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WO1997039057A1 - Composition de resine a base d'olefine et articles moules - Google Patents

Composition de resine a base d'olefine et articles moules Download PDF

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Publication number
WO1997039057A1
WO1997039057A1 PCT/JP1997/001314 JP9701314W WO9739057A1 WO 1997039057 A1 WO1997039057 A1 WO 1997039057A1 JP 9701314 W JP9701314 W JP 9701314W WO 9739057 A1 WO9739057 A1 WO 9739057A1
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WO
WIPO (PCT)
Prior art keywords
olefin
resin composition
olefin resin
rubber
polyester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP1997/001314
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English (en)
Japanese (ja)
Inventor
Shizuo Kitahara
Shinya Ikeda
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Zeon Corp
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Nippon Zeon Co Ltd
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Filing date
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Publication of WO1997039057A1 publication Critical patent/WO1997039057A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • 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
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • Olefin-based resin composition and molded article Olefin-based resin composition and molded article
  • the present invention relates to an olefin resin composition having excellent mechanical strength ⁇ impact resistance and excellent strength and solvent resistance of a coating film formed on a surface, and an olefin resin composition providing the molded article. . '' Background technology
  • plastic parts such as fenders, door panels, bumpers, spoilers, mat guards, side moldings, wheel caps, instrument panels, levers, knobs, etc. have been molded into plastic parts for the purpose of reducing the weight and simplifying the process through integration.
  • the body has been adopted.
  • bumpers are required to have mechanical strength such as flexural modulus and flexibility such as impact resistance, etc., and therefore, the bumper consists of an olefin resin consisting of an olefin resin and an olefin rubber such as ethylene-propylene copolymer rubber.
  • a molded article made of a resin composition is used.
  • the surface of a molded article made of these olefin resin compositions has a practical coating strength and coating strength because both the olefin resin and the olefin rubber, which are the main components, have no polar group in the molecule. There is a problem that film properties such as solvent resistance of the film cannot be obtained.
  • An object of the present invention is to provide an olefin resin molding excellent in mechanical strength and shock resistance and also excellent in characteristics of a coating film formed on the surface, and an olefin resin composition providing the same. It is in.
  • the present inventors have conducted intensive studies in order to overcome the problems of the prior art, and as a result, obtained by blending a rubber such as an olefin resin, an olefin rubber, and a polyester having a large hydroxyl value. Completed the present invention by discovering that the resin composition has excellent compatibility and can greatly improve surface coating properties such as coating strength and solvent resistance without impairing mechanical strength after impact and impact resistance. I came to.
  • an olefin resin composition comprising an olefin resin (a), a rubber (b), and a polyester (c) having a hydroxyl value of 30 mg KOHZg or more.
  • an olefin resin molded article obtained by molding the above olefin resin composition.
  • an olefin resin molded article obtained by coating the surface of the olefin resin molded article.
  • the olefin resin (a) used in the present invention is not particularly limited as long as it is a resin containing an olefin monomer unit as a main component.
  • examples thereof include ethylene, propylene, butene-11, and pentene. 1-Hexene-1, 4-methylpentene-11, etc.
  • ⁇ -olefin olefin homopolymer resin 2 or more ⁇ -olefin olefin copolymer resins; Copolymer resins of one-year-old fins and other copolymerizable monomers; and the like.
  • high-pressure method low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-butene-1-1 random copolymer, polypropylene, propylene-propylene Tylene random copolymer, propylene / ethylene block copolymer, propylene • 1-butene 1 random copolymer, 1-butene 1 homopolymer, poly 1-methylpentene 1, ethylene-acrylic acid copolymer, ethylene-methacrylic acid Copolymer, ethylene-crotonic acid copolymer, ethylene-maleic acid copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-vinyl acetate copolymer, etc.
  • propylene resins such as polypropylene and copolymer resins of propylene and other ⁇ -olefins are preferably used.
  • olefinic resins (a) include, for example, graft copolymerized modified olefins obtained by graft copolymerizing ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, maleic acid and their anhydrides with the above olefinic resins.
  • Block copolymer-modified olefin resin obtained by subjecting the above-mentioned olefin resin to block copolymerization of an ⁇ , ⁇ -unsaturated carboxylic acid such as acrylic acid, maleic acid and anhydride thereof; and the like.
  • the melt flow rate (hereinafter abbreviated as MFR) of the resin-based resin (a) used in the present invention which is defined by JIS K7210 and measured at a load of 23 Ots and a load of 2.16 kg, is as follows. Although there is no particular limitation, it is usually in the range of 0.1 to 100 gZl 0 minutes, preferably 1 to 80 gZl O minutes, more preferably 10 to 60 gZl 0 minutes.
  • the density of the resin (a) used in the present invention is not particularly limited, but is usually 0.90 gZcm 3 or more.
  • olefinic resins (a) can be used alone or in combination of two or more.
  • the rubber (b) used in the present invention is not particularly limited as long as it is generally used industrially.
  • natural rubber polyisoprene rubber, polybutene rubber, butadiene-isoprene copolymer Copolymer rubbers such as rubber and chloroprene rubber; styrene-butadiene random copolymer rubber, styrene-isoprene random copolymer rubber, styrene-isoprene-butadiene random Aromatic vinyl-conjugated genomic random copolymer rubbers such as copolymer rubbers; aromatic vinyl conjugated genlock copolymer rubbers and their hydrogenated products; acrylonitrile-butene Copolymer rubber with copolymerizable monomer; modified polyethylene rubber such as chlorinated polyethylene rubber and chlorosulfonated polyethylene rubber; olefin copolymer rubber and its modified products; silicone rubber.
  • aromatic vinyl-conjugated gen-block copolymer rubbers and hydrogenated products modified polyethylene rubbers, olefin-based copolymers and modified products thereof, and silicone rubber are preferred.
  • Hydrogenated copolymer rubber olefin copolymer rubber is particularly suitable.
  • the aromatic vinyl-conjugated gen-block copolymer rubber is not particularly limited.
  • a block copolymer rubber having at least one united block (A) and at least one polymer block (B) mainly containing a conjugated gen is exemplified.
  • "Aromatic vinyl-based polymer block (A) J" means aromatic vinyl in excess of 50% by weight, preferably 60 to 100% by weight, more preferably 70 to 100% by weight.
  • % More preferably from 80 to 100% by weight, and is a homopolymer of aromatic vinyl or a polymer block composed of aromatic vinyl and a conjugated diene.
  • the distribution of the conjugated gen in (A) may be random, tapered, partially block-shaped, or a combination thereof.
  • "Polymer block mainly composed of conjugated gen (B)” Is more than 50% by weight, preferably 60 to 100% by weight, more preferably 70 to 100% by weight, more preferably 80 to 100% by weight, more preferably 80 to 100% by weight.
  • Polymer block containing conjugated is a polymer block comprising a conjugated diene E emission and an aromatic vinyl.
  • the distribution of the aromatic vinyl in the polymer block (B) may be random, tapered, partially blocky, or a combination thereof.
  • polymer structure of the aromatic vinyl-conjugated diene block copolymer rubber may be either a straight chain structure or a branched structure.
  • the following general formulas (a) to (g) It has a structure shown by.
  • A is a polymer block (A) mainly composed of aromatic biel
  • B is a polymer block mainly composed of conjugated gen (B)
  • X is a multifunctional coupling.
  • n is an integer from 1 to 10
  • p is an integer from 2 to 6.
  • polyfunctional coupling agent in the above general formula examples include tin-based coupling agents such as tin tetrachloride, tin tetrabromide, tetramethoxytin, and tetraethoxytin; silicon tetrachloride, tetramethoxy silicon, Gay-based coupling agents such as triethoxy silicate; Unsaturated nitrile-based coupling agents such as ethyl acrylonitrile; Halogenated carbonization such as dichloromethane, dibromomethane, dichloroethane, dibromoethane, dichloropropane, dibromobenzene, etc. Hydrogen-based coupling agents; ester-based coupling agents such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl benzoate, and methyl adipate; and the like.
  • tin-based coupling agents such as tin
  • aromatic vinyl of the aromatic vinyl-conjugated gen copolymer rubber examples include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, ⁇ -methylstyrene, 1,3-dimethylstyrene, and vinylnaphthylene. Of these, styrene is preferred. These aromatic vinyls may be used alone or in combination of two or more.
  • conjugated gen of the aromatic vinyl-conjugated gen-block copolymer rubber examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentene. Among these, 1, 3 And isoprene are preferred, and 1,3-butadiene is particularly preferred. These conjugated diene may be used alone or in combination of two or more.
  • the aromatic vinyl content in the aromatic vinyl-conjugated diene block copolymer rubber is appropriately selected according to the purpose of use. It is usually 5 to 50% by weight, preferably 10 to 45% by weight, more preferably 10 to 40% by weight.
  • the molecular weight of the aromatic vinyl-conjugated diene block copolymer rubber is usually from 10,000 to 3,000,000, preferably 30,000 as a polystyrene equivalent weight average molecular weight (Mw) of gel permeation chromatography (GPC). The range is from 000 to 1,000,000, more preferably from 50,000 to 500,000.
  • Mw polystyrene equivalent weight average molecular weight
  • GPC gel permeation chromatography
  • olefin-based copolymer rubber examples include, for example, a copolymer rubber obtained by copolymerizing two or more of the ⁇ -olefins exemplified in the above-mentioned olefin resin, ⁇ -olefin and other copolymerizable monomers. And a copolymer rubber obtained by copolymerizing a polymer.
  • copolymer rubber of ethylene and other ⁇ -olefin such as ethylene-propylene copolymer rubber and ethylene-butene-1 copolymer rubber; isobutene (90 to 99.5% by weight) 'isoprene (10-0.5% by weight) Copolymer rubber such as copolymer rubber with ⁇ -refined olefin and gen monomer; ethylene propylene dicyclopentadiene copolymer rubber, ethylene propylene ethylidene norpolene copolymer Copolymer rubbers of ethylene such as rubber, other ⁇ -olefins, and gen-based monomers;
  • the density of the olefin copolymer rubber is not particularly limited, but is usually less than 0.90.
  • modified product of the olefin copolymer rubber examples include those obtained by modifying the above olefin copolymer rubber with a polar compound.
  • the polar vinyl compound include acrylic acid, methacrylic acid, crotonic acid, maleic acid, methyl acrylate, and vinyl acetate.
  • the iodine value of the rubber (b) to be used is not particularly limited, but is usually 100 or less, preferably 50 or less, and more preferably 35 or less because it has excellent oxidation stability.
  • the MFR of the rubber (b) used in the present invention is not particularly limited, but is in the range of 0.001 to 100 gZl 0 minutes, preferably 0.01 to 50, more preferably 0.1 to 10 is there. When the MFR of the rubber is within this range, the mechanical strength and the fluidity are highly balanced and suitable.
  • These rubbers (b) can be used alone or in combination of two or more.
  • the rubber (b) is used in an amount of usually 1 to 80 parts by weight, preferably 5 to 60 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the olefin resin (a). is there.
  • the amount of the rubber (b) used is in this range, the mechanical strength and the impact resistance are highly balanced and suitable.
  • the polyester (c) used in the present invention is characterized by having a high hydroxyl value.
  • the hydroxyl value of the polyester (c) is 3 OmgKOHZg or more, preferably in the range of 40 to 200 mgKOHZg, more preferably 50 to 150 mgKOHg, and most preferably 60 to 13 OmgKOHZg. If the hydroxyl value of the polyester is too small, the properties of the coating film are poor, which is not preferable.
  • the polyester (c) used in the present invention is not particularly limited except for the hydroxyl value, and a polyester obtained by condensation polymerization of a general polyvalent carboxylic acid component and a polyhydric alcohol component is used.
  • a polymerized fatty acid-based monomer is used as a main component.
  • Polyesters such as polyester (c-ii) are advantageously used because they have excellent compatibility with the resin and can significantly improve the coating properties without impairing mechanical strength or impact resistance.
  • the polymerized fatty acid-based monomer which is a main component of the polyester (c-i) generally, a polymerized fatty acid such as a divalent polymerized fatty acid or a trivalent or higher polymerized fatty acid obtained by polymerizing a fatty acid or a fatty acid ester by a known method; and These ester compounds are used.
  • a polymerized fatty acid such as a divalent polymerized fatty acid or a trivalent or higher polymerized fatty acid obtained by polymerizing a fatty acid or a fatty acid ester by a known method; and These ester compounds are used.
  • higher fatty acids such as oleic acid, linoleic acid, ricinoleic acid, and eleostearic acid; And natural fatty acids such as beef tallow; and the like.
  • fatty acid esters alkyl esters of higher fatty acids such as methyl, ethyl, propyl, butyl, amyl and cyclohexyl are usually used.
  • the polymerized fatty acid may be one obtained by hydrogenating a carbon-carbon unsaturated bond remaining in the polymerized fatty acid.
  • polymerized fatty acid-based monomers can be used alone or in combination of two or more.
  • a divalent polymerized fatty acid-based monomer a divalent polymerized fatty acid, a divalent polymerized fatty acid ester and a hydrogenated product thereof
  • a tri- or higher-valent polymerized fatty acid-based monomer a tri- or higher-valent polymerized fatty acid
  • the ratio of the above-mentioned polymerized fatty acid esters and their hydrogenated products is appropriately selected according to the intended use, and is usually 50% by weight of the divalent polymerized fatty acid-based monomer: the trivalent or higher-polymerized fatty acid-based monomer.
  • the amount of the polymerized fatty acid-based monomer in the polycarboxylic acid component of the polyester (c-i) is appropriately selected according to the purpose of use. 70% by weight or more, more preferably 90% by weight or more
  • the remainder other than the polymerized fatty acid monomer of the polycarboxylic acid component of the polyester (c-i) is not particularly limited.
  • a polyvalent aromatic carboxylic acid monomer or another polycarboxylic acid monomer may be used.
  • the polyvalent aromatic carboxylic acid monomer include divalent aromatic carboxylic acids such as terephthalic acid, isophthalic acid, methyl isophthalic acid, and naphthalic acid, and trivalent aromatic carboxylic acids such as trimellitic acid and trimesic acid.
  • polyvalent aromatic carboxylic acids such as acids, and ester compounds thereof.
  • divalent aromatic carboxylic acids and divalent aromatic carboxylic acid esters are preferable, and terephthalic acid, isophthalic acid, and terephthalic acid are preferable.
  • Esters and disophtalic esters are particularly preferred.
  • polycarboxylic acid monomers include, for example, succinic acid, malonic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, itaconic acid, pimelic acid, methylmalonic acid, dimethylmalonic acid, suberic acid , Azelaic acid, sebacic acid, brassic acid, 1,2-cyclohexane 'diacid, 1,3-cyclohexane' diacid, 1,4-cyclohexane 'diacid, polyalkenyl succinic acid, trialkylvalyl Acids, other polycarboxylic acids such as camphoronic acid; and ester compounds thereof.
  • the polyhydric alcohol component of the polyester (c-i) is not particularly limited, and a polyhydric alcohol component commonly used in general polyester synthesis can be used.
  • the polyhydric hindered alcohol which is a main component of the polyester (c-ii) has two or more hydroxyl groups and the carbon atom at the 3-position of the hydroxyl group has no hydrogen atom.
  • it is usually a zipene erythritol or a general formula (1)
  • Ri and R2 in the general formula (1) each independently represent an alkyl group or an alkyl group having a hydroxyl group.
  • the number of carbon atoms of the alkyl group and the hydroxyl group-containing alkyl group is not particularly limited, but is usually 1 to 50, preferably 1 to 2 It is in the range of 0, more preferably 1 to 10.
  • the carbon number of the alkyl group is in this range, the compatibility with the resin is particularly excellent, and the effect of modifying the coating film characteristics is large and suitable.
  • alkyl group examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, amyl, hexyl, heptyl, octyl, nonyl, and decyl.
  • ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, e'c-butyl Group, amyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. are preferable, and ethyl group, propyl group, butyl group, amyl group, hexyl group, heptyl group, octyl group, nonyl group are preferable.
  • decyl groups are particularly preferred.
  • polyhydric hindered alcohol represented by the general formula (1) examples include 2,2-dimethyl-1,3-propanediol, 2,2-dimethyl-1,3-butanepandiol, 2-dibutyl pill-1,3-propanediol, 2,2-diisopropyl-1,3-propanediol, 2,2-dibutyl-1,3-propanediol, 2,2-diisobutyl-1,3-propanediol Divalent hindered glycols such as, 2-methyl-2-dodecyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-propyl-12-pentyl-1,3-propanediol; tri Trivalent or higher-valent hindered alcohols such as methylolethane, trimethylolpropane, trimethylolbutane, and pen-erythritol
  • dihydric and trivalent or higher hydrinated alcohols are used alone or in combination of two or more.
  • the ratio of dihydric hindered alcohol and trihydric or higher-valent hindered alcohol is selected as appropriate according to the intended use.
  • the dihydric hindered alcohol is usually 50: 50-100: 0, preferably 60: 40-: 100: 0, more preferably 70:30, based on the ratio of hindered alcohol with 3 or more valent. ⁇ 90: 10 range.
  • the amount of the polyhydric alcohol in the polyhydric alcohol component of the polyester (c-i ⁇ ) is appropriately selected according to the purpose of use, but is preferably 50% by weight or more of the total polyhydric alcohol component. Is 70% by weight or more, more preferably 90% by weight or more. '' The remainder of the polyhydric alcohol component of the polyester (c-ii) other than the polyhydric hindered alcohol is not particularly limited.
  • the polyvalent carboxylic acid component in the polyester (c-ii) is appropriately selected without particular limitation depending on the purpose of use.
  • the polymerized fatty acid-based monomer is usually 50% by weight or more, preferably 70% by weight.
  • a polycarboxylic acid component containing more preferably 90% by weight or more is used.
  • the polyvalent aromatic carboxylic acid-based monomer is usually added in 50 minutes.
  • a polycarboxylic acid component containing at least 70% by weight, more preferably at least 90% by weight is used.
  • the polycondensation reaction between the polycarboxylic acid component and the polyhydric alcohol component may be carried out according to a conventional method, for example, at a reaction temperature of 100 to 300, preferably 150 to 280, particularly in the presence of an inert gas. It is preferred to do so. If necessary, a water-insoluble organic solvent azeotropic with water, such as toluene or xylene, may be used.
  • the reaction may be performed under reduced pressure (usually 1 to 500 mmHg, preferably 1 to 200 mmHg, more preferably 1 b or 10 to 10 OmmHg).
  • an esterification catalyst is usually used.
  • esterification catalyst examples include brenstead acid such as p-toluenesulfonic acid, sulfuric acid, and phosphoric acid; Lewis acid such as boron trifluoride complex, titanium tetrachloride, and tin tetrachloride: calcium acetate, zinc acetate, manganese acetate; Organometallic compounds such as zinc stearate, alkyltin oxide, and titanium alkoxide; metal oxides such as tin oxide, antimony oxide, titanium oxide, and vanadium oxide; and the like. From the viewpoint of the oxidation stability of the polyester, an organometallic compound belonging to Group IV of the periodic table is preferred.
  • the molecular weight of the polyester (c) used in the present invention is appropriately selected according to the purpose of use, and is determined by the polystyrene conversion weight average molecular weight (Mw) measured by gel permeation chromatography (GPC). Usually, the range is from 1,000 to 100,000, preferably from 2,000 to 50,000, more preferably from 4,000 to 30,000. When the molecular weight of the polyester (c) is in this range, the transferability to the surface of the molded article is high, and the coatability of the molded article surface is greatly improved, which is preferable.
  • polyesters (c) can be used alone or in combination of two or more.
  • the amount of the polyester (c) to be used is appropriately selected according to the purpose of use, and is usually 0.1 to 30 parts by weight, preferably 0.5 to 30 parts by weight, per 100 parts by weight of the olefin resin (a). 20 parts by weight, more preferably in the range of 1.0 to 10 parts by weight. When the amount of polyester (c) used is within this range, the properties such as mechanical strength, impact resistance and coating properties are highly balanced and suitable.
  • an inorganic filler or other compounding agents can be added as necessary.
  • the inorganic filler is not particularly limited as long as it is commonly used in general olefin resin compositions.
  • Examples include silica, carbon black, and glass fiber. Among them, calcium carbonate, barium sulfate, mite, talc and the like are preferable.
  • those obtained by subjecting the above-mentioned inorganic filler to surface treatment are particularly preferably used.
  • Specific examples of the surface treatment may be conventionally known ones, and examples thereof include those treated with a silane-titanium-based force coupling agent, an acid such as a higher fatty acid or an unsaturated organic acid. .
  • the particle size of the inorganic filler is not particularly limited, but one having an average particle size of 5 m or less is usually used.
  • inorganic fillers can be used alone or in combination of two or more.
  • the amount of the inorganic filler used is appropriately selected according to the purpose of use, but is usually 1 to 50 parts by weight, preferably 2 to 4 parts by weight, based on 100 parts by weight of the olefin resin (a). 0 parts by weight, more preferably 5 to 30 parts by weight.
  • compounding agents include various stabilizers; natural and synthetic polymer compounds described in JP-A-7-28046; and JP-A-7-26846.
  • Fiber reinforcement iron, chromium, nickel, cobalt or their alloys or their oxides; dimethylphthalate, getylfurate, dihexylfurate, butyllaurylphthalate, di (2-ethylhexyl) ) Flate rate, dilauryl phthalate, G2-octylphthalate, Gn-butylyl dipate, diisooctyl adipate, octyl decyl adipate, di-2 Plasticizers such as chill hexyl 4-thioazelate, getyl sebacate, di-n-butyl maleate and getyl malate; titanium oxide, zinc white, lead white, lead red, copper oxynitride, yellow iron oxide, iron black, cadmium Inorganic pigments such as yellow, molybdenum red, silver
  • Examples of various stabilizers in the compounding agent include phenol-based, phosphorus-based, and sulfur-based antioxidants; hindered amine-based, benzotriazole-based, and benzoate-based ultraviolet absorbers; and the like. Of these, the addition of a phosphorus-based antioxidant is preferred, and the phosphorus-based antioxidant alone or in combination with a phosphorus-based antioxidant and another stabilizing agent (that is, other antioxidants and phosphorus or ultraviolet absorbers) It is used as
  • phenolic antioxidant conventionally known ones can be used.
  • JP-A-63-17997953 Acrylate compounds described in Japanese Unexamined Patent Publication (Kokai) No.
  • Examples of the phosphorus antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) -phosphite, tris (dinonylphenyl) phosphite, and tris (2, 4-Gee t-butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (cyclohexylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) Octyl phosphite, 9,10-dihydro-1 9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) — 9,10— Jihi Draw 9-oxa
  • zeo-based antioxidants examples include dilauryl '3,3'-thiodibropionate, dimyristyl-3,3'-thiodibu-pionate, distearyl-3,3'-thiodib-pionate, laurylstearyl-3,3'-one Thiodipropionate, Penyu erythritol monotetrakisux (—lauriluthio-propionate), 3,9-bis (2-dodecylthioethyl) -1,2,4,8,10-tetraxaspiro [5,5] pentadecane No.
  • hindered amine-based UV absorber examples include 2,2,6,6-tetramethyl-4-piperidyl'benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentymethyl-4-piperidyl) 1 2- (3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate, 4- (3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) 1 1 1 (2— (3— (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl) 1 2, Compounds such as 2,6,6-tetramethylpiperidine are exemplified.
  • benzotriazole-based UV absorber examples include 2- (2-hydroxy-15-methylphenyl) benzotriazole and 2- (3-t-butyl-2-hydr) Methyl xy-5-methylphenyl) mono 5-benzobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) mono-benzobenzotriazole, 2- (3,5- Compounds such as di-t-amyl-2-hydroxyphenyl) benzotriazole.
  • benzoate-based ultraviolet absorber examples include, for example, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-1-hydroxy Compounds such as benzoate are mentioned.
  • Each of these various stabilizers can be used alone or in combination of two or more, and the amount of the stabilizer is appropriately determined within a range that does not impair the effect of the olefin resin composition of the present invention.
  • Olefin-based resin composition is Olefin-based resin composition
  • the olefin resin composition of the present invention can be obtained according to a conventional method by simultaneously or separately mixing the above components.
  • the method of dividing and mixing each component is as follows: (1) a method of mixing an olefin resin (a), a rubber (b), and a polyester (c), and then adding and mixing an inorganic filler and other compounding agents; 2) A method of adding the olefin resin (a), the rubber ⁇ b), the inorganic filler and other compounding agents, and then mixing and adding the polyester (c), and any of these methods may be employed. .
  • the method for mixing the olefin resin composition of the present invention may be a conventional method.
  • an extruder such as a single-screw extruder or a twin-screw extruder may be used. Kneading is performed using Bambari, Brabender, blast mill, kneader, roll, extruder, multi-axis kneader, double helical ribbon stirrer, etc.
  • the olefin resin composition after kneading is usually handled in the form of pellets.
  • the olefin resin molded article of the present invention having excellent surface coating properties can be obtained by molding the above olefin resin composition according to a conventional method.
  • the molding method include any of known molding methods such as injection molding, hollow molding, extrusion molding, compression molding, and rotational molding. A method may be used, and an arbitrary molded body can be obtained.
  • the application of the paint can be carried out directly on the surface of the above-mentioned molded body or, if necessary, after performing a degreasing treatment such as washing with warm water and a Z or primer treatment.
  • the method of applying the paint may be in accordance with a conventional method. For example, a method such as static turtle painting, spraying (air blow) painting, brush painting, or roller painting is used.
  • the application of the paint may be performed by a method of applying an undercoat and then applying an overcoat. After applying the paint, a method of heating and hardening by chrome wire, infrared ray, high frequency (UHF), etc. is adopted, but the method is appropriately selected depending on the material and shape of the base material surface, the properties of the paint used, etc. .
  • the paint to be applied is not particularly limited as long as it is a paint generally used in industry.
  • solvent-based thermoplastic (meth) acrylic paint solvent-based thermosetting (meth) acrylic paint, polyurethane-based paint And acrylic urethane-based paints, silicon-modified urethane-based paints, melamine-based paints, epoxy-based paints, acrylic-modified alkyd-based paints, amine alkyd-based paints, alkyd melamine-based paints, and polyethermelamine-based paints.
  • polyurethane paints acrylic urethane paints, epoxy paints, alkyd melamine paints, polyether melamine paints, and the like are preferable, and polyurethane paints and polyether melamine paints are particularly preferable.
  • the thickness of the coating film is appropriately selected according to the purpose of use of the molded body, but after drying, it is usually 1-1,000 Atm, preferably 5-500 Atm, more preferably 10-500 Atm. 2200 m.
  • the resin-based resin molded body thus painted is used for exterior parts such as automobile bumpers, corners, bumper air dam skirts, mat guards, side moldings, wheel caps, boilers, side steps, and door-mirror bases. It can be used as daily necessities such as electric appliances such as cap plugs, pots, refrigerators, lighting equipment, audio equipment, OA equipment, color boxes, and storage cases.
  • the measurement of physical properties was based on the following methods.
  • the weight average molecular weight of the polyester was calculated as a standard polystyrene equivalent amount according to the GPC method.
  • the hydroxyl value and the acid value of the polyester were measured in accordance with the "Standard Fat and Oil Analysis Test Method" (Japan Oil Chemical Association).
  • the softening point of the polyester was measured according to JIS K2207-1980.
  • the flexural modulus was measured and evaluated at a measurement temperature of 23 according to the method specified in AST D 790.
  • Izod impact strength was measured at a measurement temperature of 130 and evaluated according to the method specified in ASTM D256 (with notch).
  • a cross-cut test piece was prepared, a cellophane tape (manufactured by Nichiban Co., Ltd.) was stuck on the cross-cut, and this was quickly turned in the 90 ° direction. The number of grids that were not peeled out of the 100 grids was measured.
  • the obtained polyester 1 had a weight average molecular weight (Mw) of 7130, an acid value of 0.15 mg OH / g, a hydroxyl value of 93.5 mgKOH / g, and a softening point of 89.
  • the obtained polyester 2 had a weight average molecular weight (Mw) of 6830, an acid value of 0.15 mg KOHZg, a hydroxyl value of 83.2 mg KO HZ g and a softening point of 76.
  • the obtained polyester 3 had a weight average molecular weight (Mw) of 18500, an acid value of 0.1 SmgKOHZg, a hydroxyl value of 83.2 mg KOHZg, and a softening point of 86. '
  • the obtained polyester 5 had a weight-average molecular weight (Mw) of 950, an acid value of 0.1 SmgKOHZg, and a hydroxyl value of 79.4 mg KOHZ.
  • the obtained polyester 6 had a weight average molecular weight (Mw) of 2,500, an acid value of 0.2 mg KOHZg, and a hydroxyl value of 89.5 mg KOHZg.
  • the mixture was stirred while introducing nitrogen gas, and the temperature was raised to 100. Subsequently, the temperature was raised from 100 to 240 over 6 hours while removing water and unreacted diol generated during the reaction. Thereafter, the reaction was carried out for 10 hours while dehydrating at 240, and the reaction was further conducted for 3 hours while dehydrating under a reduced pressure of 240 "CX 10 OmmHg.
  • the obtained polyester 7 had a weight average molecular weight (Mw). ) 3 0 5 6 0, acid The value was 0.1 mg KOHZg and the hydroxyl value was 91.3 mg KO HZ g.
  • the mixture was stirred while introducing nitrogen gas, and the temperature was increased to 100. Subsequently, the temperature was raised from 100 to 240 over 6 hours while removing water and unreacted diol formed during the reaction. Thereafter, the reaction was performed for 10 hours while dehydrating at 240, and the reaction was continued for 3 hours while dehydrating under a reduced pressure of 240 * X10 OmmHg.
  • the obtained polyester 8 had a weight average molecular weight (Mw) of 13,700, an acid value of 0.1 mg KOHZg, and a hydroxyl value of 91.3 mg KOH / g.
  • the resin composition was pelletized to prepare an olefin resin composition.
  • the pellet-shaped resin composition was injected using an injection molding machine (F85, manufactured by Crocna Co.) at a mold temperature of 40, a nozzle temperature of 21 O, an injection pressure of 500 kg / cm2, and a holding pressure of 400 kg. Under the condition of / cm2, a test piece having a size of 150 ⁇ 150 mm and a thickness of 2.4 mm was formed.
  • a primer (RB-197; manufactured by Nippon Bee Chemical Co., Ltd.) was applied to the surface of the test piece so as to have a film thickness of 10 m, dried at 80 at 10 minutes, and then a urethane-based metallic paint was applied to the primer surface.
  • urethane clear paint (RB-288; Nippon Bi-Chemical Co., Ltd.) were adjusted based on the specifications of Nippon Bee Chemical Co., Ltd. It was applied to two layers to a thickness of 25 m, dried at 80 at 45 minutes, and then allowed to stand for 24 hours.
  • Each property test was performed using the obtained test pieces and the results were WO 97 / 3 ⁇ > 57 PCT / JP97 / 01314
  • Examples of the present invention using a polyester having a large molecular weight and a high hydroxyl group produced by adding a trivalent component (a trivalent carboxylic acid and / or a trihydric alcohol) It can be seen that the mechanical strength, impact resistance, and coating properties (coating strength / solvent resistance) are all well-balanced.
  • a polyester composed of a polyvalent carboxylic acid binding unit containing an aromatic dicarboxylic acid as a main component and a polyhydric alcohol binding unit containing a polyhydric binder resin as a main component is used, impact resistance is reduced. It can be seen that the properties such as mechanical strength, coating film strength and solvent resistance are highly balanced (Examples 1 to 3).
  • the mechanical strength of the olefin resin molded article composed of the olefin resin and rubber, the properties of the coating film formed on the surface thereof without impairing the impact resistance (the coating film strength and the solvent resistance) ) can be greatly improved.
  • the olefin resin composition of the present invention has an effect of improving the adhesive properties and printability in addition to the improvement of the coating properties on the surface of the olefin resin molded product, and can widely improve the surface properties of the base material. Things.
  • the olefin resin composition and the olefin resin molded article of the present invention make use of these characteristics to make use of these properties, such as parts for electric, electronic, and automobile, packaging materials, and containers for beverages and cosmetics.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Cette invention concerne une composition de résine à base d'oléfine, laquelle comprend (a) une résine à base d'oléfine, (b) un caoutchouc, et (c) un polyester possédant une valeur hydroxyle au moins égale à 30 mg KOH/g. Cette invention concerne également des articles moulés obtenus par le moulage de ladite composition. Il est possible de former, à la surface de ces articles moulés, un revêtement possédant d'excellentes qualités de résistance aux contraintes et aux solvants, tout en conservant une bonne résistance mécanique et une bonne résistance aux impacts.
PCT/JP1997/001314 1996-04-16 1997-04-16 Composition de resine a base d'olefine et articles moules Ceased WO1997039057A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11848996A JP3736582B2 (ja) 1996-04-16 1996-04-16 オレフィン系樹脂組成物
JP8/118489 1996-04-16

Publications (1)

Publication Number Publication Date
WO1997039057A1 true WO1997039057A1 (fr) 1997-10-23

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WO (1) WO1997039057A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112703236A (zh) * 2018-09-27 2021-04-23 日本瑞翁株式会社 热熔性黏合剂组合物

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4785228B2 (ja) * 2000-04-21 2011-10-05 株式会社Ａｄｅｋａ 繊維用ポリオレフィン樹脂組成物
JP4581420B2 (ja) * 2004-02-17 2010-11-17 東ソー株式会社 樹脂組成物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04202249A (ja) * 1990-11-29 1992-07-23 Toyoda Gosei Co Ltd ポリプロピレン樹脂組成物
JPH05320433A (ja) * 1992-05-18 1993-12-03 Mitsubishi Petrochem Co Ltd 熱可塑性樹脂組成物
JPH0632951A (ja) * 1992-07-15 1994-02-08 Sumitomo Chem Co Ltd 熱可塑性樹脂組成物およびその射出成形体
JPH08217864A (ja) * 1995-02-16 1996-08-27 Nippon Zeon Co Ltd ポリエステル

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04202249A (ja) * 1990-11-29 1992-07-23 Toyoda Gosei Co Ltd ポリプロピレン樹脂組成物
JPH05320433A (ja) * 1992-05-18 1993-12-03 Mitsubishi Petrochem Co Ltd 熱可塑性樹脂組成物
JPH0632951A (ja) * 1992-07-15 1994-02-08 Sumitomo Chem Co Ltd 熱可塑性樹脂組成物およびその射出成形体
JPH08217864A (ja) * 1995-02-16 1996-08-27 Nippon Zeon Co Ltd ポリエステル

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112703236A (zh) * 2018-09-27 2021-04-23 日本瑞翁株式会社 热熔性黏合剂组合物

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JP3736582B2 (ja) 2006-01-18
JPH09278948A (ja) 1997-10-28

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