WO2003002655A1 - Olefin resin composition for powder molding and process for producing the same - Google Patents

Abstract

An olefin resin composition for powder molding which comprises: (1) 20 to 80 parts by weight of a polypropylene resin composition comprising (a) 20 to 80 parts by weight of a polypropylene resin and (b) 80 to 20 parts by weight of a thermoplastic olefin elastomer (provided that the sum of (a) and (b) is 100 parts by weight); and (2) 80 to 20 parts by weight of a product of the hydrogenation of an aromatic vinyl/conjugated diene copolymer (the sum of (1) and (2) is 100 parts by weight). This olefin resin composition is easy to produce. It gives, through powder molding, a molded article satisfactory in crease resistance, heat resistance, and wearing resistance.

Description

 Description: Refined resin composition for powder molding and method for producing the same

 TECHNICAL FIELD 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). Japanese Patent Application Laid-Open No. 0871/1995, Japanese Patent Application Laid-Open No. Hei 6-2226663, Japanese Patent Application Laid-Open No. Hei 7-18742, Japanese Patent Application Laid-Open No. Hei 8-217792, etc.). However, 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.

The present inventors have studied to solve the above problems, and as a result, have found that an SBS type block copolymer (S) of styrene and butadiene having a bound styrene content of 20 to 50% by weight and a number average molecular weight in a specific range. : 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). However, molded articles using the above hydride (SEBS) have sufficient heat resistance. Therefore, a method of blending a polypropylene resin (PP) to supplement heat resistance (Japanese Patent Laid-Open No. 7-82433) and a method of blending a polyolefin (Japanese Patent Laid-Open No. 2000-336) 219) was proposed.

 However, PP has low compatibility with SEBS, so it has poor processability, making it difficult to obtain a composition in which both are uniformly mixed, and because PP has high crystallinity, demolding in slush molding In this case, there is a problem that the molded product is apt to be wrinkled. Disclosure of the invention

 In view of the circumstances described above, 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.

 Thus, according to the present invention, (Ί) (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).

 Further, according to the present invention, (1) (a) 20 to 80 parts by weight of a polypropylene resin, and (b) 80 to 20 parts by weight of a thermoplastic olefin elastomer (provided that (a) and (b) ) Is 100 parts by weight.) 20 to 80 parts by weight of a polypropylene resin composition comprising: (2) a hydride of an aromatic vinyl compound-conjugated gen copolymer of 80 to 80 parts by weight A step of kneading 20 parts by weight (the total of (1) and (2) is 100 parts by weight) and other components optionally blended to obtain a resin kneaded product; Provided is a method for producing a powdery molded olefin resin composition, comprising: a step of preparing a pellet of a kneaded material; and a step of continuously cooling and pulverizing the pellet. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a flow chart showing a process for producing a powdery resin-based resin composition of the present invention. FIG. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail.

 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).

 Polypropylene resin (a)

 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 α-lefin having 2 to 12 carbon atoms. Here, 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 α-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.

 Olefin-based thermoplastic elastomer (b)

The olefin-based thermoplastic elastomer used in the present invention is usually called TPO or TPE. For example, EPR (ethylene-propylene copolymer rubber) and EPDM (ethylene-propylene-non-conjugated gen monomer) Copolymer rubber) and PP or PP / PE (polyethylene) blended. In the matrix phase of PP or the like by so-called dynamic cross-linking of the above-mentioned blend with EP DM while melting PP or PP / PE. With EPDM dispersed in it (Elastomaro B) Reactor TPO, an ethylene / propylene copolymer (EPR) obtained by copolymerizing propylene and ethylene following polymerization of PP, propylene-based block copolymer with many block parts, etc. Is mentioned. All of these are commercially available and available. Among them, a propylene block copolymer (reactor TPO) is preferable, and is commercially available as PER manufactured by Tokuyama Corporation.

 In the preferred propylene-based block copolymer (reactor T PO), 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%. Further, 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. .

 Hydride of aromatic vinyl compound-conjugated gen copolymer (2)

 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. 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.

 As 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. . By such 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.

 When a hydride of the aromatic vinyl compound-conjugated gen copolymer having a different content of the aromatic vinyl compound unit is used in combination, 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) is usually 90 to 10% by weight, preferably 80 to 20% by weight, Preferably it is 60 to 40% by weight. If the ratio of the former is too small, the anti-blocking property of the powdery molding refin-based resin composition is insufficient, and if it is too high, the hardness of the molded article increases and the wear resistance at high temperatures decreases. Tends to.

 Refined resin composition for powder molding

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.

 As for the ratio of the hydride (2) of the above-mentioned polypropylene resin composition (1) and the aromatic vinyl compound monoconjugated copolymer, (1) is 20 to 80 parts by weight, preferably 30 to 70 parts by weight. , More preferably 40 to 60 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.

 Additional ingredients (3)

 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).

Various 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. , A hydroxyl-containing hydrocarbon polymer having an iodine value of 100 or less, (3-3) a polycarboxylic acid component (A) containing at least cyclohexanedicarboxylic acid or a derivative thereof, (J) an alkanediol having a molecular structure in which a carbon atom to which a hydrogen atom is not bonded is sandwiched between two carbon atoms to which a hydroxyl group is bonded, and (ii) a polyvalent phenoxy alcohol A polyester resin having a number average molecular weight of 7,500 to 100,000, and (3-4) a glass transition temperature of 6 obtained by polycondensing an alcohol component (B) containing A hydroxyl group-containing aromatic vinyl compound copolymer having an average primary particle size of 0.1 to 10 tm at 0 ° C. or higher is mentioned. That.

 Hereinafter, these additional components (3) will be sequentially described.

 (3-1) fatty acid amide

When a fatty acid amide is further added to the powdery refin-based resin composition of the present invention, the creasing resistance during demolding in powder molding and the heat resistance of the molded article are improved. In addition, 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.

 Specific examples of the fatty acid amide 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.

 (3-2) Hydrocarbon-containing hydrocarbon polymer

 When a specific hydroxyl group-containing hydrocarbon-based polymer is further added to the powdery refin-based resin composition of the present invention, 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. A polymer having an iodine value of 100 or less as a double bond contained in the molecule thereof, in the range of 0 to 200, 000, preferably in the range of 1, 000 to 150, 000. It is. 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. No. Of these, a hydrogenated product of a hydroxyl group-containing gen-based polymer is preferable. For example, 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. In the case of 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. In the case of anion polymerization, first, 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. To obtain a polymer having a hydroxyl group. Examples of the conjugated gen of the raw material include 1,3-butadiene, isoprene, and chloroprene. Among them, 1,3-butadiene is preferable. Examples of the copolymerization component 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.

 In addition, together with the hydroxyl group-containing hydrocarbon-based polymer (3-2), 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. Specific examples of such catalysts include organic tin compounds such as dibutyltin dilaurate and dibutyltin distearate; tertiary amines such as tetraalkylethylenediamine and N, N'-dialkylbenzylamine. Compounds, salts of fatty acids such as cobalt naphthenate, zinc stearate, and carboxylate salts of alkali metals. The amount of these catalysts to be used is about 0.01 to 5 parts by weight per 100 parts by weight of the refining resin composition for powder molding of the present invention.

 In addition, it is preferred that 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

 I I I I

H, C-SiO (SiO) _m (SiO) _n ITSi-CH a)

 I

CH ₃ CH 3 R CH 3

Side chain / both ends introduced type R (2)

 c

H

 Three

Three

 '3 3, 3

R-SiO (SiO) _ra (SiO) _n Si-R (3)

 CH3 CH3 CH3 CH3

CH ₃ CH 3

H ₃ C-SiO (SiO) _m (SiO) _n Si-R (4)

 CH3 CH '3q CH¾ 3 CH

(m, n = 1~ about 300, R = functional group) functional group _{R: - C 3 H 6 NH} 2, - C click _{2 H "4 4C, 00H,} -C, 3H" R 60, C¾C¾0H

_{- C 3 H 6 0CH 2 CH-} CH 2, -C 3 H 6 0C0C = CH 2

 . \ / 1

0 CH ₃

- 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.

 (3-3) Polyester composed of polyhydric carboxylic acid component and polyhydric alcohol

 When a specific polyester is further added to the powder-refined refin-based resin composition of the present invention, the creasing resistance during demolding in powder molding, and the abrasion resistance and heat resistance of the molded article are improved. In addition, the adhesiveness of the molded body to the polyurethane foam is improved. In addition, the powdery molded refin-based resin composition is easy to produce. 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. An alkanediol having a molecular structure in which a carbon atom having no hydrogen atom bonded between the alkanediol and (ii) an alcohol component (B) containing a polyvalent phenoxy alcohol is polycondensed to obtain a number average molecular weight Is a polyester resin of 7,500 to 100,000 (hereinafter simply referred to as “polyester resin”).

 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 Ί2,500-30,000. 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. Examples of 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. —Dicarboxylic acid and cyclohexane— 1,3-dicarboxylic acid. Of these, cyclohexane-1,4-dicarboxylic acid is preferred.

 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.

 Specific examples of 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-Ί, 4-dicarboxylic acid, 2-methyl-3-butyl-cyclohexane-1,4-dicarboxylic acid, 2-ethyl-13-propylpropylcyclohexane-1,4-dicarboxylic acid, 2-ethylethyl Cyclohexane-1,1,4-dicarboxylic acid such as 3-butyl-cyclohexane-1,4-dicarboxylic acid, 2-methyl-3-t-butyl-cyclohexane-1,4-dicarboxylic acid, and the corresponding 1 , 3-dicarboxylic acid. The proportion of cyclohexanedicarboxylic acid in the polycarboxylic acid component (A) is usually at least 50% by weight, preferably at least 80% by weight, more preferably at least 90% by weight.

The polycarboxylic acid component may contain other polycarboxylic acids other than the above. Can be. Examples of other polycarboxylic acids include aromatic polycarboxylic acids, linear or branched aliphatic polycarboxylic acids, and derivatives thereof. Examples of 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.

 Incidentally, 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.

 Specific examples of 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. Among them, 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.

Examples of (ii) polyphenolic alcohol in the polyhydric alcohol component 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.

 Examples of the polyvalent phenol 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. Of these, 2,2-bis (4'-hydroxyphenyl) propane (bisphenol A) is preferred. In addition, hydroxybiphenyl compounds such as biphenyl 2,4'-diol, biphenyl 2,2'-diol, and biphenyl 2,3'-diol can also be used. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

 Specific examples of 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.For example, the reaction temperature is 100 to 300 ° C, preferably 150 to 280 ° C, and more preferably 180 to 230 ° C. ° C. Examples of 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 χ 10 ⁴ Pa). It is also possible to carry out the reaction in the presence of an inert gas.

 For the polycondensation reaction, 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. Among them, 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.

 When using polyester resin, the adhesion between the molded body and polyurethane foam

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). In addition, 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).

 (3-4) hydroxyl group-containing aromatic vinyl compound copolymer

 When a specific hydroxyl group-containing aromatic vinyl compound copolymer is further blended with the powdery refin-based resin composition of the present invention, the crease resistance during demolding in powder molding, and Abrasion resistance and adhesion to polyurethane foam are improved, and the hydroxyl group-containing aromatic vinyl compound copolymer acts as a dusting agent. Formability is improved.

 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.

 If the 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).

When the average primary particle diameter of the powder of the hydroxyl group-containing aromatic vinyl compound copolymer is excessively small or excessively large, the powder fluidity may decrease in any case. For the measurement of the average primary particle size, 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.

 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.

 Specific examples of the hydroxyl group-containing aromatic vinyl compound include styrene, α-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.

Specific examples include 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 .; Examples of 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-hydroxypropionyl vinyl acrylate, etc .; hydroxyl group-containing vinyl dicarboxylic acid ester Examples thereof include 2-hydroxypropyl maleate and di-2-hydroxysethyl fumarate.

 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.

Among the other monomer compounds, 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. It is used in an amount of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on parts by weight. If the blending amount of the hydroxyl group-containing aromatic vinyl compound copolymer is too small, the powder fluidity may decrease.If the blending amount is too large, the molded article may be formed during powder molding. There is a possibility that it will be difficult to remove it from the mold. 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

 Various additives can be added to the powdery refin-based resin composition of the present invention, if desired. For example, 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. As other additives, various known stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, pigments, and the like can be added. In addition, a known plasticizer can be added as long as it is not sticky or does not impair moldability.

 Further, 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. Examples of such 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. Resins, polyester resins, polycarbonate resins, polybutadiene resins, and the like. Further, an aromatic vinyl compound such as styrene and an α-olefin such as ethylene and propylene are disclosed in JP-A-3-7705, JP-A-7-72023 and JP-A-10-1. An aromatic vinyl compound-α-olefin copolymer obtained by copolymerization according to the method described in, for example, Patent Publication No. 68111 or the like. 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.

 Method for producing powdery refin-based resin composition for powder molding

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. As 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. First, 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. In order to make the resin composition into a powder, 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 μm, 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.

 However, in order to easily, efficiently and economically produce a powdery refinable resin composition having a desired particle size and excellent powder fluidity, 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.

 Hereinafter, a manufacturing method having the above steps will be described in detail.

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 In the step of kneading the above to obtain a resin kneaded product, a kneading apparatus generally used for production of a thermoplastic resin composition is used. 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. Usually, 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. In addition, various components can be added from an inlet provided in the middle of the cylinder of the extruder as needed. To stabilize the discharge rate, a gear pump can be installed between the strand die and cylinder. Furthermore, it is possible to finely adjust the temperature inside the cylinder of the extruder from the strand die side. In the step of preparing a pellet of the resin composition, 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. Above all, when an extruder is used in the above-described kneading step, 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.

 In the step of continuously cooling and pulverizing the pellets, 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. . In the cooling device, the method of cooling the resin composition is not particularly limited. For example, a method of generating cold air by a refrigerator using an ammonia refrigerant and spraying the same onto the resin is preferable. Further, it is preferable that the resin composition is continuously passed through a cooling device using a belt conveyor or the like. In order to efficiently cool the resin composition, it is preferable that the resin composition is exposed to cold air from above and below. Further, the belt conveyor is preferably made of a metal net.

In the cooling device, the resin composition is preferably cooled to a temperature lower than its glass transition temperature (Tg). Here, when 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. Further, when 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.

 Next, 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.

 By classification, 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.

 It is preferable to add 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. As the 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. In addition, 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. Usually, 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.

 In order to carry out the method for producing a refin-based resin composition for powder molding, usually, first, in a step of kneading the resin and the compounding components to obtain the resin composition, 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. In a step of continuously cooling and pulverizing the resin composition after being prepared into a pellet, 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.

 As described above, in order to produce a powdery resin composition for powder molding, 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.

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to the embodiment. Parts and percentages are by weight unless otherwise specified.

 Production example of resin composition for powder molding

 In this example, a specific example of a method for producing a resin composition for powder molding will be described in detail with reference to FIG.

 FIG. 1 is a flow chart showing an example of a production process of the powdery refin-based resin composition of the present invention. In the present embodiment, the polymer component (1),

(2) a step of kneading the resin kneaded product by kneading the other components optionally blended, and a step J_ of preparing a pellet of the resin kneaded product using an underwater cut pelletizer 12. And a step of continuously cooling and grinding the pellets using a cooling device 15 provided with two cooling chambers and a hammer mill type pulverizer 24. 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.

 30 parts of polypropylene (PP, trade name PM 940 M, manufactured by San-Alomer Co., Ltd., MFR 30 gZ 10 minutes), and a refining thermoplastic elastomer elastomer (reactor I TPO, trade name PER M 1 4 2 E, 20 parts of Tokuyama Co., Ltd. and styrene-ethylene-butadiene-styrene block copolymer (SEBS, trade name: Tuftec H1221, manufactured by Asahi Kasei Kogyo Co., Ltd .; bound styrene content: 12%) 50 Parts from a hopper 10 and into a twin-screw extruder 8 (manufactured by Toshiba Machine Co., Ltd., TEM48 BS, with a gear pump), and knead the mixture. Extruded from 1 (extrusion amount: 100 kg / hour), and then extruded strands were cut using an underwater cut pelletizer 12 (GALA Co., Ltd., trade name: TWS-80). A pellet (average particle size: 5 mm) of the kneaded material was prepared.

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.

 Subsequently, 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.

 Subsequently, 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. 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. In the powder fluidity test, the fall time was Ί. Ί5 seconds, indicating good powder flowability. In 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.

 In the following Examples, methods and conditions substantially the same as the specific examples of the method for producing the resin composition for powder molding described above were used, except where otherwise noted. The physical properties of the resin composition for powder molding were measured by the following test methods.

 (1) Crease resistance

 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. . Similarly, high-temperature folding resistance was measured at 65 ° C. The smaller the value, the better the folding wrinkle resistance.

 (2) Wear resistance

The test piece 3 0 χ 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.

 A: No whitening

 B: slight whitening

 C: Whiten

 (3) Heat resistance

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: The surface is not sticky

 B: The surface is sticky

 (4) Adhesion with foamed polyurethane layer

 A 14.5 x 200 mm test piece cut in the same manner as in (1) above was placed in a 14 7 (vertical) χ 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. After leaving the mold at room temperature for 10 minutes, remove the test piece with the polyurethane foam layer laminated from the mold, peel off the test piece from the foam layer, measure the area of the foam layer that has undergone cohesion failure, and apply it to the entire area of the test piece. The occupancy ratio was determined. The higher the ratio, the better the adhesion.

 A: 90 to 100%

 B: 80% to less than 90%

 C: less than 80%

 (5) Powder flowability

 According to JIS K 672 1, 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.

 (6) Powder moldability

 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: There is no unevenness in sheet thickness and almost no pinholes.

 B: Sheet thickness is slightly uneven and pinholes are slightly.

 Examples 1-3, Comparative Examples 1-2

In this example, 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.

 The polymer components of the type and amount shown in Table 1 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 powdered resin compositions, a fusibility test was performed by slush molding, and the obtained sheets were used to evaluate creasing resistance, abrasion resistance, and heat resistance. Table 1 shows the results. table 1

Note (1) PM 940 M (MFR 30) manufactured by Sanaloma

 (2) Same as above Sun Attack (Atactic P P)

 (3) P.E.R.M1 4 2E (Reactor T PO) manufactured by Tokuyama Corporation

 (4) Asahi Kasei Corporation Tuftec HI221 (Bound styrene content: 12%) As shown in Table 1, a molded article using the resin composition for powder molding of the present invention has bending resistance and abrasion resistance. Good heat resistance and heat resistance (Examples I to 3). In contrast, when the propylene-based block copolymer was not blended (Comparative Example 1) and when the PP resin was not blended (Comparative Example 2), the bending resistance and the abrasion resistance were poor.

 Examples 4 to 10, Comparative Example 3

In this example, 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. Each resin composition for powder molding was obtained. Using each of the obtained powdery resin compositions, 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

Note (1) PM 940 M (MFR 30) manufactured by Sanaloma

 (2) Same as above Sun Attack (Atactic P P)

 (3) Tokuyama P.E.R.M1 4 2E (reactor-one TPO)

 (4) Asahi Kasei Corporation Tuftec HI 22 1 (Bound styrene content 12%)

 (5) Ethylene bisstearic acid amide

 (6) Ethylene bisbehenamide

(7) As shown in Table 2 by Mitsubishi Chemical Corporation, when the polypropylene resin composition was mixed with a refining-based thermoplastic elastomer and SEBS, and further mixed with a fatty acid amide (Examples 4 to 10), Since the bending angle is small, it has good fold wrinkle resistance and wear resistance It can be seen that the balance with the heat resistance is good. In particular, the high-temperature abrasion resistance is improved as compared with the case where no fatty acid amide is combined (Example 1). When no thermoplastic thermoplastic elastomer is blended, even when a fatty acid amide is blended (Comparative Example 2), the fold wrinkle resistance is poor.

 Examples 11 to 20 and Comparative Example 4

 In this example, 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).

 The polymer components of the types and amounts shown in Tables 3 and 4 were kneaded with a twin-screw extruder (TEM35B manufactured by Toshiba Machine Co., Ltd.), pelletized, pulverized with a turbo mill, and powdered. Was obtained. Each of the obtained powdery resin compositions was subjected to a slash molding meltability test, and the obtained sheets were used to evaluate creasing resistance, abrasion resistance, heat resistance, and adhesion. The results are shown in Tables 3 and 4.

 Table 3 Formulations (parts)

 Test result 11 12 13 14 1.5 16

 (PPO) 30 25 10 10 10 10

PP (2) 5

 PER (3) 20 20 20 20 20 20

SEBS (4) 50 50 70 70 70 70 Hydroxyl-containing hydrocarbon

 Polymer (5) 10 10 10 10 3 Hydroxyl-containing hydrocarbon

 Polymer (6) 10

 Modified silicone oil A (7) 2.5 1 2.5 2.5 2.5 Modified silicone oil B (8) 2.5

 23 ° C 23 21 9 10 9 δ

 Bending angle (degree)

 65 ° C 50 49 37 42 47 40

 23 ° C A A A A A A A

Abrasion resistance 60 ° CAAAAAA Heat resistance AAAAAA Adhesion (%) AAAAAA Table 4

(Note) (1) PM 9400 M (MFR 30) manufactured by Sanaromar

 (2) Same as above Sun Attack (Atactic P P)

 (3) P.E.R.M1 4 2E (Reactor-one TPO) manufactured by Tokuyama Corporation

 (4) Asahi Kasei Corporation Tuftec HI221 (Bound styrene content 12%)

 (5) Mitsubishi Chemical Corporation Polytail H (hydroxyl value 37 to 53, iodine value 5 or less)

(6) Mitsubishi Chemical Polytail H A (hydroxyl value 41 to 55, iodine value 5 or less)

(7) GE X Toshiba Silicon XF—42—B0970 (hydroxyl-modified silicone oil)

(8) As shown in Tables 3 and 4, Thyroprene FM-0721 manufactured by Chisso Co., Ltd., was prepared by mixing a polypropylene resin composition, a olefin-based thermoplastic elastomer, and SEBS. When 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. On the other hand, when the hydroxyl group-containing hydrocarbon polymer and the modified silicone oil were not combined (Example 1), the adhesion to the polyurethane foam was not improved, and the high-temperature abrasion resistance was not sufficient. . When modified silicone oil is not blended

(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. Example 2 1 to 28, Comparative Example 5

 In this example, 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). Production Example 1 (Production of polyester resin A)

 100 parts of cyclohexane-1,4-dicarboxylic acid, 100 parts of 2-ethyl-2-butyl-1,3-propanediol (hydroxyl value 695 mg KOH / g) 14.3 parts, ethylene oxide adduct of bisphenol A (hydroxyl value Polycondensation reaction was carried out using 64.3 parts of 344 mg KO HZg) and 0.28 part of monobutyltin oxide as an esterification catalyst. The obtained 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. Production Example 2 (Production of polyester resin B)

100 parts of cyclohexane-1,4-dicarboxylic acid, 100 parts of 2-ethyl-2-butyl-1,3-propanediol (hydroxyl value S g S mg KOH / g) 76.5 parts, bisphenol A ethylene oxide adduct ( A polycondensation reaction was carried out using 8.7 parts of a hydroxyl value of 344 mg KOHZg) and 0.22 parts of monobutyltin oxide as an esterification catalyst. The obtained polyester resin B has a number average molecular weight of 7,930, The hydroxyl value was 9.8 mg K〇H / g and the glass transition temperature was 49 ° C.

 In addition, 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

(Note) (1) PM 940 M (MFR 30) manufactured by Sanaloma

 (2) Same as above Sun Attack (Atactic P P)

 (3) P.E.R.M 142 E (Reactor-one TPO) manufactured by Tokuyama Corporation

(4) Asahi Kasei Corporation Tuftec HI2 2 1 (Bound styrene content 12%) (5) GE Toshiba Silicone XF42—B0970 (carbinol-modified silicone oil)

 (6) Thyraplane FM-0721 manufactured by Chisso (methacryloxy group-modified silicone oil at one end) As shown in Table 5, the polypropylene resin composition was mixed with a refining thermoplastic elastomer and SEBS. When 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. Above all, when the modified silicone oil was used in combination (Examples 25 and 27), the abrasion resistance was further improved without lowering the adhesiveness.

 On the other hand, when the polyester resin A or B is not blended (Example 28), the adhesiveness and the high temperature wear resistance are insufficient. In addition, when the old refining elastomer was not blended (Comparative Example 5), the fold wrinkle resistance was poor and the adhesion to the polyurethane foam was low. Examples 2 9 to 3 3, Comparative Example 6

 In this example, 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 (Hydroxyl-containing aromatic vinyl compound copolymer; production of dusting agent) The following hydroxyl-containing aromatic vinyl compound copolymers 1 and 2 (dusting agents 1 and 2) were prepared by the fine suspension polymerization method. ) Was prepared.

 Hydroxyl-containing aromatic vinyl compound copolymer 1 (dusting agent 1):

Monomer: styrene 97 parts, 2-hydroxypropyl methacrylate 3 parts

Average primary particle size: 1.4 m, Tg: 101.5 ° C, sphericity: 1

 Hydroxyl-containing aromatic vinyl compound copolymer 2 (dusting agent 2):

Monomer: 70 parts of styrene, 27 parts of methyl methacrylate, 3 parts of 2-methyl methacrylate

Average primary particle size: 3.2 μm, Tg: 85 ° C, sphericity: 0.9 Production Example 2 (Aromatic vinyl compound copolymer; production of dusting agent 3) Monomer: 77 parts of styrene, 50 parts of methyl methacrylate, 50 parts of stearyl acrylate

Average primary particle size: 3.8 μm, Tg: 72 ° C, sphericity: 1 The polymer components of the types and amounts shown in Table 6 are mixed uniformly in a tumbler mixer, and then biaxially mixed. The mixture was kneaded by an extruder (TEM35B, manufactured by Toshiba Machine Co., Ltd.), pelletized, and then pulverized by a turbo mill to obtain a fine powder through a mesh sieve. Next, a hydroxyl group-containing aromatic vinyl compound copolymer (dusting agents 1 and 2) was mixed with the powder and granules using a shell-shell mixer and mixed to obtain a resin composition for powder molding. A powder fluidity test was performed using each of the obtained powdery resin compositions, and the obtained sheets were used to evaluate fold wrinkle resistance and adhesion to a polyurethane foam. Table 6 shows the results.

 For comparison, 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. , Wrinkle resistance and adhesion to polyurethane foam were evaluated. Table 6 shows the results. Table 6 Comparative example

 29 30 31 32 33 6 Hole: Pyrene resin * 1 10 10 30 30 30 30 Distributor 7 TP0 * 2 20 20 20 20 20

 SEBS * 3 70 70 50 50 50 70 mouth Dust ink * agent 1 15 15 15

 Dusty agent 2 15

 (Part) Dustin ink agent 3 15

 Powder flowability 23 ° C 15.2 16.1 13.5 17.5 25.0 * 17.7

(Seconds)

 50 ° C 26.4 29.4 25.7 30.8 40.2 * 32.1 Trial

 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

Heat resistant AAAAAA Urethane adhesive AAABBB Note * 1 Grand Polymer J 709 (MFR 55 g / 10 min)

 * 2 Tokuyama P.E.R.M.1 4 2 A (reactor-one TPO)

 * 3 Asahi Kasei Kogyo Co., Ltd. Tuftec H I 2 21

 * 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).

 On the other hand, when polymer particles containing no hydroxyl group were used as the dusting agent, powder flowability, powder moldability, creasing resistance and heat resistance were good, but the Adhesion was insufficient (Example 32). When no dusting agent was added, the powder fluidity and powder moldability were insufficient (Example 33). In addition, when the aged refining thermoplastic elastomer was not blended, the creasing resistance was reduced (Comparative Example 6). Examples 3 4 to 3 7

 In this example, 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.

The polymer components of the type and amount shown in Table 7 were kneaded with a twin-screw extruder (TEM 35 B, 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, powder flow properties and powder moldability were tested, and the obtained sheets were used to evaluate heat resistance and high-temperature wear resistance. Table 7 shows the results. Table 7

(Note) (1) PM 940 M (MFR 30) manufactured by Sanaloma I

 (2) Tokuyama P.E.R.144E (reactor T PO)

 (3) Asahi Kasei Corporation Tuftec H I 2 2 1 (Bound styrene content 12%)

 (4) Asahi Kasei Corporation Tuftec H I 043 (Bound styrene content 67%)

 * 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.). On the other hand, when SEBS having a bound styrene content of less than 20% was blended (Example 28) and when SEBS having a bound styrene content of 20% or more was blended (Example 37), both cases were observed. Insufficient wear resistance at high temperatures. Industrial applicability

 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.

In addition, the addition of 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; a polycarboxylic acid component (A) containing at least hexanedicarboxylic acid or a derivative thereof; and (i) a hydroxyl group. An alkanediol having a molecular structure in which a carbon atom to which a hydrogen atom is not bonded is sandwiched between two carbon atoms bonded to each other, and (ii) an alcohol component containing a polyhydric phenoxy alcohol (B) and 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. (3-4) When the glass transition temperature is 60 ° C or more, When a hydroxyl group-containing aromatic vinyl compound copolymer having an average primary particle size of 0.1 to 10 m is blended, powder flowability and powder moldability are improved, wrinkle resistance and foamed polyurethane adhesiveness are improved. It is good.

 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.

Claims

The scope of the claims

1. (1) (a) 20 to 80 parts by weight of a polypropylene resin, (b) 80 to 20 parts by weight of a refining thermoplastic elastomer (however, the sum of (a) and (b) is 1 20 to 80 parts by weight of a polypropylene resin composition comprising: (2) a hydrogenated aromatic vinyl compound-conjugated gen copolymer of 80 to 20 parts by weight.

(The total of (1) and (2) is 100 parts by weight.)

 2. 30 to 70 parts by weight of a polypropylene resin composition (1) and a hydride of an aromatic vinyl compound-conjugated gen copolymer (2) 70 to 30 parts by weight ((1) and ( The total amount of 2) is 100 parts by weight.) The refining-based resin composition for powder molding according to claim 1, comprising:

 3. The refined resin composition for powder molding according to claim 1, wherein the refined thermoplastic elastomer (b) is a propylene-based block copolymer. '

 4. The hydride of an aromatic vinyl compound-conjugated gen copolymer (2) is a hydride of a block copolymer of an aromatic vinyl compound and a conjugated gen. A refin-based resin composition for powder molding according to the above.

 5. A hydride of an aromatic vinyl compound-conjugated gen copolymer (2) is an aromatic vinyl compound-conjugated gen copolymer having an aromatic vinyl compound unit content of 5 to 50% by weight. 5. The refin-based resin composition for powder molding according to any one of claims 1 to 4, which is a hydride.

 6. A hydride of an aromatic vinyl compound-conjugated gen copolymer (2) is a copolymer of an aromatic vinyl compound having an aromatic vinyl compound unit content of 20 to 80% by weight and a conjugated diene copolymer. A hydride of a combined hydride of 10 to 90% by weight and an aromatic vinyl compound-conjugated gen copolymer having an aromatic vinyl compound unit content of 5% by weight or more and less than 20% by weight. 5. The refined resin composition for powder molding according to claim 1, which is a mixture comprising 0% by weight.

7. Further, (3-1) the fatty acid amide is mixed with the polypropylene resin composition (1). The powder composition according to any one of claims 1 to 6, comprising 1 to 20 parts by weight based on a total of 100 parts by weight of the hydride (2) of the aromatic vinyl compound-conjugated gen copolymer. Shape-forming refin-based resin composition.

 8. The refining resin composition for powder molding according to claim 7, wherein the fatty acid amide (3-1) is an unsaturated fatty acid amide.

 9. (3-2) Hydroxyl-containing hydrocarbon having an average number of hydroxyl groups of 1 to 8 per molecule, a number average molecular weight of 500 to 200,000, and an iodine value of 100 or less. 1 to 20 parts by weight based on the total of 100 parts by weight of the polypropylene polymer composition (1) and the hydride (2) of the aromatic vinyl compound-conjugated gen copolymer (2). 7. The refined resin composition for powder molding according to any one of 1 to 6.

10. The powdery molded olefin resin composition according to claim 9, wherein the hydroxyl group-containing hydrocarbon polymer (3-2) is a hydrogenated polybutadiene having hydroxyl groups at both ends.

 11. Further, (3-3) a polyvalent carboxylic acid component (A) containing at least cyclohexanedicarboxylic acid or a derivative thereof, and (i) a hydrogen atom between two carbon atoms each having a hydroxyl group bonded thereto. An alkanediol having a molecular structure in which a carbon atom is not bonded and having no molecular bond, and (ii) an alcohol component (B) containing a polyvalent phenoxy alcohol are polycondensed, and have a number average molecular weight of A polyester resin having a viscosity of 7,500 to 100,000 is mixed with a polypropylene resin composition (1) and a hydride (2) of an aromatic vinyl compound and a conjugated gen copolymer (2) in total Ί100 weight. 7. The refining resin composition for powder molding according to any one of claims 1 to 6, comprising 2 to 30 parts by weight based on parts by weight.

 1 2. Further, 10 parts by weight of the modified silicone oil is added to 100 parts by weight of the total of 100 parts by weight of the polypropylene resin composition (1) and the hydride of the aromatic vinyl compound-conjugated gen copolymer (2). 12. The refin-based resin composition for powder molding according to any one of claims 9 to 11, including:

13. The refining-based resin composition for powder molding according to claim 12, wherein the modified silicone oil has a hydroxyl group, an acryloyl oxy group or a methacryloyl oxy group in a molecule.

1 4. Further, (3-4) a hydroxyl group-containing aromatic vinyl compound copolymer having a glass transition temperature of 60 ° C or more and an average primary particle size of 0.1 to 10 xm, Claims 1 to 10 containing 0.1 to 30 parts by weight based on a total of 100 parts by weight of the propylene resin composition (1) and the hydride of the aromatic vinyl compound-conjugated gen copolymer (2). 7. The resin-based resin composition for powder molding according to any one of 6.

 1 5. The hydroxyl group-containing aromatic vinyl compound copolymer (3-4) contains 99.5 to 10% by weight of an aromatic vinyl compound and 0.5 to 10% by weight of a hydroxyl group-containing vinyl compound. 15. The powdery refin-based resin composition according to claim 14, which is a copolymer of

1 6. (1) (a) 20 to 80 parts by weight of polypropylene resin, (b) 80 to 20 parts by weight of a refining thermoplastic elastomer (however, the sum of (a) and (b) is 10 0 to 80 parts by weight of a polypropylene resin composition comprising:

(2) 80 to 20 parts by weight of a hydride of an aromatic vinyl compound-conjugated gen copolymer (the sum of (1) and (2) is 100 parts by weight); A step of obtaining a kneaded resin by kneading the mixture with other components, a step of preparing a pellet of the kneaded resin, and a step of continuously cooling and pulverizing the pellet. The method for producing a powdery resin-based resin composition according to any one of items 1 to 15.

 17. The powder refining system for powder molding according to claim 16, wherein in the step of preparing a pellet of the resin kneaded material, the average particle diameter of the pellets is adjusted to be 0.5 to 10 mm. A method for producing a resin composition.

 1 8. In the step of continuously cooling and pulverizing the pellet, the powder according to claim 6 or 17 is pulverized after cooling to a temperature lower than the glass transition temperature of the thermoplastic resin contained in the pellet. A method for producing a body-forming refin-based resin composition.

 1 9. Claims 16 to 18 after the step of continuously cooling and crushing the pellets, further comprising a step of classifying the crushed material so that the average particle diameter becomes 10 to 500 tm. The method for producing a powdery refin-based resin composition according to any one of the above.

20. After the step of continuously cooling and pulverizing the pellets, or after the step of further classifying the pulverized material so that the average particle size is about 0 to 500 m, A step of blending a dusting agent into the powder obtained by the classification. 10. The method for producing a powdery resin-based refin-based resin composition according to any one of claims 16 to 19.

 21. The apparatus for producing a powdery refin-based resin composition for powder molding according to any one of claims 1 to 15, comprising a kneader, a pelletizer, and a cooling pulverizer.