JP2008106249A - Thermoplastic resin composition and composite molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition in order to solve a problem in the state of the art, which exhibits good adhesive properties regardless of kinds of thermoplastic elastomers as it is a soft material, but exhibits a good adhesion and to provide a composite molded article made of the above by melt welding a thermoplastic elastomer to a molded article made thereof. <P>SOLUTION: The thermoplastic resin composition comprises (A) a polyamide resin, (B) a polyether-ester amide resin and (C) an acid-modified polypropylene resin, in which the sum of the (A), (B) and (C) is made to be 100 wt.%., (B) the polyether-ester amide resin of 5-20 wt.% and the sum of (A) the polyamide resin and (C) the acid-modified polypropylene resin is 80-95 wt.% and also a weight ratio of (A) and (C) satisfies a relationship of 1<(A)/(C)<6. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  INDUSTRIAL APPLICABILITY The present invention has a thermoplastic resin composition having excellent strength, rigidity and impact resistance, and exhibiting good adhesiveness regardless of the type of thermoplastic elastomer, and heat fusion by integrally molding the thermoplastic elastomer on the surface thereof It relates to a composite molded product.

  Polyamide resins have excellent mechanical properties, heat resistance, and chemical resistance, and are widely used as materials for automobiles, electricity, and housings. Composite molded articles in which a thermoplastic elastomer, which is a soft material, is thermally fused for the purpose of imparting grip properties, sound absorption properties, and earthquake resistance to hard materials using these polyamide resins have been commercialized. Polyamide thermoplastic elastomers and polyurethane thermoplastic elastomers with high adhesion to polyamide resins are expensive among thermoplastic elastomers, and are being shifted to cheap polyolefin thermoplastic elastomers, polystyrene elastomers, etc. Currently. However, for the adhesion between different materials such as hard material and soft material, compatibility between the materials is extremely important, and depending on the material, adhesion is extremely difficult. Polyolefin thermoplastic elastomers and polystyrene thermoplastic elastomers are not compatible with polyamides, and there are complaints such as complaints and conplains that they peel when they are used. For this reason, soft materials are often limited with respect to hard materials to be used, and the present situation is that thermoplastic elastomers that are used as soft materials are also limited in polyamide resins.

  Patent Document 1 proposes a three-component polymer alloy of polyamide, polyether ester amide, and thermoplastic elastomer, but it is intended to impart impact properties, and there is no description regarding adhesiveness, and heat added to the polyamide. Depending on the type of plastic elastomer, the thermoplastic elastomer of the soft material is limited.

In Patent Document 2, a copolymer comprising a polymer block of crystalline polyamide, amorphous polyamide and vinyl aromatic compound and a block comprising a block of polyisobutylene, polyisoprene, and / or a copolymer of isoprene and butadiene, and / or A polyamide-based resin containing a polyolefin resin having a functional group reactive with the hydrogenated product and the polyamide resin, and a composite molded product in which a polyolefin-based thermoplastic elastomer is heat-sealed to a molded product made of these are proposed. However, the thermoplastic elastomer used in the molding composite is referred to as a polyolefin-based thermoplastic elastomer, and the problem that adhesiveness with other thermoplastic elastomers is not expressed and the soft material is limited is solved. It has not been. Further, the composition itself is different from the present invention.
Japanese Patent Laid-Open No. 62-169852 JP 2006-117818 A

  The present invention has been made to solve the problems of the prior art, a thermoplastic resin composition that exhibits good adhesiveness regardless of the type of thermoplastic elastomer that is a soft material, and molded articles made of these It is another object of the present invention to provide a composite molded product obtained by thermally fusing a thermoplastic elastomer.

  As a result of intensive studies to solve the above-mentioned problems, the present invention has been completed.

That is, the present invention
(1) A blend of (A) a polyamide resin, (B) a polyetheresteramide resin, and (C) an acid-modified polypropylene resin, and the total of (A), (B), and (C) is 100 weights %, (B) polyether ester amide resin is 5 to 20% by weight, (A) polyamide resin and (C) acid-modified polypropylene resin is 80 to 95% by weight, and (A) and ( A thermoplastic resin composition, wherein the weight ratio of C) satisfies 1 <(A) / (C) <6;
(2) The thermoplastic resin composition according to (1), wherein (A) the polyamide resin is at least one selected from nylon 6, nylon 66, nylon 610, and a nylon copolymer,
(3) (B) the polyetheresteramide resin is
(B1) at least one selected from aminocarboxylic acids having 6 or more carbon atoms, lactams having 6 or more carbon atoms, and salts having 6 or more total carbon atoms synthesized from diamine and carboxylic acid,
(B2) Poly (alkylene oxide) glycol having a number average molecular weight of 1,000 to 3,000, bisphenol A ethylene oxide adduct having a number average molecular weight of 1,000 to 3,000, and ethylene oxide addition of the bisphenol A At least one selected from block copolymers of products,
And
(B3) The thermoplastic resin composition according to (1) or (2), which is a polyether ester amide resin obtained by polymerizing a dicarboxylic acid having 4 to 20 carbon atoms,
(4) A thermoplastic resin composition obtained by further blending (D) 0 to 200 parts by weight of an inorganic filler with respect to 100 parts by weight of the total of (A), (B) and (C),
(5) (D) The inorganic filler is a glass fiber (the thermoplastic resin composition according to 4,
(6) A molded article comprising the thermoplastic resin composition according to any one of (1) to (5),
(7) A composite molded product characterized by heat-sealing a molded product containing (E) a thermoplastic elastomer to the molded product according to (6),
(8) (E) The thermoplastic elastomer is at least one selected from a polyamide-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, a polyolefin-based thermoplastic elastomer, and a polystyrene-based elastomer. (7) The composite molded article according to (7) or (8), wherein the composite molded article according to (7) and (9) the method of heat fusion is heat fusion by integral molding.

  The molded article made of the thermoplastic resin composition of the present invention expresses good adhesiveness regardless of the type of thermoplastic elastomer that becomes a soft material, and the composite molded article of the present invention has high strength, rigidity, heat resistance, It has impact resistance and also has excellent grip surface characteristics.

  Hereinafter, preferred embodiments of the present invention will be described. “Weight” in the text means “mass”.

  Specific examples of the polyamide resin (A) of the present invention include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), and polyhexamethylene sebacamide. (Nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecamide (nylon 11), polydodecamide (nylon 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene Adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / I), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (nylon 66 / 6I / 6), poly Examples thereof include xylylene adipamide (nylon XD6) and a mixture or copolymer thereof, but these are not particularly limited, and are selected from nylon 6, nylon 66, nylon 610, and nylon copolymer. It is preferable that there is at least one. The polyamide resin may be a mixture of two or more types, and a mixture of nylon 6 and nylon 66 is particularly preferable. As the nylon copolymer, semi-aromatic polyamide is preferable, and nylon 66 / 6I and nylon 66 / 6I / 6 are particularly preferable. Moreover, there is no restriction | limiting in particular in the method of manufacturing polyamide, There exist well-known melt polymerization, solid phase polymerization, solution polymerization, interfacial polymerization, etc.

  The relative viscosity (98% sulfuric acid method) of the polyamide resin of the present invention is not particularly limited as long as it is sufficient in toughness or moldability, but is preferably 1.8 to less than 5.0. If it is less than 1.8 from the viewpoint of mechanical strength, the durability is not sufficient, and if it exceeds 5.0, the fluidity is not excellent, so that it is difficult to obtain a molded product having an excellent appearance.

  The (B) polyether ester amide resin of the present invention has (b1) an aminocarboxylic acid having 6 or more carbon atoms, a lactam having 6 or more carbon atoms, and a total of 6 or more carbon atoms synthesized from a diamine and a carboxylic acid. (B2) poly (alkylene oxide) glycol having a number average molecular weight of 1,000 to 3,000, and bisphenol A having a number average molecular weight of 1,000 to 3,000 added with ethylene oxide And a polyether ester amide resin obtained by polymerizing at least one selected from a block copolymer of an ethylene oxide adduct of bisphenol A and (b3) a dicarboxylic acid having 4 to 20 carbon atoms.

  (B1) As aminocarboxylic acids having 6 or more carbon atoms, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid and 11-aminoundecanoic acid, 12- Examples include aminododecanoic acid. (B1) Examples of the lactam having 6 or more carbon atoms include caprolactam, enantolactam, capryllactam and laurolactam. (B1) Salts synthesized from diamine and carboxylic acid having 6 or more total carbon atoms include hexamethylenediamine-adipate, hexamethylenediamine-sebacate, hexamethylenediamine-decanedicarboxylate, and hexamethylenediamine And methylenediamine-isophthalate. In particular, caprolactam, 11-aminoundecanoic acid, 12-aminododecanoic acid, hexamethylenediamine-adipate and the like are preferably used, and caprolactam is more preferable. These polyamide-forming components can be used alone or in combination of two or more as required.

  (B2) Poly (alkylene oxide) glycols include polyethylene glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) ) Glycols, block or random copolymers of ethylene oxide and propylene oxide and block or random copolymers of ethylene oxide and tetrahydrofuran. Among these, polyethylene glycol is preferable, but is not particularly limited. These poly (alkylene oxide) glycols can be used alone or in combination of two or more as required. The number average molecular weight of the poly (alkylene oxide) glycol is 1,000 to 3,000, particularly preferably in the range of 1,200 to 2,000. When the number average molecular weight is 1,000 to 3,000, the polymerization time of the obtained polyetheresteramide can be shortened and the crystallization temperature can be improved. Further, if the number average molecular weight of the poly (alkylene oxide) glycol is less than 1,000, it is not preferable because the heat resistance is lowered. (B2) The number average molecular weight of the ethylene oxide adduct of bisphenol A is 1,000 to 3,000, and particularly preferably in the range of 1,200 to 2,000. A number average molecular weight of less than 1,000 is not preferable because the heat resistance is lowered.

  (B3) As the dicarboxylic acid having 4 to 20 carbon atoms, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′dicarboxylic acid , Diphenoxyethanedicarboxylic acid, and aromatic dicarboxylic acid such as sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and dicyclohexyl-4,4′-dicarboxylic acid Examples include aliphatic dicarboxylic acids such as cyclic dicarboxylic acid, succinic acid, oxalic acid, adipic acid, sebacic acid, and dodecanediic acid (decanedicarboxylic acid), and particularly terephthalic acid, isophthalic acid, and 1,4-cyclohexanedicarboxylic acid. , Sebacic acid, adipic acid and dodecanedioic acid are polymerizable Masui.

  The method for producing this polyether ester amide is not particularly limited. For example, after a polyamide-forming component and a dicarboxylic acid are reacted to produce a polyamide prepolymer having both ends of a carboxylic acid group, the polyamide prepolymer, an ethylene oxide adduct of bisphenol A, And poly (alkylene oxide) glycols are reacted under vacuum. The average molecular weight of the polyamide prepolymer is not particularly limited, but is preferably 200 to 15,000, more preferably 500 to 5,000. As another method, each compound is charged into a reaction vessel and reacted in the presence or absence of water at a temperature of 220 ° C. to 260 ° C. at normal pressure or under pressure to form a polyamide prepolymer, and then vacuum is applied. The method of proceeding the reaction below can be used. Here, “under vacuum” preferably refers to about 2 kPa or less, more preferably 0.67 kPa or less, and most preferably 0.13 kPa or less. In the polymerization reaction of the polyether ester amide, a metal catalyst can be used. As the metal catalyst, a tetraalkyl titanate such as tetrabutyl titanate or a titanium oxalate metal salt such as potassium potassium oxalate is used. Catalysts, tin catalysts such as dibutyltin oxide, dibutyltin laurate, monobutyltin oxide, zirconium catalysts such as zirconium tetrabutoxide and zirconium isopropoxide, hafnium catalysts such as hafnium tetraethoxide, antimony trioxide, etc. There is an antimony catalyst. These may be used alone or in combination of two or more as required.

  The blending amount of the polyether ester amide resin (B) of the present invention is 5 to 20% by weight, preferably 5 to 15% by weight, where the total amount of (A), (B) and (C) is 100% by weight. More preferably, it is 5 to 10% by weight. If the blending amount is less than 5% by weight, the adhesive strength to the thermoplastic elastomer is remarkably lowered.

  The (C) acid-modified polypropylene resin of the present invention is a polypropylene modified with an α, β-unsaturated carboxylic acid or a derivative thereof in order to improve compatibility with the polyamide resin, and is used here. Examples of the α, β-unsaturated carboxylic acid or derivatives thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, hymic acid, bicyclo (2,2,2) oct-5-ene-2,3- Dicarboxylic acid, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid, bicyclo (2,2,1) oct-7-ene-2,3,5 Examples include 6-tetradicarboxylic acid and 7-oxabicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic acid. Desaturated carboxylic acid derivatives include acid anhydrides, esters, amides, imides and metal salts, such as maleic anhydride, itaconic anhydride, citraconic anhydride, hymic acid anhydride, monomethyl maleate, and fumaric acid. Acid monomethyl ester, dimethylaminoethyl methacrylate, dimethylaminopropylacrylamide, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutylamide, fumaric acid-N, N-dibutylamide, maleimide, N-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate and the like can be mentioned. These unsaturated carboxylic acids or derivatives thereof can be used in combination of two or more. Maleic anhydride is preferably used.

  The total of (A) the polyamide resin and (C) the acid-modified polypropylene resin of the present invention is 100% by weight of the total amount of (A), (B) and (C). 80 to 95% by weight excluding ˜20% by weight, and the weight ratio of (A) to (C) is 1 <(A) / (C) <6, preferably 1 <(A) / ( C) <5. If the weight ratio of (A) to (C) is 1 or less, the adhesive strength with polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polystyrene-based elastomers is significantly reduced, which is not preferable. Moreover, since the adhesiveness with a polyolefin-type thermoplastic elastomer will fall remarkably that the ratio of the weight% of (A) and (C) is 6 or more, it is unpreferable.

  In the resin composition of the present invention, the (D) inorganic filler can be appropriately blended in order to increase the rigidity and heat resistance of the molded product. Specifically, one or more kinds selected from glass fiber, carbon fiber, mica, talc, kaolin, wollastonite, calcium carbonate, and potassium titanate can be used in combination. These inorganic fillers may be treated with a silane coupling agent as a surface treatment agent, and those treated with aminosilane are particularly preferred. Among these inorganic fillers, it is preferable to mainly use glass fibers and carbon fibers. As the glass fiber, those usually used for thermoplastic resins can be used, and the fiber diameter and length are not limited, and any of chopped strands, rovings, and milled fibers may be used. The method of blending these is not particularly limited, but in order to develop a reinforcing effect with the thermoplastic resin composition, the thermoplastic resin composition component of the present invention is melt-kneaded in a twin-screw extruder and dispersed. After kneading, it is preferable to knead with side feed.

  The blending amount of the (D) inorganic filler of the present invention is from 0 to 0 with respect to 100 parts by weight in total of (A) polyamide resin, (B) polyetheresteramide resin, and (C) acid-modified polypropylene resin. 200 parts by weight. Preferably it is 0-160 weight part, More preferably, it is 0-150 weight part. By setting the inorganic filler to 200 parts by weight or less, the productivity of the thermoplastic resin composition is not lowered, glossy spots are not generated on the molded product made thereof, and the appearance of the molded product is kept good. This is preferable.

  When the molded product comprising the thermoplastic resin composition of the present invention is (E) a molded product containing a thermoplastic elastomer and a heat-fusing composite molded product, the adhesiveness between (E) the molded product containing the thermoplastic elastomer It is possible to obtain a composite molded product excellent in. Here, as the thermoplastic elastomer (E) contained in the counterpart molded product to be heat-sealed, for example, a polyamide-based thermoplastic elastomer (hereinafter referred to as TPAE) produced by a rubber component such as polyol and polyamide, for example, polyol, etc. Polyurethane-based thermoplastic elastomer (hereinafter referred to as TPU) produced by rubber component and isocyanate compound, for example, polyester-based thermoplastic elastomer (hereinafter referred to as TPEE) produced by rubber component such as polyol and polyester, for example, ethylene, propylene, butylene 1 A rubber component composed of a block copolymer composed of two or more species and a polystyrene-based thermoplastic elastomer (hereinafter referred to as TPS) composed of polystyrene, for example, a polyolefin in which components such as ethylene, propylene, and diene rubber are finely dispersed. Examples include olefin-based thermoplastic elastomers (hereinafter TPO), but these are not particularly limited, and thermoplastic elastomers composed of hard and soft components are preferred and required as soft components that are heat-sealed to molded products. Can be used according to the purpose. There is no problem even if the rubber component is dynamically or partially crosslinked, blended with polymers, or alloyed with other polymers.

  In a molded article comprising the thermoplastic resin composition of the present invention and a composite molded article comprising (E) a molded article containing a thermoplastic elastomer, the thermal bond strength between them is extremely important. The thermal bond strength can be evaluated by the following method. In the case of a mold with a nesting (see FIG. 1), the nesting is set to flow only on one side, and the L-shaped test piece (see FIG. 2) is the case of (A), (B), (C) of the present invention. After molding using a thermoplastic resin composition containing the component (D), cutting the film gate portion of the L-shaped test piece, and then setting the mold nesting to flow to the opposite side After mounting the test piece on the mold, (E) a T-shaped test piece (see FIG. 3) of a composite molded product is molded by an overmolding method in which a thermoplastic elastomer is additionally molded, and a thermal adhesion test is performed. Obtain a tear specimen. This T-shaped composite molded product is joined on the back side of each L-shaped test piece made of the thermoplastic resin composition of the present invention, which is a hard material, and the thermoplastic elastomer, which is a soft material. When a tear test is performed as a thermal adhesion evaluation using this T-shaped composite molded article, the tear load is preferably 10 kgf or more. More preferably, it is 15 kgf or more. If the tear load is less than 10 kgf, a durable composite molded product cannot be obtained. The tear load between the general polyamide resin and the thermoplastic elastomer is about 0 to 8.0 kgf, and the composite molded product of the present invention has extremely high thermal adhesive strength, and a composite molded product with excellent durability can be obtained.

  The thermoplastic resin composition of the present invention includes a crystal nucleating agent, a stabilizer such as a heat-resistant agent and an ultraviolet absorber, a flame retardant, an antistatic agent, a plasticizer, and the like within a range that does not impair the purpose of the invention. An agent, a lubricant, a colorant and the like may be contained. Crystal nucleating agents include inorganic fillers such as talc and clay, organic crystal nucleating agents such as fatty acid metal salts, crystallization accelerators include low molecular weight polyamides, higher fatty acids, higher fatty acid esters and higher fatty acid alcohols, heat resistance Examples of the agent include hindered phenols, phosphites, thioethers, and copper halides. Furthermore, examples of weathering agents include hindered amines and salicylates.

  Other thermoplastic resins can be added to the thermoplastic resin composition of the present invention without departing from the scope of the present invention. Examples include general-purpose resins such as polyethylene, polypropylene, polystyrene, ABS resin, AS resin, and acrylic resin, polycarbonate, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, and other heat-resistant resins. When polyethylene or polystyrene is added, those modified with maleic anhydride or a glycyl group-containing monomer can be used.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples. In addition, evaluation in the composition obtained by the Example and the comparative example was implemented based on the following points.

1. Mechanical properties (1) Molding of test piece: In accordance with ISO1874-2, an injection molding machine PS60 manufactured by Nissei Plastic Industry Co., Ltd., cylinder temperature 260 ° C., mold temperature 80 ° C., injection-cooling time: 20-10 seconds, Parallel part flow velocity: ISO Type-A standard test piece was molded under the condition of 200 mm / sec.

  (2) Tensile strength: measured in accordance with ISO527-1,2.

  (3) Charpy impact strength: measured in accordance with ISO179.

  (4) Deflection temperature under load: measured according to ISO75-2.

2. Thermal adhesive evaluation (Thermal adhesive strength of overmolded products)
Evaluation of the thermal adhesive strength between a molded product made of a thermoplastic resin composition and a thermoplastic elastomer was performed by creating a test piece for thermal adhesion evaluation by an overmolding method in which a thermoplastic elastomer was additionally molded as described above, and The tear load, which is an index of thermal bond strength, was measured in the test. (Refer to FIGS. 1 to 4) The test piece of the thermoplastic resin composition was an IS80 type injection molding machine manufactured by Toshiba Machine Co., Ltd., cylinder temperature: 260 ° C., mold temperature: 80 ° C., injection-cooling time: 10-10. Second, injection speed: 70%, injection pressure: 60%, pressure keeping speed: 40%, pressure keeping pressure: 30%. The conditions for the additional molding of the thermoplastic elastomer are the same machine, the film gate of the molded product made of the thermoplastic resin composition is cut and set in the mold, cylinder temperature: 210 ° C., mold temperature: 30 ° C., injection − The cooling time was 15-25 seconds, the injection speed was 50%, the injection pressure was 40%, the pressure holding speed was 30%, and the pressure holding pressure was 20%. A tearing load is measured at a tearing speed of 10 mm / min using a T-shaped test piece having a width of 25 mm and a depth of 210 mm made by Shimadzu Corporation, Autograph model name AG-500B. And the adhesive strength.

<Materials used>
(A) As polyamide resin, nylon 6 (Toray Industries, Inc .: Toray Milan CM1010), nylon 66 (Toray Industries, Inc .: Torea Milan CM3001N), nylon 610 (Toray Industries, Inc .: Toray Milan CM2001) was used. Also, as the nylon copolymer, hexamethylene diamine and adipic acid equimolar salt, hexamethylene diamine and isophthalic acid equimolar salt, and ε-caprolactam were introduced in the weight ratios shown in the table, respectively, and all the raw materials introduced After adding the same amount of pure water and sufficiently replacing the inside of the polymerization canister with N2, heating was started while stirring. The final temperature reached 270 ° C. while adjusting the can internal pressure to a maximum of 20 kg / cm ² (G). A semi-aromatic polyamide resin obtained by pelletizing a polymer discharged into a water bath with a strand cutter was used.
(B) 45 parts of caprolactam as a polyetheresteramide resin, 45 parts of an ethylene oxide adduct of bisphenol A having a number average molecular weight of 1,500, 5 parts of polyethylene glycol having a number average molecular weight of 1,500, and 5 parts of terephthalic acid .82 parts, charged with 0.5 parts of antioxidant (Irganox 1098: Ciba Specialty Chemicals Co., Ltd.), purged with N ₂ , heated and stirred at 260 ° C. for 60 minutes to obtain a transparent homogeneous solution The pressure was reduced to 0.07 kPa or less. 0.1 part of tetrabutyl titanate was added, the reaction was carried out when the stirring torque reached 11 kg · m (11 r / min) under the conditions of a pressure of 0.07 kPa or less and a temperature of 260 ° C. Time), and after discharging, pelletized with a strand cutter to obtain a polyetheresteramide.
(C) Modified polypropylene (manufactured by Mitsui Chemicals, Inc .: Admer QF551) was used as the acid-modified polypropylene.
(D) Glass fiber (Nippon Electric Glass Co., Ltd. product: T-298) was used as an inorganic filler.
(E) As the thermoplastic elastomer, TPU (manufactured by BASF: Elastollan ET-385), polyester-based thermoplastic elastomer (manufactured by Mitsubishi Chemical Corporation: Primalloy A1710N), polystyrene-based thermoplastic elastomer (manufactured by Aron Kasei Co., Ltd .: AR9060) ) (Toyobo Co., Ltd .: Sirlink 3170) was used as the polyolefin-based thermoplastic elastomer. As the polyamide-based thermoplastic elastomer (TPAE), the (B) polyether ester amide was used.

  As materials for comparative examples, acid-modified ethylene propylene copolymer (Mitsui Chemical Co., Ltd .: Tafmer MP0610), acid-modified ethylene butene copolymer (Mitsui Chemicals Co., Ltd .: Tafmer MH7010), acid-modified styrene ethylene butylene styrene copolymer (Clayton Polymer Japan Co., Ltd .: Clayton FG1901X) and ethylene methacrylic acid copolymer (Mitsui / DuPont Polychemical Co., Ltd .: High Milan 1706) were used.

Examples 1-6, Comparative Examples 1-8
<Manufacture of thermoplastic resin composition>
The resin components are mixed from the components listed in Table 1 in the ratios shown in the table, and the mixture is introduced into a TEX30 type twin screw extruder manufactured by Nippon Steel Works, which is set to a cylinder temperature of 240 to 270 ° C. It mix | blended in molten resin with the side feed so that it might become a ratio, knead-extrusion, cast in water, and the pellet was obtained by cutting with a strand cutter.

  The evaluation results of Examples 1 to 6 and Comparative Examples 1 to 8 are shown in Tables 1 and 2.

  As is apparent, Examples 1 to 6 are excellent in adhesiveness with the thermoplastic elastomer. On the other hand, Comparative Example 1 shows the characteristics of a thermoplastic resin composition not containing (B) polyether ester amide resin and (C) acid-modified polypropylene resin, and Comparative Example 2 contains (B) polyether ester amide. The properties of the thermoplastic resin composition not to be exhibited, and in Comparative Examples 3 and 4, the ratio of the weight percent of (A) polyamide resin to (C) acid-modified polypropylene resin is 1 or less and 6 or more. In Comparative Examples 5 to 8, the properties of thermoplastic resin compositions made of other polyolefin resins were shown instead of (C) acid-modified polypropylene. In either case, depending on the type of elastomer, there is a product that peels off spontaneously, and no adhesiveness is exhibited at all, resulting in a limited type of thermoplastic elastomer.

  The molded article made of the thermoplastic resin composition of the present invention expresses good adhesiveness regardless of the type of thermoplastic elastomer that becomes a soft material, and the composite molded article of the present invention has high strength, rigidity, heat resistance, Because it has impact resistance and excellent grip surface characteristics, it can be expected to be used in a wide range of applications such as automobile parts, home appliance parts, electric tools, sports equipment, personal computers, furniture, etc. It is not limited to.

It is a figure which shows the test piece metal mold | die for a thermal bond strength measurement. It is a figure which shows an L-shaped test piece (molded article). It is a figure which shows a T-shaped test piece (composite molded product). It is a figure which shows the measuring method of the heat adhesiveness of a composite molded product.

Explanation of symbols

1: Movable plate 2: Fixed plate 3: Nesting (switching between molded product and composite molded product)
4: L-shaped molding runner part (for thermoplastic resin composition molding)
5: T-shaped molding runner (for thermoplastic elastomer overmold)
6: L-shaped molded product 7: T-shaped molded product 8: Film gate cut portion 9: Thermoplastic resin composition 10: Thermoplastic elastomer 11: Tensile tester chuck 12: Tensile test direction

Claims (9)

(A) Polyamide resin, (B) polyether ester amide resin, and (C) acid-modified polypropylene resin are blended, and the total of (A), (B) and (C) is 100% by weight, (B) The polyether ester amide resin is 5 to 20% by weight, the total of (A) the polyamide resin and (C) the acid-modified polypropylene resin is 80 to 95% by weight, and (A) and (C) A thermoplastic resin composition, wherein the weight ratio satisfies 1 <(A) / (C) <6. (A) The thermoplastic resin composition according to claim 1, wherein the polyamide resin is at least one selected from nylon 6, nylon 66, nylon 610, and a nylon copolymer. (B) a polyetheresteramide resin
(B1) at least one selected from aminocarboxylic acids having 6 or more carbon atoms, lactams having 6 or more carbon atoms, and salts having 6 or more total carbon atoms synthesized from diamine and carboxylic acid,
(B2) Poly (alkylene oxide) glycol having a number average molecular weight of 1,000 to 3,000, bisphenol A ethylene oxide adduct having a number average molecular weight of 1,000 to 3,000, and ethylene oxide addition of the bisphenol A At least one selected from block copolymers of products,
And
(B3) The thermoplastic resin composition according to claim 1 or 2, which is a polyetheresteramide resin obtained by polymerizing a dicarboxylic acid having 4 to 20 carbon atoms. A thermoplastic resin composition comprising 0 to 200 parts by weight of (D) an inorganic filler with respect to 100 parts by weight of the total of (A), (B) and (C). (D) The thermoplastic resin composition according to claim 4, wherein the inorganic filler is a glass fiber. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 5. A composite molded product obtained by heat-sealing a molded product containing (E) a thermoplastic elastomer to the molded product according to claim 6. (E) The thermoplastic elastomer is at least one selected from a polyamide-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, a polyolefin-based thermoplastic elastomer, and a polystyrene-based elastomer. Item 8. A composite molded article according to Item 7. The composite molded article according to claim 7 or 8, wherein the heat-sealing method is heat-sealing by integral molding.

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