JP2008144089A - Thermoplastic elastomer resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer resin composition having softness, high resilience and good moldability, enabling easy surface-treatment such as plating, vapor deposition and coating and having excellent hot-gluing property to an ABS resin and to provide a molded article produced by using the resin composition. <P>SOLUTION: The thermoplastic elastomer resin composition comprises (A) 55-99 wt.% polyester block copolymer and (B) 1-45 wt.% graft copolymer composition produced by the graft-copolymerization of 15-60 pts.wt. of a monomer mixture composed of 50-90 wt.% aromatic vinyl monomer, 9-50 wt.% vinyl cyanide monomer and 0.1-20 wt.% vinyl monomer having an α, β-unsaturated carboxylic acid group in the presence of 40-85 pts.wt. of a rubbery polymer. The invention further provides a molded article of the resin composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermoplastic elastomer resin composition and a molded article which are flexible and elastic, excellent in molding processability, easy to surface treatment such as plating, vapor deposition and coating, and excellent in thermal adhesiveness with ABS resin. .

  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.

  Polyester block copolymer has such excellent characteristics, but when the surface of the molded product is treated with a metal film or paint, the surface treatment conditions are restricted due to the mixture of hard and soft segments. However, even if the surface treatment can be performed, there is a problem that sufficient adhesion cannot be obtained or the physical properties are greatly lowered.

  In order to improve the surface treatment of the thermoplastic elastomer resin composition, various studies have been made conventionally. For example, a thermoplastic polyester composition containing a specific polymer and a specific plasticizer (for example, Patent Document 1). And a thermoplastic resin composition in which a specific polyester elastomer is blended with a rubber-reinforced thermoplastic resin at a specific ratio (for example, see Patent Document 2).

However, although the above-mentioned conventional proposals improve the primary paint adhesion, the durability is still insufficient, and the flexibility characteristic of the polyester elastomer is impaired. .
JP-A-5-86255 JP-A-6-116472

  An object of the present invention is to solve the above-described problems in the prior art, and the object of the present invention is to retain the characteristics of a polyester elastomer that is flexible, flexible and excellent in moldability, and is plated. An object of the present invention is to provide a thermoplastic elastomer composition that is easy to surface-treat, such as vapor deposition and coating, and excellent in thermal adhesiveness with an ABS resin, and a molded body using the same.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be effectively achieved by blending a specific rubbery polymer with the polyester block copolymer. The present invention has been reached.

  That is, according to the present invention, a high-melting-point crystalline polymer segment (a1) mainly composed of crystalline aromatic polyester units and a low-melting-point polymer segment mainly composed of aliphatic polyether units and / or aliphatic polyester units ( a2) polyester block copolymer (A) 55 to 99% by weight, aromatic vinyl monomer 50 to 90% by weight in the presence of 40 to 85 parts by weight of rubbery polymer, cyanide 15-60 parts by weight of a monomer mixture consisting of 9-50 wt% vinyl monomer and 0.1-20 wt% vinyl monomer having α, β-unsaturated carboxylic acid (total with the above rubber polymer) 100 parts by weight) of a graft copolymer or a graft copolymer (composition) (B) 1 to 4 obtained by copolymerizing the graft copolymer and the remaining monomer. A thermoplastic elastomer resin composition comprising 5% by weight is provided.

In the thermoplastic elastomer resin composition of the present invention,
The rubbery polymer of the graft copolymer (composition) (B) is a diene rubbery polymer;
The graft ratio of the graft copolymer or graft copolymer composition (B) is 25% or more;
The high melting point crystalline polymer segment (a1) in the polyester block copolymer (A) component is mainly composed of a polybutylene terephthalate unit, and the low in the polyester block copolymer (A) component. It is preferable that the melting point segment (a2) has a poly (tetramethylene oxide) glycol unit as a main constituent component.

  The molded article of the present invention is characterized in that the thermoplastic elastomer resin composition is molded, and one type selected from a thermoplastic resin other than the thermoplastic elastomer resin composition, a metal film, and a paint on the surface. The molded body to which the above is attached is preferable.

  According to the present invention, as described below, the characteristics of a polyester elastomer that is flexible and rich in elasticity and excellent in molding processability are maintained, and surface treatment such as plating, vapor deposition, and coating is easy, and it can be used with an ABS resin. A thermoplastic elastomer resin composition excellent in thermal adhesiveness and a molded body using them 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 crystalline polymer segment (a1) is a polybutylene terephthalate unit derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol. Also preferred are those composed of polybutylene terephthalate units derived from terephthalic acid and / or dimethyl terephthalate, and polybutylene isophthalate units derived from isophthalic acid and / or dimethyl isophthalate and 1,4-butanediol. .

  The low melting point polymer segment (a2) of the polyester block copolymer (A) used in the present invention is an aliphatic polyether. Specific examples of the aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene). Oxide) 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 copolymers of ethylene oxide and tetrahydrofuran, etc. Can be mentioned. 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 point polymer segment (a2) of the polyester block copolymer (A) used in the present invention is usually 10 to 90% by weight, preferably 30 to 85% by weight, more preferably 50 to 80%. % 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 used in the present invention or the graft copolymer (composition) (B) obtained by copolymerizing the graft copolymer and the remaining monomer is present in an amount of 40 to 85 parts by weight of a rubbery polymer. Below, the total amount of aromatic vinyl monomer 50 to 90 wt%, vinyl cyanide monomer 9 to 50 wt%, vinyl monomer having α, β-unsaturated carboxylic acid 0.1 to 20 wt% is 100 wt%. A graft copolymer obtained by graft copolymerizing 15 to 60 parts by weight of a monomer mixture consisting of 15% by weight, or a graft copolymer (composition) obtained by copolymerizing the graft copolymer and the remaining monomer. is there. When the monomer mixture is graft-polymerized to all of the rubbery polymer, it can be said that it is a “graft copolymer” as a whole, but if the rubbery polymer remains in part or the graft copolymer produced as described below In some cases, the remaining monomers may be copolymerized with the coalesced product, and in these cases, the mixture is a mixture of different types of polymers, resulting in a “composition”. In the present invention, the term “graft copolymer (composition)” is used to include these possibilities. In the present invention, the vinyl monomer having an α, β-unsaturated carboxylic acid can be all graft-copolymerized, or a copolymer obtained by copolymerizing the graft copolymer and the remaining monomer. It is possible to copolymerize by dividing into a polymer, or it is possible to copolymerize the entire amount into a copolymer obtained by copolymerizing the remaining monomers. What is most important in the present invention is that in the graft copolymer or graft copolymer composition (B), a vinyl having an aromatic vinyl monomer, a vinyl cyanide monomer and an α, β-unsaturated carboxylic acid. It is to use a graft copolymer obtained by graft-copolymerizing a monomer mixture containing an essential monomer to a rubbery 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.

  A vinyl monomer having an α, β-unsaturated carboxylic acid is a compound that shares both a radically polymerizable vinyl group and an α, β-unsaturated carboxylic acid in one molecule. Acrylic acid, methacrylic acid, etc. are mentioned, These can also be used in combination of 2 or more types.

  In addition, other copolymerizable monomers can be graft copolymerized within a range not impairing the performance of the thermoplastic elastomer resin composition of the present invention. Other monomers include methyl methacrylate, ethyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, glycidyl acrylate, glycidyl methacrylate, α, β-unsaturated carboxylic acid esters, maleic anhydride, Α, β-unsaturated dicarboxylic acid anhydrides such as itaconic anhydride, imide compounds of α, β-unsaturated carboxylic acid such as N-phenylmaleimide, N-methylmaleimide, Nt-butylmaleimide, etc. It is done.

  The graft copolymer (composition) (B) used in the present invention is an aromatic vinyl monomer, a vinyl cyanide monomer, an α, β-unsaturated carboxylic acid with respect to 40 to 85 parts by weight of the rubbery polymer. 15-60 parts by weight of a monomer mixture comprising an acid-containing vinyl monomer (total of 100 parts by weight with the rubbery polymer. In order to avoid confusion with other composition ratios, “parts by weight” are used. Here, it is synonymous with% by weight). If the rubbery polymer exceeds 85 parts by weight, good mechanical properties cannot be obtained due to the relative decrease in the graft ratio, and if it is less than 40 parts by weight or more than 85 parts by weight, it is not compatible with the polyester block copolymer. The solubility tends to decrease, which is not preferable.

  The composition ratios of the aromatic vinyl monomer, the vinyl cyanide monomer, and the vinyl monomer having an α, β-unsaturated carboxylic acid in the monomer mixture of the present invention are as follows. 50-90 wt% of the mer ("wt%" is used to avoid confusion with other composition ratios, but is synonymous with wt%), preferably 55-85 wt%, particularly preferably 57-82 wt%, The vinyl cyanide monomer is 9 to 50 wt%, preferably 15 to 45 wt%, particularly preferably 18 to 43 wt%. The vinyl monomer having an α, β-unsaturated carboxylic acid is used in the range of 0.1 to 20 wt%, preferably 0.2 to 10 wt%, particularly preferably 0.5 to 8 wt%. Used in When the aromatic vinyl monomer exceeds 90 wt%, and when the vinyl cyanide monomer is less than 9 wt%, the impact resistance of the resulting composition is low, which is not preferable. In addition, when the aromatic vinyl monomer is less than 50 wt% and when the vinyl cyanide monomer exceeds 50 wt%, the molding processability of the resulting composition is inferior, which is not practical. Furthermore, if the vinyl monomer having an α, β-unsaturated carboxylic acid is less than 0.1 wt%, the mechanical strength of the resulting composition is low, and if it exceeds 20 wt%, a crosslinking reaction is likely to occur at the time of graft polymerization. It becomes difficult to obtain things and is not practical.

    Further, other monomers copolymerizable with these can be further used, and in that case, the amount is 50 wt% or less.

  The graft ratio of the graft copolymer or graft copolymer composition (B) (synonymous with “graft copolymer (composition) B”) used in the present invention is 25% or more, preferably 30%. Above, 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, and unevenness occurs even when surface treatment such as plating or coating is performed. Tends to be undesirable.

  There is no restriction | limiting in particular regarding the manufacturing method of a graft copolymer or a graft copolymer composition, Normal methods, such as block polymerization, solution polymerization, block suspension polymerization, suspension polymerization, and emulsion polymerization, are used. There is no particular limitation on the monomer charging method, and it may be added all at once in the initial stage. In order to prevent the formation of a copolymer composition distribution, a part or all of the charging amount is continuously charged or dividedly charged. However, polymerization may be performed. It is also possible to obtain the above composition by blending separately graft copolymerized resins.

  The thermoplastic elastomer resin composition of the present invention contains 1 to 45% by weight of the graft copolymer or graft copolymer composition (B) with respect to 55 to 99% by weight of the above-mentioned polyester block copolymer (A). More preferably, it is 5 to 40% by weight, more preferably 5 to 40% by weight, based on 60 to 95% by weight of the polyester block copolymer (A). Is a resin composition obtained by blending 10 to 35 wt% of the graft copolymer or Graft copolymer composition (B) with 65 to 90 wt% of the polyester block copolymer (A). If the polyester block copolymer (A) is less than 55% by weight, the polyester elastomer cannot have excellent flexibility and molding processability. If it exceeds 99% by weight, the surface of plating, vapor deposition, coating, etc. This is not preferable because the treatment becomes insufficient and the thermal adhesiveness with the thermoplastic resin is poor.

  There is no limitation on the mixing method of the polyester block copolymer (A) and the graft copolymer or the graft copolymer composition (B), and it remains after melting (A) and (B) at one time. Examples of the kneading method include publicly known methods such as a Banbury mixer and an extruder.

  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 method for obtaining a molded article comprising the thermoplastic elastomer resin composition of the present invention is not particularly limited, and a method of melt molding with a general thermoplastic resin can be used. For example, injection molding, extrusion molding, blow molding Examples include molding. Further, as the surface treatment method, general plating, vapor deposition, ion plating, sputtering, painting, and the like can be mentioned.

  As a specific plating method, it is important to first perform preliminary treatment such as wiping off the oil film on the surface of the molded product as necessary, and then roughen the surface using an alkaline solution and / or an acidic solution. The alkali solution used for the rough surface treatment is an alkaline component such as potassium hydroxide, sodium hydroxide, magnesium hydroxide, etc., in a solvent such as water, phenols, alcohols, or a mixed solvent thereof in a concentration of 5 to 50%. Of these, a solution of sodium hydroxide and potassium hydroxide is preferably used.

  As conditions for this rough surface treatment (alkali etching) with an alkaline solution, it is desirable to immerse the molded article in an alkaline solution at 30 to 95 ° C. for 1 to 120 minutes and then thoroughly wash it.

  Examples of the acidic liquid used for the rough surface treatment include mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, and organic acids that are liquid at room temperature such as formic acid, acetic acid, and trifluoroacetic acid. Alternatively, it is an aqueous solution of 5% or more, and sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid and the like are preferably used. As conditions for the surface roughening treatment (acid etching) with the acidic liquid, it is desirable to immerse the molded product in an acidic liquid at 20 to 95 ° C. for 10 seconds to 2 hours and then thoroughly wash it.

  In order to accelerate the roughening of the surface, an appropriate oxidizing agent can be added to the alkaline solution and the acidic solution. As the oxidizing agent, sodium or potassium permanganate, dichromate, chlorate, chromate, bromate are desirable.

  In molded articles made of polyester block copolymer alone, even if this alkali etching or acid etching is performed, the surface is eroded on average, and unevenness effective in plating adhesion does not occur, and a sufficient anchor effect is obtained. Or a sufficiently rough surface cannot be achieved because the degree of surface erosion is small. However, when a thermoplastic elastomer resin molded product blended with the graft copolymer is subjected to alkali etching or acid etching, a rough surface extremely suitable for plating treatment can be obtained.

  By subjecting the thus-roughened resin molded product to normal plating treatment, a thermoplastic elastomer resin composition molded product having a remarkably excellent plating film adhesion and a good surface appearance can be obtained.

  The plating process can also be performed by, for example, sensitizing with a stannous chloride solution-activating with a palladium chloride solution-electroless copper or nickel plating-electroplating process or castlisting-accelerating-electroless plating-electroplating. The usual chemical plating method can be applied.

  Also, in the painting, general paints and painting methods can be employed, and among them, a paint mainly composed of a urethane resin can be preferably used. Among paints made of urethane resins, paints obtained by mixing two components of a coating component containing a polymeric polyol as a main component and a curing agent component containing a polyfunctional isocyanate compound as a main component are preferred. Examples of the coating component as the main component include, for example, a polyester polyol having an ester bond in the main chain, a polycaprolactone polyol, a polycarbonate polyol, an acrylic polyol having a main chain composed of a -C-C- bond, and an ether bond in the main chain. Examples thereof include polymers having a hydroxyl group such as polyether polyols and epoxy polyols having an epoxy group. The curing agent mainly composed of a polyfunctional isocyanate compound is, for example, a diisocyanate compound such as methylene bisphenyl isocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or a multimer thereof. And mixed with a coating film component mainly composed of the above-mentioned polymeritol polyol.

  In addition, as a paint coating method, a general method can be adopted, and brush coating, roller coating, spray coating, dip coating, etc. by dissolving the coating in an organic solvent can be employed. It is recommended to wash with the purpose of removing oil and dust adhering to the surface of the injection molded product with methanol, ethanol, isopropyl alcohol or the like. In addition, it is recommended to promote the formation of a coating film by baking at a temperature below the melting point of the aliphatic polyester resin composition after coating. The purpose of the present invention is to increase the efficiency of the coating operation, and it is characterized by not providing an adhesive layer such as a primer between the surface of the molded body made of the thermoplastic elastomer resin composition and the paint.

  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 physical properties 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.

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

[Thermal adhesive strength]
JIS No. 2 dumbbell test piece defined by JIS K7113 was made by injection molding using “Toyolac” type 500 (manufactured by Toray Industries, Inc.) as ABS resin, and this test piece was cut in half at the center. After cutting, one of the test pieces was set in a cavity in a mold for molding a JIS No. 2 dumbbell test piece, and then injected using an elastomer resin composition for evaluation at a cylinder temperature of 220 ° C. and a mold temperature of 50 ° C. Molded. The obtained molded product was allowed to stand at room temperature for 1 day, and then pulled at a strain rate of 20 mm / min to measure the joint strength, which was defined as the adhesive strength to the ABS resin.

[Plating properties]
A 125 mm long, 70 mm wide, 2 mm thick square plate is immersed in a 30% aqueous solution of sodium hydroxide at 70 ° C. for 3 minutes and further immersed in a 20% aqueous solution of hydrochloric acid at 70 ° C. for 2 minutes, and then thoroughly washed in running water. A rough test piece was obtained. The roughened test piece was plated by the following method.
1. Sensitizing: The test piece was immersed in a solution consisting of 30 g of stannous chloride, 60 cc of hydrochloric acid (38%) and 1000 cc of water at 25 ° C. for 2 to 5 minutes.
2. 2. Washing with water Activating: The test piece was immersed in a solution consisting of 0.1 g of palladium chloride, 10 cc of hydrochloric acid (38%) and 1000 cc of water at 25 ° C. for 1 to 3 minutes.
4). 5. Washing with water Electroless copper plating: Chemical copper plating solution (pH 10.0 to 11.11) consisting of 10 g of copper sulfate (5% hydrate), 40 cc of formalin (37%), 10 g of sodium hydroxide, 20 g of Rossiel salt and 1000 cc of water. Immerse in 5) at 25-30 ° C. for 10 minutes.
6). 6. Washing with water Electroplating: The test piece was placed in an acidic copper plating bath consisting of 50 g of concentrated sulfuric acid, 200 g of copper sulfate (5% hydrate), 4 cc of brightener (UBAC) and 1000 cc of water, temperature 25-30 ° C., electric density 4 A / Electroplating was performed for 60 minutes under the condition of dm ² to form a copper plating having a thickness of about 60 μm.

  The plating film adhesive strength of the plated product thus obtained was measured by measuring the force when the 1 cm wide adhesive surface was thinned in a 90 degree direction at a speed of 20 mm / min, and the surface appearance of the plated product was visually observed. Was judged.

[Weatherability]
A JIS No. 2 dumbbell specimen was placed in a Super Xenon Weather Meter (manufactured by Suga Test Instruments Co., Ltd.), and under a xenon lamp irradiation condition, 63 ° C. × 102 minutes, 23 ° C. × 18 minutes in a rainy cycle for 100 hours After the treatment, the surface appearance was observed. As the judgment of the surface appearance, a good one was marked with ◯, and a surface where defects such as cracks were observed was marked with ×.

[Reference example]
[Production of polyester block copolymer (A-1)]
50.5 parts of terephthalic acid, 43.8 parts of 1,4-butanediol and 35.4 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400, 0.04 part of titanium tetrabutoxide and mono-n-butyl -Both 0.02 parts of monohydroxytin oxide were charged into a reaction vessel equipped with a helical ribbon stirring blade, heated at 190 to 225 ° C for 3 hours, and the esterification reaction was carried out while allowing the reaction water to flow out of the system. 0.2 part of tetra-n-butyl titanate was added to the reaction mixture, and 0.05 part of “Irganox” 1098 (hindered phenol antioxidant manufactured by Ciba Geigy Co.) was added, and the temperature was raised to 245 ° C. Then, the pressure in the system was reduced to 27 Pa over 50 minutes, and polymerization was performed for 1 hour and 50 minutes under the conditions. The obtained polymer was discharged into water in the form of strands and pelletized by cutting.

[Production of polyester block copolymer (A-2)]
59.3 parts of terephthalic acid, 51.4 parts of 1,4-butanediol and 22.9 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400, 0.04 part of titanium tetrabutoxide and mono-n-butyl -Both 0.02 parts of monohydroxytin oxide were charged into a reaction vessel equipped with a helical ribbon stirring blade, heated at 190 to 225 ° C for 3 hours, and the esterification reaction was carried out while allowing the reaction water to flow out of the system. After adding 0.15 part of tetra-n-butyl titanate to the reaction mixture and adding 0.05 part of “Irganox” 1098 (hindered phenol antioxidant manufactured by Ciba Geigy), the temperature was raised to 245 ° C. Then, the pressure in the system was reduced to 27 Pa over 50 minutes, and polymerization was performed for 1 hour and 50 minutes under the conditions. The obtained polymer was discharged into water in the form of strands and pelletized by cutting.

[Production of Graft Copolymer or Graft Copolymer Composition (B-1)]
In the presence of 60 parts by weight (in terms of solid content) of polybutadiene latex (rubber particle size 0.25 μm, gel content 80%), 40% by weight of a monomer mixture composed of 70% styrene, 20% acrylonitrile and 10% methacrylic acid Part was continuously dropped over 4 hours to carry out emulsion polymerization. The obtained graft copolymer was coagulated with magnesium sulfate, neutralized with caustic soda, washed, filtered and dried to obtain a powdery rubbery polymer. The graft ratio of the rubbery polymer was 36%.

[Production of Graft Copolymer or Graft Copolymer Composition (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 4 hours for emulsion polymerization. The obtained polymer was coagulated with magnesium sulfate, 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-3)]
In the presence of 45 parts by weight of polybutadiene latex (in terms of solid content), 55 parts by weight of a monomer mixture composed of 70% styrene, 20% acrylonitrile, and 10% methacrylic acid was continuously dropped over 4 hours for emulsion polymerization. The obtained polymer was coagulated with magnesium sulfate, neutralized with caustic soda, washed, filtered and dried to obtain a powdery rubbery polymer. The graft ratio of the rubbery polymer was 38%.

[ABS resin]
In the following examples, “Toyolac” type 100 (manufactured by Toray Industries, Inc.) was used.

[Examples 1-8] and [Comparative Examples 1-5]
Table 1 shows graft copolymers (B-1), (B-2), and (B-3) to the polyester block copolymers (A-1) and (A-2) obtained in Reference Examples. They were mixed using a V-blender at the blending ratio (% by weight) shown, melt-kneaded at 220 ° C. using a twin screw extruder having a diameter of 45 mm and a triple thread type screw, and pelletized.

  The obtained pellets were dried at 80 ° C. for 5 hours, and then inline screw type injection molding machine set at 220 ° C., at a mold temperature of 50 ° C. (surface of the mold cavity), a JIS No. 2 dumbbell test piece and a length of 120 mm A square plate molded product having a width of 70 mm and a thickness of 2 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 7 have the characteristics of a flexible and elastic polyester elastomer, and are thermally adhesive to ABS resin by two-color molding. Excellent adhesion to plating and plating. In terms of weather resistance, the polyester elastomer alone shown in Comparative Examples 1 and 2 cracked on the surface appearance, but no abnormality in the surface appearance was observed in the thermoplastic elastomer resin composition of the present invention. Further, Comparative Examples 3 and 5 had small elongation and insufficient flexibility, and Comparative Examples 4 and 5 had low tensile breaking strength. Moreover, the comparative example 6 which does not contain the monomer which has (alpha), (beta) -unsaturated carboxylic acid brought a result inferior to Example 2 in tensile breaking strength or tensile breaking elongation.

  The thermoplastic elastomer resin composition 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, particularly plating and painting. Suitable for products with surface treatment.

  Further, a molded article made of the thermoplastic elastomer resin composition of the present invention, in particular, a composite molded article obtained by laminating a layer made of the thermoplastic elastomer resin composition of the present invention and a hard resin layer, particularly a composite of ABS resin. The molded body can be applied to various cases, covers, connectors, grips, rollers, and the like.

Claims (7)

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. Polyester block copolymer (A) 55-99% by weight and rubbery polymer 40-85 parts by weight in the presence of aromatic vinyl monomer 50-90 wt%, vinyl cyanide monomer 9-50 wt% , 15 to 60 parts by weight of a monomer mixture comprising 0.1 to 20 wt% of a vinyl monomer having an α, β-unsaturated carboxylic acid (100 parts by weight in total with the rubber polymer) is grafted. 1 to 45% by weight of a graft copolymer obtained by polymerization or a graft copolymer (composition) (B) in which the graft copolymer and the remaining monomer are copolymerized. A thermoplastic elastomer resin composition. 2. The thermoplastic elastomer resin composition according to claim 1, wherein the rubber polymer is a diene rubber polymer. The thermoplastic elastomer resin composition according to claim 1 or 2, wherein a graft ratio of the graft copolymer (composition) (B) is 25% or more. The high-melting crystalline polymer segment (a1) in the polyester block copolymer (A) component is mainly composed of a polybutylene terephthalate unit. A thermoplastic elastomer resin composition. The low-melting-point segment (a2) in the polyester block copolymer (A) component is mainly composed of a poly (tetramethylene oxide) glycol unit. The thermoplastic elastomer resin composition according to Item. A molded article obtained by molding the thermoplastic elastomer resin composition according to any one of claims 1 to 5. 8. The molded body according to claim 7, wherein at least one selected from thermoplastic resins other than claims 1 to 6, a metal film, and a paint is adhered to the surface of the molded body.