JPH0931310A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition having very excellent heat resistance and high-temperature bending modulus and a reduced dimensional change due to absorbed water or moisture by mixing a polyamide resin with a specified thermotropic liquid crystal polyester resin. SOLUTION: This resin composition comprises 5-95wt.% polyamide (desirably polyhexamethylene adipamide being an aliphatic polyamide) of a relative viscosity of 2.0-6.0 and 95-5wt.% (the total is 100wt.%) thermotropic liquid crystal polyester resin obtained by polycondensing p-hydroxybenzoic acid of formula I and 2-hydroxy-6-naphthoic acid as the essential components with optionally a diol of the formula: O-X-O (wherein X is a phenyl, a 1-6C methylene chain or the like) and a dicarboxylic acid of the formula: C-O-X-CO (wherein X is a phenyl or a 1-6C methylene chain) by heating in a nitrogen atmosphere. It is also possible to make the composition flame-retardant by adding at most 40wt.% a bromostyrene and/or a polybromostyrene resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition which is excellent in heat resistance and flexural modulus at high temperature and has little dimensional change due to water absorption and moisture absorption.

Polyamide is an acid amide (--CONH).
It is a known resin as a general term for polymers having-) in the repeating unit and is known to have excellent properties as an engineering plastic. The polymerization method is ring-opening polymerization of lactam, aminocarboxylic acid. Polycondensation of acid,
It can be classified into three types of polycondensation of diamine and dibasic acid. Generally, polyamide is tough, has excellent mechanical properties such as strength, impact resistance, and abrasion resistance, has high heat resistance, chemical resistance, and oil resistance, and has good molding processability. It is used in various applications such as automobile parts, electric and electronic parts, and mechanical parts. Polyester typified by polyethylene terephthalate and polybutylene terephthalate has excellent mechanical properties and electrical properties and is a resin widely used as fibers, films and the like. However, since polyamide has water-absorbing and moisture-absorbing properties, it has the drawback of causing dimensional change and lowering of strength of the molded product. Therefore, in order to improve the water absorption and hygroscopicity, blending with other resins has been proposed (for example, Japanese Patent Laid-Open No. Sho 5).
7-49657, JP-A-60-63256, JP-A-61-213256, and JP-A-61-2.
13257, JP-A-63-202654,
JP-A-64-31866, JP-A-64-6516
No. 8, JP-A-4-183749), but the effect is not sufficient. Polyamide and polyester are basically different types of polymers, and coarse mechanical phase separation occurs by simply mechanically mixing the two, and a material of high practical value cannot be obtained. Even if a compatibilizer is added to polyamide and polyester, there is a limit to the compatibilizing effect,
In particular, in the case of polyamide and polyester, which have greatly different melting points, it is difficult to control the miscibility of the two, and a resin composition having sufficient properties has not yet been obtained. In the field of electric and electronic parts, which is one of the applications of polyamide, various resin-based electronic parts materials are printed by the surface mounting method (SMT method) with the miniaturization and productivity improvement of electric and electronic parts in recent years. The number of cases of soldering on top is increasing, but at the same time as heat resistance, it is a connector that is an electric / electronic component.
With the progress of fine pitches, etc., it has been required that the dimensional change due to moisture absorption is small. As a method for reducing the dimensional change before and after moisture absorption, a method of blending a polyamide resin with an aromatic polyester resin (JP-A-3-190)
962, JP-A-3-263461), a method of blending a modified polyphenylene ether with a polyamide resin (JP-A-3-131655, JP-A-4-202).
361, JP-A-4-209653), a method of blending an amorphous copolyamide with a polyamide resin (JP-A-2-255764, JP-A-4-2023).
No. 58) has been proposed, but in either case, the dimensional change due to moisture absorption is reduced to some extent, but it is insufficient.
There was also a problem with thermal stability during extrusion and injection molding. Polyamides are generally non-flammable materials by virtue of their chemical structure due to the nitrogen of the amide group and are in the self-extinguishing category when tested according to ASTM D635.
However, recently, for the purpose of improving the safety of products used in general households, such as household appliances, electric devices, building materials, and automobile parts, there is a strong demand for flame retardancy, and strict regulations on flame retardancy. It has become to. For this reason, in each country, regulatory measures are taken according to national circumstances, and test methods are being established. Underwriters Laboratories (Underwriters Laboratories)
y, hereinafter abbreviated as UL) In the standard, a detailed test method is determined along with heat resistance, which contributes to the improvement of safety of electrical equipment and the like. With respect to the flame retardancy of synthetic resin compositions used in electric devices and the like, it is often required to pass the V-0 standard in a combustion test according to the UL-94 test method. Examples of the method of flame retarding a resin include flame retardation by modifying the resin itself, mixing of a nonflammable substance, coating with a nonflammable substance and a flame retardant substance, addition of a flame retardant, etc. As a method of burning, a method of adding a flame retardant, specifically, a method of blending an organic halogen compound is known, as in many other synthetic resins. Generally, the combustion process of resin is temperature rise by heating, melting, deterioration / decomposition, vaporization / diffusion, ignition, and continuation of combustion, but the elucidation of the combustion phenomenon and the elucidation of the flame retardant mechanism depend on the individual polymer material. It is not always sufficient because the way of expression is different. In addition, in the case of polyamide, due to its high processing temperature, conventional organohalogen compounds have the disadvantages of maintaining polyamide performance, heat resistance, impact resistance, and heat stability. Was insufficient, and improvement was required.

[0002]

SUMMARY OF THE INVENTION The present invention has been made against the background of the above-mentioned problems in the prior art. By blending a specific polyester with polyamide, the heat resistance and bending at high temperature, which are extremely superior to those of the prior art, are achieved. An object of the present invention is to provide a thermoplastic resin composition having an elastic modulus and having little dimensional change due to water absorption / moisture absorption.

[0003]

The present inventors have found that by blending a polyamide with a specific liquid crystal polyester,
The present inventors have found that a thermoplastic resin composition having excellent heat resistance and bending elastic modulus at high temperature as compared with conventional ones and having little dimensional change due to water absorption / moisture absorption can be obtained, and the present invention has been completed. That is, the present invention includes (1), (a) polyamide resin 5 to 95% by weight, and (b) (a) and (b) as essential components, and if necessary, (c) and (d) A thermoplastic resin composition comprising 5 to 95% by weight of a thermotropic liquid crystal polyester resin obtained by polycondensation.

[Chemical 1]

Embedded image

Embedded image

(2), (a) Polyamide resin 3 to 95% by weight, (b) Thermotropic liquid crystal polyester resin 3 to 95% by weight (c) Number average molecular weight (Mn) is 1 × 10. ^{4 to} 9 × 10 ⁴ , weight average molecular weight (Mw) / Mn
A thermoplastic resin composition comprising 2 to 40% by weight of a brominated polystyrene and / or a polybrominated styrene resin having a ratio of 5 or less. And (3),
(A) Polyamide resin 3 to 95% by weight, (b) Thermotropic liquid crystal polyester resin 3 to 95 according to claim 1.
Weight% (c) Number average molecular weight (Mn) is 1 × 10 ^{4 to} 9 ×
10 ⁴ , a brominated polystyrene and / or a polybrominated styrene resin having a weight average molecular weight (Mw) / Mn of 5 or less, 2 to 40% by weight, and (d) an inorganic filler.
A thermoplastic resin composition comprising 1 to 200 parts by weight per 100 parts by weight of the total amount of (a) + (b) + (c). Is provided.

The polyamide as the component (a) used in the present invention includes all resins having an amide bond in the unit structure, and includes, for example, lactams such as ε-caprolactam, ω-lauryllactam and ω-dodecaractam. Polyamide obtained by ring-opening polymerization, 6-aminocaproic acid, 1
1-aminoundecanoic acid, 12-aminoundecanoic acid, 1
Polyamides derived from amino acids such as 2-aminododecanoic acid and para-aminomethylbenzoic acid, ethylenediamide, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4 -Trimethylhexamethylenediamine, 5-methylnonamethylenediamine, meta-xylylenediamine, para-xylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3 -Aminomethyl-
3,5,5-Trimethylcyclohexane, bis (3-methyl
-4-aminocyclohexyl) methane, bis (4,4'-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, metaxylylenediamine,
Paraxylylenediamine 2,2-bis (aminoprosyl)
Aliphatic, alicyclic and aromatic diamines such as piperazine and aminoethylpiperazine and adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,3- and 1,4-
Cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, dimer acid, diglycol There may be mentioned polyamides derived from aliphatic, alicyclic and aromatic dicarboxylic acids such as acid and copolyamides thereof. Of these, polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 6,6), polytetramethylene adipamide (polyamide 4,6), polyundecane amide (polyamide 11),
Polydodecanamide (polyamide 12), semi-aromatic polyamide, aromatic polyamide, and copolyamide having these as the main components are useful, and in particular, polycaproamide, polyhexamethylene adipamide from the viewpoint of physical property balance. , And aliphatic polyamides typified by polytetramethylene adipamide are preferred. As a method for polymerizing the polyamide, known melt polymerization, solid phase polymerization and a method combining these can be adopted. The polymerization degree of the polyamide is not particularly limited, and 1 g of the polymer is added to 96% concentrated sulfuric acid 100%.
A polyamide having a relative viscosity in the range of 2.0 to 6.0 dissolved in 1 ml (1 g / dl) at 25 ° C. using a viscosity tube can be arbitrarily selected according to the purpose. Two or more polyamides can be mixed and used together. The blending amount of the component (a) polyamide in the present invention is 5
˜95% by weight, preferably 10 to 90% by weight, more preferably 20 to 85% by weight. If the content of the component (a) is less than 5% by weight, the flexural modulus at high temperature is poor, and if the content of the component (a) exceeds 95% by weight, the content of the component (b) is too small. Therefore, sufficient heat resistance and dimensional stability cannot be obtained.

The thermotropic liquid crystal polyester of the component (b) of the present invention contains para-hydroxybenzoic acid represented by the chemical structural formula (a) and 2-hydroxy-6-naphthoic acid represented by the chemical structural formula (b) as essential components. Depending on the chemical structural formula (C)
Diole or dicarboxylic acid of chemical structural formula (d) is used,
It is a copolymer obtained by heating, melting and polycondensing in a nitrogen atmosphere. Geo of chemical structural formula (C)
When a dicarboxylic acid of chemical structural formula (d) is used in combination, structural units derived from diol and dicarboxylic acid are randomly present in the above polymer. Even if it is added as one of the components, the basic performance does not change, so there is no problem.

[0006]

Embedded image Here, X in the chemical structural formulas (C), (D), and (E),
X ′ can be arbitrarily selected from those shown in Chemical formulas 6 and 7, and X and X ′ may be the same or different.

[0007]

[Chemical 6]

[0008]

[Chemical 7]

Since the thermotropic liquid crystal polyester of the component (b) of the present invention is a liquid crystal, it is not only dispersed as domains in the molded article of the thermoplastic resin composition of the present invention, but also has an orientation property. It can form fibrils that have a build up. Therefore, unlike the polyester added to reduce the water absorption / hygroscopicity of the conventional polyamide resin composition, the fibrils having orientation as well as reducing the water absorption / hygroscopicity have the strength of the resin composition, It also plays a role as an organic filler for improving the elastic modulus. Moreover, the thermotropic liquid crystal polyester specified as the component (b) in the present invention is excellent in thermal stability and its optimum processing temperature is very close to that of polyamide, so that it has been difficult to mix in extrusion and injection molding, which has been difficult in the past. A thermoplastic resin composition that is easy to control, has the characteristics of both polyamide and polyester, and has sufficient characteristics can be obtained. The amount of the thermotropic liquid crystal polyester (b) used in the present invention is 5 to 95% by weight, preferably 10 to 90% by weight, more preferably 15 to 80% by weight. If the blending amount of the component (b) is less than 5% by weight, sufficient heat resistance and dimensional stability cannot be obtained, and if the blending amount of the component (b) exceeds 95% by weight, the flexural modulus at high temperature becomes poor.

The component (c) used in claim 2 of the present invention is brominated polystyrene or polybrominated styrene. The brominated styrene is obtained by brominated polystyrene later, and the number of bromine bonded to the benzene ring of polystyrene instead of hydrogen is 1 to 5, preferably 2 to 3.
Polybrominated styrene is a brominated styrene monomer such as monobrominated styrene, dibrominated styrene and tribrominated styrene.
Is a polybrominated styrene obtained by polymerizing one kind or two or more kinds, preferably having a dibrominated styrene unit of 50% by weight or more, more preferably 55% by weight or more. The polybrominated styrene of the present invention may, of course, be a polymer mainly of dibrominated styrene monomer, but a copolymer of dibrominated styrene monomer and tribrominated styrene monomer also has a bromine content. It is preferable in that it goes up. The bromine content in the brominated polystyrene and polybrominated styrene of the present invention is preferably 40 to 75% by weight, more preferably 50 to 75% by weight. Further, when copolymerizing the styrene monomer and the brominated styrene monomer, other copolymerizable monomers may be used, if necessary. Examples of the copolymerizable monomer include olefin and vinyl, and may include a functional group. As olefin and vinyl, ethylene, propylene,
Butadiene, butene, hexene, pentene, methylebutene,
Methylpentene, styrene, acrylonitrile, vinyl chloride, vinyl acetate and the like can be mentioned, with ethylene, propylene, butadiene, styrene and acrylonitrile being preferred. Examples of the functional group that the copolymerizable monomer may contain include one or more functional groups selected from a carboxyl group, an acid anhydride group, an oxazoline group, and an epoxy group. Specific examples thereof include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic anhydride, vinyl oxazoline, glycidyl methacrylate and allyl glycidyl ether. Alternatively, the above-mentioned functional group may be copolymerized with styrene or brominated styrene, or the terminal of brominated polystyrene or polybrominated styrene may be modified.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) are determined by using a gel permeation chromatography (GPC) and using tetrahydrofuran (T).
HF) as a solvent, the flame retardant is dissolved in a concentration of 1 mg / ml, and the number average molecular weight (Mn) and weight average in terms of polystyrene are obtained by measuring at a flow rate of 1.0 ml / min and a temperature of 36 to 40 ° C. The molecular weight (Mw) can be obtained. The number average molecular weight (Mn) of the brominated polystyrene and polybrominated styrene of the present invention is 1 × 10 ^{4 to} 9 × 1.
0 ⁴ , preferably 1 × 10 ⁴ to 8 × 10 ⁴ , more preferably 1 × 10 ^{4 to} 7 × 10 ⁴ , and particularly preferably 1 × 10.
^{It is 4 to} 6 × 10 ⁴ . On the other hand, weight average molecular weight (Mw)
/ Mn is 5 or less, preferably 4 or less. When using a brominated polystyrene or polybrominated styrene whose number average molecular weight (Mn) and Mw / Mn are outside the scope of the present invention,
The performance of at least one of thermal stability, flame retardancy, impact resistance and dimensional stability cannot reach the object of the present invention. Among the brominated polystyrene and the polybrominated styrene of the present invention, polybrominated styrene is more preferable from the viewpoint of thermal stability at high temperature and weld strength. As the composition in which the component (c) of the present invention, which is the brominated polystyrene, the polybrominated styrene, or a mixture of the two is blended, the blending amount of each component is such that the component (a) is 3 to 95% by weight,
Preferably 5 to 90% by weight, more preferably 10 to 8
0% by weight, the component (b) is 3 to 95% by weight, preferably 5 to 90% by weight, more preferably 10 to 80% by weight, and the component (c) is 2 to 40% by weight, preferably 5%. ˜35% by weight, more preferably 7 to 30% by weight. When the content of the component (c) is 2% by weight or more, flame retardancy and dimensional stability are obtained, but when it exceeds 40% by weight, the excellent heat resistance of the thermoplastic resin composition of the present invention is impaired.

In claim 3, the above (a),
An inorganic filler is further blended as the component (d) in the components (b) and (c). By using the component (d), a thermoplastic resin composition having further improved rigidity and dimensional stability can be obtained. The component (d) is various inorganic fillers having fibrous, powdery, granular, plate-like, needle-like, cloth-like, and mat-like shapes, and typical examples are glass fiber, asbestos fiber, carbon fiber. , Graphite fiber, calcium carbonate, talc, catalbot, wollastonite, silica, alumina, silica-alumina, diatomaceous earth, clay, calcined clay, kaolin, mica (fine mica), granular glass, glass flakes, glass balloons ( Hollow glass), gypsum, red iron oxide, metal fiber, titanium dioxide,
Potassium titanate whiskers, magnesium oxide, calcium silicate, asbestos, sodium aluminate, calcium aluminate, aluminum, aluminum oxide, aluminum hydroxide, copper, stainless steel, zinc oxide,
Examples thereof include metal whiskers. For the purpose of the present invention, glass fiber, carbon fiber, kaolin, mica, talc are preferred, and especially glass fiber from its economical efficiency,
Kaolin, mica and talc are preferred. It may be subjected to a surface treatment as long as it does not impair the moldability and physical properties of the present invention, and among them, those subjected to a surface treatment represented by aminosilane, acrylsilane, acrylurethane, urethane and vinyl. Is preferred. The addition amount of the inorganic filler in the present invention is the component (a) of the present invention,
1 to 100 parts by weight of the total amount of the components (b) and (c)
To 200 parts by weight, preferably 2 to 160 parts by weight,
More preferably, it is 3 to 120 parts by weight. When the addition amount of the inorganic filler is 1 part by weight or more, the purpose of adding the component (d) can be obtained. On the other hand, when it exceeds 200 parts by weight, workability, particularly extrusion moldability and injection moldability deteriorates.

If necessary, a flame-retardant aid may be added to the thermoplastic resin composition of the present invention in order to further enhance the flame retardancy. Examples of the flame retardant aid include antimony trioxide, antimony pentoxide, antimony compounds such as triphenylantimony, and phosphoric acid ester.
Of these, preferred is antimony trioxide,
Antimony pentoxide may be mentioned. The amount of flame retardant aid added is
The total amount of the components (a), (b) and (c) is 100 parts by weight, preferably 1 to 20 parts by weight, more preferably 1 to 20 parts by weight.
10 parts by weight. The purpose of addition can be achieved with 1 part by weight or more, but if it exceeds 20 parts by weight, the mechanical strength decreases.

The thermoplastic resin composition of the present invention may contain other components such as pigments, dyes, colorants and organic reinforcing materials, depending on the performance required for its application, as long as the moldability and characteristics are not impaired. , Heat-resistant agents, stabilizers typified by copper compounds and hindered phenol compounds, anti-dripping agents during combustion typified by modified polyolefins, modified styrenic resins and epoxy resins, antioxidants, light A protective agent, a weather resistance agent, a light stabilizer, a crystal nucleating agent, a lubricant, a release agent, a plasticizer, an antistatic agent, and other polymers may be freely added and introduced. Here, as the other polymer, for example,
Polyptadiene (PB), polyethylene (PE), ethylene-propylene copolymer (EP and EPDM), butadiene-styrene copolymer, styrene-ethylene-butene-styrene copolymer (SEBS), allyl rubber (A
R), fluororubber (FR), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-
Ethylene propylene-styrene copolymer (AES), acrylonitrile-styrene copolymer (AS), polystyrene (PS), polyethylene terephthalate (PE
T), polybutylene terephthalate (PBT), polyester mixture, polycarbonate (PC), polysulfone, polyethersulfone (PES), polyimide (P)
I), polyphenylene sulfide (PPS), poly-
Teru-terketone (PEEK), vinylidene fluoride polymer (PVDF, etc.), polyoxymethylene (PO
M), polytetrafluoroethylene (PTFE), polyphenylene ether (PPE), crosslinked particles and the like, and modified products thereof, which impair the moldability and properties of the thermoplastic resin composition of the present invention. As a non-added amount, less than 30 parts by weight can be appropriately mixed with 100 parts by weight of the thermoplastic resin composition of the present invention.

For the polyamide resin composition of the present invention, the above-mentioned resin composition is used for a conventional thermoplastic resin such as known molding methods such as injection molding, extrusion molding, blow molding, vacuum molding and compression molding. It is possible to mold various molded products by subjecting the molded product to the molding. The use of the polyamide resin composition of the present invention is not particularly limited, and examples thereof include various electric / electronic parts, heat resistant containers, and various casters.
It can also be suitably used as a filter or the like. Here, what is referred to as an electronic component includes various connectors,
Main bodies of switches, relays, coil bobbins, volumes, sockets, plug boards, terminal blocks, sensors, resistors, transformers, ICs (integrated circuits), etc., or mainly housings (cases, bodies, covers). -), Frame, electrical insulator, slide (slider), base, wafer,
Typical examples include rencam, spool, card, and yoke. Among them, what is referred to as a connector may be an electric wire-to-electric wire (relay) connector-, an electric wire-to-board connector-, a board-to-board connector, etc., and may be an FFC (Flexible Flat Cable) / FPC (Flexib).
le Printed Circuit) connector, SIMM socket, ROM socket, interface connector, card edge connector, disk drive power
The connector includes a connector, a board-in connector, a jumper, a wire connector, and the like. Here, what is referred to as a heat-resistant container includes a home, various dining rooms, a coffee shop, a car, a shared vehicle (bus, taxi).
Etc.), trains, airplanes, ships (passenger ships including small ships, etc.), various trays, food heating trays,
Examples thereof include containers for heating and transporting hand towels, towels, sheets, clothes, etc., baskets, cups, cups, tableware such as bowls, and heat-resistant containers typified by ashtrays. Here, as what is referred to as a filter, in addition to an oil filter and a strainer provided in a vehicle engine oil lubrication system, and an engine oil lubrication system, for example, in the middle of a brake oil circulation pipe, or Transmission, inlet / outlet of fuel tank, clutch master-cylinder-
It can also be used inside. Further, it is not limited to a filter for oil, but can be suitably used as a filter for air or the like. Further, it can be suitably used as various filters for household appliances, various filters for industrial electric appliances, and various filters for industrial members (for example, hydraulic control system of construction machinery, lubrication system, etc.).

[0016]

EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The following materials were used in the examples and comparative examples. Component (a): Polyamide a-1: Polyamide 6, "MC110" manufactured by Kanebo Co., Ltd. Relative viscosity 2.8 at 96% sulfuric acid 1 g / dl. a-2: Polyamide 6,6, Asahi Kasei “Leona 1402
S ", 96% sulfuric acid 1 g / dl relative viscosity 2.8. a-3: Polyamide 4,6, manufactured by DSM, Netherlands, 9
Relative viscosity 2.8 at 1 g / dl of 6% sulfuric acid. a-4: Aromatic polyamide: Allene “AE4200” manufactured by Mitsui Petrochemical. a-5: Polyamide 12, manufactured by Daicel Chemical Industries, Ltd. “X185
2 ”. a-6: Amorphous copolyamide resin, "TR55" manufactured by EMS Japan.

Component (b): Polyester Under a nitrogen atmosphere, parahydroxybenzoic acid, 2-
A thermotropic liquid crystalline polyester having the following theoretical structural formulas b-1 to b-7 was obtained by heating and melting hydroxy-6-naphthoic acid, and diol and dicarboxylic acid components, and subjecting them to polycondensation. b-1:

[0018]

Embedded image b-2:

[0019]

Embedded image b-3:

[0020]

Embedded image b-4:

[0021]

Embedded image b-5:

[0022]

[Chemical 12] b-6:

[0023]

Embedded image b-7:

[0024]

Embedded image

Further, b-8 and 9 were used in the comparative examples. b-8: Liquid crystal resin (LCP), Polyplastics “A
950 ", melting point 280 [deg.] C. b-9: Polybutylene terephthalate (PBT), Kanebo "720".

Component (c): polybrominated styrene, brominated polystyrene, c-1: polybrominated styrene, bromine content 61% by weight,
Number average molecular weight Mn = 21,000, Mw / Mn = 1.8
6, a polymer of dibromostyrene. c-2: polybrominated styrene, bromine content 68% by weight,
Number average molecular weight Mn = 30,000, Mw / Mn = 2.1
3, a copolymer of dibromostyrene: tribromostyrene = 2: 8. c-3: Modified polybrominated styrene, bromine content 60% by weight, number average molecular weight Mn = 52,000, Mw / Mn = 1.
92, a copolymer of maleic anhydride (2 wt%) and dibromostyrene. c-4: Post-brominated polystyrene, bromine content 67% by weight, number average molecular weight Mn = 84,000, Mw / Mn = 2.
39. c-5: Post-brominated polystyrene, bromine content 58% by weight, number average molecular weight Mn = 32,000, Mw / Mn = 6.
12. c-6: Post-brominated polystyrene, bromine content 59% by weight, number average molecular weight Mn = 120,000, Mw / Mn =
3.30.

Component (d): Inorganic filler d-1: Glass fiber. Asahi Fiber-Made of glass, diameter about 1
Chopped strands with an average length of 3 mm made from 0 μm continuous filament strands. d-2: Kaolinite. Made by Engelhard, average diameter 1
~ 2 microns. d-3: Wallastonite. Made by NYCO, average diameter about 3 microns. d-4: Potassium titanate whisker. Otsuka Chemical, average fiber length 10-20 microns, fiber diameter 0.2-0.5 microns.

The resin compositions of Examples and Comparative Examples were melt-kneaded into pellets using a twin-screw extruder (Ikegai Tekko PCM45) in which the barrel temperature was set to a temperature 20 to 30 ° C. higher than the highest melting point of the resin to be blended. did. The obtained pellets were subjected to a performance test by producing a predetermined test piece using an injection molding machine (cylinder temperature is the same as the barrel temperature of the twin-screw extruder described above). The performance of the samples described in Examples and Comparative Examples was measured by the following method. Deflection temperature under load: According to ASTM D648. (Load 18.6 kg / cm ² ) Evaluation item regarding heat resistance. Flexural modulus at high temperature: Measured at a temperature of 120 ° C. according to ASTM D790. Water absorption dimensional change rate: Length 1 according to ASTM D570
Using an injection-molded test piece of 27 mm, width 12.7 mm, and thickness 3.2 mm, measure the size of the test piece immediately after molding (leave in a dry state for half a day) and the size of the test piece after soaking in water (room temperature) for 24 hours. Then, the dimensional change rate (increase rate) in the length direction was calculated. As examples and comparative examples, the compositions and the evaluation results of the above items are shown in Tables 1 and 2 below.

Examples 1 to 17 Evaluations were carried out by the above-mentioned methods, and the results shown in Table 1 were obtained. From these results, the flame-retardant resin composition of the present invention,
It can be seen that the heat resistance and the flexural modulus at high temperature are excellent, and the dimensional change due to water absorption is small.

[0030]

[Table 1]

Comparative Examples 1 to 9 Evaluations similar to those of the examples were carried out, and the results shown in Table 2 were obtained.

[0032]

[Table 2]

Comparative Example 1 is a case where the compounding amount of the component (a) is less than the claimed range, that is, the compounding amount of the component (b) exceeds the claimed range, and bending at high temperature (120 ° C.) Poor elastic modulus. On the contrary, Comparative Example 2 is a case where the compounding amount of the component (a) exceeds the claimed range, that is, the compounded amount of the component (b) is less than the claimed range, and heat resistance (deflection temperature under load). And the dimensional stability (water absorption dimensional change rate) is poor. Comparative Examples 3 and 4 are cases in which another resin was used in place of the resin specified as the component (b) of the present invention, and the bending elastic modulus at high temperature and the heat resistance were poor, respectively. Comparative Example 5
When the compounding amount of the component (c) exceeds the scope of claims, the heat resistance is poor. In Comparative Example 6, the heat resistance is inferior as the component (c) is out of the range of Mn / Mw specified in the present invention, and in Comparative Example 7, Mn specified in the present invention as the component (c).
And the bending elastic modulus at high temperature is inferior.
Comparative Examples 8 and 9 were cases in which the compounding amount of the component (c) of claim 2 exceeded the scope of claims, and the workability in a twin-screw extruder was poor, and pelletization could not be performed, so that evaluation was not possible.

[0034]

By blending a specific liquid crystal polyester with polyamide, the present inventors have extremely excellent heat resistance and bending elastic modulus at high temperature as compared with conventional ones, and have little dimensional change due to water absorption and moisture absorption. It was found that a thermoplastic resin composition can be obtained. In particular, (b) of the present invention
Since the component thermotropic liquid crystal polyester is a liquid crystal, it can not only be dispersed as domains but also form fibrils having orientation in the molded article of the thermoplastic resin composition of the present invention. Therefore, unlike the polyester added to reduce the water absorption / hygroscopicity of the conventional polyamide resin composition, the fibrils having orientation as well as reducing the water absorption / hygroscopicity have the strength of the resin composition, It also plays a role as an organic filler for improving the elastic modulus. Moreover, the thermotropic liquid crystal polyester specified as the component (b) in the present invention is excellent in thermal stability and its optimum processing temperature is very close to that of polyamide, so that it has been difficult to mix in extrusion and injection molding, which has been difficult in the past. A thermoplastic resin composition that is easy to control, has the characteristics of both polyamide and polyester, and has sufficient characteristics, and has an extremely high industrial value.

[Procedure amendment]

[Submission date] February 1, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction contents]

Component (b): Polyester Under a nitrogen atmosphere, parahydroxybenzoic acid, 2-
A thermotropic liquid crystal polyester having the following theoretical structural formulas b-1 to b-7 was obtained by heating, melting and polycondensing hydroxy-6-naphthoic acid, a diol and a dicarboxylic acid component. The composition ratio of each component represents a molar ratio. b-1:

Claims (3)

[Claims] 1. (a) Polyamide resin 5 to 95% by weight,
And a thermotropic liquid crystal polyester resin obtained by polycondensing (b), (a), and (b) as essential components, and optionally (c) and (d).
A thermoplastic resin composition comprising 5% by weight. Embedded image Embedded image Embedded image Embedded image 2. (a) Polyamide resin 3 to 95% by weight,
(B) Thermotropic liquid crystal polyester resin according to claim 1, 3 to 95% by weight (c) Number average molecular weight (Mn) is 1 ×
10 ^{4 to} 9 × 10 ⁴ , weight average molecular weight (Mw) / Mn of 5
A thermoplastic resin composition comprising 2 to 40% by weight of the following brominated polystyrene and / or polybrominated styrene resin. 3. (a) Polyamide resin 3 to 95% by weight,
(B) Thermotropic liquid crystal polyester resin according to claim 1, 3 to 95% by weight (c) Number average molecular weight (Mn) is 1 ×
10 ^{4 to} 9 × 10 ⁴ , weight average molecular weight (Mw) / Mn of 5
2-40% by weight of the following brominated polystyrene and / or polybrominated styrene resin, and (d) inorganic filler to 1 part with respect to 100 parts by weight of the total amount of (a) + (b) + (c). To 200 parts by weight of the thermoplastic resin composition.