JP2004211069A - Thermoplastic elastomer resin composition and molded body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer resin composition which has no blocking among the pellets, flexible properties, a high melting point and a high mechanical strength, an excellent fluidity at the time of melting and a good moldability and gives a molded article which has a beautiful external appearance without surface layer delamination and bleedout, and to provide a molded body thereof. <P>SOLUTION: The thermoplastic elastomer resin composition comprises a blend of a dynamically crosslinked thermoplastic elastomer in which a polyester block copolymer is dynamically crosslinked in a dispersion phase with one or more kinds selected from a styrenic elastomer and/or an olefinic elastomer, with at least one kind selected from the group consisting of an epoxy-modified copolymer, an acid-modified copolymer and a polyester/aromatic vinyl copolymer block copolymer. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention has no blocking between pellets, is flexible, has a small compression set, has a high rebound resilience, is excellent in rubber properties, has high mechanical properties such as breaking strength and breaking elongation, and has injection molding and extrusion molding. The present invention relates to a thermoplastic elastomer resin composition which has good moldability, does not have surface peeling or bleed-out, and provides a molded article having a beautiful surface appearance, and a molded article using the same.

  Polyester block having a crystalline aromatic polyester unit such as a polybutylene terephthalate unit as a hard segment and an aliphatic polyether unit such as a poly (alkylene oxide) glycol and / or an aliphatic polyester unit such as a polylactone as a soft segment. The copolymer is excellent in mechanical properties such as breaking strength and elongation, impact resistance, elastic recovery, flexibility, etc., low-temperature and high-temperature properties, oil resistance and chemical resistance, and it is thermoplastic and easy to mold. Because of this, its applications are expanding to automotive parts, electric and electronic parts, fibers, films, and so on. Although it is a polyester block copolymer having such excellent physical properties, if the amount of copolymerization of the soft segment is increased to obtain a more flexible product, the solidification rate will be reduced and the mold will be released from the mold. Due to the deterioration of the moldability, the moldability and productivity are greatly reduced. In addition, since the melting point is reduced and the compression set is increased, and the heat resistance and oil resistance are also reduced, the polyester block copolymer alone is used, and the surface hardness is not more than 80 Shore A and the flexibility is excellent. It has been difficult to achieve processability and excellent rubber properties, heat resistance and oil resistance. Furthermore, when the copolymerization amount of the soft segment is increased as described above, the adhesiveness to the hard resin is reduced as well as the moldability, so that it is difficult to apply the composition to composite molding applications.

  Therefore, as an attempt to improve flexibility and adhesion to a hard resin, a composition comprising a thermoplastic elastomer such as a hydrogenated SBS block copolymer and a polyester-based thermoplastic elastomer (for example, see Patent Document 1) and styrene-butadiene There is known a composition comprising a hydrogenated derivative of a block copolymer, a softener for rubber, and a polyester elastomer (for example, see Patent Document 2).

  On the other hand, a resin composition in which a plasticizer is blended with a polyester block copolymer (for example, see Patent Document 3) is also known, and a hydrogenated styrene-butadiene block copolymer modified into a polyester block copolymer and A resin composition containing a plasticizer and a resin composition containing a hydrogenated styrene-isoprene block copolymer and a plasticizer in a polyester block copolymer (for example, see Patent Document 4) have already been proposed.

  By these methods, it is possible to obtain a resin composition that is more flexible than the conventional polyester block copolymer, but even with these techniques, there is a limit to the range in which the resin can be softened. If you try to obtain it, the blocking between the pellets is large and difficult to handle, and the mechanical properties and moldability, including the rubber properties such as compression set and rebound resilience, are greatly reduced, and severe bleed out occurs. Since the surface appearance of the molded article is remarkably deteriorated and the surface of the molded article is peeled off due to the surface layer peeling, the molded article cannot be used as an actual product. Also, such as polycarbonate resin, ABS resin, polybutylene terephthalate resin (hereinafter, referred to as PBT resin), poly-1,4-cyclohexane dimethylene terephthalate / isophthalate resin (hereinafter, referred to as PCTA resin), and polypropylene resin When bonded to a hard resin, there is also a problem that the bonding strength is not sufficiently high.

Further, an elastomer composition in which an epoxy-modified polymer is blended with a polyester elastomer is known (for example, see Patent Document 5). This composition is soft and has improved hydrolysis resistance, but has a compression set. The rubber had a large rebound resilience and was not sufficiently high in rubber-like properties. Furthermore, a composition comprising a polyester elastomer, a modified olefin resin having an epoxy group or a derivative group in a molecule thereof, and an olefin-based and / or styrene-based thermoplastic elastomer (for example, see Patent Document 6) is also known. Although this composition is soft and the surface layer peeling has been eliminated to some extent, it has been present that the compression set is large, the rebound resilience is low and the rubber-like properties are not sufficiently high.
JP-A-3-100045 JP-A-1-193352 JP-A-2-43251 JP-A-8-277359 JP-A-10-245475 JP 2001-279067 A

  An object of the present invention is to solve the above-described problems in the conventional technology, and it is an object of the present invention to provide a rubber-like material having no blocking between pellets, having a low compression set, a high rebound resilience, and being flexible. Excellent properties, good mechanical properties such as rupture strength and elongation at break, good moldability such as injection molding and extrusion molding, not only give a molded body with beautiful surface appearance without surface layer peeling or bleed-out, An object of the present invention is to provide a thermoplastic elastomer resin composition having sufficiently high adhesion to a hard resin such as a polycarbonate resin, an ABS resin, a PBT resin, a PCTA resin, and a polypropylene resin, and a molded article using the same.

  The present inventors have conducted intensive studies to achieve the above object, and as a result, at least one thermoplastic elastomer selected from a styrene-based elastomer and / or an olefin-based elastomer has been added to the polyester block copolymer as a dispersed phase. Thermoplastic elastomer resin composition comprising dynamically crosslinked dynamically crosslinked thermoplastic elastomer and at least one selected from epoxy-modified copolymer, acid-modified copolymer, and polyester-aromatic vinyl copolymer block copolymer As a result, the present inventors have found that the above objects can be effectively achieved, and have reached the present invention.

That is, in order to achieve the above object, according to the present invention,
A main component comprising a high-melting crystalline polymer segment (a1) mainly composed of a crystalline aromatic polyester unit and a low-melting polymer segment (a2) mainly composed of an aliphatic polyether unit and / or an aliphatic polyester unit; Dynamically crosslinked thermoplastic elastomer obtained by dynamically crosslinking 10 to 95% by weight of a polyester block copolymer (A) to be used and one or more thermoplastic elastomers selected from a styrene-based elastomer and / or an olefin-based elastomer as a disperse phase. B) From the epoxy-modified copolymer (C), the acid-modified copolymer (D) and the polyester-aromatic vinyl copolymer block copolymer (E), based on 100 parts by weight in total of 90 to 5% by weight. A thermoplastic elastomer resin composition comprising at least one selected from 0.1 to 40 parts by weight is provided. In the thermoplastic elastomer resin composition, 1 to 100 parts by weight of a plasticizer (F) and / or a softener (G) for rubber are added to 100 parts by weight of the total of (A) and (B). It is a preferred embodiment to mix 1 to 100 parts by weight.

According to the present invention, in order to achieve the above object,
A main component comprising a high-melting crystalline polymer segment (a1) mainly composed of a crystalline aromatic polyester unit and a low-melting polymer segment (a2) mainly composed of an aliphatic polyether unit and / or an aliphatic polyester unit; Dynamically crosslinked thermoplastic elastomer (B) 95 obtained by dynamically crosslinking 5 to 95% by weight of a polyester block copolymer (A) and one or more thermoplastic elastomers selected from styrene-based elastomers and / or olefin-based elastomers To 5% by weight, based on 100 parts by weight of the epoxy-modified copolymer (C), the acid-modified copolymer (D), and the polyester-aromatic vinyl copolymer block copolymer (E). One to 0.1 to 40 parts by weight of a fatty acid amide compound (H) is mixed with 0.01 to 5 parts by weight. A thermoplastic elastomer resin composition is provided. In the thermoplastic elastomer resin composition, 1 to 100 parts by weight of a plasticizer (F) and / or 100 parts by weight of the total of the above (A) and (B) are added. Alternatively, it is a preferred embodiment to incorporate 1 to 100 parts by weight of a rubber softener (G).

Incidentally, in the thermoplastic elastomer resin composition of the present invention,
The high-melting crystalline polymer segment (a1) of the polyester block copolymer (A) comprises a polybutylene terephthalate unit, or a polybutylene terephthalate unit and a polybutylene isophthalate unit;
The low-melting polymer segment (a2) of the polyester block copolymer (A) is selected from poly (tetramethylene oxide) glycol, an ethylene oxide adduct of poly (propylene oxide) glycol, and a copolymer glycol of ethylene oxide and tetrahydrofuran. One or more of the above, and the copolymerization amount is 40 to 80% by weight;
A dynamically crosslinked thermoplastic elastomer (B) obtained by dynamically crosslinking one or more thermoplastic elastomers selected from the styrene-based elastomer and / or the olefin-based elastomer as a disperse phase is selected from a styrene-based elastomer and / or an olefin-based elastomer. Is obtained by dynamically cross-linking a part of one or more kinds of thermoplastic elastomers, and has a cross-linked structure in a thermoplastic matrix composed of one or more kinds of thermoplastic elastomers selected from styrene-based elastomers and / or olefin-based elastomers. Having a structure in which at least one thermoplastic elastomer selected from styrene-based elastomers and / or olefin-based elastomers having:
A dynamically crosslinked thermoplastic elastomer (B) obtained by dynamically crosslinking one or more thermoplastic elastomers selected from the styrene-based elastomer and / or the olefin-based elastomer as a disperse phase is selected from a styrene-based elastomer and / or an olefin-based elastomer. Is obtained by dynamically cross-linking a part of one or more kinds of thermoplastic elastomers, and has a cross-linked structure in a thermoplastic matrix composed of one or more kinds of thermoplastic elastomers selected from styrene-based elastomers and / or olefin-based elastomers. Having a structure in which one or more thermoplastic elastomers selected from styrene-based elastomers and / or olefin-based elastomers are dispersed. In the case of dynamic crosslinking, the thermoplastic matrix and the dispersed phase are converted into glycidyl groups, carboxyl groups, Group, acid anhydride group Hydroxyl, thing functional monomers or their derivatives having an amino group is obtained by graft-modified,
A dynamically crosslinked thermoplastic elastomer (B) obtained by dynamically crosslinking one or more thermoplastic elastomers selected from the styrene-based elastomer and / or the olefin-based elastomer as a disperse phase, in a thermoplastic matrix made of polypropylene by dynamic crosslinking. Having a structure in which at least one thermoplastic elastomer selected from a styrene-based elastomer and / or an olefin-based elastomer having a crosslinked structure is dispersed;
A dynamically crosslinked thermoplastic elastomer (B) obtained by dynamically crosslinking one or more thermoplastic elastomers selected from the styrene-based elastomer and / or the olefin-based elastomer as a disperse phase, in a thermoplastic matrix made of polypropylene by dynamic crosslinking. Having a structure in which at least one thermoplastic elastomer selected from a styrene-based elastomer and / or an olefin-based elastomer having a crosslinked structure is dispersed, and in the case of dynamic crosslinking, the thermoplastic matrix and the dispersed phase are Glycidyl group, carboxyl group, acid anhydride group, hydroxyl group, that is graft-modified with a functional monomer having an amino group or a derivative thereof,
The epoxy-modified copolymer (C) may be an epoxy-modified block or random copolymer of an aromatic vinyl monomer and a conjugated diene and / or a hydrogenated product thereof (C1), or an ethylene-based copolymer. At least one selected from an epoxy-modified product (C2) and an epoxy-modified product (C3) of a graft polymer comprising an olefin-based polymer main chain and a vinyl-based polymer side chain;
The acid-modified copolymer (D) comprises a block composed of an aromatic vinyl monomer and a conjugated diene or an acid-modified product of a random copolymer and / or an aromatic vinyl monomer and a conjugated diene. From an acid-modified block copolymer or random copolymer and / or a hydrogenated product thereof (D1), an acid-modified ethylene copolymer (D2), and an olefin-based polymer main chain and a vinyl-based polymer side chain At least one selected from three types of acid-modified graft polymer (D3):
The polyester-aromatic vinyl copolymer (E) is a block (e1) composed of a polyester, a block composed of an aromatic vinyl monomer and a conjugated diene, or a random copolymer and / or a hydrogenated product thereof. Being a polyester-aromatic vinyl copolymer block copolymer comprising a block (e2) formed from
The plasticizer (F) is at least one compound selected from a benzoate plasticizer, a phthalate plasticizer, a trimellitate plasticizer, and a pyromellitic ester plasticizer;
The rubber softener (G) is a paraffinic oil and / or a naphthenic oil;
The fatty acid amide compound (H) is at least one selected from alkylene bis higher fatty acid amide compounds and carboxylic acid amide waxes obtained by reacting a mixture of a higher aliphatic monocarboxylic acid and a polybasic acid with a diamine. Being a compound,
However, these are all preferable conditions, and by applying these conditions, it is possible to expect to obtain a more excellent effect.

Further, the molded article of the present invention is characterized by being obtained by injection molding the thermoplastic elastomer resin composition,
Being a composite molded body,
A composite molded article comprising a hard resin and the thermoplastic elastomer resin composition, and at least one hard resin selected from a polycarbonate resin, an ABS resin, a PBT resin, a PCTA resin, and a polypropylene resin; Being a composite molded body composed of an elastomer resin composition,
Are all preferred conditions.

  According to the present invention, as described below, there is no blocking between pellets, and it is flexible, has a high melting point, has excellent heat resistance, and has good mechanical properties, as well as excellent fluidity at the time of melting, such as injection molding. The thermoplastic elastomer resin composition which has good moldability and can provide a molded article having a beautiful appearance without surface layer peeling or bleed-out is obtained. In addition, the thermoplastic elastomer resin composition of the present invention has a high adhesive strength to hard resins such as polycarbonate resins, is familiar to hands, and provides a composite molded article excellent in tactile sensation.

  Hereinafter, the present invention will be described in detail.

  The high-melting crystalline polymer segment (a1) of the polyester block copolymer (A) used in the present invention is a polyester formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol, and is preferably Polybutylene terephthalate derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol. In addition, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, and naphthalene-2,7 A dicarboxylic acid component such as dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or an ester-forming derivative thereof, and a diol having a molecular weight of 300 or less, for example, ethylene glycol , Trimethylene glycol, pen Aliphatic diols such as methylene glycol, hexamethylene glycol, neopentyl glycol, and decamethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and tricyclodecane dimethylol; xylylene glycol; bis (p-hydroxy) Diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] a polyester derived from an aromatic diol such as cyclohexane, 4,4′-dihydroxy-p-tert-phenyl, and 4,4′-dihydroxy-p-quat-phenyl, Alternatively, these dicarboxylic acid components and It may be a copolyester in combination with component 2 or more. It is also possible to copolymerize a trifunctional or higher polyfunctional carboxylic acid component, a polyfunctional oxyacid component, a polyfunctional hydroxy component and the like in a range of 5 mol% or less.

  Two or more of these dicarboxylic acids and their derivatives or diol components may be used in combination. Examples of preferred high melting crystalline polymer segment (a) are polybutylene terephthalate units derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol. Also, a polybutylene terephthalate unit derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol, and a polybutylene terephthalate unit derived from isophthalic acid and / or dimethyl isophthalate and 1,4-butanediol Those comprising a butylene isophthalate unit are also preferably used.

  The low-melting-point polymer segment (a2) of the polyester block copolymer (A) used in the present invention is an aliphatic polyether and / or an aliphatic polyester. Examples of the aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, and poly (propylene oxide). Examples include an ethylene oxide addition polymer of glycol, and a copolymer glycol of ethylene oxide and tetrahydrofuran. Examples of the aliphatic polyester include poly (ε-caprolactone), polyenantholactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate. From the elastic properties of the polyester block copolymer obtained from these aliphatic polyethers and / or aliphatic polyesters, poly (tetramethylene oxide) glycol, ethylene oxide adduct of poly (propylene oxide) glycol, ethylene oxide and tetrahydrofuran The use of copolymer glycols, poly (ε-caprolactone), polybutylene adipate, polyethylene adipate and the like is preferred, among which poly (tetramethylene oxide) glycol, ethylene oxide adduct of poly (propylene oxide) glycol, and ethylene oxide It is preferable to use a copolymer glycol of ethylene and tetrahydrofuran. Further, the number average molecular weight of these low melting point polymer segments is preferably about 300 to 6000 in a copolymerized state.

  The copolymerization amount of the low melting point polymer segment (a2) in the polyester block copolymer (A) used in the present invention is preferably 15 to 90% by weight, more preferably 40 to 85% by weight.

  The polyester block copolymer (A) used in the present invention can be produced by a known method. For example, a lower alcohol diester of a dicarboxylic acid, an excess amount of a low-molecular-weight glycol, and a transesterification reaction of a low-melting polymer segment component in the presence of a catalyst, a method of polycondensing the obtained reaction product, an excess amount of a dicarboxylic acid and A method of subjecting glycol and the low-melting polymer segment component to an esterification reaction in the presence of a catalyst, and polycondensing the obtained reaction product, preparing a high-melting crystalline segment in advance, and adding the low-melting segment component to this. Examples include a method of randomizing by a transesterification reaction, a method of connecting a high-melting crystalline segment and a low-melting polymer segment with a chain linking agent, and further, when poly (ε-caprolactone) is used for the low-melting polymer segment. Ε-caprolactone monomer is added to the high melting crystalline segment Any of these methods may be used.

  The dynamically crosslinked thermoplastic elastomer (B) obtained by dynamically crosslinking one or more thermoplastic elastomers selected from a styrene elastomer and / or an olefin elastomer used in the present invention as a dispersed phase is a styrene elastomer and / or olefin. A thermoplastic matrix comprising one or more thermoplastic elastomers selected from styrene-based elastomers and / or olefin-based elastomers. Having a structure in which at least one kind of thermoplastic elastomer selected from a styrene-based elastomer and / or an olefin-based elastomer having a cross-linked structure is dispersed, and in the case of the dynamic cross-linking, the thermoplastic matrix and the dispersed phase are used. , Glycidyl group, carboxy Grafted with a functional monomer having a hydroxyl group, an acid anhydride group, a hydroxyl group, or an amino group or a derivative thereof, or one or more thermoplastic elastomers selected from the styrene-based elastomers and / or the olefin-based elastomers. A dynamically crosslinked thermoplastic elastomer (B) dynamically crosslinked as a disperse phase, wherein at least one selected from a styrene-based elastomer and / or an olefin-based elastomer having a crosslinked structure in a thermoplastic matrix composed of polypropylene by dynamic cross-linking; Having a structure in which a thermoplastic elastomer is dispersed, or in the case of this dynamic crosslinking, the thermoplastic matrix and the dispersed phase, a glycidyl group, a carboxyl group, an acid anhydride group, a hydroxyl group, a functional monomer having an amino group Or graft-modified with their derivatives And than, or rubber softener such as paraffinic oils, it may also contain fillers such as magnesium carbonate and talc, for example, the magazine "Plastics", Vol. 53, no. 3, P20 to P30 (2002), sold by Riken Technos Co., Ltd. under the trade name "ACTIMER" CM, and the magazine "Synthetic Resin", Vol. 44, no. 1. P11 to P12 (published in 1998) and sold by Riken Vinyl Industry Co., Ltd. under the trade name "ACTIMER" # 1000 can also be used.

  In the present invention, one or more thermoplastic elastomers selected from a styrene-based elastomer and / or an olefin-based elastomer are dynamically crosslinked as a dispersed phase with respect to 10 to 95% by weight of the polyester block copolymer (A). The crosslinked thermoplastic elastomer (B) is blended in an amount of 90 to 5% by weight, preferably 85 to 7% by weight, and more preferably 80 to 10% by weight. If the blending amount of the polyester block copolymer (A) is less than the above range, heat resistance, chemical resistance, moldability, etc. of the resin composition become insufficient, which is not preferable. If the amount of the polyester block copolymer (A) exceeds the above range, the flexibility of the resin composition becomes insufficient, which is not preferable.

  Epoxy-modified and / or aromatic vinyl-based monomer of a block or random copolymer comprising an aromatic vinyl-based monomer and a conjugated diene, which is one kind of the epoxy-modified copolymer (C) used in the present invention. The epoxy-modified block (C1) of a hydrogenated product of a block or a random copolymer composed of a conjugated diene and a conjugated diene includes styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, α- Aromatic vinyl monomers such as ethylstyrene, p-ethylstyrene, α-chlorostyrene, 1,3-dichlorostyrene, and 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene , 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butane Copolymerization of conjugated diene monomers such as -1,3-octadiene and chloroprene with glycidyl ester compounds of α, β-unsaturated acids such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate and glycidyl itaconate. It was done. Further, a diene portion formed from a conjugated diene monomer may be hydrogenated. Further, aromatic compounds such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, α-ethylstyrene, p-ethylstyrene, α-chlorostyrene and 1,3-dichlorostyrene Vinyl monomer and 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, Copolymer with a conjugated diene monomer such as 1,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and / or a hydrogenated product thereof. An epoxidized product obtained by reacting the heavy bond with an epoxidizing agent is also preferable.

  The epoxy modified product (C2) of an ethylene polymer, which is one type of the epoxy modified copolymer (C) used in the present invention, is ethylene or an α-olefin such as ethylene and propylene, butene-1, and vinyl acetate. , Vinyl esters such as vinyl propionate, copolymers with acrylates or methacrylates such as methyl, ethyl, propyl, and butyl, as well as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate Glycidyl esters of α, β-unsaturated acids are preferred, and glycidyl methacrylate is particularly preferred.

  The epoxy-modified copolymer (C3) of a graft polymer comprising an olefin-based polymer main chain and a vinyl-based polymer side chain, which is one type of the epoxy-modified copolymer (C) used in the present invention, comprises ethylene or propylene alone; Alternatively, a combination of ethylene with an α-olefin such as propylene or butene-1, vinyl acetate such as vinyl acetate or vinyl propionate, or an acrylate or methacrylate such as methyl, ethyl, propyl or butyl, and an acrylic The main chain is an olefin polymer obtained by copolymerizing glycidyl esters of α, β-unsaturated acids such as glycidyl glycidyl, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate. -Methylstyrene, pt-butylstyrene Aromatic vinyl monomers such as α-ethylstyrene, p-ethylstyrene, α-chlorostyrene, 1,3-dichlorostyrene, and vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and ethacrylonitrile , Methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, etc. Is a graft polymer having a side chain of a vinyl polymer formed from a (meth) acrylic ester monomer or the like. Among them, those obtained by copolymerizing glycidyl methacrylate in the main chain are preferable.

  An acid-modified product and / or an aromatic vinyl-based monomer of a block or random copolymer composed of an aromatic vinyl monomer and a conjugated diene, which is one kind of the acid-modified copolymer (D) used in the present invention. An acid-modified product and / or a hydrogenated product (D1) of a block or random copolymer composed of a product and a conjugated diene are styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, pt-butylstyrene. , Α-ethylstyrene, p-ethylstyrene, α-chlorostyrene, 1,3-dichlorostyrene, and other aromatic vinyl monomers, and 1,3-butadiene, isoprene, 2,3-dimethyl-1, 3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl A block or random copolymer obtained from a conjugated diene such as 1,3-octadiene or chloroprene and / or a hydrogenated product thereof modified with a carboxyl group-containing unsaturated compound or an acid anhydride-containing unsaturated compound. is there. Examples of the carboxyl group-containing unsaturated compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, and maleic acid. Examples of the acid anhydride-containing unsaturated compound include maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride and the like. Among them, those obtained by modifying a block copolymer obtained from styrene and 1,3-butadiene or isoprene and / or a hydrogenated product thereof with maleic anhydride are preferable.

  The acid-modified product (D2) of an ethylene copolymer, which is one kind of the acid-modified copolymer (D) used in the present invention, is ethylene or ethylene and an α-olefin such as propylene or butene-1; Vinyl acetate, vinyl ester such as vinyl propionate, copolymer with acrylic acid ester such as methyl, ethyl, propyl, butyl or methacrylic acid ester, maleic anhydride, nadic anhydride, itaconic anhydride, tetrahydrophthalic anhydride It is obtained by copolymerizing an acid or the like, and among them, maleic anhydride is preferably used.

  The acid-modified copolymer (D3), which is one kind of the acid-modified copolymer (D) used in the present invention, is a graft polymer having a main chain of an olefin polymer and a side chain of a vinyl polymer, and ethylene- or propylene alone. Or a combination of ethylene and propylene, an α-olefin such as butene-1, vinyl acetate, a vinyl ester such as vinyl propionate, an acrylate or methacrylate such as methyl, ethyl, propyl, or butyl; The main chain is an olefin polymer obtained by copolymerizing maleic anhydride, nadic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, etc., and styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, pt-butyl Styrene, α-ethylstyrene, p-ethylstyrene, α-chlorostyrene, 1, -Aromatic vinyl monomers such as dichlorostyrene, vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid-n- Vinyl based on (meth) acrylate monomers such as butyl, isobutyl methacrylate, methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate It is a graft polymer having a polymer as a side chain. Among them, those obtained by copolymerizing maleic anhydride in the main chain are preferable.

  The polyester-aromatic vinyl copolymer block copolymer (E) used in the present invention includes a block (e1) composed of a polyester, a block composed of an aromatic vinyl monomer and a conjugated diene, or a random copolymer. And / or a block copolymer obtained by copolymerizing a block (e2) formed from a hydrogenated product thereof with a block copolymer composed of polybutylene terephthalate, a styrene-butadiene block copolymer or a styrene-isoprene block. A block copolymer obtained by chemically bonding blocks comprising a copolymer and / or a hydrogenated product thereof is preferred. As the type of the block copolymer, one block (e1) composed of a polyester, a block composed of an aromatic vinyl monomer and a conjugated diene, or a block formed of a random copolymer and / or a hydrogenated product thereof is used. (E2) A block comprising an aromatic vinyl monomer and a conjugated diene or a random copolymer on both sides of a block (e1) composed of a diblock copolymer or polyester to which one is bonded, and / or Or a block (e2) formed from a hydrogenated product thereof, a triblock copolymer in which one block is bonded to each other, a block composed of an aromatic vinyl monomer and a conjugated diene, or a random copolymer, and / or On both sides of a block (e2) formed from these hydrogenated products, a blow made of polyester Block (e1), a block or random copolymer composed of an aromatic vinyl monomer and a conjugated diene, and a block (e1) composed of an aromatic vinyl monomer and a conjugated diene. And a multiblock copolymer in which blocks (e2) formed from hydrogenated products of the above are alternately bonded in a total number of 4 or more.

  In the present invention, by further blending a plasticizer (F), the thermoplastic elastomer resin composition is made flexible, the compatibility and the melt fluidity are improved, and the occurrence of surface peeling is further suppressed. Can be. Examples of the plasticizer (F) used in the present invention include phthalate plasticizers such as dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diundecyl phthalate and diisononyl phthalate. Phosphate plasticizers such as tricresyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trimethyl phosphate and tris-dichloropropyl phosphate, octyl trimellitate, isononyl trimellitate, Trimellitic ester plasticizers such as isodecyl melitate, dipentaerythritol esters, dioctyl adipate, di-2-e Fatty acid ester plasticizers such as lehexyl adipate, diisobutyl adipate, dibutyl adipate, diisodecyl adipate, dibutyl diglycol adipate, di-2-ethylhexyl azelate, dioctyl sebacate, methyl acetyl ricinoleate, and pyromerits such as octyl pyromellitate Acid esters, epoxidized soybean oil, epoxidized linseed oil, epoxidized plasticizers such as epoxidized fatty acid alkyl esters, adipic acid ether esters, polyether esters, polyether-based plasticizers such as polyethers, and diethylene glycol dibenzoate; Polypropylene glycol dibenzoate, tripropylene glycol dibenzoate, dipropylene glycol dibenzoate, propylene glycol diben Examples include benzoate-based plasticizers such as acrylate, dibutylene glycol dibenzoate, neopentyl glycol dibenzoate, glyceryl tribenzoate, pentaerythritol tetrabenzoate, triethylene glycol dibenzoate, polyethylene glycol dibenzoate, and trimethylolethane tribenzoate. Among these, it is preferable to be at least one compound selected from a benzoate-based plasticizer, a phthalate-based plasticizer, a trimellitate-based plasticizer, and a pyromellitic-ester-based plasticizer.

  When the plasticizer (F) is used in the present invention, the amount is 1 to 100 parts by weight of the total of the polyester block copolymer (A) and the dynamically crosslinked thermoplastic elastomer (B) obtained by dynamically crosslinking a styrene-based elastomer. -100 parts by weight, preferably 3-50 parts by weight.

  In the present invention, by further blending a softening agent for rubber (G), the thermoplastic elastomer resin composition is softened, the compatibility and the melt fluidity are improved, and the occurrence of surface peeling is further suppressed. can do. Examples of the rubber softener (G) used in the present invention include mineral oil softeners such as naphthenic oils and paraffin oils, and synthetic resin softeners such as polybutene and low molecular weight polybutadiene. Paraffinic oils and / or naphthenic oils are preferably used.

  When the rubber softener (G) is used in the present invention, the total weight of the polyester block copolymer (A) and the dynamically crosslinked thermoplastic elastomer (B) obtained by dynamically crosslinking the styrene elastomer is 100 parts by weight. 1 to 100 parts by weight, preferably 3 to 50 parts by weight is blended.

  In the present invention, by further mixing the fatty acid amide compound (H), the blocking between the pellets and the peeling of the surface layer can be further improved. The fatty acid amide compound (H) used in the present invention is a compound obtained by reacting a fatty acid with an amine compound, and is obtained by reacting a mixture of an alkylene bis higher fatty acid amide compound, a mixture of a higher aliphatic monocarboxylic acid and a polybasic acid with a diamine. One or more compounds selected from the obtained carboxylic acid amide-based wax can be exemplified. Examples of the alkylene bis higher fatty acid amide compounds include monoamide compounds such as oleyl oleamide, stearyl oleamide, oleyl stearamide, methylene bis stearamide, methylene bis oleamide, methylene bis lauric amide, and methylene bis capric acid. Amide, methylenebismyristate amide, methylenebispalmitate amide, ethylenebisstearic acid amide, ethylenebisoleic acid amide, ethylenebislauric acid amide, ethylenebiscapric acid amide, ethylenebismyristate amide, ethylenebispalmitate amide, etc. Alkylene symmetric bis higher fatty acid amides, methylene stearyl oleyl bis amide, methylene stearyl lauryl bis amide, methylene palmitoleyl oley Bisamide, ethylene stearyl oleyl bis amides, such as ethylene stearyl lauryl bis amides and ethylene palmitoleyl oleyl bis amides can be specifically exemplified. Also, a mixture of an alkylene symmetric bis higher fatty acid amide and an alkylene asymmetric bis higher fatty acid amide compound may be used. A carboxylic acid amide wax obtained by reacting a mixture of a higher aliphatic monocarboxylic acid and a polybasic acid with a diamine is obtained by a dehydration reaction of a mixture of a higher aliphatic monocarboxylic acid and a polybasic acid with a diamine. As the higher aliphatic monocarboxylic acid, a saturated aliphatic monocarboxylic acid hydroxycarboxylic acid having 16 or more carbon atoms is preferable, and examples thereof include palmitic acid, stearic acid, behenic acid, montanic acid, and 12-hydroxystearic acid. As the polybasic acid, a carboxylic acid of dibasic acid or more, for example, aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelic acid, and azelaic acid, and aromatics such as phthalic acid and terephthalic acid Alicyclic dicarboxylic acids and cycloaliphatic di- and carboxylic acids such as cyclohexanedicarboxylic acid and cyclohexylsuccinic acid. Examples of the diamine include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, metaxylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, and isophoronediamine.

  In the present invention, when these fatty acid amide compounds (H) are used, the amount of the fatty acid amide compound (H) is 0.1 part by weight based on 100 parts by weight of the total of the polyester block copolymer (A) and the hydrogenated styrene-based block copolymer (B). It is added in an amount of from 0.01 to 5 parts by weight, preferably from 0.05 to 3 parts by weight.

  Although the method for producing the thermoplastic elastomer resin composition of the present invention is not particularly limited, for example, at least one kind of heat selected from polyester block copolymer (A), styrene-based elastomer and / or olefin-based elastomer is used. Dynamically crosslinked thermoplastic elastomer (B) obtained by dynamically crosslinking a thermoplastic elastomer as a disperse phase, epoxy-modified copolymer (C), acid-modified copolymer (D) and polyester-aromatic vinyl copolymer block copolymer A method in which a raw material obtained by blending at least one or more selected from (E) together with other additives is supplied to a screw-type extruder and melt-kneaded, and the polyester block copolymer (A) is supplied to the screw-type extruder Melted and selected from styrene-based elastomer and / or olefin-based elastomer from another supply port Dynamically crosslinked thermoplastic elastomer (B) obtained by dynamically crosslinking at least one kind of thermoplastic elastomer as a disperse phase, epoxy-modified copolymer (C), acid-modified copolymer (D) and polyester-aromatic vinyl copolymer A method of feeding and kneading at least one or more selected from polymer block copolymers (E) together with other additives, and a method of feeding a polyester block copolymer (A), a styrene-based elastomer and / or an olefin-based elastomer to a screw type extruder. Dynamically crosslinked thermoplastic elastomer (B), epoxy-modified copolymer (E), acid-modified copolymer (F) and polyester-aromatic obtained by dynamically crosslinking one or more thermoplastic elastomers selected from the group consisting of: At least one kind selected from the vinyl copolymer block copolymer (G) is supplied and melted, and further supplied. A method of supplying kneading other additives from the like.

  Further, various additives can be added to the thermoplastic elastomer resin composition of the present invention as long as the object of the present invention is not impaired. For example, known hindered phenol-based, phosphite-based, thioether-based, aromatic amine-based antioxidants, benzophenone-based, benzotriazole-based, hindered amine-based light-fast agents, pigments, dyes and other colorants, and antistatic agents , A conductive agent, a flame retardant, a reinforcing agent, and the like can be arbitrarily contained.

  The thermoplastic elastomer resin composition of the present invention is molded by injection molding or extrusion molding, is flexible and has excellent rubber elasticity such as compression set, high mechanical properties such as breaking strength and breaking elongation, and bleed out. Gives a molded product with a beautiful surface appearance without delamination or surface delamination. Therefore, molded articles obtained from the thermoplastic elastomer resin composition of the present invention are useful for automobiles, electronic / electric equipment, precision equipment, various molded articles for general consumer goods, and the like. Further, it is suitable for grips, tubes, packings, gaskets, hoods, covers, dampers, cushion bodies, films, sheets, and the like.

  It is also useful to obtain a composite molded product obtained by laminating a layer made of the thermoplastic elastomer resin composition of the present invention and a hard resin layer. The hard resin constituting the hard resin layer is not particularly limited as long as the resin maintains the rigidity of the composite molded article and has a desired mechanical strength. Specifically, a polycarbonate resin, a polyester resin, a polyamide resin, a polyacetal resin, an ABS resin, an acrylic resin, a styrene resin, a polyethylene resin, a polypropylene resin, and the like. Among these, the polycarbonate resin, the ABS resin, the PBT resin, PCTA resin and polypropylene resin are preferred.

  The composite laminate is manufactured by multi-color injection molding including co-extrusion molding and two-color molding, and overmolding by insert molding. Since the thermoplastic elastomer resin composition of the present invention has excellent adhesiveness with these hard resins, a composite molded article with these hard resins can be used in various cases, antenna covers, connectors, grips, rollers, It can be used for casters, hoses, multilayer tubes and the like.

  Hereinafter, the effects of the present invention will be described with reference to examples. All percentages and parts in the examples are on a weight basis unless otherwise specified. The physical properties shown in the examples were measured as follows.

[Melting point]
Using a differential scanning calorimeter (DSC-910 manufactured by Du Pont), the top temperature of the melting peak when heated at a rate of 10 ° C./min in a nitrogen gas atmosphere was measured.

[Melt viscosity index (MFR)]
It was measured at a temperature of 220 ° C. and a load of 2160 g according to ASTM D-1238.

[Blocking property]
200 g of the pellets are placed in an assemblable box-shaped container having an inner dimension of 15 cm × 7 cm × 6 cm in height, a plate of 15 cm × 7 cm is placed on the pellets, and a load of 16 kg is applied thereto. In that state, heat treatment is performed in a hot air oven at 80 ° C. for 20 hours. After the test, a load was applied by removing the side wall of the box-shaped container, and the maximum load at which the blocking state collapsed was measured.

[Hardness (Durometer A)]
Measured according to ASTM D-2240.

[Rebound resilience]
It was measured according to BS standard 903.

[Mechanical properties]
According to JIS K7113, tensile strength at break and tensile elongation at break were measured.

[Compression permanent set]
The pellets dried at 80 ° C. for 3 hours were injection molded at a temperature of 200 ° C. to obtain a cylindrical molded product having a diameter of 29 mm and a thickness of 10 mm. This molded product was subjected to a heat treatment at 70 ° C. × 22 hours in a state of being compressed by 25%. The compression set was calculated from the ratio of the amount of strain to the amount of compression.

[Surface separation]
The pellets dried at 80 ° C. for 3 hours were injection molded at a temperature of 200 ° C. to obtain a molded product having a length of 115 mm, a width of 60 mm and a thickness of 2 mm. The surface of the molded product was visually observed to determine whether or not surface layer peeling had occurred.

[Bleed out]
Each pellet vacuum-dried at 80 ° C. for 3 hours was press-molded at a temperature of 200 ° C. to form a sheet having a thickness of 2 mm. Fine paper was sandwiched between the sheets and left for 100 hours in a constant temperature bath at 40 ° C. under a load of 55 g per 1 cm 2 to check whether or not bleeding into the high quality paper sheet had occurred.

[Reference example]
[Production of polyester block copolymer (A-1)]
208 parts of terephthalic acid, 228 parts of 1,4-butanediol, 720 parts of a copolymer of ethylene oxide and tetrahydrofuran (EO / THF molar ratio: 40/60) having a number average molecular weight of about 2000 and 720 parts of glycol together with 2 parts of titanium tetrabutoxide in a helical ribbon type The mixture was charged into a reaction vessel equipped with stirring blades, heated at 190 to 225 ° C. for 3 hours, and an esterification reaction was performed while distilling reaction water out of the system. To the reaction mixture was added 0.5 part of "Irganox" 1010 (a hindered phenol-based antioxidant manufactured by Ciba-Geigy), and the temperature was raised to 245 ° C. Under reduced pressure, polymerization was carried out under the conditions for 2 hours and 50 minutes. The obtained polymer was discharged into water in the form of a strand, and pelletized by cutting.

[Production of polyester block copolymer (A-2)]
293 parts of terephthalic acid, 85 parts of isophthalic acid, 415 parts of 1,4-butanediol, 467 parts of poly (tetramethylene oxide) glycol (number average molecular weight about 1400), 1.5 parts of titanium tetrabutoxide and trimellitic anhydride 3 parts were charged into a reaction vessel equipped with a helical ribbon type stirring blade, and heated at 210 ° C. for 2 hours 30 minutes to distill out 95% of the theoretical amount of methanol out of the system. After adding 0.75 parts of “Irganox” 1010 to the reaction mixture, the temperature was raised to 245 ° C., and then the pressure in the system was reduced to 27 Pa over 40 minutes, and polymerization was carried out for 2 hours and 40 minutes under these conditions. Was. The obtained polymer was discharged into water in the form of a strand, and pelletized by cutting.

[Production of polyester block copolymer (A-3)]
320 parts of dimethyl terephthalate, 93 parts of dimethyl isophthalate, 345 parts of 1,4-butanediol, and 550 parts of poly (propylene oxide) glycol (number average molecular weight: 2200, EO content: 26.8%) capped with ethylene oxide were added to titanium. Charge 2 parts of tetrabutoxide and 3 parts of trimellitic anhydride into a reaction vessel equipped with a helical ribbon-type stirring blade, heat at 210 ° C. for 2 hours 30 minutes, and distill 95% of the theoretical amount of methanol out of the system. Let out. After adding 0.75 parts of “Irganox” 1010 to the reaction mixture, the temperature was raised to 245 ° C., and then the pressure in the system was reduced to 27 Pa over 50 minutes. I did it. The obtained polymer was discharged into water in the form of a strand, and pelletized by cutting.

  Table 1 shows the composition and physical properties of (A-1), (A-2) and (A-3). In the table, EO / THF is a copolymer of ethylene oxide and tetrahydrofuran, PTMG is a poly (tetramethylene oxide) glycol, and EO-PPG is a poly (ethylene-capped terminal) with a low melting point polymer type. (Propylene oxide) glycol, and the numbers indicate the number average molecular weight.

[Dynamic crosslinked thermoplastic elastomer]
Table 2 shows the dynamically crosslinked thermoplastic elastomers used in the following examples.

[Epoxy-modified polymer]
Table 3 shows the epoxy-modified polymers used in the following Examples.

[Acid-modified polymer]
Table 4 shows the acid-modified polymers used in the following Examples.

[Polyester-aromatic vinyl copolymer block copolymer]
Table 5 shows the polyester-aromatic vinyl copolymer block copolymeric acid-modified polymer used in the following Examples.

[Plasticizer]
Table 6 shows the plasticizers used in the following examples.

[Rubber softener]
Table 7 shows the softeners for rubber used in the following examples.

[Fatty acid amide compound]
Table 8 shows the fatty acid amide compounds used in the following Examples.

[Examples 1 to 9]
Polyester block copolymer (A-1) obtained in Reference Example, dynamically crosslinked thermoplastic elastomer (B-1), (B-2), (B-3), epoxy-modified polymer (C-1) , (C-2), (C-3), acid-modified polymer (D-1), (D-2), (D-3), polyester-aromatic vinyl copolymer block copolymer (E-1) , (E-2) were mixed in a mixing ratio shown in Table 9 using a V-blender, and melt-kneaded at 240 ° C. using a twin-screw extruder having a diameter of 45 mm and a three-thread screw type, Pelletized. Using these pellets, the melting point, melt viscosity index (MFR), pellet blocking, hardness, rebound resilience, tensile rupture strength, tensile rupture elongation, compression set, surface peeling, and bleed out were evaluated. Table 10 shows the results.

[Comparative Examples 1 to 3]
At the compounding ratio shown in Table 9, it was melt-kneaded and pelletized in the same manner as in Examples 1 to 8. Table 9 shows the results of evaluating the physical properties in the same manner as in Examples 1 to 9.

[Comparative Examples 4 to 6]
As a flexible material, "Septon" 2063 (styrene-based elastomer) manufactured by Kuraray Co., Ltd. or "Mirastomer" 5030 (olefin elastomer) manufactured by Mitsui Chemicals, Inc. were used at the compounding ratios shown in Table 9 and in Examples 1 to 3. It was melt-kneaded in the same manner as in No. 9 and pelletized. Table 10 shows the results of evaluating the physical properties in the same manner as in Examples 1 to 9.

[Examples 10 to 18]
Polyester block copolymers (A-2) and (A-3) obtained in Reference Examples, dynamically crosslinked thermoplastic elastomers (B-1), (B-2) and (B-3), epoxy-modified polymer Combined (C-1), (C-2), (C-3), plasticizer (F-1), (F-2), (F-3), rubber softener (G-1), ( G-2), fatty acid amide compounds (H-1), (H-2), and (H-3) were mixed at a mixing ratio shown in Table 11 using a V-blender, and a diameter of 45 mm and a three-threaded screw type were used. The mixture was melt-kneaded at 240 ° C. using a twin-screw extruder having the following screws and pelletized.

  Using these pellets, the melting point, melt viscosity index (MFR), pellet blocking, hardness, rebound resilience, tensile rupture strength, tensile rupture elongation, compression set, surface peeling, and bleed out were evaluated. Table 12 shows the results.

[Comparative Examples 7 to 10]
At the compounding ratio shown in Table 11, it was melt-kneaded and pelletized in the same manner as in Examples 10 to 18. Table 12 shows the results of evaluating the physical properties in the same manner as in Examples 10 to 18.

[Example 19]
An ABS resin (“Toyolac” T-500 manufactured by Toray Industries, Inc.) was used as the hard resin, and a square plate of 80 mm square and 2 mm thick was formed as a primary molded product. Next, this square plate was mounted in a cavity of 80 mm square and 4 mm deep, and the composition No. 1 prepared in Example 1 was used. Secondary molding was performed using No. 1 as a secondary material to form a flat composite molded article. No surface peeling was observed on the surface of this composite molded article, and the appearance was beautiful. This composite molded product was cut to a width of 10 mm, the joining interface at one end was forcibly peeled off by a cutter knife by a fixed length, and each end was set on a fixture of a Tensilon tensile tester and pulled to reduce the peel strength. It was measured. The peel strength was 120N.

[Example 20]
A polypropylene resin ("Grand Polypro" J703W manufactured by Grand Polymer Co., Ltd., J703W) was injection-molded as a hard resin, and an 80 mm square and 2 mm thick square plate was molded as a primary molded product. Next, this square plate was mounted in a cavity of 80 mm square and 4 mm deep. Secondary molding was performed using No. 5 as a secondary material to form a flat composite molded article. No surface peeling was observed on the surface of this composite molded article, and the appearance was beautiful. This composite molded product was cut to a width of 10 mm, the joining interface at one end was forcibly peeled off by a cutter knife by a fixed length, and each end was set on a fixture of a Tensilon tensile tester and pulled to reduce the peel strength. It was measured. The peel strength was 100N.

[Example 21]
A PCTA resin (“Easter” AN004 manufactured by Eastman) was used as a hard resin, and a square plate of 80 mm square and 2 mm thick was molded as a primary molded product. Next, this square plate was mounted in a cavity of 80 mm square and 4 mm in depth. Secondary molding was performed using No. 22 as a secondary material to form a flat composite molded article. No surface peeling was observed on the surface of this composite molded article, and the appearance was beautiful. This composite molded product was cut to a width of 10 mm, the joining interface at one end was forcibly peeled off by a cutter knife by a fixed length, and each end was set on a fixture of a Tensilon tensile tester and pulled to reduce the peel strength. It was measured. The peel strength was 130N.

[Example 22]
A polycarbonate resin ("Iupilon" S3000 manufactured by Mitsubishi Engineering-Plastics Co., Ltd.) was injection-molded as a hard resin, and a square plate of 80 mm square and 2 mm thick was formed as a primary molded product. Next, this square plate was mounted in a cavity of 80 mm square and 4 mm deep. Secondary molding was performed using No. 16 as a secondary material to form a flat composite molded article. No surface peeling was observed on the surface of this composite molded article, and the appearance was beautiful. This composite molded product was cut to a width of 10 mm, the joining interface at one end was forcibly peeled off by a cutter knife by a fixed length, and each end was set on a fixture of a Tensilon tensile tester and pulled to reduce the peel strength. It was measured. The peel strength was 120N.

[Example 23]
A PBT resin (“Toraycon” 1401X06, manufactured by Toray Industries, Inc.) was injection-molded as a hard resin to form an 80 mm square and 2 mm thick square plate as a primary molded product. It was mounted in a 4 mm cavity, and was subjected to secondary molding using the composition No. 9 produced in Example 9 as a secondary material to form a flat composite molded product. The composite molded product was cut into a width of 10 mm, the joint interface at one end was forcibly peeled off by a cutter knife to a certain length, and each end was subjected to a tensilon tensile test. The film was set on a fixture of the machine and pulled to measure the peel strength, which was 110 N.

[Example 24]
A polypropylene resin ("Grand Polypro" J703W manufactured by Grand Polymer Co., Ltd., J703W) was injection-molded as a hard resin, and an 80 mm square and 2 mm thick square plate was molded as a primary molded product. Next, this square plate was mounted in a cavity of 80 mm square and 4 mm in depth. Secondary molding was performed using No. 4 as a secondary material to form a flat composite molded article. No surface peeling was observed on the surface of this composite molded article, and the appearance was beautiful. This composite molded product was cut to a width of 10 mm, the joining interface at one end was forcibly peeled off by a cutter knife by a fixed length, and each end was set on a fixture of a Tensilon tensile tester and pulled to reduce the peel strength. It was measured. The peel strength was 110N.

[Comparative Example 11]
An ABS resin (“Toyolac” T-500 manufactured by Toray Industries, Inc.) was used as the hard resin, and a square plate of 80 mm square and 2 mm thick was formed as a primary molded product. Next, this square plate was mounted in a cavity of 80 mm square and 4 mm in depth. Secondary molding was performed using No. 10 as a secondary material to form a flat composite molded article. This composite molded product was cut to a width of 10 mm, the joining interface at one end was forcibly peeled off by a cutter knife by a fixed length, and each end was set on a fixture of a Tensilon tensile tester and pulled to reduce the peel strength. It was measured. Although the peel strength was as high as 100 N, surface layer peeling was observed on the surface of the composite molded product, and the appearance was poor.

[Comparative Example 12]
A polycarbonate resin ("Iupilon" S3000 manufactured by Mitsubishi Engineering-Plastics Co., Ltd.) was injection-molded as a hard resin, and a square plate of 80 mm square and 2 mm thick was formed as a primary molded product. Next, this square plate was mounted in a cavity of 80 mm square and 4 mm deep, and the composition No. 1 prepared in Comparative Example 7 was prepared. Secondary molding was performed using No. 25 as a secondary material to form a flat composite molded article. No surface layer peeling was observed on the surface of the composite molded article. This composite molded product was cut to a width of 10 mm, the joining interface at one end was forcibly peeled off by a cutter knife by a fixed length, and each end was set on a fixture of a Tensilon tensile tester and pulled to reduce the peel strength. It was measured. Although the peel strength was as high as 100 N, surface layer peeling was observed on the surface of the composite molded product, and the appearance was poor.

  The thermoplastic elastomer resin composition of the present invention has no blocking between pellets, is flexible, has a high melting point and excellent heat resistance, and has good mechanical properties, as well as excellent fluidity at the time of melting, such as injection molding. The molded product obtained has good moldability and a beautiful appearance without surface delamination or bleed-out.The resulting molded product is useful for automobiles, electronic / electric equipment, precision equipment, various molded products for general consumer goods, etc. It is. Further, it is suitable for grips, tubes, packings, gaskets, hoods, dampers, covers, cushion bodies, films, sheets, and the like.

  Further, a composite molded product obtained by laminating a layer made of the thermoplastic elastomer resin composition of the present invention and a hard resin layer is excellent in the adhesiveness of both resin layers, so that various cases, antenna covers, connectors It can also be used for grips, rollers, casters, hoses, multilayer tubes, and the like.

Claims (20)

A main component comprising a high-melting crystalline polymer segment (a1) mainly composed of a crystalline aromatic polyester unit and a low-melting polymer segment (a2) mainly composed of an aliphatic polyether unit and / or an aliphatic polyester unit; Dynamically crosslinked thermoplastic elastomer obtained by dynamically crosslinking 10 to 95% by weight of a polyester block copolymer (A) to be used and one or more thermoplastic elastomers selected from a styrene-based elastomer and / or an olefin-based elastomer as a disperse phase. B) From the epoxy-modified copolymer (C), the acid-modified copolymer (D) and the polyester-aromatic vinyl copolymer block copolymer (E), based on 100 parts by weight in total of 90 to 5% by weight. A thermoplastic elastomer resin composition comprising at least one selected from 0.1 to 40 parts by weight. The plasticizer (F) is added in an amount of 1 to 100 parts by weight and / or the rubber softener (G) in an amount of 1 to 100 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). 2. The thermoplastic elastomer resin composition according to 1. A main component comprising a high-melting crystalline polymer segment (a1) mainly composed of a crystalline aromatic polyester unit and a low-melting polymer segment (a2) mainly composed of an aliphatic polyether unit and / or an aliphatic polyester unit; Dynamically crosslinked thermoplastic elastomer (B) 95 obtained by dynamically crosslinking 5 to 95% by weight of a polyester block copolymer (A) and one or more thermoplastic elastomers selected from styrene-based elastomers and / or olefin-based elastomers To 5% by weight, based on 100 parts by weight of the epoxy-modified copolymer (C), the acid-modified copolymer (D), and the polyester-aromatic vinyl copolymer block copolymer (E). One to 0.1 to 40 parts by weight of a fatty acid amide compound (H) is mixed with 0.01 to 5 parts by weight. The thermoplastic elastomer resin composition. The plasticizer (F) is added in an amount of 1 to 100 parts by weight and / or the rubber softener (G) in an amount of 1 to 100 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). 4. The thermoplastic elastomer resin composition according to 3. The high-melting crystalline polymer segment (a1) of the polyester block copolymer (A) comprises a polybutylene terephthalate unit or a polybutylene terephthalate unit and a polybutylene isophthalate unit. The thermoplastic elastomer resin composition according to claim 1. The low-melting polymer segment (a2) of the polyester block copolymer (A) is selected from poly (tetramethylene oxide) glycol, an ethylene oxide adduct of poly (propylene oxide) glycol, and a copolymer glycol of ethylene oxide and tetrahydrofuran. The thermoplastic elastomer resin composition according to any one of claims 1 to 5, wherein at least one of the thermoplastic elastomer resin compositions has a copolymerization amount of 40 to 80% by weight. A dynamically crosslinked thermoplastic elastomer (B) obtained by dynamically crosslinking one or more thermoplastic elastomers selected from the styrene-based elastomer and / or the olefin-based elastomer as a dispersed phase is selected from a styrene-based elastomer and / or an olefin-based elastomer. Is obtained by dynamically cross-linking a part of one or more kinds of thermoplastic elastomers, and has a cross-linked structure in a thermoplastic matrix composed of one or more kinds of thermoplastic elastomers selected from styrene-based elastomers and / or olefin-based elastomers. The thermoplastic elastomer resin composition according to any one of claims 1 to 6, wherein the thermoplastic elastomer resin composition has a structure in which one or more thermoplastic elastomers selected from styrene-based elastomers and / or olefin-based elastomers are dispersed. . A dynamically crosslinked thermoplastic elastomer (B) obtained by dynamically crosslinking one or more thermoplastic elastomers selected from the styrene-based elastomer and / or the olefin-based elastomer as a dispersed phase is selected from a styrene-based elastomer and / or an olefin-based elastomer. Is obtained by dynamically cross-linking a part of one or more kinds of thermoplastic elastomers, and has a cross-linked structure in a thermoplastic matrix composed of one or more kinds of thermoplastic elastomers selected from styrene-based elastomers and / or olefin-based elastomers. Having a structure in which one or more thermoplastic elastomers selected from styrene-based elastomers and / or olefin-based elastomers are dispersed. In the case of dynamic crosslinking, the thermoplastic matrix and the dispersed phase are converted into glycidyl groups, carboxyl groups, Group, acid anhydride group Hydroxyl, functional monomer or thermoplastic elastomer resin composition according to any one of claims 1 to 7 is obtained by graft-modified with a derivative thereof having an amino group. A dynamically crosslinked thermoplastic elastomer (B) obtained by dynamically crosslinking one or more thermoplastic elastomers selected from the styrene-based elastomer and / or the olefin-based elastomer as a disperse phase, in a thermoplastic matrix made of polypropylene by dynamic crosslinking. The thermoplastic resin according to any one of claims 1 to 6, wherein the thermoplastic resin has a structure in which one or more thermoplastic elastomers selected from a styrene-based elastomer and / or an olefin-based elastomer having a crosslinked structure are dispersed. Elastomer resin composition. A dynamically crosslinked thermoplastic elastomer (B) obtained by dynamically crosslinking one or more thermoplastic elastomers selected from the styrene-based elastomer and / or the olefin-based elastomer as a disperse phase, in a thermoplastic matrix made of polypropylene by dynamic crosslinking. Having a structure in which at least one thermoplastic elastomer selected from a styrene-based elastomer and / or an olefin-based elastomer having a crosslinked structure is dispersed, and in the case of dynamic crosslinking, the thermoplastic matrix and the dispersed phase are The thermoplastic resin according to any one of claims 1 to 6, wherein the thermoplastic resin is graft-modified with a functional monomer having a glycidyl group, a carboxyl group, an acid anhydride group, a hydroxyl group, or an amino group, or a derivative thereof. Elastomer resin composition. The epoxy-modified copolymer (C) may be an epoxy-modified block or random copolymer of an aromatic vinyl monomer and a conjugated diene and / or a hydrogenated product thereof (C1), or an ethylene-based copolymer. 11. An epoxy-modified product (C2) or at least one selected from epoxy-modified products (C3) of a graft polymer comprising an olefin-based polymer main chain and a vinyl-based polymer side chain. 2. The thermoplastic elastomer resin composition according to claim 1. The acid-modified copolymer (D) comprises a block composed of an aromatic vinyl monomer and a conjugated diene or an acid-modified product of a random copolymer and / or an aromatic vinyl monomer and a conjugated diene. From an acid-modified block copolymer or random copolymer and / or a hydrogenated product thereof (D1), an acid-modified ethylene copolymer (D2), and an olefin-based polymer main chain and a vinyl-based polymer side chain The thermoplastic elastomer resin composition according to any one of claims 1 to 11, wherein the thermoplastic elastomer resin composition is at least one selected from three kinds of acid-modified graft polymers (D3). The polyester-aromatic vinyl copolymer (E) is a block (e1) composed of a polyester, a block composed of an aromatic vinyl monomer and a conjugated diene, or a random copolymer and / or a hydrogenated product thereof. The thermoplastic elastomer resin composition according to any one of claims 1 to 12, which is a block copolymer of a polyester-aromatic vinyl copolymer and a block (e2) formed from: The plasticizer (F) is at least one compound selected from a benzoate plasticizer, a phthalate plasticizer, a trimellitate plasticizer, and a pyromellitic ester plasticizer. The thermoplastic elastomer resin composition according to any one of claims 4 to 13. The thermoplastic elastomer resin composition according to any one of claims 2 to 4, wherein the rubber softener (G) is a paraffinic oil and / or a naphthenic oil. The fatty acid amide compound (H) is at least one selected from alkylene bis higher fatty acid amide compounds and carboxylic acid amide waxes obtained by reacting a mixture of a higher aliphatic monocarboxylic acid and a polybasic acid with a diamine. The thermoplastic elastomer resin composition according to any one of claims 3 to 15, which is a compound. A molded article obtained by injection molding the thermoplastic elastomer resin composition according to any one of claims 1 to 16. The molded article according to claim 17, wherein the molded article is a composite molded article. The molded article according to claim 18, wherein the composite molded article is a composite molded article comprising a hard resin and the thermoplastic elastomer resin composition according to any one of claims 1 to 16. 20. The hard resin according to claim 18, wherein the hard resin is at least one selected from a polycarbonate resin, an ABS resin, a polybutarene terephthalate resin, a poly-1,4-cyclohexane dimethylene terephthalate / isophthalate resin, and a polypropylene resin. The molded article according to the above.