JP7093104B2 - A thermoplastic resin composition and a molded product obtained by molding the thermoplastic resin composition. - Google Patents

Description

The present invention relates to a thermoplastic resin composition, more particularly to a resin composition containing a semi-aromatic polyamide, and a molded product obtained by molding the same.

Polyamide is used in many electric / electronic parts and parts around automobile engines because of its excellent heat resistance, mechanical properties, and moldability.

In recent years, in particular, the method of mounting electrical and electronic components such as connectors on an electronic board has become a surface mounting method by reflow using lead-free solder from the environmental aspect. The molded body constituting the electric / electronic parts is required to have heat resistance to withstand the heating in the reflow furnace.
For example, since an aliphatic polyamide such as polyamide 6 or polyamide 66 has a low melting point, there is a problem that a molded product made of these resins is melted and deformed by reflow. Further, although the polyamide 46 has a high melting point, it easily absorbs water, and in the molded product made of the polyamide 46, moisture foams during the reflow treatment, and a blister phenomenon occurs in which the surface of the molded product swells. The body had to be stored in a low humidity environment. Therefore, in recent years, semi-aromatic polyamides having a high melting point and a low water absorption rate have been widely used in surface-mounted molded products for electrical and electronic components.

Further, since flame retardancy is required for electrical and electronic parts, as a composition in which a flame retardant is blended with polyamide, for example, Patent Document 1 describes semi-aromatic polyamide and phosphinic acid as a non-halogen flame retardant. A resin composition containing a metal salt is disclosed, and this resin composition satisfies the flame retardant standard UL94V-0 standard in a 1/32 inch (0.79 mm) molded product, and also has reflow heat resistance and 0. It is disclosed to have fluidity at a thickness of 5 mm. However, in electrical and electronic parts that are becoming smaller year by year, the molded body is required to have a thinner wall, and the thinner the wall, the lower the performance in general. Is strongly desired for improvement.

As a method for increasing the fluidity of the resin composition containing a semi-aromatic polyamide, there is a method of blending an aliphatic polyamide with the resin composition. However, since the resin composition containing the semi-aromatic polyamide contains the aliphatic polyamide, the heat resistance may be lowered and the chemical resistance required for the electric / electronic parts may be lowered. That is, electric / electronic parts have been used in automobile parts in recent years due to the progress of electrical equipment in automobiles, and the electric / electronic parts used in automobile parts are gasoline, oil, battery sulfuric acid, wax, and so on. Chemical resistance is also required because there is a high possibility that chemicals such as car wash products will adhere to it.
The semi-aromatic polyamide is excellent in heat resistance and chemical resistance, but the aliphatic polyamide is inferior in heat resistance and chemical resistance, and the resin composition containing the semi-aromatic polyamide contains the aliphatic polyamide. As a result, although the fluidity is improved, there is a problem that the heat resistance and the chemical resistance are lowered.

International Publication No. 2008/126381

An object of the present invention is to provide a resin composition containing a semi-aromatic polyamide and a flame retardant, wherein the decrease in heat resistance and chemical resistance is suppressed and the fluidity is improved. do.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a semi-aromatic polyamide resin composition having a specific composition and characteristics can solve the above-mentioned problems, and have reached the present invention.
That is, the gist of the present invention is as follows.

（式中、Ｒ^１、Ｒ^２、Ｒ^４およびＲ^５は、それぞれ独立して、直鎖または分岐鎖の炭素数１～１６のアルキル基またはフェニル基を表す。Ｒ^３は、直鎖もしくは分岐鎖の炭素数１～１０のアルキレン基、炭素数６～１０のアリーレン基、アリールアルキレン基、または、アルキルアリーレン基を表す。Ｍは、カルシウムイオン、アルミニウムイオン、マグネシウムイオンまたは亜鉛イオンを表す。ｍは、２または３である。ｎ、ａ、ｂは、２×ｂ＝ｎ×ａの関係式を満たす整数である。）
（６）さらに無機強化材（Ｄ）を含有することを特徴とする（１）～（５）のいずれかに記載の熱可塑性樹脂組成物。
（７）上記（１）～（６）のいずれかに記載の熱可塑性樹脂組成物を成形してなることを特徴とする成形体。 (1) A thermoplastic resin composition containing a total of 100 parts by mass of a semi-aromatic polyamide (A) and an aliphatic polyamide (B) and 10 to 100 parts by mass of a non-halogen flame retardant (C). The mass ratio (A / B) of the aromatic polyamide (A) and the aliphatic polyamide (B) is 70/30 to 45/55.
The melting point of the semi-aromatic polyamide (A) is 280 ° C. or higher, and the temperature is 280 ° C. or higher.
A thermoplastic resin composition having a mass increase rate R of 50% or less after being immersed in 50% sulfuric acid at 23 ° C. for 48 hours.
(2) The thermoplastic resin composition according to (1), wherein the aliphatic diamine component in the semi-aromatic polyamide (A) is 1,10-decanediamine.
(3) The thermoplastic resin composition according to (1) or (2), wherein the aliphatic polyamide (B) is a polyamide 6 and / or a polyamide 66.
(4) The semi-aromatic polyamide (A) contains an aliphatic monocarboxylic acid component, the aliphatic monocarboxylic acid has 15 to 30 carbon atoms, and the content of the aliphatic monocarboxylic acid component is semi-aromatic. The thermoplastic resin composition according to any one of (1) to (3), which is characterized by being 0.3 to 4.0 mol% with respect to all the monomers constituting the group polyamide (A).
(5) The thermoplastic according to any one of (1) to (4), wherein the non-halogen flame retardant (C) is a compound represented by the following general formula (I) or (II). Resin composition.

(In the formula, R ¹ , R ² , R ⁴ and R ⁵ independently represent an alkyl group or a phenyl group having 1 to 16 carbon atoms in a straight chain or a branched chain. R ³ is a linear or branched chain. It represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an arylalkylene group, or an alkylarylene group. M represents a calcium ion, an aluminum ion, a magnesium ion or a zinc ion. M Is 2 or 3. n, a, b are integers satisfying the relational expression of 2 × b = n × a.)
(6) The thermoplastic resin composition according to any one of (1) to (5), which further contains an inorganic reinforcing material (D).
(7) A molded product obtained by molding the thermoplastic resin composition according to any one of (1) to (6) above.

According to the present invention, a thermoplastic resin composition having excellent heat resistance (reflow resistance), chemical resistance, flame retardancy, mechanical properties, and excellent fluidity during extrusion and molding is provided. Can be done.

Hereinafter, the present invention will be described in detail.
The thermoplastic resin composition of the present invention contains a semi-aromatic polyamide (A), an aliphatic polyamide (B) and a non-halogen flame retardant (C).

In the present invention, the semi-aromatic polyamide (A) contains a dicarboxylic acid component and a diamine component as constituent components, the dicarboxylic acid component contains an aromatic dicarboxylic acid, and the diamine component contains an aliphatic diamine. be.
The dicarboxylic acid component constituting the semi-aromatic polyamide (A) preferably contains terephthalic acid (T), and the content of terephthalic acid is 95 mol% or more in the dicarboxylic acid component from the viewpoint of heat resistance. It is preferably present, and more preferably 100 mol%.
The diamine component in the semi-aromatic polyamide (A) is preferably an aliphatic diamine having 8 to 12 carbon atoms from the viewpoint of heat resistance and processability. Examples of the aliphatic diamine having 8 to 12 carbon atoms include 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine. Of these, 1,10-decanediamine is preferable because of its high versatility. These may be used alone or in combination, but are preferably used alone from the viewpoint of improving mechanical properties.
In the present invention, specific examples of the semi-aromatic polyamide (A) include polyamide 8T, polyamide 9T, polyamide 10T, polyamide 11T, and polyamide 12T.

The dicarboxylic acid component of the semi-aromatic polyamide (A) may contain a dicarboxylic acid other than terephthalic acid. Examples of dicarboxylic acids other than terephthalic acid include aromatic dicarboxylic acid components such as phthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid. Examples thereof include aliphatic dicarboxylic acids such as sebacic acid, undecanedioic acid and dodecanedioic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The dicarboxylic acid other than terephthalic acid is preferably 5 mol% or less, and more preferably substantially not contained, based on the total number of moles of the raw material monomers.
The diamine component of the semi-aromatic polyamide (A) may contain a diamine other than the aliphatic diamine component having 8 to 12 carbon atoms. Examples of other diamines include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, and the like. Aliper diamine components such as 1,13-tridecanediamine, 1,14-tetradecanediamine, and 1,15-pentadecanediamine, alicyclic diamines such as cyclohexanediamine, and aromatic diamines such as xylylene diamine and benzenediamine. Can be mentioned. Diamines other than the aliphatic diamine component having 8 to 12 carbon atoms are preferably 5 mol% or less, and more preferably substantially not contained, based on the total number of moles of the raw material monomers.

The semi-aromatic polyamide (A) may contain lactams such as caprolactam and laurolactam, and ω-aminocarboxylic acid such as aminocaproic acid and 11-aminoundecanoic acid, if necessary.

In the present invention, the semi-aromatic polyamide (A) can contain a monocarboxylic acid as a constituent, and it is preferable that the aliphatic monocarboxylic acid is a constituent. The molded product obtained from a mixture in which the semi-aromatic polyamide (A) having an aliphatic monocarboxylic acid as a constituent and the aliphatic polyamide (B) are dispersed has heat resistance in the surface layer portion of the molded product which is susceptible to heat. Since the semi-aromatic polyamide (A) having a high content is likely to be the main component, blister is less likely to occur in the reflow process.
The aliphatic monocarboxylic acid preferably has 15 to 30 carbon atoms, more preferably 18 to 29 carbon atoms. Since the semi-aromatic polyamide (A) contains an aliphatic monocarboxylic acid having 15 to 30 carbon atoms, the fluidity is improved, and the semi-aromatic polyamide component tends to be the main component in the surface layer of the molded body. When the number of carbon atoms of the monocarboxylic acid is less than 15, the semi-aromatic polyamide (A) may not have the effect of improving the fluidity. Further, when the carbon number of the aliphatic monocarboxylic acid exceeds 30, crystallization of the semi-aromatic polyamide (A) may be inhibited, and the molding processability and heat resistance may be deteriorated.

Examples of the aliphatic monocarboxylic acid having 15 to 30 carbon atoms include pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadesilic acid, arachidic acid, bechenic acid, lignoseric acid, cellotic acid, heptacosanoic acid and montanic acid. Melicic acid can be mentioned. Of these, stearic acid, behenic acid, and montanic acid are preferable because of their high versatility.
The aliphatic monocarboxylic acid may be used alone or in combination.

In the semi-aromatic polyamide (A), the content of the aliphatic monocarboxylic acid component is preferably 0.3 to 4.0 mol% with respect to all the monomers constituting the semi-aromatic polyamide (A). , 0.6-3.5 mol%, more preferably. When the content of the aliphatic monocarboxylic acid component is less than 0.3 mol%, the molecular weight of the obtained semi-aromatic polyamide (A) is high, decomposition gas is generated during extrusion or molding, and fluidity is improved. It may not be effective. On the other hand, if the content of the aliphatic monocarboxylic acid component exceeds 4.0 mol%, the mechanical properties of the semi-aromatic polyamide (A) may deteriorate.

The semi-aromatic polyamide (A) needs to have a melting point of 280 ° C. or higher, and preferably 300 ° C. or higher. If the melting point of the semi-aromatic polyamide (A) is less than 280 ° C., the thermoplastic resin composition may be melted or deformed in reflow.

The semi-aromatic polyamide (A) preferably has a relative viscosity of 1.5 to 3.5 when measured at 25 ° C. and a concentration of 1 g / dL in 96% sulfuric acid, which is an index of molecular weight. It is more preferably .7 to 3.5, and even more preferably 1.9 to 3.1. If the relative viscosity of the semi-aromatic polyamide (A) is less than 1.5, the thermoplastic resin composition may have reduced mechanical properties.

The higher the crystallinity of the semi-aromatic polyamide resin (A), the higher the crystallinity of the obtained molded product, and the higher the heat resistance, reflow resistance, mechanical strength, and low water absorption. It is preferable that the crystallinity of the group polyamide (A) is controlled within a specific range. In the present invention, the crystal melting energy (ΔH) measured by a differential scanning calorimeter (DSC) is used as an index of the crystallinity, and the ΔH of the semi-aromatic polyamide resin (A) is 50 J / g or more. Is preferable, and 55 J / g or more is more preferable. When ΔH of the semi-aromatic polyamide resin (A) is less than 50 J / g, the crystallinity cannot be sufficiently enhanced, and the obtained molded product may generate blister in the reflow step.

The semi-aromatic polyamide (A) can be produced by using a conventionally known method of heat polymerization method or solution polymerization method. The heat polymerization method is preferably used because it is industrially advantageous. The heat polymerization method includes a step (i) of obtaining a reaction product from a dicarboxylic acid component, a diamine component, and a monocarboxylic acid component, and a step (ii) of polymerizing the obtained reaction product. Can be mentioned.

In the step (i), for example, the dicarboxylic acid powder and the monocarboxylic acid are mixed and heated in advance to a temperature equal to or higher than the melting point of the diamine and lower than the melting point of the dicarboxylic acid, and the dicarboxylic acid powder and the monocarboxylic acid at this temperature are combined. In addition, there is a method of adding a diamine without substantially containing water so as to maintain the state of the powder of the dicarboxylic acid. Alternatively, as another method, a suspension consisting of a molten diamine and a solid dicarboxylic acid is stirred and mixed to obtain a mixed solution, and then at a temperature below the melting point of the semi-aromatic polyamide finally produced. , A method of producing a salt by a reaction of a dicarboxylic acid, a diamine and a monocarboxylic acid and a reaction of producing a low polymer by polymerizing the produced salt to obtain a mixture of the salt and the low polymer can be mentioned. In this case, crushing may be carried out while allowing the reaction, or crushing may be carried out after taking out the reaction once after the reaction. As the step (i), the former is preferable because the shape of the reaction product can be easily controlled.

In the step (ii), for example, the reaction product obtained in the step (i) is solid-phase polymerized at a temperature lower than the melting point of the semi-aromatic polyamide finally produced to increase the molecular weight to a predetermined molecular weight. , A method of obtaining a semi-aromatic polyamide can be mentioned. The solid phase polymerization is preferably carried out at a polymerization temperature of 180 to 270 ° C. and a reaction time of 0.5 to 10 hours in a stream of an inert gas such as nitrogen.

The reaction apparatus for the step (i) and the step (ii) is not particularly limited, and a known apparatus may be used. The step (i) and the step (ii) may be carried out by the same device or may be carried out by different devices.

In the production of the semi-aromatic polyamide (A), a polymerization catalyst may be used to increase the efficiency of polymerization. Examples of the polymerization catalyst include phosphoric acid, phosphorous acid, hypophosphoric acid or salts thereof. The amount of the polymerization catalyst added is usually preferably 2 mol% or less with respect to all the monomers constituting the semi-aromatic polyamide (A).

The aliphatic polyamide (B) in the present invention is a polyamide containing no aromatic component in the main chain, and is, for example, polyε-couplemid (polyamide 6), polytetramethylene adipamide (polyamide 46), or polyhexamethylene. Adipamide (polyamide 66), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyundecamethylene adipamide (polyamide 116), polyundecanamid (polyamide 11), Examples thereof include polydodecanamid (polyamide 12) and a polyamide copolymer containing at least two different polyamide components thereof, or a mixture thereof. Among them, polyamide having 6 or less carbon atoms as a constituent unit is preferable, and polyamide 6, polyamide 46, and polyamide 66 are preferable from the viewpoint of fluidity and economy.

The relative viscosity of the aliphatic polyamide (B) is not particularly limited and may be appropriately set according to the intended purpose. For example, in order to obtain a thermoplastic resin composition that can be easily molded, the aliphatic polyamide (B) preferably has a relative viscosity of 1.9 to 4.0, preferably 2.0 to 3.5. Is more preferable. If the relative viscosity of the aliphatic polyamide (B) is less than 1.9, the toughness may be insufficient depending on the molded product, which may lead to deterioration of mechanical properties. Further, when the relative viscosity of the aliphatic polyamide (B) exceeds 4.0, the thermoplastic resin composition becomes difficult to be molded, and the obtained molded product may have an inferior appearance.

The mass ratio (A / B) of the semi-aromatic polyamide (A) to the aliphatic polyamide (B) needs to be 90/10 to 45/55, and may be 85/15 to 50/50. It is preferably 80/20 to 55/45, more preferably 80/20 to 55/45. If the semi-aromatic polyamide (A) exceeds 90% by mass, that is, if the aliphatic polyamide (B) is less than 10% by mass, the fluidity of the thermoplastic resin composition may decrease. On the other hand, if the semi-aromatic polyamide (A) is less than 45% by mass, that is, the aliphatic polyamide (B) is more than 55% by mass, the reflow resistance of the thermoplastic resin composition may decrease.

Examples of the non-halogen flame retardant (C) in the present invention include phosphorus-based flame retardants, nitrogen-based flame retardants, nitrogen-phosphorus flame retardants, and inorganic flame retardants, and phosphorus is used from the viewpoint of heat resistance and flame retardancy. Flame retardants are preferred.

Examples of the phosphorus-based flame retardant include phosphinic acid metal salts. Examples of the phosphinic acid metal salt include a phosphinic acid metal salt represented by the following general formula (I) and a diphosphinic acid metal salt represented by the general formula (II).

In the formula, R ¹ , R ² , R ⁴ and R ⁵ are required to be an alkyl group or a phenyl group having 1 to 16 carbon atoms in a straight chain or a branched chain, respectively, and have 1 to 8 carbon atoms. Is preferably an alkyl group or a phenyl group, and is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, an n-octyl group, or a phenyl group. More preferably, it is more preferably an ethyl group. R ¹ and R ² and R ⁴ and R ⁵ may form rings with each other.
R ³ needs to be a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an arylalkylene group, or an alkylarylene group. Examples of the alkylene group having 1 to 10 carbon atoms in the linear or branched chain include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an isopropylidene group, an n-butylene group, a tert-butylene group and n-. Examples thereof include a pentylene group, an n-octylene group and an n-dodecylene group. Examples of the arylene group having 6 to 10 carbon atoms include a phenylene group and a naphthylene group. Examples of the alkylarylene group include a methylphenylene group, an ethylphenylene group, a tert-butylphenylene group, a methylnaphthylene group, an ethylnaphthylene group and a tert-butylnaphthylene group. Examples of the arylalkylene group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group and a phenylbutylene group.
M represents a metal ion. Examples of the metal ion include calcium ion, aluminum ion, magnesium ion and zinc ion, and aluminum ion and zinc ion are preferable, and aluminum ion is more preferable.
m and n represent the valence of the metal ion. m is 2 or 3. a represents the number of metal ions, b represents the number of diphosphinic acid ions, and n, a, and b are integers satisfying the relational expression of “2 × b = n × a”.

The phosphinic acid metal salt and the diphosphinic acid metal salt are produced in an aqueous solution using the corresponding phosphinic acid or diphosphinic acid and the metal carbonate, metal hydroxide or metal oxide, respectively, and usually exist as a monomer. Depending on the reaction conditions, it may exist in the form of a polymer phosphinate having a degree of condensation of 1 to 3.

Specific examples of the phosphinate represented by the above general formula (I) include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, and ethylmethylphosphine. Magnesium Acid, Aluminum Ethylmethylphosphinate, Zinc Ethylmethylphosphinate, Calcium diethylphosphinate, Magnesium diethylphosphinate, Aluminum diethylphosphinate, Zinc diethylphosphinate, Calcium methyl-n-propylphosphinate, Methyl-n-propylphosphine Magnesium Acid, Aluminum Methyl-n-propylphosphinate, Zinc Methyl-n-propylphosphinate, Calcium Methylphenylphosphinate, Magnesium Methylphenylphosphinate, Aluminum Methylphenylphosphinate, Zinc Methylphenylphosphinate, Calcium diphenylphosphinate, Examples thereof include magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate. Among them, aluminum diethylphosphinate and zinc diethylphosphinate are preferable, and aluminum diethylphosphinate is more preferable because of the excellent balance of flame retardancy and electrical characteristics.

Examples of the diphosphinic acid used for producing the diphosphinate include methanedi (methylphosphinic acid) and benzene-1,4-di (methylphosphinic acid).

Specific examples of the diphosphinate represented by the above general formula (II) include, for example, methanedi (methylphosphinic acid) calcium, methanedi (methylphosphinic acid) magnesium, methanedi (methylphosphinic acid) aluminum, and methanedi (methylphosphinic acid). ) Zinc, benzene-1,4-di (methylphosphinic acid) calcium, benzene-1,4-di (methylphosphinic acid) magnesium, benzene-1,4-di (methylphosphinic acid) aluminum, benzene-1,4 -Di (methylphosphinic acid) zinc can be mentioned. Of these, methanedi (methylphosphinic acid) aluminum and methanedi (methylphosphinic acid) zinc are preferable because they have an excellent balance of flame retardancy and electrical characteristics.

Specific trade names of the phosphinic acid metal salt include, for example, "Exolit OP1230", "Exolit OP1240", "Exolit OP1312", "Exolit OP1314" and "Exolit OP1400" manufactured by Clariant.

Examples of the nitrogen-based flame retardant include a melamine-based compound, cyanuric acid, or a salt of isocyanuric acid and a melamine compound. Specific examples of melamine-based compounds include melamine, melamine derivatives, compounds having a structure similar to melamine, and condensates of melamine. Specifically, melamine, ammeline, ammeline, formoguanamine, guanyl melamine, and cyano. Examples thereof include compounds having a triazine skeleton such as melamine, benzoguanamine, acetoguanamine, succinoguanamine, melam, melem, methone, and melon, and sulfates and melamine resins thereof. The salt of cyanuric acid or isocyanuric acid and a melamine compound is an equimolar reaction product of cyanuric acid or isocyanuric acid and a melamine-based compound.

Examples of the nitrogen-phosphorus flame retardant include an adduct (melamine adduct) formed from melamine or a condensation product thereof and a phosphorus compound, and a phosphazene compound.
Examples of the phosphorus compound constituting the melamine adduct include phosphoric acid, orthophosphoric acid, phosphonic acid, phosphinic acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid and the like. Specific examples of the melamine adduct include melamine phosphate, melamine pyrophosphate, dimelamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, and melamine polyphosphate, with melamine polyphosphate being preferred. The number of phosphorus is preferably 2 or more, and more preferably 10 or more.
Specific trade names of phosphazene compounds include, for example, "Rabbitl FP-100" and "Rabbitl FP-110" manufactured by Fushimi Pharmaceutical Co., Ltd., "SPS-100" and "SPB-100" manufactured by Otsuka Chemical Co., Ltd. Be done.

Examples of the inorganic flame retardant include metal hydroxides such as magnesium hydroxide and calcium hydroxide, phosphates such as zinc borate and aluminum phosphate, phosphite such as aluminum phosphite, and calcium hypophosphite. Such as hypophosphite, calcium aluminate and the like. These inorganic flame retardants may be blended for either purpose of improving flame retardancy or reducing metal corrosiveness.

The content of the non-halogen flame retardant (C) needs to be 10 to 100 parts by mass with respect to 100 parts by mass in total of the semi-aromatic polyamide (A) and the aliphatic polyamide (B). It is preferably up to 80 parts by mass, more preferably 25 to 50 parts by mass. If the content of the non-halogen flame retardant (C) is less than 10 parts by mass, the flame retardancy may not be sufficient, and if it exceeds 100 parts by mass, the mechanical strength and fluidity are significantly reduced or melted. Workability during kneading may be impaired, making it difficult to obtain the desired resin composition.

The thermoplastic resin composition of the present invention may further contain an inorganic reinforcing material (D). Examples of the inorganic reinforcing material (D) include a fibrous reinforcing material.
Examples of the fibrous reinforcing material include glass fiber, carbon fiber, boron fiber, asbestos fiber, polyvinyl alcohol fiber, polyester fiber, acrylic fiber, aramid fiber, polybenzoxazole fiber, kenaf fiber, bamboo fiber, linen fiber and bagus fiber. , High-strength polyethylene fiber, alumina fiber, silicon carbide fiber, potassium titanate fiber, brass fiber, stainless fiber, steel fiber, ceramics fiber, genbu rock fiber. Among them, glass fiber, carbon fiber, and aramid fiber are preferable because they have a high effect of improving mechanical properties, have heat resistance that can withstand the heating temperature at the time of melt-kneading with polyamide, and are easily available. Specific product names of glass fiber include, for example, "CS3G225S" manufactured by Nitto Boseki Co., Ltd., "T-781H" and "T-262H" manufactured by Nippon Electric Glass Co., Ltd., and specific product names of carbon fiber include. For example, "HTA-C6-NR" manufactured by Toho Tenax Co., Ltd. can be mentioned. The fibrous reinforcing material may be used alone or in combination.

The fiber length and fiber diameter of the fibrous reinforcing material are not particularly limited, but the fiber length is preferably 0.1 to 7 mm, more preferably 0.5 to 6 mm. By setting the fiber length of the fibrous reinforcing material to 0.1 to 7 mm, the resin composition can be reinforced without adversely affecting the moldability. The fiber diameter is preferably 3 to 20 μm, more preferably 5 to 13 μm. By setting the fiber diameter to 3 to 20 μm, the resin composition can be efficiently reinforced without breaking during melt-kneading. Examples of the cross-sectional shape include a circular shape, a rectangular shape, an ellipse, and other irregular cross-sectional shapes, and a circular shape is preferable.

As the inorganic reinforcing material (D), a needle-shaped reinforcing material or a plate-shaped reinforcing material may be used in addition to the fibrous reinforcing material. In particular, by using the fibrous reinforcing material in combination with the needle-shaped reinforcing material or the plate-shaped reinforcing material, it is possible to reduce the warp of the molded body and improve the drip resistance during the flame retardant test. Examples of the needle-shaped reinforcing material include wollastonite, potassium titanate whiskers, zinc oxide whiskers, magnesium sulfate whiskers and the like. Examples of the plate-shaped reinforcing material include talc, mica, and glass flakes.

The content of the inorganic reinforcing material (D) is preferably 5 to 200 parts by mass with respect to 100 parts by mass in total of the semi-aromatic polyamide (A) and the aliphatic polyamide (B), and is 5 to 180 parts by mass. Is more preferable, and 10 to 170 parts by mass is further preferable. If the content of the inorganic reinforcing material (D) is less than 5 parts by mass, the reinforcing effect of the mechanical strength may not be sufficient, and if it exceeds 200 parts by mass, the reinforcing efficiency of the mechanical strength is lowered or heat is generated. The plastic resin composition may have reduced workability during melt-kneading, or it may be difficult to obtain pellets.

The thermoplastic resin composition of the present invention may further contain an antioxidant (E). Examples of the antioxidant (E) include phosphorus-based antioxidants, hindered phenol-based antioxidants, hindered amine-based antioxidants, triazine-based compounds, and sulfur-based compounds. Among them, phosphorus-based antioxidants are used. preferable. When the thermoplastic resin composition containing the inorganic reinforcing material (D) stays in a high-temperature cylinder for a long time, or when the inorganic reinforcing material (D) is surface-treated, the surface treatment agent thermally decomposes. May cause a decrease in mechanical strength. However, in the present invention, even when the resin composition is accumulated in the cylinder for a long time, that is, when the molding cycle is long during injection molding or when the injection amount is small and the resin stays in the cylinder for a long time, it is oxidized. By containing the inhibitor (E), it is possible to suppress a decrease in the tensile strength of the resin composition. The antioxidant (E) is usually contained for the purpose of lowering the molecular weight of the semi-aromatic polyamide (A) and degenerating the color. In the present invention, in addition to these effects, the retention stability of the resin composition can be improved. When the antioxidant (E) is contained, the content thereof may be 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the semi-aromatic polyamide (A) and the aliphatic polyamide (B). It is preferably 0.2 to 5 parts by mass, and more preferably 0.2 to 5 parts by mass.

The phosphorus-based antioxidant may be an inorganic compound or an organic compound, and is not particularly limited. For example, monosodium phosphate, disodium phosphate, trisodium phosphate, sodium phosphite, calcium phosphite, and phosphite. Inorganic phosphates such as magnesium acid and manganese phosphite, triphenylphosphite, trioctadecylphosphite, tridecylphosphite, trinonylphenylphosphite, diphenylisodecylphosphite, bis (2,6-di-tert) -Butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylylene phosphite can be mentioned. Of these, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylylene phosphite are preferred. .. Specific product names include, for example, "Adecastab PEP-36" (bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite) and "Adecastab PEP-8" manufactured by Adeca. (Distealyl pentaerythritol diphosphite), "Adecastab PEP-4C" (bis (nonylphenyl) pentaerythritol diphosphite), Clariant "Hostanox P-EPQ" (Tetrakiss (2,4-di-t-) Butylphenyl) -4,4-biphenylylene phosphite) can be mentioned. These may be used alone or in combination.

The thermoplastic resin composition of the present invention may further contain other polymers, if necessary. Examples of other polymers include alicyclic polyamides such as polyamide 9C, polyethylene terephthalates, polybutylene terephthalates, liquid crystal polymers, polyarylates, polyesters such as polycyclohexanedimethylene terephthalates, polyolefins such as polyethylene, polystyrene and polypropylene, and polyphenylene sulfides. , Polyphenylene ether, polyether ether ketone and the like.

The thermoplastic resin composition of the present invention may contain other additives, if necessary. Other additives include, for example, fillers such as talc, swellable clay minerals, silica, alumina, glass beads, graphite, flame retardant aids, pigments, dyes, antistatic agents, plate-like reinforcing materials, heat stabilizers. , Impact resistance improver, plasticizer, mold release agent, lubricant, crystal nucleating agent, organic peroxide, terminal sequestering agent, slidability improving agent. The method of adding the other additives is not particularly limited as long as the effect is not impaired, and is added, for example, at the time of polymerization or melt kneading of the polyamide.

Further, the thermoplastic resin composition of the present invention may contain a light stabilizer. When a molded product of a thermoplastic resin composition containing a white pigment such as titanium oxide is used outdoors as an exhaust finisher or an LED reflector, titanium oxide may promote photodecomposition, so that the thermoplastic resin composition is light. It preferably contains a stabilizer. Examples of the light stabilizer include benzophenone-based compounds, benzotriazole-based compounds, salicylate-based compounds, hindered amine-based compounds, and hindered phenol-based compounds, and among them, hindered amine-based compounds are preferable. When the light stabilizer is contained, the content thereof is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition. .. The thermoplastic resin composition can improve the light stability by containing 0.1 to 5 parts by mass of the light stabilizer.
In the thermoplastic resin composition, it is preferable to use a light stabilizer and an antioxidant in combination, and the combined use improves the retention stability during molding and efficiently prevents photodegradation due to ultraviolet rays and the like during use. be able to.

The thermoplastic resin composition of the present invention comprises the above-mentioned constituent components, and by being manufactured by the following manufacturing method, in addition to excellent heat resistance (reflow resistance), chemical resistance, flame retardancy, and mechanical properties. Excellent fluidity during extrusion and molding.
In the present invention, the chemical resistance is evaluated by the mass increase rate R after immersion in a sulfuric acid immersion test in which the thermoplastic resin composition is immersed in 50% sulfuric acid at 23 ° C. for 48 hours, and the mass increase rate R is 50% or less. It is preferably 40% or less, and more preferably 30% or less. When the mass increase rate R of the thermoplastic resin composition exceeds 50%, it may be difficult to use the obtained molded product for automobile parts or the like to which chemicals may adhere.

In the present invention, the method for mixing the raw materials is not particularly limited, but the melt-kneading method is preferable. Examples of the melt-kneading method include a method using a batch type kneader such as lavender, a Banbury mixer, a Henschel mixer, a helical rotor, a roll, a single-screw extruder, and a twin-screw extruder. The melt-kneading temperature is selected from the region where the semi-aromatic polyamide (A) is melted and does not decompose. If the kneading temperature is too high, not only the semi-aromatic polyamide (A) but also the aliphatic polyamide (B) and the non-halogen flame retardant (C) may be decomposed. The temperature is preferably (Tm-20 ° C.) to (Tm + 50 ° C.) with respect to the melting point (Tm) of the semi-aromatic polyamide (A).
In the melt-kneading, the semi-aromatic polyamide (A) is first melted, and then the aliphatic polyamide (B) is additionally supplied to the melt-kneader to obtain the semi-aromatic polyamide (A) and the aliphatic polyamide (B). ) Is preferably mixed. Specifically, for example, a semi-aromatic polyamide (A), a flame retardant, or the like is supplied from the root (main supply port) of the twin-screw extruder, melted, and then used in the extruder by using a side feeder or the like. A method of supplying the aliphatic polyamide (B) from the above is mentioned.

As a method for granulating the thermoplastic resin composition of the present invention, a method of extruding the melt into a strand shape into a pellet shape, a method of hot-cutting or underwater-cutting the melt into a pellet shape, or a method of forming a sheet shape. Examples thereof include a method of extruding and cutting, and a method of extruding into a block and crushing into a powder shape.

Examples of the molding method of the thermoplastic resin composition of the present invention include an injection molding method, an extrusion molding method, a blow molding method, and a sintering molding method. The injection molding method is preferable. The injection molding machine is not particularly limited, and examples thereof include a screw inline type injection molding machine and a plunger type injection molding machine. The thermoplastic resin composition heated and melted in the cylinder of the injection molding machine is weighed for each shot, injected into the mold in a molten state, cooled and solidified in a predetermined shape, and then molded as a mold. Taken from. The resin temperature at the time of injection molding is preferably (Tm) to (Tm + 50 ° C.). When the thermoplastic resin composition is heated and melted, it is preferable to use sufficiently dried thermoplastic resin composition pellets.

The thermoplastic resin composition of the present invention can be used in a wide range of applications such as automobile parts, electric / electronic parts, miscellaneous goods, industrial equipment parts, civil engineering and construction supplies, and has excellent flame retardancy. Suitable for.
Examples of automobile parts include thermostat members, IGBT module members for inverters, insulators, motor insulators, exhaust finishers, power device housings, ECU housings, motor members, coil members, cable coverings, in-vehicle camera housings, and the like. Automotive camera lens holder, automotive connector, engine mount, intercooler, bearing retainer, oil seal ring, chain cover, ball joint, chain tensioner, starter gear, reducer gear, automotive lithium ion battery tray, automotive high voltage fuse Cases and turbocharger impellers for automobiles can be mentioned.
Electrical and electronic components include, for example, connectors, ECU connectors, main ten lock connectors, modular jacks, reflectors, LED reflectors, switches, sensors, sockets, pin sockets, condensers, jacks, fuse holders, relays, coil bobbins, breakers, circuits. Parts, electromagnetic switches, holders, covers, plugs, housing parts for electrical and electronic equipment such as portable personal computers and word processors, impellers, vacuum cleaner impellers, resistors, variable resistors, ICs, LED housings, camera housings Body, camera barrel, camera lens holder, tact switch, tact switch for lighting, hair iron housing, hair iron comb, small switch for all mold DC, organic EL display switch, material for 3D printer, bond magnet for motor Materials are mentioned.
Examples of miscellaneous goods include trays, sheets, and cable ties.
Examples of industrial equipment parts include insulators, connectors, gears, switches, sensors, impellers, and Plarail chains.
Examples of civil engineering and construction supplies include fences, storage boxes, construction switchboards, anchor bolt guides, anchor rivets, and solar cell panel raising materials.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

1. 1. Measuring method The physical properties of the semi-aromatic polyamide and the thermoplastic resin composition were measured by the following methods.

(1) Relative Viscosity Measured at a concentration of 1 g / dL and 25 ° C. using 96% by mass sulfuric acid as a solvent.

(2) Melting point and crystal melting energy of semi-aromatic polyamide (A) Using a differential scanning calorimeter DSC-7 manufactured by PerkinElmer, the temperature was raised to 350 ° C at a heating rate of 20 ° C / min and then 350 ° C. The temperature was lowered to 25 ° C. at a temperature lowering rate of 20 ° C./min. Then, after holding at 25 ° C. for 5 minutes, the top of the endothermic peak when the temperature was raised again at a temperature rising rate of 20 ° C./min was defined as the melting point (Tm). Further, the value obtained by dividing the area of the endothermic peak by the mass of the sample was taken as the crystal melting energy (ΔH).

(3) Melt flow rate (MFR)
According to JIS K7210, the measurement was performed at 340 ° C. and a load of 1.2 kgf.

(4) Mechanical Properties The thermoplastic resin composition was injection molded using an injection molding machine S2000i-100B type (manufactured by FANUC) to prepare a test piece (dumbbell piece). The cylinder temperature was the melting point (Tm) + 15 ° C., and the mold temperature was 135 ° C.
Using the obtained test piece, bending strength and flexural modulus were measured according to ISO178.
Practically, the bending strength is preferably 110 MPa or more, more preferably 120 MPa or more, still more preferably 140 MPa or more. Further, in practice, the flexural modulus is preferably 3 GPa or more, and more preferably 5 GPa or more.

(5) Using an injection molding machine S2000i-100B type (manufactured by FANUC), the barflow fluid thermoplastic resin composition is subjected to cylinder temperature (Tm + 15 ° C.), mold temperature 135 ° C., injection pressure 150 MPa, injection time 8 The flow length of the test piece when molded at a set injection speed of 150 mm / sec was measured and used as the bar flow flow length. As the mold, a bar flow test mold having a thickness of 0.5 mmt, a width of 20 mm, and a total length of 980 mm was used. The bar flow flow length is an indicator of liquidity. Practically, the bar flow flow length is preferably 100 mm or more, more preferably 110 mm or more.

(6) Using a flame-retardant injection molding machine J35AD (manufactured by Japan Steel Works, Ltd.), a plate shape of 127 mm x 12.7 mm x thickness 0.3 mm under the conditions of cylinder temperature (Tm + 25 ° C) and mold temperature 135 ° C. A test piece was prepared.
The obtained test pieces were evaluated according to the UL94 (standard defined by Under Writer's Laboratories Inc., USA) standard shown in Table 1. If none of the criteria was met, it was set to not V-2. Practically, the flame retardancy is preferably V-1 and more preferably V-0.

(7) Chemical resistance (sulfuric acid immersion test)
Using an injection molding machine J35AD (manufactured by Japan Steel Works, Ltd.), a plate-shaped test piece having a cylinder temperature (Tm + 25 ° C.) and a mold temperature of 135 ° C. was produced to have a thickness of 20 mm × 20 mm × thickness 0.5 mm. The obtained test piece was immersed in 50% sulfuric acid in an environment of 23 ° C. for 48 hours, the mass before and after the immersion treatment was measured, and the mass increase rate R represented by the following formula was calculated.
R = (Wp-Wi) / ((1-Cf / 100) x Wi) x 100
Wp: Specimen mass (g) after immersion treatment
Wi: Test piece mass (g) before immersion treatment
Cf: Content (% by mass) of the inorganic reinforcing material (D) in the thermoplastic resin composition

(8) Heat resistance (reflow resistance)
The test piece prepared by the method described in (7) above was left in a constant temperature and humidity chamber (FTAC type FH14C manufactured by ETAC) at 85 ° C. and 85% RH for 168 hours, and reflow tester (FT-02 manufactured by CIF).
I put it in and confirmed the change in appearance. The temperature conditions of the reflow tester were controlled by preheating (150 ° C.-220 ° C., 115 seconds), reflow (220 ° C. or higher, 50 seconds), and maximum temperature during reflow (260 ° C., 10 seconds or less). Those with no change in appearance were evaluated as ◯, and those with blister on the appearance were evaluated as ×.

2. 2. Raw Materials The raw materials used in Examples and Comparative Examples are shown below.

(1) Semi-aromatic polyamide (A)
-Semi-aromatic polyamide (A-1)
Ribbon blender containing 4.70 kg of powdered terephthalic acid (TPA) as an aromatic dicarboxylic acid component, 0.33 kg of stearic acid (STA), and 9.3 g of sodium hypophosphite monohydrate as a polymerization catalyst. It was placed in the reaction apparatus of the formula and heated to 170 ° C. with stirring at a rotation speed of 30 rpm under a sealed nitrogen. Then, while keeping the temperature at 170 ° C. and the rotation speed at 30 rpm, 4.97 kg of 1,10-decanediamine (DDA) heated to 100 ° C. as a diamine component using a liquid injection device was added to 2. . Addition was made continuously (continuous liquid injection method) over 5 hours to obtain a reaction product. The molar ratio of the raw material monomer was TPA: DDA: STA = 48.5: 49.6: 1.9 (the equivalent ratio of the functional groups was TPA: DDA: STA = 49: 50: 1).
Subsequently, the obtained reaction product was polymerized by heating in the same reaction apparatus at 250 ° C. and a rotation speed of 30 rpm for 8 hours in the same reaction apparatus to prepare a powder of semi-aromatic polyamide.
Then, the obtained semi-aromatic polyamide powder was made into strands using a twin-screw kneader, the strands were passed through a water tank to be cooled and solidified, and the strands were cut with a pelletizer to form a semi-aromatic polyamide (A-1). Pellets were obtained.

-Semi-aromatic polyamides (A-2) to (A-9)
A semi-aromatic polyamide was obtained by performing the same operation as in the case of producing the semi-aromatic polyamide (A-1) except that the resin composition was changed as shown in Table 2.

Table 2 shows the resin composition and characteristic values of the obtained semi-aromatic polyamide.

(2) Aliphatic polyamide B-1: Polyamide 66, Leona 1200 manufactured by Asahi Kasei Chemicals, relative viscosity 2.45
B-2: Polyamide 6, Unitika A1015, Relative viscosity 2.02
B-3: Polyamide 46, DSM TW300, relative viscosity 2.75

(3) Non-halogen flame retardant ・ C-1: Aluminum diethylphosphinate, Exolit OP1230 manufactured by Clariant AG
-C-2: Hexaphenoxycyclotriphosphazene, Ravitor FP-100 manufactured by Fushimi Pharmaceutical Co., Ltd.

(4) Inorganic reinforcing material ・ D-1: Glass fiber, CS3G225S manufactured by Nitto Boseki, average fiber diameter 9.5 μm, average fiber length 3 mm

(5) Antioxidant E-1: Tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene-di-phosphonite, Clariant Hostanox P-EPQ

Reference example 1
90 parts by mass of semi-aromatic polyamide (A-1), 30 parts by mass of non-halogen flame retardant (C-1) and 0.5 parts by mass of antioxidant (E-1) are dry-blended, and loss-in-weight type continuous. Weigh using a fixed quantity supply device CE-W-1 type (manufactured by Kubota) and supply it to the main supply port of the TEM26SS type (manufactured by Toshiba Machinery Co., Ltd.) isodirectional twin-screw extruder with a screw diameter of 26 mm and L / D50. , Molten kneading was performed. On the way, 10 parts by mass of the aliphatic polyamide (B-1) was supplied from the side feeder 1, and 70 parts by mass of the inorganic reinforcing material (D-1) was further supplied from the side feeder 2 on the downstream side, and further kneading was performed. After being taken into a strand shape from the die, it was cooled and solidified by passing it through a water tank, and it was cut with a pelletizer to obtain a thermoplastic resin composition pellet. The barrel temperature of the extruder was set to 310 to 340 ° C., a screw rotation speed of 250 rpm, and a discharge rate of 25 kg / hour.

Examples 3 to 7, 10 to 30, Comparative Examples 1, 4 to 6 , Reference Examples 2 to 4
The same operation as in Reference Example 1 was performed except that the composition of the resin composition was changed as shown in Table 3. In Comparative Example 1, the aliphatic polyamide (B) was not supplied from the side feeder 1.

Comparative Examples 2 and 3
Aliphatic polyamide (B-1) is not supplied from the side feeder 1, but is fat together with semi-aromatic polyamide (A-1), non-halogen flame retardant (C-1), and antioxidant (E-1). Example 3 except that the group polyamide (B-1) was dry-blended and supplied to the main supply port of the twin-screw extruder in the same direction, and the inorganic reinforcing material (D-1) was supplied from the side feeder 2 on the downstream side. Melt kneading was carried out in the same manner as in No. 7 to obtain thermoplastic resin composition pellets.

The composition of the thermoplastic resin composition and the obtained properties are shown in Table 3.

The thermoplastic resin compositions of Examples 3 to 7 , 10 to 30 had a component content within the range specified in the present invention, and the aliphatic polyamide (B) was supplied by a side feeder and melt-kneaded. Therefore, it was excellent in heat resistance, chemical resistance, flame retardancy, mechanical properties, and excellent fluidity.

Since the resin composition of Comparative Example 1 did not contain the aliphatic polyamide (B), it had low fluidity.
Since the resin compositions of Comparative Examples 2 and 3 contained the aliphatic polyamide (B), the fluidity was improved, but the aliphatic polyamide (B) was not side-fed, and the semi-aromatic polyamide (semi-aromatic polyamide) was used from the main supply port. Since it was produced by supplying it at the same time as A) and the like and melting and kneading it, the chemical resistance was low, blister was generated even during reflow, and the heat resistance was also low.
The resin composition of Comparative Example 4 had a low content of aliphatic polyamide (B), and therefore had low chemical resistance and heat resistance.
The resin composition of Comparative Example 5 had low chemical resistance and heat resistance because the content of the non-halogen flame retardant (C) was small.
In Comparative Example 6, since the content of the non-halogen flame retardant (C) was high, the extrusion operability was low and the strands were difficult to pick up, so that pellets of the resin composition could not be obtained.

Claims (7)

A thermoplastic resin composition containing a total of 100 parts by mass of a semi-aromatic polyamide (A) and an aliphatic polyamide (B) and 10 to 100 parts by mass of a non-halogen flame retardant (C).
The mass ratio (A / B) of the semi-aromatic polyamide (A) and the aliphatic polyamide (B) is 70/30 to 45/55.
The melting point of the semi-aromatic polyamide (A) is 280 ° C. or higher, and the temperature is 280 ° C. or higher.
A thermoplastic resin composition having a mass increase rate R of 50% or less after being immersed in 50% sulfuric acid at 23 ° C. for 48 hours. The thermoplastic resin composition according to claim 1, wherein the aliphatic diamine component in the semi-aromatic polyamide (A) is 1,10-decanediamine. The thermoplastic resin composition according to claim 1 or 2, wherein the aliphatic polyamide (B) is a polyamide 6 and / or a polyamide 66. The semi-aromatic polyamide (A) contains an aliphatic monocarboxylic acid component, the aliphatic monocarboxylic acid has 15 to 30 carbon atoms, and the content of the aliphatic monocarboxylic acid component is a semi-aromatic polyamide (a semi-aromatic polyamide (A). The thermoplastic resin composition according to any one of claims 1 to 3, wherein the content is 0.3 to 4.0 mol% with respect to all the monomers constituting A). The thermoplastic resin composition according to any one of claims 1 to 4, wherein the non-halogen flame retardant (C) is a compound represented by the following general formula (I) or (II).

(In the formula, R ¹ , R ² , R ⁴ and R ⁵ independently represent an alkyl group or a phenyl group having 1 to 16 carbon atoms in a straight chain or a branched chain. R ³ is a linear or branched chain. It represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an arylalkylene group, or an alkylarylene group. M represents a calcium ion, an aluminum ion, a magnesium ion or a zinc ion. M Is 2 or 3. n, a, b are integers satisfying the relational expression of 2 × b = n × a.) The thermoplastic resin composition according to any one of claims 1 to 5, further comprising an inorganic reinforcing material (D). A molded product obtained by molding the thermoplastic resin composition according to any one of claims 1 to 6.