JP2008189715A - Thermoplastic elastomer resin composition for composite molding and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer resin composition for composite molding, having flexibility, elasticity and excellent molding processability, an excellent thermal adhesiveness to an ABS resin and a blend material of an ABS resin and a polycarbonate resin and a molded article using the same, especially a composite molded article. <P>SOLUTION: The thermoplastic elastomer resin composition for composite molding comprises 55-98 wt.% of a polyester block copolymer (A), 1-44 wt.% of a graft copolymer (B) obtained by copolymerizing a monomer component containing an aromatic vinyl monomer and a vinyl cyanide monomer as main components in the presence of a rubbery polymer and 1-44 wt.% of a polycarbonate resin (C). The molded article thereof is obtained. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is a composite molding excellent in heat fusion between a conjugated diene rubber reinforced styrene resin and a blend of a conjugated diene rubber reinforced styrene resin and a polycarbonate, which is flexible and rich in elasticity and excellent in processability. The present invention relates to a thermoplastic elastomer resin composition and a molded product, particularly a composite molded product.

  A polyester block copolymer having a crystalline aromatic polyester unit as a hard segment and an aliphatic polyether unit such as poly (alkylene oxide) glycol and / or an aliphatic polyester unit such as polylactone as a soft segment has a strength, Excellent mechanical properties such as impact resistance, elastic recovery, and flexibility, low temperature and high temperature characteristics, and thermoplasticity makes it easy to mold, so it can be used in fields such as automobiles, electrical / electronic parts, and consumer goods. Widely used.

  However, such a polyester block copolymer has excellent properties, but on the other hand, it has a problem of insufficient heat fusion with a hard resin, particularly with a conjugated diene rubber reinforced styrene resin. was there.

  Various studies have been made in order to improve the heat-fusibility between a thermoplastic elastomer resin composition containing a polyester block copolymer as a main component and a hard resin. For example, a hydrogenated styrene block copolymer or the like A thermoplastic elastomer composition comprising a thermoplastic elastomer comprising a block copolymer in which carboxylic acid has been modified and a thermoplastic polyester having a melting point in the range of 80 ° C. to 180 ° C. (see, for example, Patent Document 1), hydrogenated SBS block copolymer A thermoplastic elastomer composition comprising a thermoplastic elastomer such as a polyester elastomer (for example, see Patent Document 2), a composition comprising a specific styrene elastomer and a thermoplastic elastomer such as a polyester elastomer (for example, Patent Document 2) 3) has been proposed.

  However, in these conventional techniques, although the heat-bonding property between the conjugated diene rubber reinforced styrene resin and the blend of the conjugated diene rubber reinforced styrene resin and the polycarbonate is certainly improved, the mechanical strength is low. There was a problem that it was too low to be practical.

  On the other hand, a thermoplastic resin composition comprising polycarbonate having excellent chemical resistance and weld strength, conjugated diene rubber reinforced styrene resin, and polyester elastomer (see, for example, Patent Document 4), impact resistance, breakage / deformation due to thermal cycle A thermoplastic resin composition comprising a polycarbonate, a thermoplastic polyester, and an ABS graph copolymer (see, for example, Patent Document 5) excellent in the above-mentioned is proposed.

However, these conventional techniques have a problem that although the mechanical strength is excellent, the flexibility which is a characteristic of the elastomer is lost and it cannot be put into practical use.
Japanese Patent Laid-Open No. 1-230660 Japanese Patent Laid-Open No. 3-100045 Japanese Patent Laid-Open No. 9-12487 JP 60-219250 A JP-A-11-138642

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue.

  Accordingly, an object of the present invention is to retain the characteristics of a polyester elastomer which is flexible, rich in elasticity and excellent in molding processability, and is composed of a conjugated diene rubber reinforced styrene resin, a conjugated diene rubber reinforced styrene resin and a polycarbonate. It is an object of the present invention to provide a thermoplastic elastomer composition for composite molding excellent in thermal adhesiveness with a blend and a molded product using the same, particularly a composite molded product.

  As a result of intensive studies to achieve the above object, the present inventors have achieved the above object effectively by blending a specific rubbery polymer and a polycarbonate resin into the polyester block copolymer. The present invention has been found.

  That is, according to the present invention, a high-melting crystalline polymer segment (a1) mainly composed of crystalline aromatic polyester units and a low-melting polymer segment mainly composed of aliphatic polyether units and / or aliphatic polyester units ( a polyester block copolymer (A) comprising 60 to 98% by weight of a2) as a main constituent, and a monomer containing an aromatic vinyl monomer and a vinyl cyanide monomer as main components in the presence of a rubbery polymer. A thermoplastic elastomer resin composition for composite molding comprising 1 to 39% by weight of a graft copolymer (B) obtained by copolymerizing a monomer component and 1 to 39% by weight of a polycarbonate resin (C) Is provided.

In the thermoplastic elastomer resin composition for composite molding of the present invention,
The rubbery polymer of the graft copolymer (B) is a diene rubbery polymer;
In the presence of 40 to 85 parts by weight of the diene rubber polymer, the graft copolymer (B) is a monomer component 15 to 15 containing an aromatic vinyl monomer and a vinyl cyanide monomer as main components. Preferred conditions are that the polymer is obtained by polymerizing 60 parts by weight, and that the graft ratio of the graft copolymer (B) is 25% or more.

Further, the composite molded body of the present invention is characterized by being formed by injection molding the above-described thermoplastic elastomer resin composition for composite molding,
It is a composite molded body comprising a hard resin and the above-mentioned thermoplastic elastomer resin composition for composite molding, and the hard resin is a conjugated diene rubber reinforced polystyrene resin, a blend of a conjugated diene rubber reinforced polystyrene resin and a polycarbonate resin. A composite molded body that is a resin selected from
Are mentioned as preferable conditions.

  According to the present invention, as will be described below, the characteristics of a polyester elastomer that is flexible, rich in elasticity, and excellent in moldability are maintained, and heat fusion between ABS resin, a blend of ABS resin and polycarbonate resin is performed. A thermoplastic elastomer resin composition for composite molding having excellent properties and a molded body using them, particularly a composite molded body can be obtained.

  Hereinafter, the present invention will be described in detail.

  The high melting point crystalline polymer segment (a1) of the polyester block copolymer (A) used in the present invention is mainly formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. Specific examples of aromatic dicarboxylic acids that are polyesters include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, anthracene dicarboxylic acid, diphenyl-4,4. Examples include '-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, and sodium 3-sulfoisophthalate. Although aromatic dicarboxylic acid is mainly used, if necessary, a part of the aromatic dicarboxylic acid may be converted to alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, 4,4′-dicyclohexyldicarboxylic acid, etc. Alternatively, it may be substituted with an aliphatic dicarboxylic acid such as adipic acid, succinic acid, oxalic acid, sebacic acid, dodecanedioic acid, and dimer acid. Of course, ester-forming derivatives of dicarboxylic acids such as lower alkyl esters, aryl esters, carbonates, and acid halides can be used equally.

  Specific examples of the diol include diols having a molecular weight of 400 or less, for example, aliphatic diols such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, , 1-cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, alicyclic diols such as tricyclodecane dimethanol, and xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxy) diphenylpropane, 2,2′-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane Aromatic diols such as 4,4′-dihydroxy-p-terphenyl and 4,4′-dihydroxy-p-quarterphenyl are preferred, and such diols are ester-forming derivatives such as acetyl compounds and alkali metal salts. It can also be used in the form.

  Two or more of these dicarboxylic acids, derivatives thereof, diol components and derivatives thereof may be used in combination. An example of a preferable high melting point crystalline polymer segment (a) is a polybutylene terephthalate unit derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol. Also preferred are those comprising a polybutylene terephthalate unit derived from terephthalic acid and / or dimethyl terephthalate and a polybutylene isophthalate unit derived from isophthalic acid and / or dimethyl isophthalate and 1,4-butanediol. Used.

  The low melting point polymer segment (a2) of the polyester block copolymer (A) used in the present invention is an aliphatic polyether, and specific examples of the aliphatic polyether include poly (ethylene oxide) glycol, poly ( Propylene oxide) glycol, poly (trimethylene ether) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, ethylene oxide adducts of poly (propylene oxide) glycol, and Examples thereof include a copolymer of ethylene oxide and tetrahydrofuran. Of these, poly (tetramethylene oxide) glycol and / or poly (propylene oxide) glycol ethylene oxide adducts and / or copolymers of ethylene oxide and tetrahydrofuran are preferred. The number average molecular weight of these low-melting polymer segments is preferably about 300 to 6000 in the copolymerized state.

  The copolymerization amount of the low-melting polymer segment (a2) of the polyester block copolymer (A) used in the present invention is usually 10 to 90% by weight, preferably 15 to 85% by weight.

  The polyester block copolymer (A) used in the present invention can be produced by a known method. Specific examples thereof include, for example, a method of transesterifying a lower alcohol diester of a dicarboxylic acid, an excessive amount of a low molecular weight glycol and a low melting point polymer segment component in the presence of a catalyst, and polycondensing the resulting reaction product, and Any method such as a method in which a dicarboxylic acid, an excess amount of glycol and a low melting point polymer segment component are esterified in the presence of a catalyst and the resulting reaction product is polycondensed may be used.

  The graft copolymer (B) used in the present invention is composed of a rubbery polymer, an aromatic vinyl monomer, a vinyl cyanide monomer, or other vinyl monomers copolymerizable therewith. A graft formed by graft polymerization of an aromatic vinyl monomer and a vinyl cyanide monomer or another vinyl monomer copolymerizable therewith, usually in the presence of a rubbery polymer. It is a polymer.

  Examples of rubber polymers include polybutadiene, styrene-butadiene copolymers, diene polymers such as acrylonitrile-butadiene copolymers, ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, and other ethylene. -A propylene-type copolymer, an acrylate-type copolymer, a chlorinated polyethylene etc. are mentioned, 1 type (s) or 2 or more types can be used. Among these, a diene polymer is preferably used in terms of good moldability and dispersibility with the polyester block copolymer.

  Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, and pt-butylstyrene. Of these, styrene and / or α-methylstyrene is preferably used.

  Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. Among them, acrylonitrile is preferable.

  Examples of other copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, α, such as methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, and cyclohexyl methacrylate. α, β-unsaturated dicarboxylic acid anhydrides such as β-unsaturated carboxylic acid esters, maleic anhydride, itaconic anhydride, α, such as N-phenylmaleimide, N-methylmaleimide, Nt-butylmaleimide Examples thereof include imide compounds of β-unsaturated dicarboxylic acid.

  The graft polymer (B) used in the present invention is composed of an aromatic vinyl monomer, a vinyl cyanide monomer and other monomers copolymerizable therewith with respect to 40 to 85 parts by weight of the rubber-like polymer. It is obtained by graft polymerization of 15 to 60 parts by weight of the resulting monomer mixture. When the rubbery polymer exceeds 85 parts by weight, good mechanical properties cannot be obtained due to the relative decrease in the graft ratio, and even if it is less than 40 parts by weight or exceeds 85 parts by weight, This is not preferable because the compatibility tends to decrease.

  The ratio of the aromatic vinyl monomer to be graft-polymerized is preferably 50 to 99% by weight, more preferably 60 to 90% by weight, and still more preferably 70 to 80% by weight, based on the total vinyl monomers. The proportion of the vinyl halide monomer is preferably 1 to 50% by weight, more preferably 10 to 40% by weight, and still more preferably 20 to 30% by weight. Whether the proportion of aromatic vinyl monomer exceeds 99% by weight or less than 50% by weight, and the proportion of vinyl cyanide monomer exceeds 50% by weight or less than 1% by weight, the polyester block copolymer In some cases, compatibility with the polymer is lowered, and good mechanical properties cannot be obtained. Further, other vinyl monomers copolymerizable with these are preferably used in an amount of 50% by weight or less.

  The graft ratio of the graft copolymer (B) used in the present invention to the rubbery polymer is 25% or more, preferably 30% or more, more preferably 35% or more. When the graft ratio is less than 25%, the mechanical properties of the thermoplastic elastomer resin composition obtained by agglomeration of the rubbery polymers during melt-kneading are impaired, which is not preferable.

  There is no restriction | limiting in particular about the manufacturing method of the graft copolymer (B) of this invention, Generally it can manufacture by a well-known method, for example, can obtain by emulsion graft polymerization. As the emulsifier, the polymerization initiator and the chain transfer agent used here, reagents used in ordinary emulsion polymerization can be used. Typical emulsifiers include potassium rosinate, potassium stearate, and potassium oleate. Polymerization initiators include organic hydroperoxide and sugar-containing pyrophosphate-ferrous sulfate and persulfates. The chain transfer agent is preferably an alkyl thiol compound, but the present invention is not limited thereto.

  As the polycarbonate resin (C) used in the present invention, those obtained by producing a divalent phenol or a derivative thereof as a raw material by a transesterification method or a phosgene method can be preferably used.

  Specific examples of the divalent phenol include bis (4-hydroxyphenyl) -methane, 1,1-bis (4-hydroxyphenyl) -ethane, 1,2-bis (4-hydroxyphenyl) -ethane, 2, 2-bis (4-hydroxyphenyl) -propane, 1-1-bis (4-hydroxyphenyl) -propane, 2,2-bis (4-hydroxy-3-chlorophenyl) -propane, 2,2-bis (4-hydroxy-) 3,5-dichlorophenyl) -propane, 2,2-bis (4-hydroxy-3-bromophenyl) -propane, 2,2-bis (4-dihydroxy-3,5-dibromophenyl) -propane, 2,2 -Bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-methoxyphenyl) -propane, 1,4-bis ( Droxyphenyl) -cyclohexane, 1,2-bis (4-hydroxyphenyl) -ethylene, 1,4-bis (4-hydroxyphenyl) -benzene, bis (4-hydroxyphenyl) -phenylmethane, bis (4- Hydroxyphenyl))-diphenylmethane, 1,1-bis (4-hydroxyphenyl) -2,2,2-trichloroethane, bis (4-hydroxyphenyl) -ketone, bis (4-hydroxyphenyl) -sulfide, bis- ( 4-hydroxyphenyl) -sulfone, 4,4-dihydroxydiphenyl ether, 4,4-hydroxybiphenyl, 3,3-dihydroxybiphenyl, hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, phenolphthalein Etc. , 2- bis (4-hydroxyphenyl) - propane (commonly called bisphenol A) is preferably used. Two or more divalent phenols may be used in combination.

  Among these, polycarbonate resin of 2,2-bis (4-hydroxyphenyl) -propane (commonly called bisphenol A) can be used particularly preferably.

  The polycarbonate resin (C) used in the present invention can have a viscosity average molecular weight in the range of 5,000 to 80,000, preferably in the range of 8,000 to 50,000, and 10,000 to 40,000. The thing of the range of is more preferable.

The viscosity average molecular weight here is a value obtained by conversion using the following Schnell equation based on the intrinsic viscosity obtained by measuring the methylene chloride solution at 20 ° C. using an Ostwald viscometer.
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
(Where [η] is the intrinsic viscosity and M is the viscosity average molecular weight)

  The thermoplastic elastomer resin composition of the present invention comprises the polyester block copolymer (A) 60 to 98% by weight, the graft polymer (B) 1 to 39% by weight, and the polycarbonate resin (C) 1 to 39% by weight. It is a resin composition formed by blending, preferably 60 to 90% by weight of the polyester block copolymer (A), 3 to 35% by weight of the graft polymer (B), 3 to 35% by weight of the polycarbonate resin (C), and further A resin composition comprising a polyester block copolymer (A) 60 to 85, a graft polymer (B) 5 to 30% by weight, and a polycarbonate resin (C) 5 to 30% by weight is preferable.

  If the polyester block copolymer (A) is less than 60% by weight, the flexibility and molding processability of the polyester elastomer are impaired, and if it exceeds 98% by weight, the heat-sealing force becomes insufficient. . If the graft copolymer (B) is less than 1% by weight, the heat-sealing force is insufficient, and if it exceeds 39% by weight, the molding processability is impaired. If the polycarbonate resin (C) is less than 1% by weight, the heat-sealing force is insufficient, and if it exceeds 39% by weight, the flexibility of the polyester elastomer is impaired, or the resin melts when released from the mold in injection molding. Since the solidification speed of the resin becomes slow, the molded product projected by the ejector pin in a state where the resin is not completely solidified is not preferable.

  There is no limitation on the mixing method of the polyester block copolymer (A), the graft polymer (B) and the polycarbonate resin (C) of the present invention, and any one of (A), (B) and (C) can be mixed together. A method of mixing components remaining after melting is used, and known methods such as a Banbury mixer and an extruder can be adopted as a kneading method.

  Furthermore, in the thermoplastic elastomer resin composition of the present invention, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a lubricant, a dye, a pigment, a plasticizer, Additives and reinforcing agents such as flame retardants, mold release agents, glass fibers, metal fibers, carbon fibers and metal flakes can be added.

  The thermoplastic elastomer resin composition of the present invention retains the characteristics of a polyester elastomer that is flexible, highly elastic, and excellent in moldability, so that it can be directly injection molded into a molded product. Diene rubber reinforced styrene resin (ABS resin), because it is excellent in heat fusion with a resin selected from a blend of ABS resin and polycarbonate resin, it can be a composite molded body with these hard resins, These composite molded bodies are manufactured by a multicolor injection molding method including two-color molding, an overmolding by an insert molding method, or the like. These composite molded bodies can be applied to various cases, covers, connectors, grips, rollers, casters, hoses, multilayer tubes, and the like.

  The effects of the present invention will be described below with reference to examples. In the examples, “%” and “parts” are based on weight unless otherwise specified. The characteristics shown in the examples were measured as follows.

[Graft ratio]
Acetone was added to a predetermined amount M (g) of the rubbery polymer and refluxed for 4 hours. This solution was centrifuged at 9000 rpm for 30 minutes, and the insoluble matter was filtered off. The insoluble matter was dried under reduced pressure at 60 ° C. for 5 hours, the weight N (g) was measured, and the graft ratio was calculated by the following formula.
Graft ratio = 100 × (N−M × L) / (M × L)
Here, L represents the rubber content in the rubbery polymer.

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

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

[Bending characteristics]
The flexural modulus was measured according to ASTM D790.

[Heat adhesion strength]
First, an L-shape having a width of 20 mm, a length of 60 mm, and a thickness of 3 mm shown in FIG. 1 was prepared by injection molding under conditions of a cylinder temperature of 240 ° C. and a mold temperature of 50 ° C. After the L-shaped molded product (A) was set in a mold having the shape shown in FIG. 2, the ABS resin (B) was injection molded under conditions of a cylinder temperature of 250 ° C. and a mold temperature of 50 ° C. After leaving at room temperature for 1 day, a tensile test was performed by the method shown in FIG. 2 under the condition of a strain rate of 50 mm / min, and the maximum tensile force obtained was measured as a fusion adhesive force.

[Deformation degree at injection mold release]
A JIS No. 2 dumbbell specimen was molded under the conditions of a cylinder temperature of 240 ° C., a mold temperature of 50 ° C. and a cooling time of 10 seconds, and released from the mold by an ejector. Judged to.
Deformation degree judgment ○: No deformation ×: Large deformation

[Reference example]
[Production of polyester block copolymer (A-1)]
362 parts of terephthalic acid, 392 parts of 1,4-butanediol and 134 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1000 are placed in a reaction vessel equipped with a helical ribbon stirring blade together with 0.15 part of titanium tetrabutoxide. The esterification reaction was performed while charging and heating at 190 to 225 ° C. for 3 hours while allowing reaction water to flow out of the system. After adding 0.75 parts of “Irganox” 1010 (hindered phenol antioxidant manufactured by Ciba Geigy) 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. And polymerization was carried out for 2 hours and 30 minutes under these conditions. The obtained polymer was discharged into water in the form of strands and pelletized by cutting.

[Production of polyester block copolymer (A-2)]
445 parts of terephthalic acid, 241 parts of 1,4-butanediol and 439 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400 were charged into a reaction vessel equipped with a helical ribbon stirring blade together with 2 parts of titanium tetrabutoxide, The mixture was heated at 190 to 225 ° C. for 3 hours to conduct esterification reaction while distilling the reaction water out of the system. After adding 0.75 parts of “Irganox” 1010 (hindered phenol antioxidant manufactured by Ciba Geigy) 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. The polymerization was carried out for 3 hours and 50 minutes under these conditions. The obtained polymer was discharged into water as a strand and cut into pellets.

[Production of Graft Copolymer (B-1)]
In the presence of 60 parts by weight of polybutadiene latex (in terms of solid content), 40 parts by weight of a monomer mixture composed of 70% styrene and 30% acrylonitrile was continuously dropped over 4 hours for emulsion polymerization. The obtained polymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to obtain a powdery rubbery polymer. The graft ratio of the rubbery polymer was 39%.

[Production of Graft Copolymer (B-2)]
In the presence of 60 parts by weight of polybutadiene latex (in terms of solid content), 40 parts by weight of a monomer mixture composed of 70% styrene and 30% acrylonitrile was continuously dropped over 1 hour for emulsion polymerization. The obtained polymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to obtain a powdery rubbery polymer. The graft ratio of the rubbery polymer was 15%.

[Production of Graft Copolymer (B-3)]
In the presence of 35 parts by weight of polybutadiene latex (in terms of solid content), 65 parts by weight of a monomer mixture composed of 70% styrene and 30% acrylonitrile was continuously dropped over 4 hours for emulsion polymerization. The obtained polymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to obtain a powdery rubbery polymer. The graft ratio of the rubbery polymer was 43%.

[Polycarbonate resin (C)]
“Iupilon” S-2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used.

[ABS resin]
In the following examples, ABS330 manufactured by Technopolymer Co., Ltd. was used.

[Examples 1 to 5] and [Comparative Examples 1 to 4]
The polyester block copolymers (A-1) and (A-2) obtained in Reference Examples are graft copolymers (B-1), (B-2), (B-3), and polycarbonate (C). Were mixed using a V-blender at a blending ratio (% by weight) shown in Table 1, and melt-kneaded at 240 ° C. using a twin screw extruder having a diameter of 45 mm and a triple thread type screw, and pelletized. .

  These pellets were dried at 80 ° C. for 5 hours, and then a JIS No. 2 dumbbell test piece and a length of 129 mm × at a mold temperature of 50 ° C. (mold cavity surface) using an in-line screw injection molding machine set at 240 ° C. A bending test piece having a width of 12.8 mm and a thickness of 6.3 mm was injection molded. Table 1 shows the results of examining the characteristics of each test.

  From the above results, the thermoplastic elastomer resin compositions of the present invention shown in Examples 1 to 6 have the characteristics of a flexible and elastic polyester elastomer, and are heat-bonded to the ABS resin by composite molding. It has excellent properties and there is no deformation of the molded product after mold release.

  On the other hand, the resin compositions shown in Comparative Example 1, Comparative Example 3, and Comparative Example 5 are not deformed in the molded product released from the mold, but are preferable because the heat fusion force with the ABS resin is low. Absent. The resin compositions shown in Comparative Example 2 and Comparative Example 4 have high heat-sealing power with ABS, but are not preferable because the molded product released from the mold is deformed.

  The thermoplastic elastomer resin composition for composite molding of the present invention is useful for automobiles, electronic / electric equipment, precision equipment, and various molded articles for general consumer goods, taking advantage of the above-described excellent characteristics.

  Furthermore, the thermoplastic elastomer resin composition for composite molding of the present invention is excellent as a heat-bonding property between the ABS resin and the blend of ABS resin and polycarbonate resin, and is therefore useful as a composite molded body with these hard resins. . These composite molded products are manufactured by multi-color injection molding methods including two-color molding, overmolding by insert molding methods, etc., and various housings, covers, connectors, grips, rollers, casters, hoses, multilayers It can be applied to tubes.

The top view (I) and side view (B) which show schematic shape of the heat-fusion-molded article of an Example and a comparative example. It is a side view showing a schematic shape for measuring heat fusion power.

Explanation of symbols

(A) Thermoplastic elastomer resin composition for composite molding (B) ABS resin

Claims (8)

The main component is a high-melting-point crystalline polymer segment (a1) mainly composed of a crystalline aromatic polyester unit and a low-melting-point polymer segment (a2) mainly composed of an aliphatic polyether unit and / or an aliphatic polyester unit. A polyester block copolymer (A) 60 to 98% by weight and a monomer component containing an aromatic vinyl monomer and a vinyl cyanide monomer as main components in the presence of a rubbery polymer; A thermoplastic elastomer resin composition for composite molding, comprising 1 to 39% by weight of a graft copolymer (B) and 1 to 39% by weight of a polycarbonate resin (C). 2. The thermoplastic elastomer resin composition for composite molding according to claim 1, wherein the rubbery polymer of the graft copolymer (B) is a diene rubbery polymer. In the presence of 40 to 85 parts by weight of the diene rubber polymer, the graft copolymer (B) is a monomer component 15 to 15 containing an aromatic vinyl monomer and a vinyl cyanide monomer as main components. The thermoplastic elastomer resin composition for composite molding according to claim 1 or 2, wherein 60 parts by weight is polymerized. The thermoplastic elastomer resin composition for composite molding according to any one of claims 1 to 3, wherein the graft ratio of the graft copolymer (B) is 25% or more. A molded article obtained by injection-molding the thermoplastic elastomer resin composition for composite molding according to any one of claims 1 to 4. The molded body according to claim 5, wherein the molded body is a composite molded body. The molded body according to claim 6, wherein the molded body is a composite molded body comprising a hard resin and the thermoplastic elastomer resin composition for composite molding according to any one of claims 1 to 4. . The molded product according to claim 6 or 7, wherein the hard resin is a resin selected from a conjugated diene rubber-reinforced styrene resin and a blend of a conjugated diene rubber-reinforced styrene resin and a polycarbonate resin. .

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