JP2015105359A - Glassfiber reinforced thermoplastic composition and molding thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glassfiber reinforced thermoplastic composition excellent in fluidity, heat resistance, high temperature rigidity, mechanical strength, shock resistance and surface appearance and capable of obtaining a molding having a small warp.SOLUTION: The glassfiber reinforced thermoplastic composition is formed by mixing (A) 100 pts.wt. of at least one kind of thermoplastic resins selected from a group consisting of polyamide, polyester and polyphenylene sulfide and (B) 5-200 pts.wt of glass fibers including SiOof 57-63 wt.%, AlOof 19-23 wt.%, CaO of 5.5-11 wt.% and MgO of 10-15 wt.% in the total amount of 99.5 wt.% or more and having SiO/AlOof 2.7-3.2 and MgO/CaO of 0.9-2.0 in a weight ratio.

Description

  The present invention relates to a glass fiber reinforced thermoplastic resin composition obtained by blending glass fibers having a specific composition with at least one thermoplastic resin selected from the group consisting of polyamide, polyester and polyphenylene sulfide, and molding the same. It relates to a molded product.

  Thermoplastic resins are used in various applications by taking advantage of their excellent properties. Among thermoplastic resins, for example, polyamides and polyesters that have a good balance between mechanical strength and toughness are used for various electrical and electronic parts, machine parts, automobile parts, etc. mainly for injection molding, as well as heat resistance, chemical resistance, Liquid crystalline polymer (LCP) and polyphenylene sulfide (PPS), which have excellent rigidity and flame retardancy, and good moldability and dimensional stability, are used as engineering plastics for injection molding, such as electrical and electronic parts, automotive parts and precision equipment. Widely used in parts.

  The mechanical strength, heat resistance, and dimensional accuracy required for these thermoplastic resins have been reduced in recent years as electrical and electronic parts have become smaller and more complicated in shape, and molded products have become thinner for modularization and weight reduction of large automotive parts. It has become more advanced. As a means for improving these properties, composite of thermoplastic resin and glass fiber is generally used. However, composite of glass fiber has several problems such as surface appearance deterioration due to fluidity drop and warpage. It was.

As glass fiber used for resin reinforcement etc. currently marketed, E glass of the following composition occupies most from a viewpoint of productivity, economical efficiency, and physical property balance. However, the molded product obtained from the thermoplastic resin composition using such E glass has a problem that mechanical strength, impact resistance and high-temperature rigidity are still insufficient in addition to the above problems.
· _SiO 2: 52~56 weight%
· _B 2 _O 3: 5~10 wt%
· _Al 2 _O 3: 12~16 wt%
-CaO: 16 to 25% by weight
MgO: 0 to 6% by weight
_{· Na 2 O + K 2 O} : 0~2 wt%
TiO ₂ : 0 to 1.5% by weight
· _Fe 2 _O 3: 0~0.8 wt%
· _F 2: 0~1% by weight.

A glass composition (S glass) having a basic composition composed of SiO ₂ , Al ₂ O _3, and MgO is known as a glass for glass fibers that is superior in strength and elastic modulus to E glass. For S glass, for example, SiO ₂ / Al ₂ O ₃ is 2.35 to 3.40 in weight ratio, Al ₂ O ₃ / MgO is 1.25 to 2.30 in weight ratio, SiO ₂ , Glass composition for glass fiber in which the total weight of Al ₂ O ₃ and MgO is 98% by weight or more based on the total weight of the glass composition (for example, see Patent Document 1), or the inclusion of SiO _{2 based on} the total weight The amount is 57.0 to 63.0% by weight, the content of Al ₂ O ₃ is 19.0 to 23.0% by weight, the content of MgO is 10.0 to 15.0% by weight, and the content of CaO is A glass fiber having a composition of 4.0 to 11.0% by weight and a total content of SiO ₂ , Al ₂ O ₃ , MgO and CaO of 99.5% by weight or more (see, for example, Patent Document 2) ) Etc. have been proposed. However, there is no description regarding the effect of compounding with the thermoplastic resin.

JP 2002-154843 A International Publication No. 2011/155362

  The present invention provides a glass fiber reinforced thermoplastic resin composition having excellent fluidity, excellent heat resistance, high temperature rigidity, mechanical strength, impact resistance and surface appearance, and capable of obtaining a molded product with reduced warpage. With the goal.

As a result of intensive studies to solve such problems, the present inventors have specifically described the above problems by using a glass fiber reinforced thermoplastic resin composition formed by blending a specific thermoplastic tree and glass fibers having a specific composition. It was found that the problem can be solved, and the present invention was achieved. That is, the present invention
(1) (B) With respect to 100 parts by weight of at least one thermoplastic resin selected from the group consisting of polyamide, polyester and polyphenylene sulfide, (B) SiO ₂ content is 57 to 63% by weight, Al ₂ O ₃ content The amount is 19 to 23% by weight, the CaO content is 5.5 to 11% by weight, the MgO content is 10 to 15% by weight, the total of these is 99.5% by weight or more, and SiO _{2 is} contained. 5 to ₂₀₀ weight percent of glass fiber with a weight / Al ₂ O ₃ content of 2.7 to 3.2 by weight and a MgO content / CaO content of 0.9 to 2.0 by weight. Glass fiber reinforced thermoplastic resin composition,
(2) The glass fiber reinforced thermoplastic resin composition according to (1), wherein the cross-sectional shape of the glass fiber (B) is a circular shape or a flat shape,
(3) The glass fiber reinforced thermoplastic resin composition according to (2), wherein the cross-sectional shape of the glass fiber (B) is a flat shape,
(4) The glass fiber reinforced thermoplastic resin composition according to (3), wherein the flat shape is an elliptical shape, an oval shape, or an eyebrows shape, and a ratio of a major axis to a minor axis of a cross section is 1.3 to 10. ,
(5) The weight average fiber length of said (B) glass fiber in a composition is 100-1000 micrometers, and contains 20-50 weight% of 300-500 micrometers glass fiber in said (B) glass fiber total amount (1 ) To (4), a glass fiber reinforced thermoplastic resin composition,
(6) A molded product formed by molding the glass fiber reinforced thermoplastic resin composition according to any one of (1) to (5),
(7) The molded product according to (6), which is an electric / electronic part, an automobile interior part or an automobile exterior part.

  The glass fiber reinforced thermoplastic resin composition of the present invention is excellent in fluidity. According to the glass fiber reinforced thermoplastic resin composition of the present invention, a molded product having excellent heat resistance, high temperature rigidity, mechanical strength, impact resistance, and surface appearance and reduced warpage can be obtained. By using the glass fiber reinforced thermoplastic resin composition and molded article of the present invention for electrical and electronic parts such as connectors, the snap fit and pin press-fit properties can be greatly improved.

It is the schematic of the box formation type article used for evaluation of curvature in an example. It is the schematic which shows the measurement site | part of the curvature amount in the box formation type | mold product shown in FIG.

Hereinafter, the present invention will be described in detail. The glass fiber reinforced thermoplastic resin composition of the present invention (hereinafter sometimes referred to as “resin composition”) is (A) at least one thermoplastic resin selected from the group consisting of polyamide, polyester and polyphenylene sulfide. On the other hand, (B) glass fiber containing SiO ₂ , Al ₂ O ₃ , CaO, and MgO at a specific composition ratio is blended. In the thermoplastic resin, polar groups such as an amide group, an ester group, an amino group, a carboxyl group, and a sulfide group are excellent in the interaction (adsorption property, hydrogen bonding property) with SiO ₂ that is a component constituting the glass fiber. . Furthermore, by making the composition of the glass fiber into a specific range and increasing the interaction between the polar group in the thermoplastic resin and SiO ₂ constituting the glass, the balance of heat resistance, high temperature rigidity, mechanical strength, impact resistance and A molded article having excellent surface appearance and reduced warpage can be obtained. Of the thermoplastic resins, polyamide is preferred.

  The polyamide used in the present invention is a polymer or copolymer mainly composed of amino acids, lactams or diamines and dicarboxylic acids. Representative examples of the raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetramethylenediamine, penta Methylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5 -Aliphatic diamines such as methylnonamethylenediamine, aromatic diamines such as metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1- Ami No-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane , Alicyclic diamines such as bis (aminopropyl) piperazine and aminoethylpiperazine, aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid Acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and other aromatic dicarboxylic acids, 1,4-cyclohexane Dicarboxylic acid, 1,3-cyclohexa Dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-like alicyclic dicarboxylic acids such as cyclopentane dicarboxylic acid. In the present invention, two or more polyamide homopolymers or copolymers derived from these raw materials may be blended.

  Specific examples of polyamides include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sebacamide (nylon 410), Polypentamethylene adipamide (nylon 56), polypentamethylene sebamide (nylon 510), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide ( Nylon 106), polydecane methylene sebamide (nylon 1010), polydecane methylene dodecane (nylon 1012), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polycaproamide / polyhexamethylene adipa Mid copolymer Nylon 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / Polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / polydodecanamide copolymer (nylon 6T / 12), poly Hexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (Niro XD6), polyxylylene sebacamide (nylon XD10), polyhexamethylene terephthalamide / polypentamethylene terephthalamide copolymer (nylon 6T / 5T), polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer ( Nylon 6T / M5T), polypentamethylene terephthalamide / polydecamethylene terephthalamide copolymer (nylon 5T / 10T), polynonamethylene terephthalamide (nylon 9T), polynonamethylene terephthalamide / poly-2-methyloctamethylene terephthalamide Copolymer (nylon 9T / M8T), polydecamethylene terephthalamide (nylon 10T), polydecamethylene terephthalamide / polyhexamethylene adipamide (na Iron 10T / 66), polydecane methylene terephthalamide / polyhexamethylene dodecanamide (nylon 10T / 612), polydodecane methylene terephthalamide (nylon 12T), and copolymers thereof. Here, “/” represents a copolymer, and the same applies hereinafter.

  In particular, a polyamide having a melting point of 220 ° C. to 330 ° C. is preferable. By using a polyamide having a melting point of 220 ° C. or higher, the heat resistance (deflection temperature under load) can be further improved. On the other hand, by using a polyamide having a melting point of 330 ° C. or lower, the decomposition of the polyamide can be suppressed during the production of the resin composition, and the heat resistance, high-temperature rigidity, mechanical strength, and resistance of the molded product obtained from the resin composition can be suppressed. Impact properties can be further improved. Here, the melting point of the polyamide in the present invention is 20 ° C./min after the temperature of the polyamide is lowered from the molten state to 30 ° C. at a temperature lowering rate of 20 ° C./min using a differential scanning calorimeter. Is defined as the temperature of the endothermic peak that appears when the temperature is raised to the melting point + 40 ° C. However, when two or more endothermic peaks are detected, the temperature of the endothermic peak having the highest peak intensity is defined as the melting point.

  In the present invention, the glass transition temperature of the polyamide is preferably 30 ° C to 150 ° C. When the glass transition temperature is 30 ° C. or higher, the high-temperature rigidity, mechanical strength, and impact resistance of the molded product can be further improved. More preferably, it is 45 ° C. or higher. On the other hand, when the glass transition temperature is 150 ° C. or lower, a resin composition suitable for molding can be obtained by moderately suppressing the crystallization rate during molding. Here, the glass transition temperature of the polyamide in the present invention was raised at a rate of temperature increase of 20 ° C./min after rapidly cooling the polyamide with liquid nitrogen in an inert gas atmosphere using a differential scanning calorimeter. It is defined as the temperature at the midpoint of the stepped endothermic peak that appears in the case.

  Examples of the polyamide having a melting point of 220 ° C. to 330 ° C. and a glass transition temperature of 30 ° C. to 150 ° C. include nylon 6, nylon 610, nylon 66, nylon 46, nylon 410, nylon 56, nylon 6T / 66. Copolymers, copolymers having hexamethyl terephthalamide units such as nylon 6T / 6I copolymer, nylon 6T / 12, nylon 6T / 5T, nylon 6T / M5T, nylon 6T / 6 copolymer, nylon 9T, nylon 9T / M8T, Nylon 10T, nylon 10T / 612, nylon 10T / 66, nylon 12T, etc. can be mentioned. It is also practically preferable to blend two or more of these polyamides as required.

  The relative viscosity of the polyamide is preferably in the range of 1.5 to 5.0. If the relative viscosity is 1.5 or more, the mechanical strength, impact resistance, heat resistance and high-temperature rigidity of the obtained molded product can be further improved. 2.0 or more is more preferable from the viewpoint of improving moldability, suppressing breakage of glass fibers, and further enhancing the effects of the present invention. On the other hand, if the relative viscosity is 5.0 or less, the fluidity is excellent and the molding processability is excellent. 3.0 or less is more preferable from the viewpoint of improving moldability, suppressing breakage of glass fibers, and further enhancing the effects of the present invention. The relative viscosity of the polyamide in the present invention is a value measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a resin concentration of 0.01 g / ml.

  As a method for producing the polyamide used in the present invention, for example, in the case of a polyamide using diamine and dicarboxylic acid as main raw materials, a low-order condensate is obtained by heating the diamine and dicarboxylic acid or salts thereof as raw materials, Examples thereof include a method for increasing the degree of polymerization by solid phase polymerization and / or melt polymerization. Two-stage polymerization in which the low-order condensate is once taken out and solid-phase polymerization and / or melt polymerization is performed. Following the production process of the low-order condensate, solid-phase polymerization and / or melt polymerization in the same reaction vessel Either of these may be used. Solid phase polymerization refers to a step of heating in a temperature range of 100 ° C. or higher and lower than the melting point under reduced pressure or in an inert gas, and melt polymerization refers to a step of heating to a melting point or higher under normal pressure or reduced pressure. Point to.

  The polyester used in the present invention is selected from (i) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, (b) a hydroxycarboxylic acid or an ester-forming derivative thereof, and (c) a lactone. It is a polymer or copolymer having one or more main ingredients. Moreover, the liquid crystalline polyester mentioned later may be sufficient. Two or more of these may be blended.

  Examples of the dicarboxylic acid or ester-forming derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, and anthracene dicarboxylic acid. Acid, 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, aromatic dicarboxylic acid such as 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid And aliphatic dicarboxylic acids such as malonic acid, glutaric acid and dimer acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

  Examples of the diol or ester-forming derivative thereof include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, and cyclohexanedi. C2-C20 aliphatic glycols such as methanol, cyclohexanediol and dimer diol, long-chain glycols having a molecular weight of 200 to 100,000 such as polyethylene glycol, poly-1,3-propylene glycol and polytetramethylene glycol, 4,4 ′ -Aromatic dioxy compounds such as dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F, and ester-forming derivatives thereof And the like.

  Examples of the polymer or copolymer using dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as raw materials include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyhexylene. Terephthalate, polyethylene isophthalate, polypropylene isophthalate, polybutylene isophthalate, polycyclohexanedimethylene isophthalate, polyhexylene isophthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / Terephthalate, polybutylene isophthalate / terephthalate, Reethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate, polybutylene terephthalate / decane dicarboxylate, polyethylene terephthalate / cyclohexanedimethylene terephthalate, polyethylene terephthalate / 5-sodium sulfoisophthalate, polypropylene terephthalate / 5-sodium sulfo Isophthalate, polybutylene terephthalate / 5-sodium sulfoisophthalate, polyethylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polyethylene terephthalate / polytetramethylene glycol, poly Pyrene terephthalate / polytetramethylene glycol, polybutylene terephthalate / polytetramethylene glycol, polyethylene terephthalate / isophthalate / polytetramethylene glycol, polypropylene terephthalate / isophthalate / polytetramethylene glycol, polybutylene terephthalate / isophthalate / polytetramethylene glycol Polyethylene terephthalate / succinate, polypropylene terephthalate / succinate, polybutylene terephthalate / succinate, polyethylene terephthalate / adipate, polypropylene terephthalate / adipate, polybutylene terephthalate / adipate, polyethylene terephthalate / sebacate, polypropylene terephthalate / sebacate, Polybutylene terephthalate / sebacate, polyethylene terephthalate / isophthalate / adipate, polypropylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / succinate, polybutylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / sebacate, etc. Aromatic polyester, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyneopentyl glycol adipate, polyethylene sebacate, Polypropylene Sebakei , Polybutylene sebacate, polyethylene succinate / adipate, polypropylene succinate / adipate, and aliphatic polyesters such as polybutylene succinate / adipate and the like.

  Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and these. Examples thereof include ester-forming derivatives. Examples of the polymer or copolymer using these as raw materials include aliphatic polyesters such as polyglycolic acid, polylactic acid, polyglycolic acid / lactic acid, polyhydroxybutyric acid / β-hydroxybutyric acid / β-hydroxyvaleric acid, and the like. It is done.

  Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Examples of the polymer or copolymer having these as a structural unit include polycaprolactone, polyvalerolactone, polypropiolactone, polycaprolactone / valerolactone, and the like.

  Of these, preferred are polymers or copolymers mainly composed of dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative, aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or A polymer or copolymer having the ester-forming derivative as a main structural unit is more preferable, and terephthalic acid or an ester-forming derivative thereof and an aliphatic diol selected from ethylene glycol, propylene glycol, or butanediol or an ester-forming derivative thereof. More preferred are polymers or copolymers whose main raw material is. Among these, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate are more preferable. Polybutylene terephthalate is most preferred.

  In the present invention, the ratio of terephthalic acid or an ester-forming derivative thereof to the total dicarboxylic acid in a polymer or copolymer mainly comprising a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof is: 30 mol% or more is preferable and 40 mol% or more is more preferable.

  The amount of carboxyl end groups of the polyester used in the present invention is not particularly limited, but is preferably 50 eq / t or less and more preferably 40 eq / t or less in terms of further improving fluidity, hydrolysis resistance and heat resistance. The lower limit is 0 eq / t. In the present invention, the amount of carboxyl terminal groups of polyester is a value obtained by dissolving polyester in o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide.

The amount of the vinyl terminal group of the polyester used in the present invention is not particularly limited, but is preferably 15 eq / t or less and more preferably 5 eq / t or less in terms of further improving the color tone and fluidity. The lower limit is 0 eq / t. In the present invention, the vinyl end group amount of the polyester is a value measured by ¹ H-NMR using a deuterated hexafluoroisopropanol solvent.

The amount of hydroxyl terminal groups of the polyester used in the present invention is not particularly limited, but is preferably 50 eq / t or more, more preferably 80 eq / t or more, in terms of moldability and fluidity, and 100 eq / t is more preferably t or more, and particularly preferably 120 eq / t or more. The upper limit is not particularly limited, but is 180 eq / t. In the present invention, the hydroxyl terminal group amount of (A) the thermoplastic resin is a value measured by ¹ H-NMR using a deuterated hexafluoroisopropanol solvent.

  The intrinsic viscosity of the polyester used in the present invention is 0.36 to 1.60 dl / g from the viewpoint of further improving fluidity, suppressing breakage of glass fibers, and further enhancing the effects of the present invention. Is preferable, and the range of 0.50 to 1.50 dl / g is more preferable. Most preferably, it is 0.6 to 0.9 dl / g. In the present invention, the intrinsic viscosity of the polyester is a value obtained by measuring an o-chlorophenol solution at 25 ° C.

  The production method of the polyester used in the present invention is not particularly limited, and a known polycondensation method or ring-opening polymerization method can be applied. Either batch polymerization or continuous polymerization may be used, and both transesterification and direct polymerization reactions can be applied, but the amount of carboxyl end groups can be reduced and the effect of improving fluidity is increased. In view of this, continuous polymerization is preferable, and direct polymerization is preferable in terms of cost.

  When the polyester used in the present invention is a polymer or copolymer obtained by a condensation reaction using dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as main raw materials, The ester-forming derivative can be produced by subjecting the diol or the ester-forming derivative to an esterification reaction or a transesterification reaction, and then a polycondensation reaction. In order to effectively advance the esterification reaction or transesterification reaction and polycondensation reaction, it is preferable to add a polymerization reaction catalyst during these reactions. Specific examples of the polymerization reaction catalyst include organic titanium compounds, tin compounds, zirconia compounds, antimony compounds and the like. Two or more of these may be used in combination. Among these, an organic titanium compound and a tin compound are preferable, tetra-n-propyl ester, tetra-n-butyl ester and tetraisopropyl ester of titanic acid are more preferable, and tetra-n-butyl ester of titanic acid is particularly preferable. The addition amount of the polymerization reaction catalyst is preferably in the range of 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the polyester in terms of further improving mechanical strength, impact resistance, heat resistance, moldability and color tone.

  The liquid crystalline polyester used in the present invention is a resin that forms an anisotropic molten phase, and includes, for example, aromatic oxycarbonyl units, aromatic and / or aliphatic dioxy units, aromatic and / or aliphatic dicarbonyls. Consists of structural units selected from units.

  Examples of the aromatic oxycarbonyl unit include structural units generated from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and the like, and p-hydroxybenzoic acid is preferable. Examples of the aromatic and / or aliphatic dioxy unit include 4,4′-dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, t-butylhydroquinone, Phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether, ethylene glycol, 1,3-propylene glycol, 1, Examples include structural units generated from 4-butanediol, and 4,4′-dihydroxybiphenyl and hydroquinone are preferred. Examples of the aromatic and / or aliphatic dicarbonyl units include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4, Examples include structural units generated from 4′-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, adipic acid, sebacic acid, and the like. Terephthalic acid and isophthalic acid are preferred.

  Specific examples of the liquid crystalline polyester include a liquid crystalline polyester composed of a structural unit generated from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, a structural unit generated from p-hydroxybenzoic acid, and 6-hydroxy-2. A structural unit produced from naphthoic acid, a liquid crystalline polyester comprising a structural unit produced from an aromatic dihydroxy compound, an aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid, a structural unit produced from p-hydroxybenzoic acid, 4, 4 A liquid crystalline polyester comprising a structural unit produced from a structural unit produced from '-dihydroxybiphenyl, an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid and / or an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, p-hydroxybenzoic acid Structural units generated from acids, 4,4 ' Liquid crystalline polyester comprising structural units generated from dihydroxybiphenyl, structural units generated from hydroquinone, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and / or structural units generated from aliphatic dicarboxylic acids such as adipic acid and sebacic acid , A structural unit produced from p-hydroxybenzoic acid, a structural unit produced from ethylene glycol, a liquid crystalline polyester comprising a structural unit produced from terephthalic acid and / or isophthalic acid, a structural unit produced from p-hydroxybenzoic acid, ethylene A liquid crystalline polyester comprising a structural unit produced from glycol, a structural unit produced from 4,4′-dihydroxybiphenyl, a structural unit produced from an aliphatic dicarboxylic such as terephthalic acid and / or adipic acid, sebacic acid, Structural units generated from loxybenzoic acid, structural units generated from ethylene glycol, structural units generated from aromatic dihydroxy compounds, structures generated from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid Liquid crystalline polyester composed of units, structural units formed from 6-hydroxy-2-naphthoic acid, structural units formed from 4,4′-dihydroxybiphenyl, and liquid crystalline composed of structural units formed from 2,6-naphthalenedicarboxylic acid Examples include polyester.

  Among these liquid crystalline polyesters, liquid crystalline polyesters composed of the following structural units (I), (II), (III), (IV) and (V) are preferable.

  The structural unit (I) represents a structural unit generated from p-hydroxybenzoic acid. The structural unit (II) represents a structural unit formed from 4,4'-dihydroxybiphenyl. The structural unit (III) is a structural unit generated from hydroquinone. The structural unit (IV) represents a structural unit generated from terephthalic acid. The structural unit (V) represents a structural unit generated from isophthalic acid.

  The structural unit (I) is preferably 65 to 80 mol% with respect to the total of the structural units (I), (II) and (III). Since wettability with glass fiber is improved and mechanical strength is further improved, the content is more preferably 68 to 78 mol%.

  As for structural unit (II), 55-85 mol% is preferable with respect to the sum total of structural unit (II) and (III). From the point which improves adhesiveness with the glass fiber mentioned later and improves a pin press-fit characteristic more, More preferably, it is 55-78 mol%, Most preferably, it is 58-73 mol%.

  As for structural unit (IV), 50-95 mol% is preferable with respect to the sum total of structural unit (IV) and (V). More preferably, it is 55-90 mol%, Most preferably, it is 60-85 mol%.

  The sum of the structural units (II) and (III) and the sum of (IV) and (V) are preferably equimolar. Here, “substantially equimolar” indicates that the structural unit constituting the polymer main chain excluding the terminal is equimolar. For this reason, the aspect which does not necessarily become equimolar when it includes even the structural unit which comprises the terminal can satisfy the requirement of “substantially equimolar”. An excess of dicarboxylic acid component or dihydroxy component may be added to adjust the end groups of the polymer.

In addition, content of each structural unit in liquid crystalline polyester is computable with the following method. The liquid crystalline polyester is weighed into an NMR (nuclear magnetic resonance) test tube, dissolved in a solvent in which the liquid crystalline polyester is soluble (for example, a pentafluorophenol / heavy tetrachloroethane-d ₂ mixed solvent), and a ¹ H-NMR spectrum. Measure. The content of each structural unit can be calculated from the peak area ratio derived from each structural unit.

The liquid crystalline polyester composed of the structural units (I), (II), (III), (IV) and (V) can be obtained by a known polycondensation method of polyester. For example, the following production method is preferable.
(1) A method for producing a liquid crystalline polyester from p-acetoxybenzoic acid and 4,4′-diacetoxybiphenyl, diacetoxybenzene, terephthalic acid, and isophthalic acid by a deacetic acid polycondensation reaction.
(2) p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone and terephthalic acid, isophthalic acid is reacted with acetic anhydride to acylate the phenolic hydroxyl group, and then the liquid crystalline polyester is subjected to deacetic acid polycondensation reaction. How to manufacture.
(3) A method for producing a liquid crystalline polyester from a phenyl ester of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, and diphenyl ester of isophthalic acid by a dephenol polycondensation reaction.
(4) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid to form a diphenyl ester, and then aromatics such as 4,4'-dihydroxybiphenyl and hydroquinone. A method for producing a liquid crystalline polyester by adding a group dihydroxy compound and dephenol polycondensation reaction.

  In an embodiment of the present invention, when a liquid crystalline polyester is produced by a deacetic acid polycondensation reaction, a melt polymerization method is used in which the polycondensation reaction is completed by reacting under reduced pressure at a temperature at which the liquid crystalline polyester melts. It is preferable. For example, in the case of a liquid crystal polyester composed of the structural units (I), (II), (III), (IV) and (V), the following method may be mentioned. That is, in a reaction vessel equipped with a predetermined amount of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid, acetic anhydride, a stirring blade, a distillation pipe, and a discharge port at the bottom. Prepare. Then, they are heated under stirring in a nitrogen gas atmosphere to acetylate the hydroxyl group, and then the temperature is raised to the melting temperature of the liquid crystalline polyester, and polycondensation is performed under reduced pressure to complete the reaction.

Under the temperature at which the obtained polymer melts, the inside of the reaction vessel can be pressurized to, for example, approximately 1.0 kg / cm ² (0.1 MPa). And the obtained polymer can be discharged in strand form from the discharge outlet provided in the reaction container lower part. The melt polymerization method is an advantageous method for producing a uniform polymer, and is preferable in that an excellent polymer with less gas generation can be obtained.

  The polycondensation reaction of the liquid crystalline polyester proceeds even without a catalyst, but metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and magnesium metal can also be used.

  From the viewpoint of further improving the heat resistance of the molded product, the melting point (Tm) of the liquid crystalline polyester is preferably 220 ° C. or higher, more preferably 270 ° C. or higher, and further preferably 300 ° C. or higher. On the other hand, from the viewpoint of moldability, 350 ° C. or lower is preferable, 345 ° C. or lower is more preferable, and 340 ° C. or lower is further preferable. In the embodiment of the present invention, the melting point (Tm) can be measured using a differential scanning calorimeter as follows. After observing the endothermic peak temperature (Tm1) observed when the liquid crystalline polyester is measured from room temperature under a temperature rising condition of 40 ° C./min, it is held at a temperature of Tm1 + 20 ° C. for 5 minutes. Then, it is once cooled to room temperature under a temperature drop condition of 20 ° C / min. And it heats up again on the temperature rising conditions of 20 degree-C / min. The endothermic peak temperature (Tm2) observed at the temperature rise is calculated as the melting point (Tm).

  The melt viscosity of the liquid crystalline polyester is preferably from 1 to 200 Pa · s, preferably from 10 to 200 Pa · s, from the viewpoint of improving moldability, suppressing breakage of the glass fiber, and further enhancing the effects of the present invention. s is more preferable, and 10 to 100 Pa · s is particularly preferable. Most preferably, it is 5 to 40 Pa · s. The melt viscosity is a value measured with a Koka flow tester under the condition of melting point of liquid crystalline polyester + 10 ° C. and shear rate of 1,000 / s.

  The polyphenylene sulfide (PPS) used in the present invention is a polymer having a repeating unit represented by the following structural formula.

  From the viewpoint of further improving the heat resistance, the PPS preferably contains 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by the above structural formula. In addition, PPS may be composed of a repeating unit represented by the following structural formula in which less than 30 mol% of the repeating unit. Since the PPS copolymer having such a structure in part has a low melting point, it is advantageous in terms of moldability.

  The melt viscosity of the PPS used in the present invention is not particularly limited, but it is preferable to suppress the thermal decomposition caused by shearing heat generation during melt kneading and molding and to suppress the breakage of the glass fiber and to describe the fiber length distribution later. From the viewpoint of adjusting the range, 200 Pa · s or less is preferable, 100 Pa · s or less is more preferable, 70 Pa · s or less is more preferable, and 50 Pa · s or less is more preferable. On the other hand, from the viewpoint of improving the toughness of the molded product and further improving the impact resistance and snap fit, 1 Pa · s or more is preferable, and 5 Pa · s or more is more preferable. The melt viscosity of PPS is a value measured under the conditions of a temperature of 300 ° C. and a shear rate of 1216 / s using a capillograph manufactured by Toyo Seiki Seisakusho.

  The PPS melt flow rate (MFR) used in the present invention is 10 g / 10 min or more from the viewpoint of further improving the fluidity, suppressing breakage of the glass fiber, and further enhancing the effects of the present invention. Is preferable, 20 g / 10 min or more is more preferable, 50 g / 10 min or more is more preferable, and 500 g / 10 min or more is further preferable. On the other hand, from the viewpoint of chemical resistance of the molded product, it is preferably 10,000 g / 10 min or less, more preferably 5000 g / 10 min or less, more preferably 3000 g / 10 min or less, and further preferably 1500 g / 10 min or less. Here, PPS The MFR indicates a value measured at a temperature of 315.5 ° C. and a load of 5 kg in accordance with ASTM D1238.

  The ash content of the PPS used in the embodiment of the present invention is preferably 0.3% by weight or less, more preferably 0.2% by weight or less from the viewpoint of improving fluidity, molding processability and tracking resistance of the molded product, 0.1 wt% or less is more preferable. Although the mechanism is not clear, it is considered that the presence of a metal-containing substance measured as an ash content contributes to tracking generation at the time of voltage application. The ash content of PPS can be measured by the following method. Weigh 5 g of dry PPS bulk powder in a crucible and bake until it becomes a black lump on an electric stove. Next, firing is continued in an electric furnace set at 550 ° C. until the carbide is completely fired. Then, after cooling in a desiccator, the weight is measured, and the ash content is calculated from comparison with the initial weight.

  The amount of volatile components when the PPS resin used in the embodiment of the present invention is heated and melted at 320 ° C. for 120 minutes under vacuum from the viewpoint of further improving tracking resistance and mechanical strength and reducing the amount of gas generated. 0.8 wt% or less is preferable, 0.6 wt% or less is more preferable, and 0.4 wt% or less is more preferable. By setting the volatile component serving as an index of the content of decomposed PPS and low molecular weight in the above range, the mechanical strength of the molded product can be further improved. The “volatile component amount” of PPS means the amount of an adhesive component that is liquefied or solidified by cooling the component that volatilizes when the PPS resin is heated and melted under vacuum. The amount of volatile components can be measured by heating a glass ampoule in which a PPS resin is vacuum-sealed in a tubular furnace. As for the shape of the glass ampoule, the abdomen is 100 mm × 25 mm, the neck is 255 mm × 12 mm, and the wall thickness is 1 mm. As a specific measurement method, only the body of a glass ampoule in which PPS is vacuum-sealed is inserted into a 320 ° C. tubular furnace and heated for 120 minutes, so that a volatile gas is generated at the neck of the ampoule not heated by the tubular furnace. Is cooled and adheres. After the neck is cut out and weighed, the attached volatile components are dissolved in chloroform and removed. The neck is then dried and weighed again. The weight difference between the necks of the ampoule before and after the removal of the volatile component is obtained, and the amount of the volatile component is calculated as a ratio to the weight of the PPS resin used for the measurement.

  Although the manufacturing method of PPS used for embodiment of this invention is demonstrated below, if PPS of the said structure is obtained, it will not be limited to the following method.

  PPS can be produced in a high yield by, for example, recovering a resin obtained by reacting a polyhalogen aromatic compound and a sulfidizing agent in a polar organic solvent and performing post-treatment. More specifically, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, and a method described in JP-B-52-12240 and JP-A-61-7332 are comparatively described. Examples thereof include a method for obtaining a polymer having a large molecular weight. The PPS obtained as described above is subjected to crosslinking / high molecular weight by heating, heat treatment under an inert gas atmosphere such as nitrogen or reduced pressure, washing with an organic solvent, hot water, acid aqueous solution, acid anhydride, amine, etc. Various treatments such as activation with functional group-containing compounds such as isocyanate and functional group-containing disulfide compounds may be applied.

  A polyhalogen aromatic compound refers to a compound having two or more halogen atoms in one molecule. Preferably p-dichlorobenzene is used. Examples of the sulfidizing agent include alkali metal sulfides, alkali metal hydrosulfides, hydrogen sulfide, and the like. As the polar organic solvent, N-methyl-2-pyrrolidone is preferable.

  As a specific method for crosslinking / high molecular weight PPS by heating, in an oxidizing gas atmosphere such as air or oxygen or in a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon, Examples of the method include heating in a heating container at a predetermined temperature until a desired melt viscosity is obtained. The heat treatment temperature is usually 170 to 280 ° C, preferably 200 to 270 ° C. Moreover, the heat treatment time is usually selected from 0.5 to 100 hours, preferably from 2 to 50 hours. PPS having a target viscosity level can be obtained by appropriately adjusting the heat treatment temperature and the heat treatment time. The heat treatment apparatus may be a normal hot air dryer, a rotary type or a heating apparatus with a stirring blade. However, in order to perform processing more efficiently and uniformly, a heating apparatus with a rotary type or a stirring blade is used. It is preferable to use it.

  When heat-treating PPS in an inert gas atmosphere such as nitrogen or under reduced pressure, the heat treatment temperature is usually selected from 150 to 280 ° C, preferably from 200 to 270 ° C. Moreover, the heat treatment time is usually selected from 0.5 to 100 hours, preferably from 2 to 50 hours. The heat treatment apparatus may be a normal hot air dryer, a rotary type or a heating apparatus with a stirring blade. However, in order to perform processing more efficiently and uniformly, a heating apparatus with a rotary type or a stirring blade is used. It is preferable to use it.

  The PPS used in the present invention is preferably subjected to a cleaning treatment. Specific examples of the washing treatment include an acid aqueous solution washing treatment, a hot water washing treatment, and an organic solvent washing treatment. Two or more of these treatments may be combined.

The resin composition of the present invention comprises (B) a glass fiber having a specific composition of 5 to 200 parts by weight with respect to 100 parts by weight of at least one thermoplastic resin selected from the group consisting of the above-mentioned (A) polyamide, polyester and polyphenylene sulfide. Part. Here, (B) a glass fiber having a specific composition (hereinafter sometimes referred to as “(B) glass fiber”) refers to a glass fiber having a composition satisfying the following (1) to (7). In addition, content of following (1)-(5) is based on the total weight of a composition of glass fiber.
(1) SiO ₂ content: 57 to 63% by weight
(2) Al ₂ O ₃ content: 19 to 23% by weight
(3) CaO content: 5.5 to 11% by weight
(4) MgO content: 10 to 15% by weight
(5) Total of the above (1) to (4): 99.5% by weight or more (6) SiO ₂ content / Al ₂ O ₃ content (weight ratio): 2.7 to 3.2
(7) MgO content / CaO content (weight ratio): 0.9 to 2.0

  The composition of the glass fiber can be determined by a known method. For example, the sample glass can be crushed and obtained in accordance with fluorescent X-ray analysis and JIS R3101.

If (B) glass fiber used by this invention has the above-mentioned composition, components other than said (1)-(4), such as a component mixed unavoidable from the raw material of each component, ( B) You may contain 0.5 weight% or less in 100 weight% of the whole composition of glass fiber. Examples of other components include alkali metal oxides such as Na ₂ O ₃ , Fe ₂ O ₃ , TiO ₂ , ZrO ₂ , MoO ₂ , and Cr ₂ O ₃ .

  Said (B) glass fiber is excellent in intensity | strength and an elasticity modulus compared with conventionally well-known glass, such as E glass. The resin composition of the present invention combines the above-mentioned specific thermoplastic resin and the glass fiber having the above-mentioned specific composition, so that (A) the adsorbing action on the surface of the glass fiber by the polar group of the thermoplastic resin and hydrogen Due to the interaction between (A) thermoplastic resin and (B) glass fiber such as bonding, the adhesion between (A) thermoplastic resin and (B) glass fiber is improved, and melt-kneaded (B) glass In order to suppress fiber breakage, the glass fibers are easily oriented in the flow direction of the molded product. This orientation effect suppresses interfacial delamination between the thermoplastic resin and glass fiber in the molded product, improves the mechanical strength, impact resistance, heat resistance, and high-temperature rigidity of the molded product, and improves snap fit and pin press-fit characteristics. It is estimated that.

  In the resin composition of the present invention, the amount of the (B) glass fiber is 5 to 200 parts by weight with respect to 100 parts by weight of the (A) thermoplastic resin. (B) When the blending amount of the glass fiber is less than 5 parts by weight, the mechanical strength, elastic modulus, impact resistance, heat resistance and high temperature rigidity of the molded product obtained from the resin composition are lowered, pin press-fitting property, snap fit property. Also decreases. 10 parts by weight or more is preferable. On the other hand, if the blending amount of (B) glass fiber exceeds 200 parts by weight, the fluidity is lowered and the surface appearance of the molded product is lowered. Further, since the pressure required for molding increases, stress is generated in the molded product, and warpage increases. Further, since the molded product is hard and brittle, the snap fit property and the pin press-fit property are deteriorated. 190 parts by weight or less is preferable.

  Although there is no restriction | limiting in particular in the fiber length of (B) glass fiber mix | blended with the resin composition of this invention, 1-10 mm is preferable for an average fiber length. If the average fiber length is 1 mm or more, the mechanical strength, impact resistance, heat resistance, high-temperature rigidity and snap fit property, and pin press-fitting characteristics of the molded product can be further improved. On the other hand, if the average fiber length is 10 mm or less, troubles such as a bridge in the supply hopper of the injection molding machine are unlikely to occur during molding. 6 mm or less is more preferable. The average fiber length of glass fibers is determined by measuring the length of 1000 glass fibers randomly selected from a micrograph (magnification 120 times) using an image analysis processor (Quick Grain Standard), and calculating the weight average value thereof. Can be obtained.

  In the resin composition of the present invention, the weight average fiber length of the (B) glass fiber in the composition is preferably 100 to 1000 μm. If the weight average fiber length in the composition is 100 μm or more, the adhesion area with the thermoplastic resin per single fiber is high and the glass fiber is prevented from coming off. Mechanical strength, impact resistance, heat resistance and high temperature rigidity are further improved. In addition, the snap fit and pin press-fit characteristics of the molded product are further improved. 150 μm or more is more preferable, and 200 μm or more is more preferable. On the other hand, if the weight average fiber length is 1000 μm or less, the fiber ends exposed on the surface of the molded product can be reduced even in a small and thin molded product, and the surface appearance is further improved. 800 μm or less is preferable, and 600 μm or less is more preferable.

  In the resin composition of the present invention, it is preferable that 20 to 50% by weight of glass fiber having a fiber length of 300 to 500 μm is contained in the total amount of (B) glass fiber in the composition. Glass fibers having a fiber length of 300 to 500 μm affect properties such as fluidity of the resin composition, high temperature rigidity of the molded product, surface appearance, warpage, snap fit, and pin press-fitting properties. By containing 20% by weight or more of glass fiber having a fiber length of 300 to 500 μm, the high-temperature rigidity, snap fit property, and pin press-fitting property of the molded product can be further improved. On the other hand, by including 50% by weight or less of glass fiber having a fiber length of 300 to 500 μm, the number of glass fibers protruding on the surface of the molded product can be further reduced, and the surface appearance is further improved. Moreover, since the fluidity | liquidity of a resin composition improves, the pressure at the time of shaping | molding can be made small, and it can be excellent in snap fit property and pin press-fit property, and can obtain the molded article with which the curvature | sledge was reduced more. The amount of the glass fiber of 300 to 500 μm is more preferably 45% by weight or less, and further preferably 40% by weight or less.

In addition, the ratio of the glass fiber of the weight average fiber length of (B) glass fiber in a composition and fiber length 300-500 micrometers can be calculated | required with the following method. Under general molding conditions, the weight average fiber length of the (B) glass fiber does not change before and after molding. Therefore, in the present invention, measurement is performed using a test piece obtained by injection molding. First, pellets made of the composition are injection-molded into 1/8 mold notched Izod impact pieces and heated in air at 550 ° C. for 8 hours to remove the resin. Here, in order to suppress the change in the fiber length of the (B) glass fiber before and after molding, the molding temperature is in the range of (melting point + 5 ° C.) to (melting point + 50 ° C.) of the thermoplastic resin. The remaining glass fibers are observed using an optical microscope at a magnification of 120 times, and the fiber lengths of 1000 or more randomly selected glass fibers are measured. From the fiber length of each glass fiber, the weight average fiber length and the ratio of glass fibers having a fiber length of 300 to 500 μm are calculated. The glass fiber content of the weight average fiber length and the fiber length of 300 to 500 μm can be determined using analysis software Quick Grain Standard. When the fiber diameter and density of the glass fiber are constant, the weight average fiber length is represented by (Σni · Li ² ) / (Σni · Li). Here, Li is the range (section) of the fiber length of the glass fiber. ni is calculated by (fiber length is the number of glass fibers contained in Li) / (total number of measured glass fibers). The ratio (% by weight) of the glass fiber having a fiber length of 300 to 500 μm is represented by {(Σna · La) / (Σni · Li)} × 100. Here, La is the range (section) of the fiber length of the glass fiber included in the range of 300 to 500 μm. na is calculated by (the number of glass fibers whose fiber length is included in La) / (total number of measured glass fibers).

  In addition, as a method of adjusting the fiber length distribution of the glass fiber (B) in the composition to the above range, for example, a method of using glass fibers having an average fiber length in the above-mentioned preferable range as a raw material, or a resin composition In the manufacturing method, there is a method of adjusting the degree of breakage of the glass fiber (B), which is described later.

  The cross-sectional shape of the (B) glass fiber used in the present invention is not particularly limited, and may be either a circular cross-sectional shape or a non-circular cross-sectional shape.

  A circular cross section refers to a perfect circle that is equidistant from the center point from all parts of the circumference, that is, those having the same major axis and minor axis. The cross-sectional diameter of the circular cross-section glass is preferably 5 to 30 μm, the glass fiber can be easily spun, and the strength of the glass fiber can be maintained high. More preferably, it is 6-15 micrometers.

  On the other hand, a non-circular cross-section refers to a cross-sectional shape different from a perfect circular shape. The major axis / minor axis ratio in the non-circular cross section is defined as the quotient of the longest linear dimension of the glass fiber cross section, the linear dimension passing through the central point of the major axis and orthogonal to the major axis. , Star shape, cross shape, polygonal shape, donut shape and the like. Among these, a flat shape is preferable. Here, the flat cross-sectional shape refers to a non-circular cross section having a major axis / minor axis ratio exceeding 1 in a cross section perpendicular to the fiber direction.

  The glass fiber having a flat cross-sectional shape preferably has a long diameter of 10 to 80 μm in cross-section, so that the glass fiber can be easily spun and the strength of the glass fiber can be maintained high. More preferably, they are 15 micrometers or more and 50 micrometers or less. Moreover, it is preferable that the minor axis of the cross section is 2-20 micrometers, it becomes easy to spin glass fiber, and the intensity | strength of glass fiber can be maintained high. More preferably, it is 4 μm or more and 15 μm or less. The major axis and minor axis here refer to the long side length (major axis) and the short side length (minor axis) of the rectangle when assuming a rectangle with the smallest area circumscribing the flat cross-section glass fiber. .

  In addition, the major axis / minor axis ratio (flatness) of the cross section of the glass fiber was observed with a scanning electron microscope, and the ratio was calculated by measuring the major axis and minor axis of the section of 50 randomly selected glass fibers. The value obtained by calculating the number average.

  A glass fiber having a flat cross-sectional shape has a larger specific surface area than a glass fiber having an equivalent cross-sectional area and a circular cross-sectional shape. Moreover, since glass fiber is easy to orient in the flow direction of a molded article, there is little collision between glass fibers at the time of shaping | molding, and breakage is suppressed more. Further, the orientation suppresses the interfacial peeling between the thermoplastic resin and the glass fiber in the molded product, and the adhesion is further improved. For this reason, the raising of the glass fiber to the surface of the molded product is suppressed, the surface appearance of the molded product is further improved, and warpage is further reduced. In addition, the mechanical strength, impact resistance, heat resistance, and high-temperature rigidity of the molded product are further improved, and a molded product having excellent snap fit and pin press-fit characteristics can be obtained.

  The flatness (major axis / minor axis) of the glass having a flat cross-sectional shape is preferably 1.3 to 10. When the average flatness is 1.3 or more, the specific surface area increases and the adhesive effect with the thermoplastic resin is improved, so the mechanical strength, impact resistance, heat resistance, snap fit, pin press-fit strength of the molded product. Can be further improved. Moreover, the surface appearance of the molded product can be further improved, and warpage can be further reduced. Two or more are more preferable. On the other hand, when the average flatness is 10 or less, the glass fiber can be prevented from cracking, and the mechanical strength, impact resistance, heat resistance, and high-temperature rigidity are further improved, and the snap fit and pin press-fit characteristics are more excellent. A molded product can be obtained. 5 or less is more preferable.

  Specific examples of the flat shape include an elliptical shape, an oval shape, an eyebrow shape, a semicircular shape, an arc shape, or a similar shape thereof. An elliptical shape, an elliptical shape, and an eyebrows shape are preferable, and an elliptical shape is more preferable. The ellipse shape here is different from the ellipse shape, and two or more parallel straight line portions and a part of the circle, such as a rounded quadrangular shape or a shape formed by combining a rectangle and two semicircles. Means a shape having two or more places. When glass fibers having an oval cross-sectional shape are used, it is preferable because strength and dimensional stability are higher than those of an elliptical or eyebrow-shaped cross-sectional shape.

The glass fiber (B) used in the present invention is preferably treated with an epoxy-based, urethane-based, acrylic-based coating agent or sizing agent, and its surface is coupled with a coupling agent. May be. Examples of the coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, and γ-anilinopropyl. Silane coupling agents such as trimethoxysilane, hydroxypropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, vinylacetoxysilane, isopropyltrisisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraoctylbis (ditridecyl) Phosphite) titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tri (dioctyl Examples thereof include titanium coupling agents such as (tylphosphate) titanate and aluminum coupling agents such as acetoalkoxyaluminum diisopropylate. Two or more of these may be used. Of these, silane coupling agents are preferably used. The glass fiber (B) used in the present invention has a higher SiO ₂ ratio than the conventional E glass, so it is possible to further increase the affinity with the thermoplastic resin due to a synergistic effect with the silane coupling agent. Thus, the properties of the molded product can be further improved.

  In the resin composition of the present invention, in addition to the specific (A) thermoplastic resin and (B) glass fiber, other resins, flame retardants, and heat resistant materials can be used as long as the effects of the present invention are not impaired. Various additives such as an agent, a coupling agent, and other additives can be further blended.

  Specific examples of other resins include polyolefin, modified polyphenylene ether, polysulfone, polyketone, polyetherimide resin polyarylate, polyethersulfone, polyetherketone resin polythioetherketone, polyetheretherketone, polyimide, polyamideimide, four Examples include fluorinated polyethylene. Two or more of these may be blended. When blending these resins, the blending amount is preferably 45 parts by weight or less, more preferably 25 parts by weight or less, based on 100 parts by weight of the thermoplastic resin (A) in order to make full use of the characteristics of the matrix resin.

  Although it does not specifically limit as a flame retardant, Specifically, a non-halogen flame retardant which does not contain halogen atoms, such as a phosphorus flame retardant, a nitrogen flame retardant, and a metal hydroxide flame retardant, a bromine flame retardant, etc. And halogen-based flame retardants. Two or more of these flame retardants may be used.

  The phosphorus-based flame retardant is a flame retardant composed of a compound containing phosphorus element, specifically, polyphosphoric acid-based compounds such as red phosphorus, ammonium polyphosphate, and melamine polyphosphate, metal phosphinate or metal diphosphinate. (Hereinafter, these may be collectively referred to as (di) phosphinic acid metal salts), phosphazene compounds, aromatic phosphate esters, aromatic condensed phosphate esters, halogenated phosphate esters, and the like. Among these, (di) phosphinic acid metal salts, phosphazene compounds, and aromatic condensed phosphates are preferable, and (di) phosphinic acid metal salts are more preferable.

  Examples of the nitrogen-based flame retardant include compounds that form a salt of a triazine compound with cyanuric acid or isocyanuric acid. Usually, it is a 1-to-1 (molar ratio) adduct of cyanuric acid or isocyanuric acid and a triazine-based compound, and optionally a 1-to-2 (molar ratio) adduct. More preferred are salts with melamine, benzoguanamine, and acetoguanamine.

As the metal hydroxide flame retardant, magnesium hydroxide is preferable. The particle diameter, specific surface area, and shape of magnesium hydroxide are not particularly limited, but the particle diameter is 0.1 to 20 μm, the specific surface area is 3 to 75 m ² / g, the shape is spherical, needle-shaped or platelet Is preferred. Magnesium hydroxide may or may not be surface treated. Examples of the surface treatment method include coating formation with a thermosetting resin such as a silane coupling agent, an anionic surfactant, a polyfunctional organic acid, and an epoxy resin.

  Examples of the brominated flame retardant include ethylene bis (tetrabromophthalimide), brominated epoxy polymer, brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate. Brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate are more preferred.

  As for the compounding quantity of the flame retardant in the resin composition of this invention, 1-50 weight part is preferable with respect to 100 weight part of (A) thermoplastic resins. When the blending amount of the flame retardant is 1 part by weight or more, the flame retardancy can be improved. Moreover, if it is 50 weight part or less, the toughness of the molded article obtained can be improved. When using a phosphorus-type flame retardant as a flame retardant, the compounding quantity is preferably 2 to 40 parts by weight, more preferably 3 to 35 parts by weight with respect to 100 parts by weight of the (A) thermoplastic resin. When using a nitrogen-type flame retardant as a flame retardant, the compounding quantity is preferably 3 to 30 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the (A) thermoplastic resin. When using a metal hydroxide-based flame retardant as the flame retardant, the blending amount is preferably 10 to 50 parts by weight, more preferably 20 to 50 parts by weight with respect to 100 parts by weight of the (A) thermoplastic resin. . When a brominated flame retardant is used as the flame retardant, the blending amount is preferably 10 to 50 parts by weight, more preferably 20 to 50 parts by weight with respect to 100 parts by weight of the (A) thermoplastic resin.

  Moreover, in the resin composition of this invention, a flame retardant adjuvant may be mix | blended with said flame retardant, and a flame retardance can be improved synergistically. Examples of the flame retardant aid include antimony trioxide, antimony tetraoxide, antimony pentoxide, antimony deoxydioxide, crystalline antimonic acid, sodium antimonate, lithium antimonate, barium antimonate, antimony phosphate, zinc borate, and tin. Examples include zinc oxide, basic zinc molybdate, zinc stannate, calcium zinc molybdate, molybdenum oxide, zirconium oxide, zinc oxide, iron oxide, red phosphorus, swellable graphite, and carbon black. Of these, zinc stannate, antimony trioxide, and antimony pentoxide are more preferable. The blending amount of the flame retardant aid is preferably 0.2 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A) from the viewpoint of flame retardancy improvement effect. is there.

  Examples of the heat-resistant agent include phenolic compounds, phosphorus compounds, and copper compounds. By blending a heat-resistant agent, the thermal stability of the resin composition can be maintained. It is particularly preferable to use a phenolic compound and a phosphorus compound in combination because of their large heat resistance, thermal stability, and fluidity retention effect. The blending amount of the heat-resistant agent is preferably 0.02 parts by weight or more with respect to 100 parts by weight of the thermoplastic resin (A) from the viewpoint of the effect of improving heat resistance. On the other hand, 1 part by weight or less is preferable from the viewpoint of suppressing a gas component generated during molding.

  As the phenolic compound, a hindered phenolic compound is preferable. Specifically, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3 -(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane or the like is preferably used.

  Examples of phosphorus compounds include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite and bis (2,4-di-t-butylphenyl) pentaerythritol-di. -Phosphite, bis (2,4-di-cumylphenyl) pentaerythritol-di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) ) -4,4′-bisphenylene phosphite, di-stearyl pentaerythritol di-phosphite, triphenyl phosphite, 3,5-dibutyl-4-hydroxybenzyl phosphonate diethyl ester and the like. Among them, those having a high melting point are preferably used in order to suppress volatilization and decomposition of the heat-resistant agent during the production of the resin composition.

  As a coupling agent, what was illustrated as a coupling agent used for (B) surface treatment of glass fiber can be mentioned. As for the compounding quantity of a coupling agent, 0.1-2 weight part is preferable with respect to 100 weight part of said (A) thermoplastic resins. By using 0.1 parts by weight or more, the reinforcing effect is sufficiently exhibited, and by using 2 parts by weight or less, gas generation during molding can be suppressed and the surface appearance can be kept better.

  Other additives include UV absorbers (resorcinol, salicylate, etc.), anti-coloring agents such as phosphites, hypophosphites, lubricants and mold release agents (stearic acid, montanic acid and metal salts thereof, esters thereof, The usual additives such as carbon black, crystal nucleating agent, plasticizer, lubricant and antistatic agent as colorants including dyes and pigments, conductive agents or colorants, such as half esters, stearyl alcohol, stearamide and polyethylene wax) Can be mentioned.

  The method for obtaining the resin composition of the present invention is not particularly limited. For example, the raw material (A) thermoplastic resin, (B) glass fiber and, if necessary, other components such as a flame retardant, a known melt kneader And a method of melt kneading. The raw material supply method to the melt kneader is not particularly limited, but the glass fiber is preferably blended using a side feeder or the like after the resin component is melted from the viewpoint of preventing breakage.

  Examples of the method of bringing the fiber length of the glass fiber in the resin composition into the above-mentioned range include, for example, a method of adjusting the degree of breakage of the glass fiber by selecting a screw arrangement, and adjusting the shearing force applied to the glass fiber, Examples thereof include a method of adjusting the degree of fiber breakage. Examples of the means for adjusting the shearing force include a method of adjusting the melt viscosity of the molten resin by adjusting the screw rotation speed and the cylinder temperature.

  Examples of the melt kneader include extruders such as a short screw extruder and a twin screw extruder. From the viewpoint of ease of screw configuration and prevention of glass fiber breakage, a co-rotating twin screw extruder is more preferable.

  The ratio (L / D) between the total screw length L and the screw diameter D of the extruder is preferably 25 or more. When the L / D is 25 or more, the resin component is sufficiently heated up to the glass fiber supply position, and it becomes easy to supply the glass fiber in a molten state, thereby suppressing breakage of the glass fiber due to shearing force. The weight average fiber length of glass fibers and the ratio of glass fibers having a fiber length of 300 to 500 μm can be easily adjusted to the above-mentioned range. The screw length here is the length from the upstream end of the screw segment at the position (feed port) where the (A) resin component of the screw base is supplied to the tip of the screw.

  (B) It is preferable to supply glass fiber from the supply port provided in the downstream from 1/2 of screw length. (B) By setting the glass fiber supply position downstream of 1/2 the screw length, (B) the glass fiber can be supplied in a state where (A) the thermoplastic resin is sufficiently heated and melted. It becomes easy, the breakage of the glass fiber due to the shearing force is suppressed, and the ratio of the weight average fiber length and the glass fiber having a fiber length of 300 to 500 μm can be easily adjusted to the aforementioned range.

  (B) The melt viscosity of (A) the thermoplastic resin at the glass fiber supply position is 200 Pa · s or less at the melting temperature of (A) the thermoplastic resin at the glass fiber supply position at a shear rate of 1000 / sec. Is preferred. (A) By making the melt viscosity of the thermoplastic resin 200 Pa · s or less, breakage of the glass fiber is suppressed, and the ratio of the weight average fiber length and the glass fiber having a fiber length of 300 to 500 μm is easily within the above-mentioned range. Can be adjusted. (A) Examples of a method for bringing the melt viscosity of the thermoplastic resin into the above range include (1) (B) a method of increasing the heating temperature upstream from the glass fiber supply position, and (2) (B) glass fiber. And a method of generating a shearing heat by providing a kneading zone upstream from the supply position, and a method of generating a shearing heat by increasing the screw rotation speed of the twin screw extruder (3). The kneading zone here is composed of one or more kneading screw pieces. When the total length of the kneading zone on the upstream side of the glass fiber supply position is Ln1, Ln1 / L is preferably 0.01 to 0.40. By setting Ln1 / L to 0.01 or more, the heating temperature can be increased by shearing heat generation. On the other hand, by setting Ln1 / L to 0.40 or less, it is possible to suppress shearing heat generation and suppress thermal decomposition of the resin. 0.20 or less is more preferable. Moreover, although there is no restriction | limiting in particular in the melting temperature of (A) thermoplastic resin, In order to suppress the molecular weight fall by thermal decomposition, 350 degrees C or less is preferable. The melt kneading temperature is preferably 5 to 50 ° C. higher than the melting point of the thermoplastic resin (A). By setting the melt-kneading temperature to the melting point + 5 ° C. or higher, the viscosity at the time of melt-kneading can be moderately suppressed, and the resin decomposition and glass fiber breakage due to shearing heat generation can be further suppressed. The melting point + 15 ° C. or higher is more preferable. On the other hand, by setting it as melting | fusing point +50 degrees C or less, decomposition | disassembly of resin can be suppressed and the dispersibility of glass fiber can be improved. The melting point + 30 ° C. or lower is more preferable.

  As the screw configuration of the extruder, it is preferable that the screw piece on the downstream side of the (B) glass fiber supply position uses a forward flight. From the viewpoint of suppressing breakage of the (B) glass fiber due to shearing, it is more preferable to use an angular flight. (B) It is preferable to provide at least one kneading zone on the downstream side of the glass fiber supply position. When the total length of the kneading zone on the downstream side of the glass fiber supply position is Ln2, Ln2 / L is preferably 0.01 to 0.30, and more preferably 0.04 to 0.16. When Ln2 / L is in the range of 0.01 to 0.30, a resin composition in which glass fibers are more uniformly dispersed can be easily obtained, and breakage of glass fibers can be further suppressed. Although there is no restriction | limiting in particular in the screw piece of a kneading zone, a forward feed kneading screw piece, a reverse feed kneading screw piece, and an orthogonal kneading screw piece are used preferably, It is also possible to use combining them. However, when using a reverse feed kneading screw piece, Lb / Ln2 is preferably 0.5 or less, where Lb is the total length of the reverse feed kneading screw piece. When Lb / Ln2 is 0.5 or less, breakage of the glass fiber can be further suppressed.

  The resin composition of the present invention and the molded product thereof are used for various applications such as automobile parts, electrical / electronic parts, building materials, sports equipment, various containers, daily necessities, household goods and sanitary goods, taking advantage of their excellent characteristics. Can do.

  Examples of automotive parts applications include engine covers, air intake pipes, timing belt covers, intake manifolds, filler caps, throttle bodies, cooling fan and other automotive engine peripheral parts, cooling fans, radiator tank tops and bases, cylinder head covers, Automotive underhood parts such as oil pan, brake piping, fuel piping tube, waste gas system parts, automobile gear parts such as gear, actuator, bearing retainer, bearing cage, chain guide, chain tensioner, shift lever bracket, steering lock bracket , Key cylinder, door inner handle, door handle cowl, interior mirror bracket, air conditioner switch, instrumental pa Car interior parts, such as console, glove box, steering wheel, trim, front fender, rear fender, fuel lid, door panel, cylinder head cover, door mirror stay, tailgate panel, license garnish, roof rail, engine mount bracket, rear garnish, Rear exterior parts such as rear spoiler, trunk lid, rocker molding, molding, lamp housing, front grille, mudguard, side bumper, air intake manifold, intercooler inlet, exhaust pipe cover, inner bush, bearing retainer, engine mount, engine head cover, Intake and exhaust system parts such as resonators and throttle bodies, Engine cooling water system parts such as engine covers, thermostat housings, outlet pipes, radiator tanks, oil naters, and delivery pipes, connectors and wire harness connectors, motor parts, lamp sockets, sensor on-vehicle switches, combination switches, etc. be able to.

  Examples of electrical / electronic component applications include generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, breakers, knife switches, other pole rods, electricity Parts, motor cases, laptop housings and internal parts, CRT display housings and internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, various gears, various cases, cabinets Electrical components such as: connectors, coils, sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickup chassis, oscillators, various terminal boards, transformers, plugs, printed boards , Ju Electronic parts such as a speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, transformer member, parabolic antenna, computer related parts, etc. it can.

  Examples of building materials include civil engineering building walls, roofs, ceiling materials-related parts, window material-related parts, heat insulating material-related parts, flooring-related parts, seismic isolation / vibration control parts-related parts, lifeline-related parts, etc. Can be mentioned.

  Examples of sports equipment include golf-related equipment such as golf clubs and shafts, masks such as American football and baseball, softball, body protection equipment for sports such as helmets, breast pads, elbow pads, knee pads, and the bottom of sports shoes. Shoes-related products such as materials, fishing gear-related products such as fishing rods and fishing lines, summer sports-related products such as surfing, winter sports-related products such as skiing and snowboarding, and other indoor and outdoor sports-related products.

  Especially, it is preferably used for automobile engine peripheral parts, automobile under hood parts, automobile gear parts, automobile interior parts, automobile exterior parts, intake / exhaust system parts, engine cooling water system parts and electrical / electronic parts, and automobile interior parts and automobile exterior parts. It is particularly preferably used for electrical and electronic component applications.

The present invention will be described more specifically with reference to the following examples. The characteristic evaluation was performed according to the following method.

(1) Flatness of glass fiber Glass fiber before blending was observed with a scanning electron microscope (600 times magnification). Using a ruler, measure the cross-section of 50 glass fibers randomly selected from the micrograph, calculate the ratio of the major axis to the minor axis (major axis / minor axis), and flatten the number average value. Rate.

(2) Thermal characteristics of thermoplastic resin About 5 mg of the thermoplastic resin was sampled, and the melting point and glass transition temperature of the thermoplastic resin were measured under the following conditions in a nitrogen atmosphere using a robot DSC RDC220 manufactured by Seiko Instruments Inc. The temperature was raised to the melting point of the thermoplastic resin + 40 ° C. to obtain a molten state, then the temperature was lowered to 30 ° C. at a rate of temperature reduction of 20 ° C./min, followed by holding at 30 ° C. for 3 minutes, The melting point was determined from the temperature of the endothermic peak observed when the temperature was raised to the melting point + 40 ° C. at the rate of temperature rise. Further, the temperature at the midpoint of the stepwise endothermic peak of the DSC curve observed when a sample rapidly quenched with liquid nitrogen from a molten state of the melting point of the thermoplastic resin + 30 ° C. is heated at a rate of temperature increase of 20 ° C./min. From this, the glass transition temperature was determined.

(3) Fiber length of glass fiber in the composition The pellet made of the resin composition obtained in each Example and Comparative Example was dried under reduced pressure at 80 ° C. for 12 hours, and subjected to SG75H-MIV (manufactured by Sumitomo Heavy Industries, Ltd.) Cylinder temperature: melting point of each resin + 20 ° C., mold temperature: 80 ° C. for resin composition containing polyamide 66, 140 ° C. for resin composition containing polyamide 10T, resin composition containing polybutylene terephthalate 1/8 mold under the conditions of 80 ° C., 90 ° C. for a resin composition containing liquid crystalline polyester, 130 ° C. for a resin composition containing polyphenylene sulfide, and 40 ° C. for a resin composition containing polypropylene. A notched Izod impact test piece was injection molded. One of the molded articles was heated in air at 550 ° C. for 8 hours to remove the resin. The remaining glass fibers were observed with an optical microscope at a magnification of 120 times, the fiber lengths of 1000 or more randomly selected glass fibers were measured at a magnification of 120 times, and analysis software Quick Grain Standard was used. Thus, the weight average fiber length and the glass fiber content with a fiber length of 300 to 500 μm were determined. In each example and comparative example, there is one glass fiber, and since the fiber diameter and density of the glass fiber are constant, the weight average fiber length is represented by (Σni · Li ² ) / (Σni · Li). . Here, Li is the range (section) of the fiber length of the glass fiber. ni is calculated by (fiber length is the number of glass fibers contained in Li) / (total number of measured glass fibers). The glass fiber content (% by weight) having a fiber length of 300 to 500 μm is represented by {(Σna · La) / (Σni · Li)} × 100. Here, La is the range (section) of the fiber length of the glass fiber included in the range of 300 to 500 μm. na is calculated by (the number of glass fibers whose fiber length is included in La) / (total number of measured glass fibers).

(4) Fluidity The resin composition pellets obtained in each Example and Comparative Example were vacuum-dried at 80 ° C. overnight and then subjected to FANUC ROBOSHOTα-30C. Cylinder temperature: Melting point of thermoplastic resin + 20 ° C., injection Pressure: 98 MPa, mold temperature: 80 ° C. for resin composition containing polyamide 66, 140 ° C. for resin composition containing polyamide 10T, 80 ° C. for resin composition containing polybutylene terephthalate, liquid crystal In the case of a resin composition containing polyester, 90 ° C., in the case of a resin composition containing polyphenylene sulfide, 130 ° C., and in the case of a resin composition containing polypropylene, 40 ° C., 200 mm long × 10 mm wide × 0.5 mm thick A 10 mm wide x 0.5 mm thick rod flow test piece was injection-molded using the above mold, and the holding pressure was reduced to 0 for each of the 5 samples. The kick bar flow length was measured and the average thereof was calculated. The larger the flow length, the better the fluidity.

(5) Mechanical strength The resin composition pellet obtained by each Example and the comparative example was vacuum-dried at 80 degreeC for 12 hours, and used for SG75H-MIV (made by Sumitomo Heavy Industries), and the same molding conditions as said (4) were carried out. An ASTM No. 1 dumbbell specimen having a thickness of 1/8 inch was injection molded. For each of these three test pieces, a tensile test was performed at a crosshead speed of 10 mm / min using a tensile tester Tensilon UTA2.5T (manufactured by Orientec) according to ASTM D638, and the tensile strength was measured. Asked.

(6) High-temperature rigidity The resin composition pellets obtained in each Example and Comparative Example were vacuum-dried at 80 ° C. for 12 hours, and subjected to SG75H-MIV (manufactured by Sumitomo Heavy Industries), under the same molding conditions as in (4) above. An ASTM No. 1 dumbbell specimen having a thickness of 1/8 inch was injection molded. For each 3 samples of this test piece, 2 in a high-temperature bath adjusted to a temperature near 23 ° C. and the Tg temperature of each thermoplastic resin using a bending tester Tensilon RTA-1T (manufactured by Orientec) according to ASTM D790. Under the conditions, a bending test was performed at a crosshead speed of 3 mm / min, the flexural modulus under each condition was measured, and the average value was obtained. The retention rate of the flexural modulus was calculated by the following formula.
Retention rate of flexural modulus [%] = (flexural modulus near Tg temperature / flexural modulus at 23 ° C.) × 100.

(7) Impact resistance After resin composition pellets obtained in each example and comparative example were vacuum dried at 80 ° C. overnight, they were subjected to SG75H-MIV (manufactured by Sumitomo Heavy Industries, Ltd.) and the same as in (4) above. An Izod impact test piece with a 1/8 inch thick mold notch was injection molded according to molding conditions. For each 3 samples of this test piece, the Izod impact strength of the 3 mm thick notched molded product at 23 ° C. was measured according to ASTM-D256, and the average value was obtained.

(8) Heat resistance The resin composition pellets obtained in each example and comparative example were vacuum-dried at 80 ° C. for 12 hours and subjected to SG75H-MIV (manufactured by Sumitomo Heavy Industries), under the same molding conditions as in (4) above. An ASTM No. 1 dumbbell specimen having a thickness of 1/8 inch was injection molded. In accordance with ASTM648, the thermal deformation temperature (the deflection temperature under load) of the thermoplastic resin was measured under edge-wise test conditions with a test load of 1.82 MPa.

(9) Sled The resin composition pellets obtained in each Example and Comparative Example were dried under reduced pressure at 80 ° C. for 12 hours and subjected to SG75H-MIV (Sumitomo Heavy Industries, Ltd.). Under the mold temperature condition, injection / cooling time: 10/20 seconds, the bottom of the molded product shown in FIG. 1 is released, and the side of the molded product has a submarine one-point gate G1 30 mm long × 30 mm wide, thickness 1 A 5 mm box-formed product was injection molded. Each 10 samples of the box-shaped product thus obtained were allowed to stand in an atmosphere of 23 ° C. and 50% humidity, the amount of warpage was measured, and the average value was obtained as the amount of warpage. The smaller the amount of warp, the better. FIG. 2 is a schematic view showing a measurement site of the amount of warpage in the box-shaped product shown in FIG. Reference numerals A and B are the same as those in FIG. On the surface opposite to the surface having the gate, the line segment A-B is defined as the reference position a, and the distance from the maximum deformed position b after deformation is defined as the amount of warp.

(10) Surface appearance The resin composition pellets obtained in each example and comparative example were dried under reduced pressure at 80 ° C. for 12 hours and subjected to SG75H-MIV (manufactured by Sumitomo Heavy Industries), cylinder temperature: melting point of thermoplastic resin + 20 ° C, mold temperature: 80 ° C for resin composition containing polyamide 66, 140 ° C for resin composition containing polyamide 10T, 80 ° C for resin composition containing polybutylene terephthalate, liquid crystalline polyester In the case of a resin composition containing 90 ° C., in the case of a resin composition containing polyphenylene sulfide, 130 ° C., in the case of a resin composition containing polypropylene, 40 ° C., injection / cooling time: 80 mm × An 80 mm × 3 mm thick mirror polished square plate (film gate) was injection molded. The surface roughness around the center of the obtained square plate surface (eject pin side) is measured in the resin flow direction (MD) using a surface roughness meter (ACCUTECH Surfcom 130A), and arithmetic average roughness (Ra) Asked. The measurement conditions were a cut-off value of 0.8 mm, an evaluation length of 10 mm, and a measurement speed of 0.6 mm / s.

(11) Snap-fit characteristics The resin composition pellets obtained in each example and comparative example were subjected to FANUC ROBOSHOTα-30C, cylinder temperature: melting point of thermoplastic resin + 20 ° C., mold temperature: resin composition containing polyamide 66 80 ° C. for a resin composition containing polyamide 10T, 80 ° C. for a resin composition containing polybutylene terephthalate, 90 ° C. for a resin composition containing liquid crystalline polyester, polyphenylene sulfide In the case of a resin composition containing 100 ° C. and in the case of a resin composition containing polypropylene at 40 ° C., the inner diameter is 50 mm × width 80 mm × height 5 mm × wall thickness 4 mm. There are 3 types of molded products with 0.8 mm x 2 mm long nails and 50 x 80 x 1 mm thick square plates. It was co-injection molding. About 30 each, the center of the square plate was pushed and the fitting test to the box formation type product was done. The number of box-shaped products that were not broken and the square plate was fitted was counted to evaluate the snap fit. The larger the number, the better the snap fit.

(12) Pin press-fitting properties The resin composition pellets obtained in each of the examples and comparative examples were subjected to FANUC ROBOSHOT α-30C, cylinder temperature: melting point of thermoplastic resin + 20 ° C, mold temperature: resin composition containing polyamide 66 80 ° C. for a resin composition containing polyamide 10T, 80 ° C. for a resin composition containing polybutylene terephthalate, 90 ° C. for a resin composition containing liquid crystalline polyester, polyphenylene sulfide In the case of a resin composition containing 30 mm, the resin composition containing polypropylene has a thickness of 3 mm with 20 square holes of 1.5 mm × 1.5 mm at a pitch of 2.8 mm under the conditions of 40 ° C. 20 pieces of the pin press-fitting test pieces were injection molded. A square bar made of brass of 1.6 mm × 1.6 mm was inserted into each square hole of each of the 20 test pieces obtained, and the number of test pieces that did not crack in the square hole was counted, and the pin was press-fitted Characteristics were evaluated. The greater the number, the better the pin press-fit strength.

  Moreover, the raw material used for the present Example and the comparative example is as follows.

Thermoplastic resin (A-1): polyamide 66 synthesized in Reference Example 1 below
(A-2): Polyamide 66 synthesized according to Reference Example 2 below
(A-3): Polyamide 10T synthesized according to Reference Example 3 below
(A-4): Polybutylene terephthalate synthesized in Reference Example 4 below (A-5): Liquid crystalline polyester synthesized in Reference Example 5 below (A-6): Polyphenylene sulfide synthesized in Reference Example 6 below (A ′ -7): Polypropylene (J106G manufactured by Prime Polymer Co., Ltd., melting point 130 ° C., MFR = 45 g / 30 minutes (230 ° C., 2.16 kg load), glass transition temperature 0 ° C.).

Reference Example 1 Synthesis of Polyamide 66 (A-1) An equimolar salt of hexamethylenediamine and adipic acid (66 salt, manufactured by Rhodia) and benzoic acid (manufactured by Sigma Aldrich Japan) were mixed with benzoic acid per 1 salt of 66 salts. Water was charged into the reaction vessel so that the water content in the total charge was 30% by weight, sealed, and purged with nitrogen. After heating was started and the internal pressure of the can reached 1.72 MPa, the internal pressure of the can was maintained at 1.72 MPa for 2 hours while releasing moisture out of the system. Thereafter, the internal pressure of the can was released to normal pressure over 1 hour, and further reacted at 280 ° C. for 10 minutes under a reduced pressure of −21.3 kPa (80 kPa) to complete the polymerization. The relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution with a sample concentration of 0.01 g / ml of polyamide 66 was 2.5, the melting point was 265 ° C., and the glass transition temperature was 50 ° C.

(Reference Example 2) Synthesis of polyamide 66 (A-2) An equimolar salt of hexamethylenediamine and adipic acid (66 salt, manufactured by Rhodia) and benzoic acid (manufactured by Sigma Aldrich Japan) were mixed with 1 mol of 66 salts of benzoic acid. Water was charged into the reaction vessel so that the water content in the total charge was 30% by weight, sealed, and purged with nitrogen. After heating was started and the internal pressure of the can reached 1.72 MPa, the internal pressure of the can was maintained at 1.72 MPa for 2 hours while releasing moisture out of the system. Thereafter, the internal pressure of the can was released to normal pressure over 1 hour, and further reacted at 280 ° C. for 20 minutes under a reduced pressure of −21.3 kPa (80 kPa) to complete the polymerization. The relative viscosity of the obtained polyamide 66 measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml was 3.4, the melting point was 265 ° C., and the glass transition temperature was 50 ° C.

Reference Example 3 Synthesis of Polyamide 10T (A-3) Decamethylenediamine (manufactured by Tokyo Chemical Industry) and terephthalic acid (manufactured by Tokyo Chemical Industry) were added in equimolar amounts so that the total amount was 10 kg. Furthermore, 0.5 mol% of decamethylenediamine is added excessively with respect to the total amount of decamethylenediamine, and 30 parts by weight of water is added to and mixed with 70 parts by weight of these raw materials. And then purged with nitrogen. After heating was started and the internal pressure of the can reached 2.0 MPa, the internal pressure of the can was maintained at 2.0 MPa and the internal temperature of 240 ° C. for 2 hours while releasing moisture out of the system. Thereafter, the contents were discharged from the pressurized container to obtain a polyamide oligomer. The obtained polyamide oligomer was pulverized, vacuum dried at 100 ° C. for 24 hours, and solid-phase polymerized at 50 Pa and 240 ° C. to obtain polyamide 10T. The relative viscosity of the obtained polyamide 10T measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml was 2.50, the melting point was 318 ° C., and the glass transition temperature was 125 ° C. .

(Reference Example 4) Synthesis of polybutylene terephthalate (A-4) After heating 100 g of 1,4-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) to 100 ° C., titanium compound (D-1): tetra-n-butoxy titanate ( TBT) (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed to obtain a catalyst solution.

A rectifying tower was prepared by using 780 g of terephthalic acid (TPA) (manufactured by Tokyo Chemical Industry Co., Ltd.) as a dicarboxylic acid component, 760 g of 1,4-butanediol as a diol component, and 4.6 mL of the catalyst solution obtained by the above method as an esterification reaction catalyst. Was charged into the reactor with. At this time, the molar ratio of 1,4-butanediol to terephthalic acid (1,4-butanediol) / (terephthalic acid) was 1.8, and the amount of TBT added to 100 g of polybutylene terephthalate produced was 1.3 × 10 ^{−. 4} mol (0.045 parts by weight with respect to 100 parts by weight of polybutylene terephthalate). After starting the esterification reaction under a reduced pressure of 160 ° C. and 93 kPa, the temperature was gradually raised, and finally the esterification reaction was carried out for 270 minutes at a temperature of 225 ° C. As a polycondensation reaction catalyst to the obtained reaction product, 0.5 × 10 ⁻² mol (0.05 parts by weight with respect to 100 parts by weight of polybutylene terephthalate) with respect to 100 g of polybutylene terephthalate produced by the addition of TBT Thus, 0.49 mL of the catalyst solution obtained by the above method was added, and a polycondensation reaction was performed for 190 minutes under the conditions of a temperature of 245 ° C. and a pressure of 100 Pa to obtain polybutylene terephthalate. The resulting polybutylene terephthalate had a carboxyl end group content of 35 eq / t, an intrinsic viscosity of 0.7 dl / g measured with a 0.5% solution in o-chlorophenol, a melting point of 225 ° C., and a glass transition temperature of 50 ° C. .

Reference Example 5 Synthesis of Liquid Crystalline Polyester Resin (A-5) 870 g (6.30 mol) of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl were added to a 5 L reaction vessel equipped with a stirring blade and a distillation tube. 327 g (1.89 mol), hydroquinone 89 g (0.81 mol), terephthalic acid 292 g (1.76 mol), isophthalic acid 157 g (0.95 mol) and acetic anhydride 1367 g (1.03 equivalents of total phenolic hydroxyl groups) ) And stirred for 2 hours at 145 ° C. with stirring in a nitrogen gas atmosphere, and then heated to 320 ° C. over 4 hours. Thereafter, the polymerization temperature is maintained at 320 ° C., the pressure is reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction is continued for another 90 minutes, and the polycondensation is completed when the torque required for stirring reaches 15 kg · cm. It was. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer is discharged onto a strand through a base having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter. A liquid crystalline polyester resin was obtained.

  This liquid crystalline polyester resin comprises p-oxybenzoate units (structural units (I)), 4,4′-dioxybiphenyl units (structural units (II)), 1,4-dioxybenzene units (structural units (III) )), Terephthalate units (structural units (IV)) and isophthalate units (structural units (V)). This liquid crystalline polyester resin has 70 mol% of p-oxybenzoate units based on the total of p-oxybenzoate units, 4,4'-dioxybiphenyl units) and 1,4-dioxybenzene units, The amount of 4,4′-dioxybiphenyl units is 70 mol% based on the total of 4,4′-dioxybiphenyl units and 1,4-dioxybenzene units, and the terephthalate units are terephthalate units and isophthalate units. 65 mol% with respect to the total of the above. The total of 4,4′-dioxybiphenyl units and 1,4-dioxybenzene units was 23 mol% with respect to the total structural units. The total of terephthalate units and isophthalate units was 23 mol% with respect to the total structural units. After observing the endothermic peak temperature (Tm1) observed when the liquid crystalline polyester resin is measured from room temperature at a temperature rising condition of 40 ° C./min, holding at a temperature of Tm1 + 20 ° C. for 5 minutes and then decreasing the temperature by 20 ° C./min The endothermic peak temperature (Tm2: melting point) observed when the temperature was once cooled to room temperature under the conditions and the temperature was raised again under the temperature rising condition of 20 ° C./min was 314 ° C. The melt viscosity measured using a Koka flow tester (orifice 0.5φ × 10 mm) at a temperature of 324 ° C. and a shear rate of 1,000 / s was 20 Pa · s.

(Reference Example 6) Synthesis of polyphenylene sulfide resin (A-6) In a 70 liter autoclave equipped with a stirrer and a bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 96% sodium hydroxide 2.94 kg (70.63 mol), N-methyl-2-pyrrolidone (NMP) 11.45 kg (115.50 mol), 1.89 kg (23.1 mol) sodium acetate and 5.50 kg of ion-exchanged water are charged. The mixture was gradually heated to 245 ° C. over about 3 hours while flowing nitrogen at normal pressure, and 9.77 kg of water and 0.28 kg of NMP were distilled off, and then the reaction vessel was cooled to 200 ° C. The residual water content in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Thereafter, the mixture was cooled to 200 ° C., 10.42 kg (70.86 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 6 ° C./min and reacted at 270 ° C. for 140 minutes. Thereafter, 2.40 kg (133 mol) of water was injected while cooling from 270 ° C. to 250 ° C. over 15 minutes. Next, the mixture was gradually cooled from 250 ° C. to 220 ° C. over 75 minutes, and then rapidly cooled to near room temperature, and the contents were taken out.

  The contents were diluted with about 35 liters of NMP, stirred as a slurry at 85 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh (aperture 0.175 mm) to obtain a solid. The obtained solid was similarly washed and filtered with about 35 liters of NMP. The operation of diluting the obtained solid with 70 liters of ion-exchanged water, stirring at 70 ° C. for 30 minutes, and filtering through an 80 mesh wire net to collect the solid was repeated 3 times in total. The obtained solid and 32 g of acetic acid were diluted with 70 liters of ion exchange water, stirred at 70 ° C. for 30 minutes, filtered through an 80 mesh wire mesh, and further obtained solids were diluted with 70 liters of ion exchange water. The mixture was stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire net to collect a solid. The solid material thus obtained was dried at 120 ° C. under a nitrogen stream to obtain dry PPS.

  The obtained PPS was measured using a melt indexer (orifice: length 8.00 mm, hole diameter 2.095 mm) at a temperature of 315.5 ° C., a load of 5 kg, and a preheating time of 5 minutes until the start of measurement. MFR was 800 g / 10 min.

Glass fiber (B-1): Circular cross-section glass fiber (Glass composition: SiO ₂ : 60.1 wt%, Al ₂ O ₃ : 20.1 wt%, CaO: 9.5 wt%, MgO: 10.1 wt% %, Fe ₂ O ₃ : 0.1% by weight, Na ₂ O: 0.1% by weight, cross-sectional diameter: 10.5 μm, flatness: 1.0, cross-sectional shape: circular, surface treatment agent: silane-based cup (Ring agent, average fiber length: 3 mm)
(B′-2): Circular cross-section glass fiber (glass composition: SiO ₂ : 54.6 wt%, B ₂ O ₃ : 6.4 wt%, Al ₂ O ₃ : 14.3 wt%, CaO: 22. 3 wt%, MgO: 0.8 _wt%, TiO 2: 0.2 _wt%, Na 2 O: 0.4 _wt%, K 2 O: 0.2 _{wt%, Fe} 2 O 3: 0.2 wt %, F ₂ : 0.6% by weight, cross-sectional diameter: 10.5 μm, flatness: 1.0, cross-sectional shape: circular, surface treatment agent: silane coupling agent, average fiber length: 3 mm)
(B-3): flat cross-section glass fiber (glass composition: SiO ₂ : 60.1 wt%, Al ₂ O ₃ : 20.1 wt%, CaO: 9.5 wt%, MgO: 10.1 wt%, Fe ₂ O ₃ : 0.1% by weight, Na ₂ O: 0.1% by weight, major axis 28 μm, minor axis 7 μm, flatness 4.0, cross-sectional shape: oval, surface treatment agent: silane coupling agent, Average fiber length 3mm)
(B′-4): flat cross-section glass fiber (glass composition: SiO ₂ : 54.6 wt%, B ₂ O ₃ : 6.4 wt%, Al ₂ O ₃ : 14.3 wt%, CaO: 22. 3 wt%, MgO: 0.8 _wt%, TiO 2: 0.2 _wt%, Na 2 O: 0.4 _wt%, K 2 O: 0.2 _{wt%, Fe} 2 O 3: 0.2 wt %, F ₂ : 0.6% by weight, major axis 28 μm, minor axis 7 μm, oblateness 4.0, cross-sectional shape: oval, surface treatment agent: silane coupling agent, average fiber length 3 mm).

(Examples 1 and 3)
After metering the thermoplastic resin at the ratio shown in Table 1, a TEX30 type twin screw extruder (L / D = manufactured by Nippon Steel Co., Ltd.) with the cylinder set temperature set to the melting point of the thermoplastic resin + 10 ° C. and the screw rotation speed set to 200 rpm. 45) from the main feeder and melt-kneaded. Next, glass fibers were supplied from the side feeder to the twin screw extruder so as to have a weight ratio shown in Table 1 with respect to 100 parts by weight of the thermoplastic resin, and melt kneading was performed. This side feeder was supplied from a side feeder installed at a position of about 0.35 when viewed from the downstream side when the total length of the screw was 1.0, that is, downstream of 1/2 of the screw length. The screw configuration of the extruder is such that the kneading zone length Ln1 / L on the upstream side of the glass fiber supply position is 0.14, and the kneading zone length Ln2 / L on the downstream side of the glass fiber supply position. Was 0.07, and the total length Lb / Ln2 of the reverse feed kneading screw pieces in the kneading zone was 0.3. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter.

(Examples 2, 4, 9-18, Comparative Examples 1-16)
A pellet was obtained in the same manner as in Example 1 except that the thermoplastic resin and the glass fiber were blended in the ratios shown in Tables 1 to 4 and the cylinder set temperature was changed to the melting point of the thermoplastic resin + 20 ° C.

(Examples 5 and 7)
After measuring the thermoplastic resin at the ratio shown in Table 1, the TEX30 type twin screw extruder (L / D = manufactured by Nippon Steel Co., Ltd.) with the cylinder set temperature set to the melting point of the thermoplastic resin + 20 ° C. and the screw rotation speed set to 350 rpm. 45) from the main feeder and melt-kneaded. Next, glass fibers were supplied from the side feeder to the twin screw extruder so as to have a weight ratio shown in Table 1 with respect to 100 parts by weight of the thermoplastic resin, and melt kneading was performed. The side feeder is melted by being supplied from a side feeder installed at a position about 0.55 when viewed from the downstream side when the total length of the screw is 1.0, that is, upstream from 1/2 of the screw length. Kneading was performed. The screw configuration of the extruder is such that the kneading zone length Ln / L on the upstream side of the glass fiber supply position is 0.14, and the kneading zone length Ln2 / L on the downstream side of the glass fiber supply position. Was 0.32, and the total length Lb / Ln2 of the reverse feed kneading screw pieces in the kneading zone was 0.6. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter.

(Examples 6 and 8)
After measuring the thermoplastic resin at the ratio shown in Table 1, the TEX30 type twin screw extruder (L / D = manufactured by Nippon Steel Co., Ltd.) with the cylinder set temperature set to the melting point of the thermoplastic resin + 30 ° C. and the screw rotation speed set to 100 rpm. 45) from the main feeder and melt-kneaded. Next, glass fibers were supplied from the side feeder to the twin screw extruder so as to have a weight ratio shown in Table 1 with respect to 100 parts by weight of the thermoplastic resin, and melt kneading was performed. This side feeder is melted by being supplied from a side feeder installed at a position of about 0.2 when viewed from the downstream side when the total length of the screw is 1.0, that is, downstream of 1/2 of the screw length. Kneading was performed. The screw configuration of the extruder is such that the kneading zone length Ln / L on the upstream side of the glass fiber supply position is 0.34, and the kneading zone length Ln2 / L on the downstream side of the glass fiber supply position. Was 0.07, and the total length Lb / Ln2 of the reverse feed kneading screw pieces in the kneading zone was 0.3. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter.

  The compositions and evaluation results of the examples and comparative examples are shown in Tables 1 to 4.

  Examples 1 and 3 have a fiber length distribution equivalent to that of Comparative Examples 1 and 2, but mechanical strength, heat resistance, high-temperature rigidity, surface appearance are improved, and warpage is also reduced. Moreover, it turns out that the molded article which is excellent in snap fit property and pin press-fit property can be obtained. Further, by adjusting the weight average fiber length and fiber length distribution to more preferable ranges as in Examples 2 and 4, the mechanical strength, heat resistance, high temperature rigidity, surface appearance, snap fit, and pin press-fit characteristics are further enhanced. It can be seen that warpage can be further reduced.

  From the comparison between Examples 1-2 and 3-4, it can be seen that the effect of the present invention becomes more remarkable by changing the cross-sectional shape of the glass fiber from a circular shape to a flat shape.

  Further, from the comparison between Example 2 and Comparative Example 3, when the glass fiber content is less than 5 parts by weight, the mechanical strength, heat resistance, high temperature rigidity, and impact resistance are reduced, and snap fit, pin press-fitting is performed. It can be seen that both characteristics deteriorate. On the other hand, from the comparison between Example 2 and Comparative Example 4, when the glass fiber content exceeds 200 parts by weight, although the heat resistance is improved, the fluidity is remarkably lowered, resulting in a decrease in surface appearance and a large warp. It can also be seen that the snap fit and pin press-fit properties are insufficient.

  On the other hand, from the comparison of Examples 1, 2, 5, and 6 and the comparison of Examples 3, 4, 7, and 8, the weight average fiber length of the glass fibers in the composition was 100 to 1000 μm, and 300 in the total amount of glass fibers. By making the ratio of glass fiber of ˜500 μm 20 to 50% by weight, the mechanical strength, impact resistance, heat resistance, high temperature rigidity, snap fit property, pin press fit property, surface appearance are further improved, and the warp is further improved. Can be reduced. Moreover, it can be seen from the comparison between Examples 2 and 9 and the comparison between Examples 4 and 10 that the effect of the present invention becomes more remarkable by using polyamide 66 having a specific relative viscosity.

  In Examples 11 to 12 using polyamide 10T, mechanical strength, heat resistance, high temperature rigidity, impact resistance, fluidity, surface appearance, snap fit, and pin press-fit characteristics are improved as compared with Comparative Examples 5 to 6. It can be seen that warpage is reduced.

  Further, from the comparison between Examples 13 to 15 and Comparative Examples 7 to 9 and the comparison between Examples 16 to 18 and Comparative Examples 12 to 14, even when polybutylene terephthalate, liquid crystalline polyester, polyphenylene sulfide is used, (B ) It can be seen that the effect of the present invention can be obtained by the combination with glass fiber.

  On the other hand, as shown in Comparative Examples 10, 11, 15, and 16, it is understood that the effect cannot be obtained when a thermoplastic resin other than the thermoplastic resin (A) used in the present invention is used.

G1: Submarine 1-point gate G1
a: Reference position (line segment AB)
b: Maximum deformation position

Claims (7)

(A) With respect to 100 parts by weight of at least one thermoplastic resin selected from the group consisting of polyamide, polyester and polyphenylene sulfide, (B) SiO ₂ content is 57 to 63% by weight, and Al ₂ O ₃ content is 19 to 23 wt%, CaO content is 5.5 to 11 wt%, a MgO content of 10 to 15% by weight, at these total 99.5% by weight or more, and, SiO ₂ content / Al ₂ O ₃ content is 2.7 to 3.2 by weight ratio, MgO content / CaO content is 0.9 to 2.0 by weight ratio, 5 to 200 parts by weight of glass fiber is blended. A glass fiber reinforced thermoplastic resin composition. The glass fiber reinforced thermoplastic resin composition according to claim 1, wherein the cross-sectional shape of the (B) glass fiber is a circular shape or a flat shape. The glass fiber reinforced thermoplastic resin composition according to claim 2, wherein the cross-sectional shape of the glass fiber (B) is a flat shape. 4. The glass fiber reinforced thermoplastic resin composition according to claim 3, wherein the flat shape is an elliptical shape, an oval shape, or an eyebrows shape, and a ratio of a major axis to a minor axis of a cross section is 1.3 to 10. 5. The weight average fiber length of said (B) glass fiber in a composition is 100-1000 micrometers, and contains 20-50 weight% of 300-500 micrometers glass fiber in said (B) glass fiber total amount. The glass fiber reinforced thermoplastic resin composition according to any one of the above A molded article formed by molding the glass fiber reinforced thermoplastic resin composition according to claim 1. The molded article according to claim 6, which is an electric / electronic part, an automobile interior part or an automobile exterior part.

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