modified resin (A), A resin composition, wherein the modified resin (B) has an average particle size of 0.1 to 100 ⁇ m.
• [6] The resin composition according to any one of [1] to [5] above, wherein the difference (Tem-Tim) between the extrapolated melting end temperature (Tem) and the extrapolated melting onset temperature (Tim) of the resin (B) measured at a heating rate of 10°C/min using a differential scanning calorimeter in accordance with JIS K7121-1987 is 5 to 20°C.
• a primer comprising the resin composition according to any one of [1] to [7] above.
• An adhesive comprising the resin composition according to any one of [1] to [7] above.
• a coating material comprising the resin composition according to any one of [1] to [7] above.
• An ink comprising the resin composition according to any one of [1] to [7] above.
• a method for producing the resin composition according to any one of [1] to [7] above comprising a step of simultaneously modifying a mixture of resin (A) and resin (B) with one or more compounds selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acids and derivatives thereof to obtain the resin composition, or (2) A step of modifying resin (A) with one or more compounds selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acids and derivatives thereof to obtain a modified product of resin (A), a step of modifying resin (B) with one or more compounds selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acids and derivatives thereof to obtain a modified product of resin (B), and a step of mixing the modified product of resin (A) and the modified product of resin (B) obtained to obtain the resin composition.
• the present invention provides a resin composition that exhibits excellent heat resistance and excellent solution stability for poorly adherent substrates.
• AA-BB means "greater than or equal to AA and less than or equal to BB.”
• AA and BB each represent a numerical value, with AA ⁇ BB.
• the units of “AA” are the same as those of “BB” unless otherwise specified.
• (meth)acrylic acid includes “acrylic acid”, “methacrylic acid”, and combinations thereof;
• (meth)acrylate encompasses “acrylate,”"methacrylate,” and combinations thereof.
• the present invention provides a resin composition
• a resin composition comprising a modified product of polyolefin resin (A) having a melting point of 100° C. or less modified with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof, and a modified product of polyolefin resin (B) having an extrapolated melting onset temperature (Tim) of 120° C. or more modified with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof, the modified product of resin (B) being dispersed in the modified product of resin (A) and the average particle size of the modified product of resin (B) being 0.1 to 100 ⁇ m.
• Such a resin composition can exhibit excellent heat resistance and solution stability to poorly adherent substrates.
• resin (A) may be simply referred to as component (A)
• resin (B) may be simply referred to as component (B).
• the resin composition of the present invention includes a modified product obtained by modifying a polyolefin resin (A) having a melting point of 100°C or less with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof, and a modified product obtained by modifying a polyolefin resin (B) having an extrapolated melting onset temperature (Tim) of 120°C or more with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof.
• A polyolefin resin
• Tim extrapolated melting onset temperature
• Polyolefin resins are polymers of olefins (preferably ⁇ -olefins).
• ⁇ -olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.
• the polyolefin resin may be a polymer of one type of olefin (preferably ⁇ -olefin) or a copolymer of two or more types of olefins (preferably ⁇ -olefins).
• the polyolefin resin may be a random copolymer or a block copolymer.
• the mass ratio of the modified product of component (A) to the modified product of component (B) is preferably 40:60 to 95:5, more preferably 50:50 to 95:5, even more preferably 60:40 to 95:5, still more preferably 70:30 to 95:5, and particularly preferably 75:25 to 95:5.
• Component (A) Polyolefin resin having a melting point of 100°C or less
• the polyolefin resin of component (A) is preferably polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, or a mixture thereof.
• polypropylene refers to a polymer whose constituent units are propylene-derived constituent units.
• Ethylene-propylene copolymer refers to a copolymer containing ethylene-derived constituent units and propylene-derived constituent units as constituent units.
• Propylene-1-butene copolymer refers to a copolymer containing propylene-derived constituent units and 1-butene-derived constituent units as constituent units.
• “Ethylene-propylene-1-butene copolymer” refers to a copolymer containing ethylene-derived constituent units, propylene-derived constituent units, and 1-butene-derived constituent units as constituent units.
• these (co)polymers may contain small amounts of other olefin-derived constituent units as constituent units.
• the polyolefin resin of component (A) preferably contains 15 mol % or more, and more preferably 50 mol % or more, of propylene-derived structural units out of 100 mol % of all structural units. When the propylene-derived structural units are contained in the above range, good adhesion can be maintained.
• the polyolefin resin of component (A) is an ethylene-propylene copolymer or a propylene-1-butene copolymer, preferably, out of 100 mol% of all constituent units, the constituent units derived from ethylene or the constituent units derived from 1-butene are 3 to 85 mol% (more preferably 3 to 50 mol%), and the constituent units derived from propylene are 15 to 97 mol% (more preferably 50 to 97 mol%).
• the lower limit of the melting point (Tm) of the polyolefin resin of component (A) is preferably 60°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, and particularly preferably 95°C or higher.
• the melting point (Tm) of the polyolefin resin of component (A) can be measured by a differential scanning calorimeter at a heating rate of 10°C/min in accordance with JIS K7121-1987.
• the weight average molecular weight (Mw) of the polyolefin resin of component (A) is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 30,000 or more, even more preferably 50,000 or more, and particularly preferably 100,000 or more, and the upper limit is preferably 200,000 or less, more preferably 180,000 or less, even more preferably 170,000 or less, even more preferably 160,000 or less, and particularly preferably 150,000 or less.
• the weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
• component (B) Polyolefin resin with extrapolated melting temperature of 120°C or higher
• the polyolefin resin of component (B) is preferably polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-propylene-1-butene copolymer or a mixture thereof.
• the lower limit of the melting point (Tm) of the polyolefin resin of component (B) is preferably 140°C or higher, more preferably 145°C or higher, even more preferably 150°C or higher, and particularly preferably 155°C or higher, and the upper limit is preferably 200°C or lower, more preferably 190°C or lower, even more preferably 180°C or lower, and particularly preferably 170°C or lower.
• the melting point (Tm) of the polyolefin resin of component (B) can be measured using a differential scanning calorimeter at a heating rate of 10°C/min in accordance with JIS K7121-1987.
• the lower limit of the extrapolated melting onset temperature (Tim) of the polyolefin resin of component (B) is 120°C or higher, preferably 125°C or higher, more preferably 130°C or higher, even more preferably 135°C or higher, and particularly preferably 140°C or higher, and the upper limit is preferably 200°C or lower, more preferably 190°C or lower, even more preferably 180°C or lower, and particularly preferably 170°C or lower.
• the extrapolated melting onset temperature (Tim) of the polyolefin resin of component (B) can be measured by a differential scanning calorimeter at a heating rate of 10°C/min in accordance with JIS K7121-1987.
• the lower limit of the extrapolated melting end temperature (Tem) of the polyolefin resin of component (B) is preferably 135°C or higher, more preferably 140°C or higher, even more preferably 145°C or higher, and particularly preferably 150°C or higher, and the upper limit is preferably 210°C or lower, more preferably 200°C or lower, even more preferably 190°C or lower, and particularly preferably 180°C or lower.
• the extrapolated melting end temperature (Tem) of the polyolefin resin of component (B) can be measured using a differential scanning calorimeter at a heating rate of 10°C/min in accordance with JIS K7121-1987.
• the difference (Tem-Tim) between the extrapolated melting end temperature (Tem) and the extrapolated melting start temperature (Tim) of the polyolefin resin of component (B) is preferably 5 to 20°C, more preferably 10 to 20°C, even more preferably 10 to 19°C, and particularly preferably 12 to 18°C.
• the weight average molecular weight (Mw) of the polyolefin resin of component (B) is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 30,000 or more, even more preferably 40,000 or more, and particularly preferably 50,000 or more, and the upper limit is preferably 500,000 or less, more preferably 400,000 or less, even more preferably 300,000 or less, even more preferably 200,000 or less, and particularly preferably 180,000 or less.
• the resin composition of the present invention is, for example, (1) A method including a step of simultaneously modifying a mixture of component (A) and component (B) with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof to obtain the resin composition of the present invention (hereinafter sometimes referred to as “simultaneous modification”); (2) A method including a step of modifying component (A) with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof to obtain a modified product of component (A), a step of modifying component (B) with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof to obtain a modified product of component (B), and a step of mixing the modified product of component (A) and the modified product of component (B) obtained to obtain the resin composition of the present invention (hereinafter sometimes referred to as "individual modification"). It can be produced by the
• Modification with ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative can be carried out, for example, by graft copolymerizing ⁇ , ⁇ -unsaturated carboxylic acid or its derivative onto the polyolefin chain of the raw material polyolefin resin. Modification with ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative can be carried out using a melting method.
• the modification with ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative is preferably carried out, for example, by heating and melting the polyolefin resin to react with the ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative.
• the heating and melting temperature may be equal to or higher than the melting point of the raw polyolefin resin (component (B) in the case of simultaneous modification), and is preferably equal to or higher than the melting point of the raw polyolefin resin (component (B) in the case of simultaneous modification) but not exceeding 300°C, more preferably equal to or higher than the melting point of the raw polyolefin resin (component (B) in the case of simultaneous modification) but not exceeding 250°C, and particularly preferably equal to or higher than the melting point of the raw polyolefin resin (component (B) in the case of simultaneous modification) but not exceeding 200°C.
• Modification with ⁇ , ⁇ -unsaturated carboxylic acids and/or derivatives thereof can be carried out using equipment such as a Banbury mixer, kneader, or extruder, and is preferably carried out using an extruder (extrusion modification).
• the extrusion modification method may include, for example, a process in which a mixture of components (A) and (B) is supplied as raw materials to the supply section of an extruder (e.g., a co-rotating multi-screw extruder, a twin-screw extruder), and in the extruder, the raw materials are mixed, melt-kneaded, reacted, and devolatilized together with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof, for example, at the heating and melting temperature described above, and cooled, and the resin emerging from the tip die of the extruder is further cooled (e.g., immersed in a water tank) to obtain the resin composition of the present invention.
• the progress of the modification reaction and kneading can be adjusted by adjusting the temperature of each part of the barrel of the extruder and the screw rotation speed.
• the extrusion modification method may include, for example, a step of supplying component (A) as a raw material to the supply section of an extruder, mixing the raw materials, melt-kneading, reacting, and devolatilizing together with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof in the extruder, for example, at the above-mentioned heat-melting temperature, cooling, and further cooling the resin that emerges from the tip die of the extruder, to obtain a modified product of component (A); a step of supplying component (B) as a raw material to the supply section of an extruder, mixing the raw materials, melt-kneading, reacting, and devolatilizing together with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof in the extruder, for example, at the above-mentioned heat-melting temperature, cooling, and further cooling the resin that emerges from the tip die of the extruder
• Examples of derivatives of ⁇ , ⁇ -unsaturated carboxylic acids include ⁇ , ⁇ -unsaturated carboxylic anhydrides, ⁇ , ⁇ -unsaturated carboxylic esters, ⁇ , ⁇ -unsaturated carboxylic amides, and ⁇ , ⁇ -unsaturated carboxylic imides.
• the ⁇ , ⁇ -unsaturated carboxylic acid and its derivatives used to modify component (A) and the ⁇ , ⁇ -unsaturated carboxylic acid and its derivatives used to modify component (B) may be the same or different.
• Examples of ⁇ , ⁇ -unsaturated carboxylic acids and derivatives thereof include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, himic anhydride, (meth)acrylic acid, (meth)acrylic acid esters, etc. It is preferable that the ⁇ , ⁇ -unsaturated carboxylic acids and derivatives thereof include one or more selected from maleic anhydride and (meth)acrylic acid esters.
• the ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative more preferably contains a (meth)acrylic acid ester.
• alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, 2,4,6-trimethylheptyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, te
• the number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is preferably 1 to 30, more preferably 4 to 20, even more preferably 8 to 16, and particularly preferably 10 to 14.
• the alkyl (meth)acrylate is most preferably lauryl (meth)acrylate.
• the ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative more preferably contains maleic anhydride.
• the cyclic structure derived from the maleic anhydride contained in the modified polyolefin resin may be partially hydrolyzed and ring-opened.
• the content of maleic anhydride in the ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more, assuming that the total amount of the ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative is 100% by mass.
• the amount of ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative used for modification with ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative is preferably 50% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, and particularly preferably 10% by weight or less, relative to 100% by weight of the raw material polyolefin resin.
• the modification with ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative is preferably carried out in the presence of a radical reaction initiator.
• the radical reaction initiator may be, for example, a thermal polymerization initiator that generates free radicals when heated, such as organic peroxides and azonitriles.
• organic peroxides examples include di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, dibenzoyl peroxide, benzoyl m-tolyl peroxide, di(m-tolyl)benzoyl, dilauryl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butylperoxy)-
• the azonitriles include 3,5,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)-cyclohexane, cyclohexanone peroxide, tert-butylperoxybenzoate, tert-butylperoxyisobutyrate, tert-butylperoxy-3,5,5-trimethylhexanoate,
• azonitriles examples include 2,2-azobis(2-methylbutyronitrile), 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), and 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile).
• the amount of radical reaction initiator used for modification with ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative is preferably 0.01% to 3% by weight, more preferably 0.1% to 2% by weight, based on 100% by weight of the raw material polyolefin resin.
• the mass ratio (component (A):component (B)) of the amount of raw material component (A) to the amount of raw material component (B) required to obtain the resin composition of the present invention is preferably 40:60 to 95:5, more preferably 50:50 to 95:5, even more preferably 60:40 to 95:5, even more preferably 70:30 to 95:5, and particularly preferably 75:25 to 95:5.
• a mixture of components (A) and (B) blended in the above mass ratio is used as a raw material to perform modification and obtain a resin composition.
• the above mass ratio is used as the mass ratio of the raw materials used to perform modification of components (A) and (B) individually, and the resulting modified products are mixed to obtain a resin composition.
• the total graft weight (modification degree) of the ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative in the resin composition of the present invention is preferably 50% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, and particularly preferably 10% by weight or less, when the total amount of the modified product of component (A) and the modified product of component (B) is taken as 100% by weight, and the lower limit is not particularly limited, but is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and even more preferably 1% by weight or more.
• the graft weight (weight%) can be determined, for example, by alkali titration, Fourier transform infrared spectroscopy, 1 H-NMR, or the like.
• the resin composition of the present invention is in a form in which the modified product of component (B) is dispersed in the modified product of component (A).
• the modified product of component (B) may be in a particulate form.
• the modified product of component (B) may be in a particulate form in which the unmodified polyolefin resin of component (B) and the modified polyolefin resin of component (B) are non-uniformly mixed.
• the resin composition of the present invention may contain a hydrophobic solvent.
• the resin composition of the present invention may be in a solid form in which a solid particulate modified product of component (B) is dispersed in a solid modified product of component (A), or in a liquid form in which a solid particulate modified product of component (B) is dispersed in a solution in which a modified product of component (A) is dissolved.
• the resin composition obtained by cooling the resin coming out of the tip die of the extruder can be in a solid form in which the solid particulate modified product of component (B) is dispersed in the solid modified product of component (A).
• the solid resin composition thus obtained can be mixed with a hydrophobic solvent to form a liquid form in which the solid particulate modified product of component (B) is dispersed in a solution in which the modified product of component (A) is dissolved.
• Hydrophobic solvents include, for example, aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl butyl ketone; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane; and aliphatic hydrocarbon solvents such as hexane, nonane, and decane.
• aromatic hydrocarbon solvents such as toluene and xylene
• ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and butyl acetate
• ketone solvents such as acetone
• the average particle size of the modified product of component (B) is 0.1 to 500 ⁇ m, and is not particularly limited, but is preferably 0.1 to 200 ⁇ m, more preferably 0.1 to 100 ⁇ m, even more preferably 0.3 to 50 ⁇ m, even more preferably 0.4 to 20 ⁇ m, and particularly preferably 0.5 to 10 ⁇ m.
• the average particle size of the modified product of component (B) may be the volume-based median diameter Dv50 (the maximum particle size below which 50% of the sample volume falls).
• the average particle size of the modified product of component (B) can be measured and calculated, for example, as in Test Example 1 below.
• the resin composition of the present invention has a low water vapor permeability when molded into a film.
• the resin composition of the present invention has a water vapor permeability of preferably 15 g/( m2 ⁇ 24h) or less, more preferably 12 g/(m2 ⁇ 24h) or less, and usually more than 0 g/( m2 ⁇ 24h), and may be 0.5 g/( m2 ⁇ 24h) or more, when molded into a film having a thickness of 30 ⁇ m.
• the water vapor transmission rate can be measured by the method described in the Examples section based on JIS K 7129-1 (humidity sensor method).
• the resin composition of the present invention can be used in primers, adhesives, paints, or inks.
• the primers, adhesives, paints, or inks may contain additives such as hydrophobic solvents, hydrophilic solvents, curing agents, adhesive components, basic substances, emulsifiers, crosslinking agents, diluents, light stabilizers, ultraviolet absorbers, pigments, dyes, and inorganic fillers in addition to the resin composition of the present invention.
• hydrophilic solvents include water; glycol-based solvents such as ethylene glycol; alcohol-based solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and 2-ethyl-hexanol; and glycol monoether-based solvents such as ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, and propylene glycol monobutyl ether. Solvents may be used alone or in combination of two or more.
• the curing agent may be, for example, a polyisocyanate compound, an epoxy compound, a polyamine compound, a polyol compound, a crosslinking agent in which the functional groups of these are blocked with a protecting group, or a combination of two or more of these.
• the content of the curing agent may be appropriately selected depending on the content of the modified polyolefin resin.
• a catalyst such as an organotin compound or a tertiary amine compound may be used in combination depending on the purpose.
• the curing agent may be used alone or in combination of two or more.
• the adhesive component may be, for example, a known adhesive component such as a polyester adhesive, a polyurethane adhesive, or an acrylic adhesive.
• the adhesive component may be used alone or in combination of two or more types.
• the resin composition contains a basic substance. This allows the pH to be appropriately adjusted, and the dispersibility and storage stability of the resin in the solvent to be further improved.
• Examples of basic substances include sodium hydroxide, potassium hydroxide, ammonia, methylamine, propylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N,N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholine, dimethylethanolamine, and 2-amino-2-ethyl-1,3-propanediol, and preferably include ammonia, triethylamine, 2-amino-2-methyl-1-propanol, morpholine, dimethylethanolamine, and 2-amino-2-ethyl-1,3-propanediol.
• the basic substance may be used alone or in combination of two or more.
• the resin composition contains a diluent.
• diluents include alcohol and propylene-based glycol ethers.
• alcohol include methanol, ethanol, propanol, isopropanol, and butanol.
• propylene-based glycol ethers include propylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol tert-butyl ether.
• the diluent may be used alone or in combination of two or more types.
• the resin composition contains a crosslinking agent.
• the crosslinking agent may be a compound that can react with groups such as hydroxyl groups, carboxyl groups, and amino groups present in the resin composition to form a crosslinked structure, and may be, for example, either a water-soluble crosslinking agent or an aqueous dispersion of a crosslinking agent (a crosslinking agent that is dispersed in water by some method).
• crosslinking agents include blocked isocyanate compounds, aliphatic or aromatic epoxy compounds, amine compounds, and amino resins.
• the crosslinking agents may be used alone or in combination of two or more types.
• the resin composition contains an emulsifier.
• emulsifiers include surfactants such as nonionic surfactants and anionic surfactants, with nonionic surfactants being preferred.
• nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene derivatives, polyoxyethylene fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyethylene polyoxypropylene polyols, sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ethers, polyoxyethylene alkylamines, alkyl alkanolamides, and polyalkylene glycol (meth)acrylates.
• Polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene alkylamines are preferred.
• anionic surfactants include alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate salts, alkylbenzene sulfonates, ⁇ -olefin sulfonates, methyl tauryl salts, sulfosuccinate salts, ether sulfonates, ether carboxylate salts, fatty acid salts, naphthalenesulfonic acid-formaldehyde condensates, alkylamine salts, quaternary ammonium salts, alkyl betaines, and alkylamine oxides. Polyoxyethylene alkyl ether sulfate salts and sulfosuccinate salts are preferred.
• the emulsifiers may be used alone or in combination of two or more.
• the present invention will be described in detail below using examples, but the present invention is not limited to these examples.
• the unit “parts” means “parts by weight”.
• “%” means “% by weight.”
• the temperature conditions are at room temperature (25°C), and the pressure conditions are at normal pressure (760 mmHg).
• the total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.0% by weight, with the total amount of the modified polyolefin resin being 100% by weight.
• the total graft weight of maleic anhydride was measured by alkali titration. The same applies below.
• the melting point (Tm) of component (A), as well as the melting point (Tm), extrapolated melting start temperature (Tim), and extrapolated melting end temperature (Tem) of component (B) were measured using a differential scanning calorimeter at a heating rate of 10°C/min in accordance with JIS K7121-1987.
• the total graft weight of maleic anhydride in the modified polyolefin resin composition was 2.9% by weight, assuming the total amount of the modified polyolefin resin to be 100% by weight.
• the total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.4% by weight, with the total amount of the modified polyolefin resin being 100% by weight.
• the total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.1% by weight, with the total amount of the modified polyolefin resin being 100% by weight.
• 90 parts of the resin composition (1) as the modified product of component (A) and 10 parts of the resin composition (2) as the modified product of component (B) were kneaded in a twin-screw extruder set at a reaction temperature of 170°C.
• the mixture was cooled to room temperature to obtain a modified polyolefin resin composition.
• the total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.0% by weight, based on the total amount of the modified polyolefin resin being 100% by weight.
• Example 6 Except for not using lauryl methacrylate, a modified polyolefin resin composition was obtained in the same manner as in Example 1.
• the total graft weight of maleic anhydride in the modified polyolefin resin composition was 2.9% by weight, with the total amount of the modified polyolefin resin being 100% by weight.
• the total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.1% by weight, with the total amount of the modified polyolefin resin being 100% by weight.
• the total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.0% by weight, with the total amount of the modified polyolefin resin being 100% by weight.
• the total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.0% by weight, with the total amount of the modified polyolefin resin being 100% by weight.
• the total graft weight of maleic anhydride in the modified polyolefin resin composition was 2.9% by weight, with the total amount of the modified polyolefin resin being 100% by weight.
• the total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.2% by weight, with the total amount of the modified polyolefin resin being 100% by weight.
• ⁇ Test Example 1 Measurement and calculation of average particle size of modified product of component (B)> The volumetric particle size distribution was measured using a Malvern Mastersizer 3000, and the average particle size was calculated as the volumetric median diameter Dv50 (the maximum particle size below which 50% of the sample volume falls).
• the melting point peak of resin (A) was observed from the solid obtained from the supernatant, and the melting point peak of resin (B) was observed from the solid obtained from the precipitate (i.e., the solid that was not dissolved and existed as particles).
• the Fourier transform infrared spectroscopy (FT-IR) spectrum (ATR method) of each of the obtained supernatant and precipitate was measured.
• FT-IR FT-IR
• the peak appearing at wave numbers of 1700 to 1750 cm ⁇ 1 was assigned to a peak derived from the carbonyl group of the ring-opened ⁇ , ⁇ -unsaturated carboxylic anhydride, and the peak appearing at wave numbers of 1750 to 1820 cm ⁇ 1 was assigned to a peak derived from the carbonyl group of the non-ring-opened ⁇ , ⁇ -unsaturated carboxylic anhydride.
• the coating film was then dried in a thermostatic dryer adjusted to 100° C., and the coated aluminum foil was laminated with a non-oriented polypropylene (CPP) sheet, and thermocompression bonding was performed under conditions of 200° C., 0.1 MPa, and 1 second, and then aging was performed for 3 days in a thermostatic dryer adjusted to 60° C.
• a test piece was prepared by cutting into a width of 15 mm, and the laminate adhesive strength was measured under conditions of a peel angle of 180°, a peel speed of 100 mm/min, and an atmosphere of 120° C.
• the evaluation criteria were as follows: a sample that maintained fluidity after standing for one day was rated as "G”, and a sample that had no fluidity and was in a gel state or solidified was rated as "NG”.
• Table 1 summarizes the melting points, extrapolated melting start temperatures, and extrapolated melting end temperatures of the raw materials used in Examples 1 to 6 and Comparative Examples 1 to 5, as well as the evaluation and measurement results of Test Examples 1 to 3.
• PET polyethylene terephthalate
• the resin composition of the present invention which contains a modified product obtained by modifying polyolefin resin (A) having a melting point of 100°C or less with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof, and a modified product obtained by modifying polyolefin resin (B) having an extrapolated melting onset temperature (Tim) of 120°C or more with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof, wherein the modified product of component (B) is dispersed in the modified product of component (A) and the average particle size of the modified product of component (B) is 0.1 to 100 ⁇ m, can exhibit excellent heat resistance and excellent solution stability to polypropylene sheets and metal materials, which are poorly adhesive substrates. It is also clear that the resin compositions according to the examples have significantly smaller water vapor permeation amounts than the resin composition according to Comparative Example 1.

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