WO2003002655A1 - Composition de resine olefinique pour moulage a partir de poudres, et procede de production associe - Google Patents

Composition de resine olefinique pour moulage a partir de poudres, et procede de production associe Download PDF

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Publication number
WO2003002655A1
WO2003002655A1 PCT/JP2002/006602 JP0206602W WO03002655A1 WO 2003002655 A1 WO2003002655 A1 WO 2003002655A1 JP 0206602 W JP0206602 W JP 0206602W WO 03002655 A1 WO03002655 A1 WO 03002655A1
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Prior art keywords
weight
resin composition
parts
vinyl compound
aromatic vinyl
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PCT/JP2002/006602
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English (en)
Japanese (ja)
Inventor
Seiki Yada
Shiniti Yoshikawa
Koichi Yanai
Manabu Ogiwara
Satoshi Iwabuchi
Toshiya Kobayashi
Original Assignee
Zeon Corporation
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Priority claimed from JP2001198109A external-priority patent/JP2003011121A/ja
Priority claimed from JP2001366915A external-priority patent/JP3994725B2/ja
Priority claimed from JP2001399439A external-priority patent/JP3961284B2/ja
Priority claimed from JP2001399440A external-priority patent/JP3961285B2/ja
Priority claimed from JP2001399125A external-priority patent/JP3989726B2/ja
Priority claimed from JP2002024430A external-priority patent/JP3998989B2/ja
Priority claimed from JP2002091952A external-priority patent/JP3994776B2/ja
Application filed by Zeon Corporation filed Critical Zeon Corporation
Publication of WO2003002655A1 publication Critical patent/WO2003002655A1/fr

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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
    • C08L23/10—Homopolymers or copolymers of propene
    • 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—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a powdery resin-based resin composition and a method for producing the same. More specifically, it contains a hydride of a polypropylene resin, a thermoplastic resin elastomer, and a hydride of an aromatic vinyl compound and a conjugated gen copolymer, and has excellent heat resistance, bending resistance and abrasion resistance.
  • the present invention relates to a powdery molded refin-based resin composition which gives a molded article and is easy to prepare, and a method for producing the composition. Background art
  • Soft vinyl chloride resin has often been used as a skin material for interior parts such as instrument panels, console boxes, door trims, and glove boxes for automobiles. Refined resin materials that do not generate hydrogen chloride and that can be easily recycled are being used. Therefore, many refining-based resin compositions have been proposed as powder molding materials (for example, JP-A-5-11883, JP-A-5-5500, JP-A-6-17).
  • molded articles obtained from these proposed powdery refin-based resin compositions generally have poor light resistance, and are not as flexible as conventional soft vinyl chloride resins, and a softener is added. Then, there was a problem that bleeding occurred on the surface of the molded product and it became sticky.
  • Polystyrene block, B: polybutadiene block) hydride (SEBS) was found to be suitable as a powder molding material for the skin of automobile interior materials (Japanese Patent Laid-Open No. 5-27979). No. 484).
  • molded articles using the above hydride (SEBS) have sufficient heat resistance.
  • an object of the present invention is to provide a molded product that is easy to produce, has excellent creasing resistance during demolding in powder molding, and provides a molded product having improved heat resistance.
  • An object of the present invention is to provide a refining resin composition.
  • ( ⁇ ) (a) 20 to 80 parts by weight of a polypropylene resin, and (b) 80 to 20 parts by weight of a refining thermoplastic elastomer (where (a) and (b) Is a total of 100 parts by weight.) 20 to 80 parts by weight of a polypropylene resin composition comprising: and (2) a hydride of an aromatic vinyl compound-conjugated gen copolymer of 80 to 2 parts by weight.
  • a refin-based resin composition for powder molding comprising 0 parts by weight (the total of (1) and (2) is 100 parts by weight).
  • FIG. 1 is a flow chart showing a process for producing a powdery resin-based resin composition of the present invention.
  • the powdery resin composition for powder molding of the present invention comprises a polypropylene resin composition (1) comprising a polypropylene resin (a) and a polypropylene resin (b) and an aromatic vinyl compound-conjugated gen. It contains a polymer hydride (2).
  • the polypropylene resin used in the present invention is a propylene homopolymer (crystalline) or a copolymer of 50% by weight or more of propylene and another ⁇ -lefin having 2 to 12 carbon atoms.
  • copolymers of propylene with other a-olefins having 2 to 12 carbon atoms include random copolymers, alternating copolymers, and linear and radial block copolymers.
  • These polypropylene resins are usually produced by polymerization using a Cidara-Natta catalyst or the like. Examples of the above ⁇ -refined copolymerized with propylene include ethylene, butene-1,4-methyl-pentene-1, and octene-1.
  • the melt flow rate (hereinafter referred to as MFR) of the polypropylene resin is not particularly limited, but the MFR according to JISK7210 (load 2.16 k, measurement temperature 230 ° C) is 5 g / 10 min. Those having an MFR of 20 gZl 0 min or more are more preferable. If the MFR of the polypropylene resin is too small, the meltability is poor and pinholes are likely to occur in the molded product.
  • the olefin-based thermoplastic elastomer used in the present invention is usually called TPO or TPE.
  • TPO olefin-based thermoplastic elastomer
  • EPR ethylene-propylene copolymer rubber
  • EPDM ethylene-propylene-non-conjugated gen monomer
  • PP or PP / PE polyethylene
  • the ratio of the ethylene / propylene copolymer block component (EPR component) to the polypropylene block component (PP component) is 1 to 40%. %, Preferably 5 to 20% by weight, and the EPR component is 60 to 99% by weight, preferably 80 to 95% by weight.
  • the EPR component is composed of a random copolymer of ethylene and propylene, and usually has a proportion of monomer units based on ethylene of 10 to 40 mol%, preferably 15 to 35 mol%.
  • the molecular weight of the propylene-based block copolymer is 13 to 35 ° C and the intrinsic viscosity measured in a tetralin solvent is 6 to 30 dI 7 g, preferably 10 to 20 dI Zg. Equivalent to. If the intrinsic viscosity of the propylene-based block copolymer is less than 6 dl / g, the elastic recovery property is impaired, and if it exceeds 30 dl / g, the melt fluidity decreases and the molding of the resin composition becomes extremely difficult. .
  • Examples of the hydrogenated aromatic vinyl compound-conjugated gen copolymer used in the present invention include at least one aromatic vinyl compound such as styrene, a-methylstyrene, and vinyltoluene, butadiene, isoprene, 1,3- Examples thereof include those obtained by hydrogenating a conjugated gen unit of a random copolymer or a block copolymer obtained by random or block copolymerization of at least one kind of a syngene such as pen-yen. Especially preferred are hydrogenated block copolymers.
  • the random copolymer is styrene-butadiene copolymer rubber (SBR), and the block copolymer is an ABA-type linear and radial block copolymer (A is a polystyrene block, B is a polygenoblock or polyisoprene copolymer). Block) is preferred.
  • the above hydrogenated block copolymer is SEBS, SEPS (S: polystyrene, E: polyethylene, B: poly). Ributylene, P: polypropylene) is usually called.
  • SEPS polystyrene
  • E polyethylene
  • B poly
  • Ributylene, P polypropylene
  • These hydrides are usually those obtained by hydrogenating at least 80 mol%, preferably at least 90 mol%, more preferably at least 95 mol% of the unsaturated double bonds in the polymer chain. .
  • the content of the aromatic vinyl compound unit in the hydride of the aromatic vinyl compound-conjugated gen copolymer (hereinafter, sometimes referred to as the amount of bound aromatic vinyl) is usually from 5 to 50% by weight, preferably from 5 to 50% by weight. It is 10 to 30% by weight. If the amount of bound aromatic vinyl is too small, blocking tends to occur during powder molding. Conversely, if it is too large, the hardness of the molded article increases.
  • a hydride of an aromatic vinyl compound-conjugated gen copolymer one having a relatively high content of an aromatic vinyl compound unit and one having a relatively low content of an aromatic vinyl compound unit can be used in combination.
  • a combination not only good creasing resistance and heat resistance at the time of demolding as described above, but also powder characteristics such as anti-blocking property at the time of storage are improved, and Thus, a refining-based resin composition for powder molding capable of producing a molded article having wear resistance is obtained.
  • the content of the aromatic vinyl compound unit is 20 to 80% by weight, It is preferred to mix 25 to 70% by weight with 5% to less than 20% by weight, preferably 10 to 18% by weight.
  • the mixing ratio of the two is usually 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 40 to 100% by weight (content of aromatic vinyl compound unit: 20 to 80% by weight).
  • the latter content of the aromatic vinyl compound unit: 5% by weight or more and less than 20% by weight
  • the polypropylene resin composition (1) in the powder-refined refin-based resin composition of the present invention comprises: (a) 20 to 80 parts by weight, preferably 30 to 70 parts by weight of a polypropylene resin, and (b) ) Refined thermoplastic elastomer 80 to 20 parts by weight, preferred Or 70 to 30 parts by weight (however, the total of (a) and (b) is 100 parts by weight). If the amount of the polypropylene resin is too small, the heat resistance is reduced, and if the amount is too large, folding wrinkles are likely to occur when the mold is removed.
  • (1) is 20 to 80 parts by weight, preferably 30 to 70 parts by weight.
  • (2) is 80 to 20 parts by weight, preferably 70 to 30 parts by weight, more preferably 60 to 40 parts by weight (provided that (1) and (The total of (2) is 100 parts by weight.) If the amount of the polypropylene resin composition (1) is too small, the meltability decreases. On the other hand, if the amount is too large, wrinkling tends to occur, and the molded article has poor scratch resistance.
  • the powdery resin composition for powder molding according to the present invention is a polypropylene resin composition comprising a polypropylene resin (a) and a polypropylene resin (b).
  • Typical additional components (3) can be contained in addition to (1) and a hydride of an aromatic vinyl compound-conjugated gen copolymer (2).
  • Typical additional components (3) are (3-1) fatty acid amide, (3-2) average number of hydroxyl groups per molecule is 1 to 8, and number average molecular weight is 500 to 20.
  • the creasing resistance during demolding in powder molding and the heat resistance of the molded article are improved.
  • the wear resistance of the molded body at room temperature and high temperature is improved.
  • the fatty acid amide used is not particularly limited, but usually includes primary fatty acid amides and bis fatty acid amides, which are derivatives of higher fatty acids having 7 or more carbon atoms.
  • Higher fatty acids include saturated and unsaturated fatty acids. Examples of the saturated higher fatty acids include caprylic acid, lauric acid, tridecylic acid, penicillic acid, palmitic acid, stearic acid, araquinic acid, and lignoceric acid. Examples of the unsaturated fatty acids include pendecylic acid, oleic acid, elaidic acid, sorbic acid, and linoleic acid.
  • fatty acid amide examples include stearamide, peroxy amide, palmito amide, coconut fatty acid amide, methylene bis-stearamide, ethylene bis-stearamide, and ethylenediamine of xistearic acid. These can be used alone or in combination of two or more. Among these fatty acid amides, unsaturated fatty acid amides are preferred. Taylor amide is particularly preferred.
  • the amount of the fatty acid amide is 1 to 20 parts by weight based on 100 parts by weight of the total of the polypropylene resin composition (1) and the hydride (2) of the aromatic vinyl compound-conjugated gen copolymer. preferable. If the amount of the fatty acid amide is too small, the wear resistance of the molded article at high temperatures (about 60 ° C) is not improved, and if it is excessively large, the molded article is liable to be spread on the surface of the molded article. However, for example, when used for interior parts such as those for instrument panels for automobiles, the adhesiveness with polyurethane foam may be reduced.
  • the crease resistance at the time of demolding during powder molding and the heat resistance of the molded body are improved.
  • the abrasion resistance is improved, and the adhesion of the molded body to the polyurethane foam is improved.
  • the hydroxyl group-containing hydrocarbon polymer used herein has an average number of hydroxyl groups per molecule (hereinafter referred to as “number of hydroxyl groups”) of 1 to 8 in the molecule, and has a number average molecular weight of 50.
  • the method for producing such a hydroxyl group-containing hydrocarbon polymer is not particularly limited.For example, various vinyl monomers and gen monomers are polymerized by polymerization methods such as radical polymerization, anion polymerization, and force polymerization.
  • a method in which a terminal is hydroxylated and hydrogenation is carried out by a known method as necessary.
  • Other methods include oxidative decomposition of an isobutylene-monomer copolymer, or a non-conjugated gen (or conjugated gen) copolymer, such as ethylene or propylene, and then reducing it.
  • a hydrogenated product of a hydroxyl group-containing gen-based polymer is preferable.
  • a hydrogenated double bond of a polybutadiene polyol having a hydroxyl group at both terminals is preferable.
  • the hydroxyl group-containing gen-based polymer can be obtained from a conjugated gen or a conjugated gen and a vinyl monomer by a known method, for example, radical polymerization, anion polymerization or the like.
  • radical polymerization a conjugated diene polymer or copolymer having a hydroxyl group at the terminal of the produced polymer can be directly obtained by polymerizing hydrogen peroxide as a polymerization initiator.
  • an anion polymerization catalyst is used to polymerize, for example, a living polymer to which an alkali metal is bonded, and then a lipopolymer is reacted with a monoepoxy compound, formaldehyde, etc., and then hydrolyzed.
  • a polymer having a hydroxyl group examples include 1,3-butadiene, isoprene, and chloroprene. Among them, 1,3-butadiene is preferable.
  • copolymerization component examples include styrene, acrylonitrile, methyl acrylate, methyl methacrylate, and vinyl acetate such as vinyl acetate.
  • the use amount of the copolymer component is preferably 30% by weight or less of the total amount of the monomers.
  • the hydride of the hydroxyl group-containing gen-based polymer can be obtained by a conventional method under hydrogen pressure using a hydrogenation catalyst such as nickel, cobalt, platinum, palladium, ruthenium, and rhodium alone or using a carrier supported on a carrier. It is produced by hydrogenation in At this time, in order to obtain sufficient adhesion and weather resistance between the molded article and the polyurethane foam, the double bond contained in the hydroxyl group-containing gen-based polymer has an iodine value of 100 or less, preferably 500 or less.
  • the hydrogenation is carried out below, more preferably to 20 or less.
  • the above hydroxyl group-containing hydrocarbon polymer is commercially available (Polytail (low molecular weight polyolefin polyol) manufactured by Mitsubishi Chemical Corporation) and is available.
  • the amount of the above-mentioned hydroxyl group-containing hydrocarbon-based polymer is 1 to 100 parts by weight based on a total of 100 parts by weight of the polypropylene resin composition (1) and the hydride of the aromatic vinyl compound-conjugated gen copolymer (2). 20 parts by weight is preferred. The content is more preferably 2 to 10 parts by weight. If the amount is too small, the adhesiveness between the molded article and the polyurethane foam is insufficient, while if it is too large, the molded article surface is pre-deposited depending on the molecular weight of the hydroxyl-containing hydrocarbon polymer. There is fear.
  • the powdery molded refin-based resin composition of the present invention contains, in order to enhance the adhesiveness between the molded article and the polyurethane foam, It is preferable to add a catalyst that promotes the reaction with the isocyanate compound in the foam-forming raw material liquid.
  • a catalyst that promotes the reaction with the isocyanate compound in the foam-forming raw material liquid.
  • organic tin compounds such as dibutyltin dilaurate and dibutyltin distearate
  • tertiary amines such as tetraalkylethylenediamine and N, N'-dialkylbenzylamine.
  • the modified refin-based resin composition for powder molding of the present invention contains a modified silicone oil in addition to the above-mentioned hydroxyl-containing hydrocarbon polymer (3-2).
  • the modified silicone oil used here is a silicone oil in which a functional group has been introduced into polysiloxane, and is roughly classified into four types: those in which the functional group has been introduced into the side chain, both ends, both the side chain and both ends, and one end. Is done. Both terminal introduction type is preferable.
  • Specific examples of the functional group include a carboxyl group, a hydroxyl group, a mercapto group, an amino group, an epoxy group, and an unsaturated bond (such as an acryloyloxy group, a methacryloyloxy group, and a vinyl group).
  • Preferred functional groups are those having active hydrogen reactive with the isocyanate as the raw material of the polyurethane foam, and include a hydroxyl group, an acryloyloxy group and a methacryloyloxy group.
  • the molecular weight of the oil is not particularly limited. It has a molecular weight of about 1,000 to about 30,000 °.
  • Various modified silicone oils are commercially available. The chemical structures of typical modified silicone oils are shown by general formulas (1) to (4), but are not limited thereto. And l. CH3 CH3 CH3
  • the amount of modified silicone oil such as C 3 H 6 SH is a polypropylene resin composition (1) and the aromatic vinyl-compound - conjugated diene copolymer hydrides (2) and the hydroxyl group-containing hydrocarbon
  • the amount is usually 10 parts by weight or less, preferably 0.5 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight in total with the polymer (3). If the proportion of the modified silicone oil is too small, the effect of improving the abrasion resistance of the molded product is small. Conversely, if the amount is too large, it may bleed on the surface of the molded product, which may reduce the adhesiveness to the polyurethane foam.
  • the polyester (3-3) used here is composed of a polycarboxylic acid component (A) containing cyclohexanedicarboxylic acid or a derivative thereof, and (i) two carbon atoms each having a hydroxyl group bonded thereto.
  • the glass transition temperature of the polyester resin (3-3) is usually 20 ° C or higher, preferably 30 to 100 ° C, more preferably 40 to 80 ° C, and most preferably 50 to 70 ° C.
  • the hydroxyl value is usually in the range of O.I.Z Omg KOH / g, preferably 1 to 10 mg KOHZg, more preferably 2 to 5 mg KOH / g.
  • the number average molecular weight (number average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC)) of this polyester resin is in the range of 7,500 to 100,000, preferably 1 0,000 to 50,000, more preferably ⁇ 2,500-30,000. When the molecular weight is excessively small, the strength characteristics of a molded article using the refin-based resin composition for powder molding of the present invention are reduced. Conversely, if it is too large, the miscibility and dispersibility in the resin composition will decrease.
  • the polycarboxylic acid component (A) used in the synthesis of the polyester resin (3-3) It contains at least cyclohexanedicarboxylic acid or a derivative thereof.
  • cyclohexanedicarboxylic acids include cyclohexanedicyclic acids having a cyclohexane ring as a basic skeleton and a carboxyl group bonded to the 1- and 4-position or 3-position carbons, respectively.
  • Examples of these cyclohexanedicarboxylic acid derivatives include ester compounds and acid halides. Among them, an ester compound is preferable, and a compound having an ester group having an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, amyl, and hexyl, is preferable.
  • cyclohexane-1,4-dicarboxylic acid and 1,3-dicarboxylic acid include cyclohexane-1,4-dicarboxylic acid, 2-methyl-cyclohexane-1,4-dicarboxylic acid, and 2-ethyl-cyclocarboxylic acid.
  • Hexane-1,4-dicarboxylic acid 2-propyl-cyclohexane-1,4-dicarboxylic acid, 2-t-butyl-cyclohexane-1,4-dicarboxylic acid, 2-t-butyl-cyclohexane-1,4 Dicarboxylic acid, 2,3-dimethyl-cyclohexane-1,4-dicarboxylic acid, 2,3-diethylcyclohexane-1,4-dicarboxylic acid, 2,3-dipropylcyclohexane-1,4-dicarboxylic acid, 2 1,3-Dibutyl-cyclohexane-1,4-dicarboxylic acid, 2-methyl-3-ethyl-cyclohexane-1,4-dicarboxylic acid, 2-methyl-3-propyl Chlohexane- ⁇ , 4-dicarboxylic acid, 2-methyl-3-butyl-cyclohexane-1,4-dicar
  • the polycarboxylic acid component may contain other polycarboxylic acids other than the above. Can be.
  • other polycarboxylic acids include aromatic polycarboxylic acids, linear or branched aliphatic polycarboxylic acids, and derivatives thereof.
  • these polycarboxylic acid derivatives include ester compounds and acid halides. Among them, ester compounds are preferred, and those having an ester group having an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, amyl, and hexyl, are preferred.
  • the polyvalent carboxylic acid component may contain a monovalent carboxylic acid or a derivative thereof as long as the effect of the polyester resin is not impaired. 0% by weight or less, preferably 5% by weight or less, more preferably 2% by weight or less.
  • Examples of the monovalent carboxylic acid derivative include the same as the above-mentioned examples of the other polyvalent rubonic acid derivatives.
  • the polyhydric alcohol component (B) used in the synthesis of the polyester resin has (i) a non-hydrogen bonded carbon atom between the two carbon atoms bonded to the hydroxyl groups, respectively. It contains an alkanediol having a molecular structure (hereinafter sometimes referred to as "hindered glycol") and (ii) a polyhydric phenoxy alcohol.
  • hindered glycols include 2,2-dimethyl-1,3-propanediyl, 2,2-getyl-1,3-propanediol, 2,2-dipropyl-1,3,3-propanediyl 2, 2-dibutyl-1,3-propanediol, 2-methyl-2-hexyl-1,3-propanediyl, 2-methyl-2-pentyl-1,3-propanediol, 2-ethyl-2- —Butyl-1,3-propanediol, 2-ethyl-2-pentyl-1,3-propanediol, and the like.
  • 2,2-diethyl-1,3-propanediol, 2,2-dipropyl-1,3-propanediyl, 2,2-dibutyl-1,3-propanediyl, 2-ethyl —2—butyl-1,3-propanediol and 2-methyl-2-pentyl-1,3-propanediol are preferred.
  • polyphenolic alcohol in the polyhydric alcohol component examples include those obtained by the addition reaction of polyhydric phenol and alkylene oxide, Examples include those obtained by modifying a phenolic hydroxyl group in a polyhydric phenol to an alcoholic hydroxyl group via an ether bond.
  • polyvalent phenol examples include divalent phenols such as catechol, resorcinol, hydroquinone, 4-methylpyrocatechol, 4-methylresorcinol, 5-methylresorcinol, and 2-methylhydroquinone; 1,2,3-benzenetriol Trivalent phenols such as 1,2,4-benzenetriol and 1,3,5-benzenetriol; 4,4'-dihydroxydiphenylmethane, 2,2-bis (4'-hydroxyphenyl) Non-condensed polycyclic phenols such as propane (bisphenol A;), 3,4-bis (4'-hydroxyphenyl) hexane, and 4,4 ', 4 triphenylmethanetriol.
  • divalent phenols such as catechol, resorcinol, hydroquinone, 4-methylpyrocatechol, 4-methylresorcinol, 5-methylresorcinol, and 2-methylhydroquinone
  • 1,2,3-benzenetriol Trivalent phenols such as 1,2,4-benzenetriol
  • 2,2-bis (4'-hydroxyphenyl) propane bisphenol A
  • hydroxybiphenyl compounds such as biphenyl 2,4'-diol, biphenyl 2,2'-diol, and biphenyl 2,3'-diol can also be used.
  • alkylene oxide include ethylene oxide and propylene oxide.
  • polyhydric phenolic alcohols include ethylene oxide adducts of 4,4'-dihydroxydiphenylmethane, ethylene adducts of bisphenol A, and ethylene adducts of biphenyl-4,4'-diols. Oxides and the like. Among these, an ethylene oxide adduct of bisphenol A is preferred.
  • the ratio of (i) the hindered glycol and (ii) the polyvalent phenoxy alcohol in the polyhydric alcohol component is usually 80 to 100% by weight, preferably 90 to 100% by weight, and more preferably. Is 95 to 100% by weight.
  • the ratio of (i) hindered glycol to (ii) polyhydric phenoxy alcohol is 5/95 to 50/50 in terms of molar ratio, preferably 793-40 / 60, More preferably, the number is from 100 to 300.
  • the polyhydric alcohol component can contain another polyhydric alcohol, and examples of the specific examples thereof include other alkane diols other than the above-mentioned hindered glycol, cyclohexane diol, aromatic diol, and the like. .
  • the polyhydric alcohol component may contain monohydric alcohol as long as the effects of the present invention are not impaired.
  • the allowable amount is usually 10% by weight or less, preferably at most 10% by weight in the polyhydric alcohol component. It is at most 5% by weight, more preferably at most 3% by weight.
  • the polyester resin (3-3) can be synthesized, for example, by polycondensing a polyvalent carboxylic acid component (A) and a polyvalent alcohol component (B).
  • the polycondensation reaction may be performed according to a conventional method.
  • the reaction temperature is 100 to 300 ° C, preferably 150 to 280 ° C, and more preferably 180 to 230 ° C. ° C.
  • the solvent include water-insoluble organic solvents azeotropic with water, such as toluene and xylene.
  • the pressure of the reaction 0. "! ⁇ 2 0 0 mmH g (1. 3 x 1 0 2 ⁇ 2. 7 x 1 0 5 P a), preferably 0. 5 ⁇ 1 OO mmH g (6. 6 x 10 2 to 1.3 x 10 5 Pa), more preferably 1 to 30 mmHg (1.3 x 10 3 to 4.0 ⁇ 10 4 Pa). It is also possible to carry out the reaction in the presence of an inert gas.
  • esterification catalysts conventionally used, for example, Bronsted acids such as P-toluenesulfonic acid, sulfuric acid, phosphoric acid; calcium acetate, zinc acetate, manganese acetate, zinc stearate, alkyl tin
  • Organic metal compounds such as oxides, dialkyltin oxides, and titanium alkoxides; metal oxides such as tin oxide, antimony oxide, titanium oxide, and vanadium oxide are used.
  • organometallic compounds belonging to Group IV of the periodic table are preferable because the obtained polyester resin has good oxidation stability.
  • the polyester resin is used in an amount of 2 to 30 parts by weight based on a total of 100 parts by weight of the polypropylene resin composition (1) and the hydride (2) of the aromatic vinyl compound-conjugated gen copolymer. Parts, preferably 5 to 20 parts by weight. If the added amount of the polyester resin is too small, the adhesion between the molded article and the polyurethane foam is not sufficiently improved.On the other hand, if the added amount is too large, the adhesion reaches a saturated state, which is uneconomical. There is a possibility that the strength of the molded body is reduced.
  • a catalyst that promotes the reaction with the isocyanate compound in the foam-forming raw material liquid In order to enhance (adhesion), it is preferable to add a catalyst that promotes the reaction with the isocyanate compound in the foam-forming raw material liquid. Specific examples and amounts thereof are as described for the hydroxyl group-containing hydrocarbon polymer (3-2).
  • the refin-based resin composition for powder molding of the present invention is modified to improve the wear resistance and mold releasability of the molded article without deteriorating the adhesiveness between the molded article and the polyurethane foam. It is preferable to add silicone oil.
  • the properties, type and amount of the modified silicone oil used here are as described for the hydroxyl group-containing hydrocarbon polymer (3-2).
  • the hydroxyl group-containing aromatic vinyl compound copolymer (3-4) used here is a copolymer of an aromatic vinyl compound and a hydroxyl group-containing vinyl compound, or an aromatic vinyl compound and a hydroxyl group-containing vinyl compound, and Having a glass transition temperature (T g) of 60 ° C. or higher, preferably 70 to 200 ° C., and an average primary particle It is a powder having a diameter of 0.1 to 10 m, preferably 0.5 to 5 tm.
  • Tg of the hydroxyl group-containing aromatic vinyl compound copolymer (3-4) is excessively low, the improvement in powder fluidity is insufficient. If the Tg is excessively high, the compatibility with the hydride of the polypropylene resin composition or the aromatic vinyl compound-conjugated gen copolymer may be reduced. In addition, T g can be obtained by a differential thermal analyzer (DSC).
  • DSC differential thermal analyzer
  • the powder fluidity may decrease in any case.
  • a suspension in which the hydroxyl group vinyl compound copolymer powder was dispersed in water was prepared, and the suspension was subjected to an oscillation frequency of 50 kHz using an ultrasonic shaker. After shaking for 1 minute, allow to stand for 3 minutes, and then determine the integrated particle size distribution by the centrifugal sedimentation turbidity method.
  • the average primary particle size is represented by the particle size that gives a cumulative value of 50%.
  • the powder of the hydroxyl group-containing aromatic vinyl compound copolymer preferably has spherical particles.
  • the sphericity which is a measure representing a spherical shape, is preferably from 0.7 to 1, and more preferably from 0.8 to 1. If the sphericity is too small, the powder fluidity may decrease.
  • the sphericity is measured by using a transmission electron microscope (SEM) at a magnification of 100, 0 ⁇ 0, and measuring the ratio of the minor axis to the major axis of particles 100, and calculating the additive value. Calculate as the average value.
  • SEM transmission electron microscope
  • the hydroxyl group-containing aromatic vinyl compound copolymer (3-4) contains 99.5 to 10% by weight, preferably 99 to 93% by weight of an aromatic vinyl compound, and has a hydroxyl group-containing vinyl compound content of 0%. It is preferably a copolymer with 5 to 10% by weight, preferably 1 to 7% by weight. If the weight-% of the hydroxyl group-containing vinyl compound is too small, the powder fluidity may be reduced. If the weight-% of the hydroxyl-containing vinyl compound is excessively large, the releasability during powder molding may be reduced.
  • hydroxyl group-containing aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, 8-methylstyrene, p-methylstyrene, t-butylstyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, and vinyl vinyl.
  • examples include toluene. Of these, styrene is preferred.
  • the hydroxyl group-containing vinyl compound is not particularly limited, and examples thereof include a hydroxyl group-containing acrylic ester, a hydroxyl group-containing methacrylic ester, a hydroxyl group-containing vinyl ether, a hydroxyl group-containing vinyl monocarboxylic acid ester, a hydroxyl group-containing vinyl dicarbonate ester, and vinyl alcohol. And the like.
  • hydroxyl group-containing acrylates such as hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyamyl acrylate 2-hydroxydodecyl acrylate, 2-hydroxydodecyl acrylate, etc .
  • Methacrylic acid esters include hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid 2,3-dihydroxypropyl acid, 2-hydroxyamyl methacrylate, 2-hydroxymethyl methacrylate, 2-hydroxydodecyl methacrylate, etc .
  • hydroxyl group-containing vinyl ethers include 2-hydroxypropyl vinyl ether; 2-hydroxybutyl vinyl ether, 2,4, -dihydroxy octyl ether, etc .
  • Examples of hydroxyl group-containing vinyl monocarboxylates hydroxy acetate vinyl, 3-hydroxypropion
  • Other monomer compounds copolymerizable with the aromatic vinyl compound and the hydroxyl group-containing vinyl compound include, but are not particularly limited to, for example, acrylates such as ethyl acrylate; methacrylates such as methyl methacrylate; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and vinylidene cyanide; vinyl monocarboxylic acid esters such as vinyl acetate and vinyl propyl formate; vinyl dicarboxylic acid esters such as monobutyl malate; Vinyl ether compounds such as ter and methyl vinyl ether; functional group-containing acrylates such as butoxysher acrylate and glycidyl acrylate; Estel; Fine vinyl chloride, and the like.
  • acrylates such as ethyl acrylate
  • methacrylates such as methyl methacrylate
  • Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and vinylidene cyanide
  • copolymerization of acrylate or methacrylate is preferred because it tends to increase the compatibility with the polypropylene resin and the olefin-based thermoplastic elastomer.
  • These other monomer compounds are used in an amount of less than 40% by weight, preferably less than 30% by weight of the total monomers constituting the hydroxyl group-containing aromatic vinyl compound copolymer (3-4). be able to.
  • the hydroxyl group-containing aromatic vinyl compound copolymer (3-4) is a total of 100% of the propylene resin composition (1) and the hydride (2) of the aromatic vinyl compound-conjugated gen copolymer.
  • the method for producing the hydroxyl-containing aromatic vinyl compound copolymer (3-4) is not particularly limited, but is usually an emulsion polymerization method (including a seeded emulsion polymerization method) or a fine suspension polymerization method (a seeded fine suspension polymerization method). ).
  • Other ingredients including a seeded emulsion polymerization method) or a fine suspension polymerization method (a seeded fine suspension polymerization method).
  • additives can be added to the powdery refin-based resin composition of the present invention, if desired.
  • metal stones such as barium stearate, calcium stearate, magnesium stearate, zinc stearate, and aluminum stearate, and polyvalent are used to improve releasability during molding and prevent blocking during storage.
  • Fatty acid esters of alcohols can be added.
  • various known stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, pigments, and the like can be added.
  • a known plasticizer can be added as long as it is not sticky or does not impair moldability.
  • a polymer other than the above-mentioned polymer components can be used in combination as long as the gist of the present invention is not impaired.
  • a polymer include acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-styrene resin (AS resin), ethylene vinyl acetate resin (EVA resin), norbornene resin, and polyamide resin.
  • ABS resin acrylonitrile-butadiene-styrene resin
  • AS resin acrylonitrile-styrene resin
  • EVA resin ethylene vinyl acetate resin
  • norbornene resin norbornene resin
  • polyamide resin polyamide resin.
  • Resins polyester resins, polycarbonate resins, polybutadiene resins, and the like.
  • an aromatic vinyl compound such as styrene and an ⁇ -olefin such as ethylene and propylene are disclosed in JP-A-3-7705, JP-A-7-72023 and JP
  • the amount of these other polymers used is in the range of 40% by weight or less, preferably 30% by weight or less in the resin composition of the present invention.
  • the method for producing the refin-based resin composition for powder molding of the present invention is not particularly limited as long as each polymer component is contained in the above ratio. Further, the form and shape of each polymer component used are not particularly limited.
  • a production method for example, all the polymer components including the polypropylene resin composition (1) and the hydride of the aromatic vinyl compound-conjugated gen copolymer (2) are put into a mixer at once and mixed.
  • the polypropylene resin composition (1) is prepared using a conventional mixer such as a roll, a single-screw or twin-screw extruder, a Banbury mixer, a kneader, etc.
  • the combined hydride (2) is mixed in the same manner as above. And a method of manufacturing them in combination.
  • the resin composition for powder molding of the present invention is used in a powder form.
  • a conventionally known pulverizer such as a turbo mill, a roller mill, a pole mill, a centrifugal pulverizer, and a pulverizer is used.
  • the particle size of the powder is usually in the range of ⁇ 0 to 500 ⁇ m, preferably 50 to 500 ⁇ , more preferably 100 to 300 m. If the average particle size is too small, the efficiency of the pulverization process is low, and coagulation and shrinkage occur during storage.On the other hand, if the average particle size is too large, the texture of the molded product becomes rough, and pinholes occur in the case of a thin molded product. It will be easier.
  • a method including the following steps, that is, Optionally blended with a polypropylene resin composition (1) consisting of a polypropylene resin and a thermoplastic resin (1), and a hydrogenated aromatic vinyl compound-conjugated gen copolymer (2)
  • a production method comprising the steps of kneading other components to obtain a kneaded resin, preparing a pellet of the kneaded resin, and continuously cooling and pulverizing the pellet is preferred.
  • Polypropylene resin composition (1) comprising a polypropylene resin and a refining thermoplastic elastomer, a hydride of an aromatic vinyl compound-conjugated gen copolymer (2), and other optional components
  • a kneading apparatus generally used for production of a thermoplastic resin composition.
  • the kneading apparatus is not particularly limited, but usually includes a single-screw or twin-screw extruder. Banbury mixers and rolls can also be used.
  • the extruder is capable of extruding from a strand die by melt-kneading a thermoplastic resin fed from a hopper together with various components to be mixed as required.
  • various components can be added from an inlet provided in the middle of the cylinder of the extruder as needed.
  • a gear pump can be installed between the strand die and cylinder.
  • a pelletizer generally used in the production of a thermoplastic resin composition is used, and the average particle diameter is 0.5 to 1 Omm, preferably 0.5 to 10 mm. A pellet of about 5 mm is prepared. If the average particle size of the pellets is too small, efficient production is difficult. Further, when the average particle diameter of the pellets is excessively large, the efficiency of cooling the resin composition is low.
  • the pelletizer is not particularly limited, and includes, for example, an underwater cutter pelletizer, a strand pelletizer, a hot cutter pelletizer, a sheet pelletizer, and the like.
  • the underwater cut pelletizer or the strand pelletizer is used in combination with the resin composition strand discharged from the extruder to adjust the melting temperature of the resin component.
  • the pellets can be continuously cooled from the temperature to around room temperature.
  • a plurality of divided rooms arranged in series are provided in a direction in which the thermoplastic resin composition passes, as a cooling device, and the inlet side to the outlet side It is preferable to use a system in which the resin composition to be conveyed to the room is gradually cooled as it passes through each of the divided rooms.
  • the number of the plurality of divided rooms provided in the cooling device is appropriately determined according to the type and amount of the resin composition, but practically, it is preferable to cool the cooling device by dividing into two or three chambers. .
  • the method of cooling the resin composition is not particularly limited.
  • a method of generating cold air by a refrigerator using an ammonia refrigerant and spraying the same onto the resin is preferable.
  • the resin composition is continuously passed through a cooling device using a belt conveyor or the like.
  • the resin composition is exposed to cold air from above and below.
  • the belt conveyor is preferably made of a metal net.
  • the resin composition is preferably cooled to a temperature lower than its glass transition temperature (Tg).
  • Tg glass transition temperature
  • the composition contains a plurality of thermoplastic resins and the respective glass transition temperatures are observed, it is preferable to cool to a temperature lower than the lowest glass transition temperature among these.
  • the solidification temperature of a plasticizer, a softener, or the like is lower than the glass transition temperature of the thermoplastic resin, it is preferable to cool at a temperature lower than the solidification temperature.
  • the measurement of the glass transition temperature was performed. The determination method is performed using a differential thermal analyzer, a dynamic viscoelasticity meter, or the like.
  • the resin composition pellets cooled as described above are pulverized by a pulverizer.
  • the crusher to be used is not particularly limited, and for example, a crusher such as a turbo mill, a hammer mill, a roller mill, a ball mill, a centrifugal crusher, and a pulverizer can be used. Further, in order to remove heat generated when the resin is crushed, the crusher is preferably provided with a cooling device.
  • the pulverized resin composition is classified into a predetermined particle size. That is, those having a particle size smaller than a predetermined value and those having a larger particle size are separated through a classification screen having an appropriate size, and those having a particle size larger than the predetermined value are returned to the pulverizer again. If necessary, particles having a predetermined particle size or less are classified and removed by a cyclone or the like.
  • the particles are usually prepared into particles having an average particle diameter of 10 to 500 im, preferably 50 to 500 m, more preferably 100 to 300 x m. If the average particle diameter is too small, the efficiency of the pulverizing process is low and the particles tend to agglomerate during storage.On the other hand, if the average particle diameter is too large, the texture of the molded product is rough. Holes are likely to occur.
  • a dusting agent to the powder obtained after the step of pulverizing or after the step of further classifying the pulverized product using a suitable stirrer.
  • a dusting agent an organic or inorganic fine powder having a glass transition temperature or a melting point higher than room temperature is preferably used.
  • the average particle size of the fine powder is smaller than the average particle size of the powdery resin composition described above, and is preferably one tenth or less of the average particle size of the powdery resin composition.
  • Specific examples of the dusting agent include, as an organic material, plastic fine particles of 10 m or less and a fine powder of a polyolefin resin obtained by an emulsion polymerization or a micro-suspension polymerization method. Examples include talc, silicon oxide, and alumina oxide.
  • the amount of the dusting agent is usually in the range of 0.01 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the resin composition. If the added amount is too small, the effect of improving powder fluidity cannot be obtained, while if the added amount is too large, the physical properties of the molded product obtained by molding are impaired, and the moldability is deteriorated. Inconvenience that is damaged Often.
  • the agitator is not particularly limited, and various types such as a Henschel mixer, a Ripon blender, and a tumbler mixer can be used.
  • the particles of the resin composition obtained by freezing and pulverization often absorb moisture in the atmosphere, and include water used for cooling the pellets produced by a kneading apparatus and a pelletizer. Therefore, it is preferable to use a stirrer having a self-heating function by external heating or stirring. It is also possible to add a required amount of a release agent in order to make it easier to remove a molded product obtained by performing powder molding using the resin composition from a mold.
  • the classification step and the stirring step may be performed either continuously or separately.
  • particles of the resin composition having a predetermined average particle diameter obtained in the classification step are stored in a tank or the like, and then transferred to the stirring step.
  • the resin is compounded as necessary. Melt kneading together with the various components to be extruded from a strand die, and then, in a step of preparing a pellet of the resin composition, the strand has an average particle diameter of about 0.5 to 10 mm by a die pelletizer.
  • the pellet is cooled at a temperature lower than the glass transition temperature of the resin composition, and then pulverized.
  • the particles of the pulverized resin composition are subjected to a step of classifying the particles so that the average particle diameter becomes 10 to 500 m, and a step of blending a dusting agent with the particles to obtain powder.
  • a resin composition suitable for molding can be produced.
  • an apparatus for producing a resin composition for powder molding comprising a kneader, a pelletizer and a cooling pulverizer is used. It is preferable to provide a classifier for classifying the pulverized resin composition to a predetermined particle size, and a stirrer for mixing the resin composition and the dusting agent.
  • FIG. 1 is a flow chart showing an example of a production process of the powdery refin-based resin composition of the present invention.
  • the polymer component (1) the polymer component (1),
  • the method further includes a classifying step having a classifier 25 having a screen of 80 mesh, and a step 6 of mixing a dusting agent into the resin powder using a Henschel mixer 26.
  • SEBS styrene-ethylene-butadiene-styrene block copolymer
  • SEBS styrene-ethylene-butadiene-styrene block copolymer
  • the pellets were conveyed to a dehydrator 14 by a pump 13 and dehydrated. Then, it is supplied to the inlet 19 of the cooler 15, placed on the wire mesh belt conveyor 20, and circulated through the cool unit C 1 at first to cool air cooled to 50 ° C. After passing through a certain pre-cooling chamber 21 and then passing through a main cooling chamber 22 in which cold air cooled to 90 ° C. by the cooling unit C 2 is circulated, the temperature of the It will be 80 ° C I adjusted it. The time required for the pellet to pass through the pre-cooling chamber 21 and the main cooling chamber 22 was 10 minutes, and the passing amount was 100 kg / hour.
  • the cooled pellet was put into a hammer mill type pulverizer 24 and pulverized to obtain a particulate resin composition.
  • the crushing section 23 of the crusher was blown with cold air cooled to 190 ° C. by the cooling unit C 3 to prevent the resin from rising due to heat generated during the crushing.
  • the particulate resin composition was classified through an 80 mesh classification screen 25, and then passed through a Henschel mixer 26 (manufactured by Mitsui Miike Co., Ltd., capacity: 75 liters). I put it in.
  • a Henschel mixer 26 100 parts of the particulate resin composition was added to a dusting agent 27 (methyl methacrylate styrene (1/3) having an average particle size of 1 m obtained by microsuspension polymerization. 1) Copolymer powder) 10 parts were added, and stirring was continued for 1 minute to obtain a powder molding resin composition having an average particle diameter of 15.5 m.
  • the water adsorbed by the particulate resin composition was removed by self-heating by stirring and by heating with steam heating. Thereafter, the temperature of the particulate resin composition was cooled to 50 ° C. by pouring water into a jacket of a Henschel mixer.
  • the thus obtained resin composition for powder molding was evaluated for average particle diameter, powder fluidity and sintering moldability.
  • the fall time was ⁇ . ⁇ 5 seconds, indicating good powder flowability.
  • the sinter molding test a good sheet having a uniform thickness and no pinholes was obtained.
  • the average particle size was determined by using a mouth-to-tap shaker to determine the particle size (D50) corresponding to the opening where the cumulative particle size distribution curve obtained by the sieving method showed 50%, and the average particle size was determined. did.
  • the powder flowability was determined by measuring the fall time by the method described below. The shorter the fall time, the better the powder fluidity. If the time is longer than 25 seconds, the fluidity is poor and the uniformity of the thickness of a sheet or the like after molding often becomes poor.
  • the sintering moldability was determined by heating a powdery thermoplastic resin composition to a temperature of 250 ° C, 250 ° C, and 200 ° C in a nickel mold (150 mm X 100 ° C). (mmX 3 mm), sprinkle 500 g of each powder evenly.After 10 seconds, remove unmelted excess powder, Next, the particles adhered to the mold and melted were held for another 30 seconds to promote the melting. Thereafter, the mold was rapidly cooled with water. When the temperature reached 60 ° C., the cooled and solidified sheet was peeled off from the mold, and the condition of the sheet and pinholes on the sheet surface were visually evaluated.
  • the resin composition powder for powder molding is subjected to slush molding, and the obtained sheet-like molded product (thickness: about 1 mm) is released from the mold so that no bent wrinkles remain, and 15 x 5 A 0 mm specimen was cut.
  • the test piece was bent at 180 ° in a room at 23 ° C, placed on a horizontal surface in that state, a 1 kg weight was placed on the surface for 10 seconds, removed, and the angle between the horizontal surface and the bending sheet was measured immediately. .
  • high-temperature folding resistance was measured at 65 ° C. The smaller the value, the better the folding wrinkle resistance.
  • test piece 3 0 ⁇ 8 0 mm taken in the same manner as in (1), 2 3 ° C odor Te, it is placed on reciprocally movable table, steel Masatsuko width 2 O mm (Coated with four sheets of width 3) was placed on the test piece, a load of 2.5 kgf was applied to the test piece, and the surface of the test piece was reciprocated 5 times at a speed of 60 cycles / min. The degree of whitening of the surface of the test piece was observed. Similarly, high-temperature wear resistance was measured at 65 ° C. The results were displayed according to the following three-grade evaluation method.
  • the 150 mm x 100 mm test piece cut in the same manner as in (1) above is left open for 120 hours at 120 ° C. Thereafter, the removed test piece was allowed to stand at room temperature for 1 hour, and the degree of stickiness on the surface was evaluated with a tentacle. The results were displayed according to the following two-grade evaluation method.
  • a 14.5 x 200 mm test piece cut in the same manner as in (1) above was placed in a 14 7 (vertical) ⁇ 2 17 (horizontal) 10 (depth) mm mold.
  • Forming solution polymeric MDI having 2.7 functional groups (4,4'-diphenylmethanediisocyanate) 16 g, polyether polyol (trifunctionality, hydroxyl value 50) (triethylenediamine 1.0%, Water (containing 1.6%) 31.4 g of the mixture) was poured and the mold was sealed.
  • the falling time (unit: second) of the resin composition for powder molding 100 cc at a temperature of 23 ° C. was measured using a bulk specific gravity measuring device. The shorter the fall time, the better the powder flowability.
  • a resin mold for powder molding is filled into a nickel mold (inner dimension: 200 mm x 300 mm x 2 mm) heated to a temperature of 260 ° C, and after 10 seconds, the mold is turned over and surplus Except for the above composition, the resin composition adhering to the mold was held for 30 seconds to gel. Next, the mold was cooled to 60 ° C, the gelled sheet was peeled off from the mold, and evaluated by the following two-grade evaluation method.
  • a polypropylene resin (a) and a thermoplastic resin The properties of a resin composition for powder molding comprising (b) and a hydride of an aromatic vinyl compound-conjugated gen copolymer are shown.
  • a fatty acid was added to a resin composition for powder molding comprising a polypropylene resin (a), a thermoplastic resin (b) and a hydride of an aromatic vinyl compound-conjugated gen copolymer (2). Shows the properties of amide (3-1) added.
  • the polymer components of the type and amount shown in Table 2 were kneaded with a twin-screw extruder (TEM35B, manufactured by Toshiba Machine Co., Ltd.), pelletized, and then pulverized.
  • TEM35B twin-screw extruder
  • Each resin composition for powder molding was obtained.
  • a melting test was performed by slush molding, and the obtained sheets were used to evaluate creasing resistance, abrasion resistance, and heat resistance. The results are shown in Table 2.
  • Table 2 Table 2
  • a resin composition for powder molding comprising a polypropylene resin (a), a thermoplastic resin (b) and a hydride of an aromatic vinyl compound-conjugated gen copolymer (2) is used. Shows the properties of those containing a hydroxyl group-containing hydrocarbon polymer (3-2) (or modified silicone oil).
  • Thyroprene FM-0721 manufactured by Chisso Co., Ltd. was prepared by mixing a polypropylene resin composition, a olefin-based thermoplastic elastomer, and SEBS.
  • the hydrogen polymer and the modified silicone oil were blended (Examples 11 to 16)
  • the bending angle was small, so that the fold wrinkle resistance was good, and the abrasion resistance, heat resistance, and polystyrene foam were obtained. Good adhesion to the body.
  • Examples 17 and 19 have insufficient high-temperature wear resistance. Furthermore, when the hydroxyl group-containing hydrocarbon polymer is not blended (Examples 18 and 20), the adhesiveness to the polyurethane foam is not improved. If you do not mix the refining elastomer
  • Comparative Example 4 has a large bending angle, does not improve the folding wrinkle resistance, and has poor abrasion resistance and poor adhesion to the polyurethane foam.
  • a resin composition for powder molding comprising a polypropylene resin (a), a thermoplastic resin (b) and a hydride of an aromatic vinyl compound-conjugated gen copolymer (2), 3-3) Polyester resin obtained by polycondensing polyhydric carboxylic acid component (A) with (i) alkanediol and (M) alcohol component (B) containing polyhydric phenoxy alcohol, (or And modified silicone oil).
  • Polyester resin obtained by polycondensing polyhydric carboxylic acid component (A) with (i) alkanediol and (M) alcohol component (B) containing polyhydric phenoxy alcohol, (or And modified silicone oil).
  • polyester resin A had a number average molecular weight of 13,660, a hydroxyl value of 7.2 mg KOH / g, and a glass transition temperature of 53 ° C.
  • polyester resin B has a number average molecular weight of 7,930, The hydroxyl value was 9.8 mg K ⁇ H / g and the glass transition temperature was 49 ° C.
  • the number average molecular weight of the polyester resin is measured by GPC and is a standard polystyrene equivalent molecular weight.
  • the hydroxyl value was determined by acetylating the polyester resin with acetic anhydride and then titrating with a mixed solution of potassium hydroxide / ethanol.
  • the glass transition temperature was measured by DSC.
  • the polymer components of the type and amount shown in Table 5 were kneaded with a twin-screw extruder (TEM35B, manufactured by Toshiba Machine Co., Ltd.), pelletized, pulverized by a turbo mill, and powdered.
  • a resin composition for body molding was obtained. Using each of the obtained powdery resin compositions, a fusibility test was performed by slush molding, and the obtained sheets were used to evaluate creasing resistance, abrasion resistance, heat resistance, and adhesion. Table 5 shows the results. Table 5
  • Thyraplane FM-0721 manufactured by Chisso (methacryloxy group-modified silicone oil at one end)
  • the polypropylene resin composition was mixed with a refining thermoplastic elastomer and SEBS.
  • polyester resin A or B was mixed with this (Examples 21 to 27)
  • the fold wrinkle resistance was good and the adhesion to the polyurethane foam was good.
  • the modified silicone oil was used in combination (Examples 25 and 27), the abrasion resistance was further improved without lowering the adhesiveness.
  • a resin composition for powder molding comprising a polypropylene resin (a), a thermoplastic resin (b) and a hydride of an aromatic vinyl compound-conjugated gen copolymer (2), 3-4)
  • the properties of the product added with a hydroxyl group-containing aromatic vinyl compound copolymer having a high glass transition temperature are shown.
  • Production Example 1 Hydrophill-containing aromatic vinyl compound copolymer; production of dusting agent
  • the following hydroxyl-containing aromatic vinyl compound copolymers 1 and 2 were prepared by the fine suspension polymerization method. ) was prepared.
  • Monomer 70 parts of styrene, 27 parts of methyl methacrylate, 3 parts of 2-methyl methacrylate
  • each powdered resin composition was prepared in the same manner when an aromatic vinyl copolymer containing no hydroxyl group (dusting agent 3) was added and when no dusting agent was added.
  • Dusting agent 3 an aromatic vinyl copolymer containing no hydroxyl group
  • Table 6 shows the results. Table 6 Comparative example
  • Powder formability A A A A B A Folding resistance 23 ° C 8 10 12 12 30 40 Test (degrees) 65 ° C 37 39 43 45 55.60
  • Powder fluidity test The measuring instrument was vibrated and forcibly dropped. As shown in Table 6, when the polypropylene resin composition was mixed with a refining-based thermoplastic elastomer and SEBS, and the dusting agent 1 or 2 was added thereto, the powder flowability and powder moldability The sheets obtained by slush molding using these had good folding wrinkle resistance and good adhesion to polyurethane foam (Examples 29 to 31).
  • a powder composed of a hydride of a polypropylene resin (a), a thermoplastic resin (b), and two kinds of aromatic vinyl compounds having different aromatic vinyl compound contents and a conjugated gen copolymer is used.
  • the properties of the resin composition for body molding are shown.
  • Powder fluidity test The measuring instrument was vibrated and forcibly dropped. As shown in Table 7, a powder blended with a polypropylene resin composition, a refining-based thermoplastic elastomer, SEBS having a bound styrene content of 20% or more, and SEBS having a bound styrene content of less than 20%
  • the molding resin compositions (Examples 34 to 36) are excellent in powder properties such as powder fluidity, and are also excellent in wear resistance at high temperatures (60 ° C.).
  • the powder-forming resin of the present invention comprising a polypropylene resin (a), a thermoplastic resin-based thermoplastic elastomer (b), and a hydrogenated aromatic vinyl compound-conjugated gen copolymer (2).
  • the resin composition provides a powder molded article which is easy to produce and has excellent creasing resistance, heat resistance, abrasion resistance and the like.
  • fatty acid amide (3-1) improves hot wear resistance
  • 1 minute Hydroxyl-containing hydrocarbon polymer having an average number of hydroxyl groups per molecule of 1 to 8, a number average molecular weight of 500 to 200,000, and an iodine value of 100 or less (3-2 )) Improves the adhesion to the polyurethane foam and the high-temperature abrasion resistance
  • the polyester resin (3-3) having a number average molecular weight of 7,500 to 1,000,000 is blended with the polyurethane resin to improve the adhesion to the polyurethane foam and the high-temperature abrasion resistance.
  • Such a powdery refin-based resin composition for powder molding can be applied to various powder molding methods such as powder slush molding, fluid immersion molding or powder rotary molding. It is unlikely to cause defects such as thickness, thickness and pinholes, and has excellent moldability and excellent inflow into the undercut part.
  • Molded articles obtained by powder molding the powdery refin-based resin composition include, for example, interior skin materials such as automobile instrument panels, console boxes, and hamlets; and home appliances and OA. It is used in the equipment field, sports equipment field, construction, and housing. In particular, it is suitable as a molding material for the surface layer of automobile interior parts such as instrument panels, headrests, console boxes, door trims, armrests, and the like.

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Abstract

L'invention concerne une composition de résine oléfinique pour moulage à partir de poudres, qui comprend: 1) 20 à 80 parties en poids d'une composition de résine de polypropylène contenant a) 20 à 80 parties en poids d'une résine de polypropylène et b) 80 à 20 parties en poids d'un élastomère oléfinique thermoplastique (à condition que la somme de a) et b) constitue 100 parties en poids); et 2) 80 à 20 parties en poids d'un produit de l'hydrogénation d'un copolymère de vinyle aromatique et de diène conjugué (la somme de 1) et 2) constituant 100 parties en poids). Cette composition de résine oléfinique est facile à produire. Elle donne, par moulage à partir de poudres, un article moulé présentant une infroissabilité, une résistance à la chaleur et une résistance à l'usure satisfaisantes.
PCT/JP2002/006602 2001-06-29 2002-06-28 Composition de resine olefinique pour moulage a partir de poudres, et procede de production associe WO2003002655A1 (fr)

Applications Claiming Priority (14)

Application Number Priority Date Filing Date Title
JP2001-198109 2001-06-29
JP2001198109A JP2003011121A (ja) 2001-06-29 2001-06-29 粉体成形用熱可塑性樹脂組成物の製造方法
JP2001-366915 2001-11-30
JP2001366915A JP3994725B2 (ja) 2001-11-30 2001-11-30 粉体成形用樹脂組成物
JP2001399439A JP3961284B2 (ja) 2001-12-28 2001-12-28 粉体成形用樹脂組成物
JP2001399440A JP3961285B2 (ja) 2001-12-28 2001-12-28 粉体成形用樹脂組成物
JP2001-399440 2001-12-28
JP2001399125A JP3989726B2 (ja) 2001-12-28 2001-12-28 粉体成形用樹脂組成物
JP2001-399125 2001-12-28
JP2001-399439 2001-12-28
JP2002-24430 2002-01-31
JP2002024430A JP3998989B2 (ja) 2002-01-31 2002-01-31 粉体成形用樹脂組成物
JP2002-91952 2002-03-28
JP2002091952A JP3994776B2 (ja) 2002-03-28 2002-03-28 芳香族系ビニル化合物−共役ジエン共重合体の水素化物を配合してなる粉体成形用樹脂組成物

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CN116003906A (zh) * 2022-12-13 2023-04-25 武汉金发科技有限公司 一种低比重聚丙烯复合材料及其制备方法与应用

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JPH05320442A (ja) * 1992-05-21 1993-12-03 Mitsui Petrochem Ind Ltd プロピレン系重合体組成物
WO1997000911A1 (fr) * 1995-06-20 1997-01-09 Sumitomo Chemical Company, Limited Composition elastomere thermoplastique et articles moules a partir de cette composition
EP0811657A2 (fr) * 1996-06-06 1997-12-10 Mitsuboshi Belting Ltd. Composition élastomère thermoplastique pour le moulage à poudre et procédé pour la préparation de cette composition
JPH1192602A (ja) * 1997-07-24 1999-04-06 Mitsuboshi Belting Ltd 粉末スラッシュ成形用熱可塑性エラストマー組成物および粉末スラッシュ成形材料
JPH11255981A (ja) * 1998-03-10 1999-09-21 Mitsuboshi Belting Ltd 粉末スラッシュ成形用熱可塑性エラストマー組成物
JP2973353B2 (ja) * 1995-08-10 1999-11-08 三ツ星ベルト株式会社 粉末成形に使用する粉末樹脂組成物
JP2000109609A (ja) * 1998-10-07 2000-04-18 Mitsuboshi Belting Ltd 熱可塑性エラストマー組成物およびこれを用いたスラッシュ成形表皮
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JPH05179100A (ja) * 1992-01-07 1993-07-20 Mitsubishi Petrochem Co Ltd 塗装された軟質成形体
JPH05320442A (ja) * 1992-05-21 1993-12-03 Mitsui Petrochem Ind Ltd プロピレン系重合体組成物
WO1997000911A1 (fr) * 1995-06-20 1997-01-09 Sumitomo Chemical Company, Limited Composition elastomere thermoplastique et articles moules a partir de cette composition
JP2973353B2 (ja) * 1995-08-10 1999-11-08 三ツ星ベルト株式会社 粉末成形に使用する粉末樹脂組成物
EP0811657A2 (fr) * 1996-06-06 1997-12-10 Mitsuboshi Belting Ltd. Composition élastomère thermoplastique pour le moulage à poudre et procédé pour la préparation de cette composition
JPH1192602A (ja) * 1997-07-24 1999-04-06 Mitsuboshi Belting Ltd 粉末スラッシュ成形用熱可塑性エラストマー組成物および粉末スラッシュ成形材料
JPH11255981A (ja) * 1998-03-10 1999-09-21 Mitsuboshi Belting Ltd 粉末スラッシュ成形用熱可塑性エラストマー組成物
JP2000109609A (ja) * 1998-10-07 2000-04-18 Mitsuboshi Belting Ltd 熱可塑性エラストマー組成物およびこれを用いたスラッシュ成形表皮
JP2000204207A (ja) * 1999-01-18 2000-07-25 Mitsuboshi Belting Ltd 粉末スラッシュ成形用熱可塑性エラストマ―組成物および粉末スラッシュ成形材料
JP2001049052A (ja) * 1999-06-04 2001-02-20 Sumitomo Chem Co Ltd 粉末成形用熱可塑性エラストマー組成物、該組成物のパウダー、該パウダーを用いる粉末成形方法及び該パウダーを粉末成形してなる成形体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116003906A (zh) * 2022-12-13 2023-04-25 武汉金发科技有限公司 一种低比重聚丙烯复合材料及其制备方法与应用

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