JP3365071B2 - Thermoplastic resin composition and molded article thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition comprising a liquid crystalline resin and a thermoplastic resin, which have excellent mechanical properties and weld strength and are useful as electric / electronic equipment parts, automobile parts, mechanical parts and the like.

[0002]

2. Description of the Related Art In recent years, demands for higher performance of plastics have been increasing, and many polymers having various new properties have been developed. Among them, an optically anisotropic liquid crystal characterized by parallel arrangement of molecular chains. Resin has attracted attention because it has excellent fluidity and mechanical properties. However,
At present, the applications are limited because the molding shrinkage and mechanical properties are different in the direction perpendicular to the molecular chain orientation direction and the cost is high. On the other hand, it is known that many non-liquid crystalline thermoplastic resins are not necessarily sufficient in mechanical properties and heat resistance as compared with liquid crystalline resins.

In order to solve the drawbacks of both, a blend of a liquid crystalline resin and a non-liquid crystalline thermoplastic resin has been attracting attention (for example, JP-A-57-25354).

[0004]

However, even if both polymers are simply blended, the compatibility is not sufficient, so that the physical properties are not significantly improved and the toughness is low. In particular, the compatibility with nylon resin was very poor, and almost no improvement in physical properties was observed. Further, a method of adding a reactive compatibilizing agent in order to improve the compatibility of both is also known (for example, JP-A-4-53).
853, JP-A-4-53854, etc.), there is a drawback that the fluidity is lowered when a reactive compatibilizer is added. A method of melt-blending a liquid crystalline resin obtained by copolymerizing an ionic group with a thermoplastic resin is also known (JP-A-3-54222). However, in this way, an ionic group is co-polymerized in the molecular chain. In the present situation, a blended product having a sufficient weld strength has not been obtained by the polymerization method. An object of the present invention is to solve the above problems and obtain a liquid crystalline resin composition having excellent weld strength.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the copolymerization of a metal salt compound at the terminal of the molecular chain further improves the compatibility, especially the weld strength. It was found that the present invention has been reached.

That is, the present invention is different from (A) containing 99 to 1% by weight of one or more non-liquid crystalline thermoplastic resins and (B) containing units represented by the following (I) and / or (II). Liquid crystalline resins 1 to 99 forming an anisotropic molten phase
It is intended to provide a thermoplastic resin composition composed of wt%.

--X--Y--SO ₃ M (I) --XY--COOM (II) (wherein X represents --O-- and / or --CO-- and Y represents a divalent organic group. Further, M represents an alkali metal.) Hereinafter, the compound specifically used in the present invention will be described in detail.

Preferred specific examples of the non-liquid crystalline thermoplastic resin (A) used in the present invention are polyester, polyamide, polyarylene sulfide, polyoxymethylene,
Examples thereof include polyolefin-based polymers, crystalline resins such as polystyrene, and amorphous resins such as polycarbonate, polyarylate, and polyarylene oxide. Among these, polyester, polyamide, polyarylene sulfide, polypropylene, polyethylene and polycarbonate are preferable, and polyester and polyamide are most preferable. Further, two or more kinds of the non-liquid crystal thermoplastic resin may be used.

The above-mentioned polyester is a polyester having an aromatic ring as a chain unit of a polymer and is a condensation reaction containing an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative) as main components. The polymer or copolymer obtained by the above is preferably mentioned. Examples of the dicarboxylic acid here include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid,
1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,
Examples thereof include 4'-biphenylcarboxylic acid, 4,4'-diphenylethercarboxylic acid, 1,2-bis (p-carboxyphenoxy) ethane, and ester-forming derivatives thereof. If it is 30 mol% or less, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid,
It may be substituted with an aliphatic dicarboxylic acid such as dimer acid or an alicyclic carboxylic acid such as 1,4-cyclohexanedicarboxylic acid or 1,3-cyclohexanedicarboxylic acid. As the diol component, an aliphatic diol having 2 to 10 carbon atoms, that is, ethylene glycol, propylene glycol, butylene glycol, 1,5-pentane glycol, decamethylene glycol, 3-methyl-1,3-
Examples include, but are not limited to, propene diol, neopentyl glycol, cyclohexane dimethanol, cyclohexane diol, and the like. Specific examples of preferable polyesters include polyethylene terephthalate, polybutylene terephthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate, polyethylene-2,6-naphthalate, poly-1,4-. Cyclohexane dimethylene terephthalate etc. and polyethylene terephthalate / isophthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / sebacate, polybutylene terephthalate / decane dicarboxylate, poly-1,4-cyclohexane dimethylene terephthalate / isophthalate etc. Polymerized polyester can be used. Among these, preferred polyesters include polybutylene terephthalate, polyethylene terephthalate, and poly-1,4-cyclohexanedimethylene terephthalate. Furthermore, polybutylene terephthalate is more preferable. The logarithmic viscosity of polybutylene terephthalate is preferably 0.9 to 1.3,
More preferably, it is 0.92-1.25. The logarithmic viscosity of polybutylene terephthalate is 0.
It can be determined by dividing the logarithm of the relative viscosity obtained using a 5% orthochlorophenol solution by the concentration.

As the polyamide, polyamide obtained from ω-amino acid or ω-lactam, or dicarboxylic acid such as diamine or m-xylenediamine and adipic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid, terephthalic acid or isophthalic acid. And homopolymers or copolymers obtained from the above, mixed polymers and the like. Preferred polyamides are homopolyamides such as nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, and adipic acid / terephthalic acid / hexamethylenediamine, adipic acid / 1,4-cyclohexanedicarboxylic acid / hexamethylenediamine, adipine. Examples thereof include copolyamides such as acid / 1,3-cyclohexanedicarboxylic acid / hexamethylenediamine, terephthalic acid / isophthalic acid / hexamethylenediamine / bis (paraaminocyclohexyl) methane.

The polyarylene sulfide is a bond of an aromatic ring and sulfur. Preferred polyarylene sulfides include polyparaphenylene sulfide, which may be partially branched.

Examples of polyoxymethylene include polyoxymethylene homopolymers and copolymers whose main chain is composed mainly of oxymethylene chains.

Examples of the polyolefin-based polymer include homopolymers or copolymers containing a repeating unit formed from α-olefins such as ethylene and propylene as a main component. For example, a homopolymer of propylene, a homopolymer of ethylene, and A block or random copolymer obtained by copolymerizing ethylene with another α-olefin (for example, propylene and butene-1), specifically, a copolymer of ethylene and an α-olefin having 3 or more carbon atoms (for example, ethylene / propylene copolymer). Polymer, ethylene / butene-
1 copolymer), a copolymer composed of ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated diene (for example, an ethylene / propylene / 1,4-hexadiene copolymer,
Ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / ethylidene norbornene copolymer, etc.), and these may be used alone or in combination of two or more. Preferred polyolefin-based polymers are polypropylene homopolymer, polyethylene homopolymer, copolymers of ethylene having an ethylene content of 50 mol% or more and α-olefins having 3 or more carbon atoms (for example, ethylene / propylene copolymer, ethylene / butene-polymer). 1
Copolymer, etc.), a propylene / ethylene copolymer having an ethylene content of 30 mol% or less, an elastomeric copolymer composed of 50 wt% or less of ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated diene, and polypropylene homo. Composition comprising a polymer, composition comprising an elastomeric copolymer comprising 50% by weight or less of ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated diene, and polyethylene homopolymer and propylene having a propylene content of 30 mol% or less / Ethylene copolymer is mentioned.

Further, the above polyolefin-based polymer is
More preferably, it is modified with an unsaturated carboxylic acid or its derivative. Examples of the unsaturated carboxylic acid to be modified include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 5-norbornene-
2,3-dicarboxylic acid, tetrahydrophthalic acid, dimer acid and the like can be mentioned. Examples of the derivative include anhydrides, esters, amides, imides and salts of the above acids.

As polystyrene, in addition to polystyrene homopolymer, HIPS (high impact polystyrene), A
S (acrylonitrile / styrene copolymer), ABS
(Acrylonitrile / butadiene / styrene copolymer), MBS (methyl methacrylate / butadiene / styrene copolymer) and the like.

Examples of the polycarbonate or polyarylate include bis (4-hydroxyphenyl), bis (3,
5-dialkyl-4-hydroxyphenyl) or hydrocarbon derivatives having bis (3,5-dihalo-4-hydroxyphenyl) substitution are preferred.
Polycarbonates or polyarylates based on 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) are particularly preferred. Moreover, these may contain a small amount of copolymerization components.

As the polyarylene oxide, poly (2,6-dimethyl-1,4-phenylene) ether,
2,6-dimethylphenol / 2,4,6-trimethylphenol copolymer, 2,6-dimethylphenol /
2,3,6-triethylphenol copolymer and the like can be mentioned. These can be used by modifying with unsaturated carboxylic acid or its derivative by graft reaction. The unsaturated carboxylic acid to be modified is acrylic acid, methacrylic acid,
Crotonic acid, maleic acid, fumaric acid, itaconic acid, 5
-Norbornene-2,3-dicarboxylic acid, tetrahydrophthalic acid, dimer acid and the like. Examples of the derivative include anhydrides, esters, amides, imides and salts of the above acids. Further, styrene resins such as polystyrene and high impact polystyrene can be added to the polyarylene oxide.

The liquid crystalline resin (B) used in the present invention is a liquid crystalline polyester containing the following structural units (I) and / or (II) and capable of forming anisotropy when melted. ) And / or (II) is present as a terminal group in a form linked to the end of the molecular chain.

--X--Y--SO ₃ M (I) --XY--COOM (II) Y in the formulas of the structural units (I) and (II) used in the present invention is 2
A valent organic group is shown, and examples thereof include an aromatic group, a chain aliphatic group, and an alicyclic aliphatic group. Of these, an aromatic group is preferable, and a phenyl group and a naphthalene group are particularly preferable.

The divalent organic group represented by Y preferably does not contain a carboxyl group.

Specific examples of the above (I) and (II) include the following structural units

[Chemical 5] (However, M in the formula represents an alkali metal.)

[Chemical 6] And / or

[Chemical 7] Is preferred.

The structural units (I) and / or (II) are
When X is -O-, it is 0.01 to 2 with respect to the total of the carboxyl group and the carboxyl group residue in the liquid crystal polyester.
Mol%, particularly 0.1 to 1 mol% is preferable, and X is -CO.
In the case of −, 0.01 to 2 mol%, particularly 0.1 to 1 mol% is preferable with respect to the total of hydroxy groups and hydroxy group residues in the liquid crystal polyester. Further, the structural unit (I)
, (II) in the formula, M is an alkali metal, Na, K,
Li is preferred and Na is particularly preferred.

In order to introduce the structural unit (I) and / or (II) at the end of the molecular chain, the structural unit (I) and / or
Alternatively, the hydroxy compound and / or carboxy compound of (II) can be used as a raw material, and preferably 4
-Hydroxybenzenesulfonic acid, 4- (2-hydroxyethoxy) benzenesulfonic acid, 6-hydroxy-2
-Sulfonic acid, 6- (2-hydroxyethoxy) -2-
Alkali metal salts such as sulfonic acid, 3-carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid can be used.

The structural units (I) and (II) referred to in the present invention
The component constituting the liquid crystal polyester other than is a polyester forming an anisotropic melt phase obtained by copolymerizing hydroxycarboxylic acid, diol, dicarboxylic acid or the like, or specifically, p-hydroxyl. Benzoic acid / polyethylene terephthalate liquid crystal polyester, p-hydroxybenzoic acid / 6-hydroxy-2
-Naphthoic acid type liquid crystal polyester, p-hydroxybenzoic acid / 4,4'-dihydroxybiphenyl / terephthalic acid / isophthalic acid type liquid crystal polyester, and the like. Among them, the following structural units (V), (VI), (VII) , A liquid crystalline polyester comprising (VIII) is preferably used.

[0025]

[Chemical 8] (However, in the formula, R ₁ is

[Chemical 9] R ₁ represents one or more groups selected from

[Chemical 10] Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit [(VI) + (VII)]
And structural unit (VIII) are equimolar. ) The above structural unit (V)
Is a structural unit of polyester produced from p-hydroxybenzoic acid, and the structural unit (VI) is 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-
4,4'-dihydroxybiphenyl, hydroquinone,
t-butyl hydroquinone, phenyl hydroquinone,
A structural unit formed from an aromatic dihydroxy compound selected from 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether is The unit (VII) is a structural unit produced from ethylene glycol, and the structural unit (VIII) is terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy). ) Ethane-4,4'-dicarboxylic acid, 1,
2-bis (2-chlorophenoxy) ethane-4,4'-
Structural units formed from an aromatic dicarboxylic acid selected from dicarboxylic acid and diphenyl ether dicarboxylic acid are shown below. Of these, R ₁

[Chemical 11] Is 70 mol% or more of the structural unit (VI), and R ₂ is

[Chemical 12] Particularly preferably those which account for 70 mol% or more of the structural unit (VIII) .

The structural unit [(V) + (VII)] is [(V)
+ (VI) + (VII)] is 55 to 95 mol%, preferably 70 to 95 mol%. Structural unit (VII) is [(V) +
(VI) + (VII)] is preferably 40 to 5 mol%, 30 to 8
Mol% is more preferred. The molar ratio of structural unit (V) / (VI) is preferably 75/25 to 95/5, more preferably 78/22 to 93/7. Also, the structural unit
(VIII) is equimolar with structural units [(VI) + (VII) ].

When the above preferred liquid crystalline polyester is polycondensed, 3,3'-diphenyldicarboxylic acid, 2,2 'is contained in addition to the components constituting the structural units (I) to (IV).
An aromatic dicarboxylic acid such as diphenyldicarboxylic acid,
Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, methylhydroquinone, 4,4'-dihydroxydiphenyl sulfone, 4,4 ' -Dihydroxydiphenyl sulfide, aromatic diol such as 4,4'-dihydroxybenzophenone, 1,4-butanediol, 1,6-
Hexanediol, neopentyl glycol, 1,4-
Aliphatic and alicyclic diols such as cyclohexanediol and 1,4-cyclohexanedimethanol, and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, and p-aminophenol and p-aminobenzoic acid An acid or the like may be copolymerized in an amount that does not impair the object of the present invention.

The method for producing the liquid crystalline resin (B) in the present invention is not particularly limited, and it can be produced according to the following known condensation polymerization method of polyester.

(1) p-acetoxybenzoic acid and 4,
A method for producing a diacylated aromatic dihydroxy compound such as 4′-diacetoxybiphenyl and an aromatic dicarboxylic acid such as terephthalic acid by deacetic acid condensation polymerization reaction.

(2) p-hydroxybenzoic acid and 4,
A method in which an aromatic dihydroxy compound such as 4'-dihydroxybiphenyl and an aromatic dicarboxylic acid such as terephthalic acid are reacted with acetic anhydride to acylate a phenolic hydroxyl group, and then a deacetic acid polycondensation reaction is performed.

(3) A method for producing a phenyl ester of p-hydroxybenzoic acid and an aromatic dihydroxy compound such as 4,4'-dihydroxybiphenyl and a diphenyl ester of an aromatic dicarboxylic acid such as terephthalic acid by a dephenol polycondensation reaction. .

(4) Aromatic dicarboxylic acids such as p-hydroxybenzoic acid and terephthalic acid are reacted with a predetermined amount of diphenyl carbonate to form diphenyl esters, and then aromatic dihydroxy such as 4,4'-dihydroxybiphenyl. A method of producing a compound by adding a compound and performing a dephenol polycondensation reaction.

(5) Polyester polymers such as polyethylene terephthalate, oligomers or bis (β-
A method for producing by the method (1) or (2) in the presence of a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as hydroxyethyl) terephthalate.

As a method of introducing the structural unit (I) and / or (II) into the liquid crystal polyester terminal, a structural unit
Polymerization can be carried out by adding a hydroxy compound or a carboxy compound forming (I) and / or (II) at any stage. As the timing of addition, the liquid crystal polyester and the metal salt compound produced by the methods (1) to (5) can be added before or during the polymerization using a Banbury mixer, a rubber roll machine, a kneader, or a single-screw or twin-screw extruder. It can be melt-kneaded and reacted at a temperature of 200 to 350 ° C. In the production method (3), the reaction may be carried out in advance before the production of polyester such as polyethylene terephthalate. The liquid crystal polyester thus obtained is a liquid crystal polyester in which at least a part of the terminal of the molecular chain is sealed with the structural units (I) and / or (II).

Although these polycondensation reactions can be carried out without a catalyst, stannous acetate, tetrabutyl titanate, potassium acetate, antimony trioxide, metal compounds such as sodium acetate and magnesium may be added.

The liquid crystalline resin (B) used in the present invention is capable of measuring logarithmic viscosity in pentafluorophenol, and in that case, it is measured at a concentration of 0.1 g / dl at 60 ° C. The value obtained is preferably 0.5 or more, more preferably 1.0 to 10 dl / g.

The melt viscosity is preferably 10 to 20,000 poise, more preferably 20 to 10,000 poise. The melt viscosity is 1 m in diameter under the condition of melting point (Tm) + 10 ° C and shear rate of 1,000 / sec.
It is a value measured by a high-pressure capillary viscometer using a capillary with m and a length l ≧ 5 mm. Here, the melting point (Tm) is the difference between room temperature and 2
After observing the endothermic peak temperature (Tm1) observed when measured under a temperature rising condition of 0 ° C./min, the temperature was 5 at a temperature of Tm1 + 20 ° C.
After being held for a minute, the temperature is once cooled to room temperature under a temperature lowering condition of 20 ° C./min, and then the endothermic peak temperature (Tm2) observed when measured again under a temperature rising condition of 20 ° C./min. The liquid crystal starting temperature (TN) is the temperature at which opalescence is emitted under shear stress by heating the sample on a sample stage of a polarizing microscope.

The composition of the non-liquid crystalline thermoplastic resin (A) and the liquid crystalline resin (B) is 99-1% by weight of (A) and 1 (B).
Is about 99 to 50% by weight, but (B) is preferably 1 to 50% by weight with respect to (A) 99 to 50% by weight, and (A) 9
Most preferably, the content of (B) is 10 to 40% by weight with respect to 0 to 60% by weight. Addition amount of liquid crystalline resin (A) is 99%
If it exceeds 1%, the anisotropy and the decrease in weld strength, which are the defects of the liquid crystalline resin, become large, and if it is less than 1%, the effect of improving the physical properties is very small, which is not preferable.

In the present invention, the non-liquid crystalline thermoplastic resin (A)
In addition to the liquid crystalline resin (B), an epoxy compound may be added in an amount that does not impair the effects of the present invention. The epoxy compound is a compound having one or more epoxy groups and is not necessarily limited, and known compounds can be used.

As a method for mixing the non-liquid crystal thermoplastic resin (A) and the liquid crystal resin (B), various methods can be applied. Examples of the apparatus for melt-mixing include a mixing roll, a Banbury mixer, a kneader, an extruder, and the like. Among them, an extruder is preferable. As this extruder, either a single-screw extruder or a twin-screw extruder can be used, but it is particularly preferable to use a twin-screw extruder. The kneading temperature is preferably higher than the liquid crystal starting temperature of the liquid crystalline resin (B) and higher than the melting point of the non-liquid crystalline thermoplastic resin (A), and higher than the melting point of the non-liquid crystalline thermoplastic resin (A). It is more preferable that the temperature is higher than the melting point of the liquid crystalline resin (B).

When a molded article is obtained from the thermoplastic resin composition of the present invention, usual methods such as injection molding, extrusion molding, blow molding and press molding can be applied, but especially injection molding, extrusion molding and press molding. Is preferred, and injection molding is most preferred.

Since the resin composition of the present invention is excellent in weld strength, it has excellent characteristics as a molded article having a weld portion.

In producing the thermoplastic resin composition of the present invention, conventionally known polyester polymerization catalysts, heat-resistant agents, weathering agents, antistatic agents, dyes, colorants, crystal nucleating agents, flame retardants, etc. Additives, talc, clay, mica,
Add inorganic fillers such as calcium metasilicate, silica sand, glass beads, glass flakes, graphite, potassium titanate whiskers, and gypsum fibers as reinforcing agents such as glass fibers, asbestos fibers and carbon fibers as compatibilizers. Is also possible.

[0044]

EXAMPLES The present invention will be described in more detail with reference to examples below, but these examples do not limit the scope of application of the present invention.

The parts in the examples are parts by weight. PB
As T, PBT resin 1400S manufactured by Toray Industries, Inc. was used, and as nylon 6, CM1010 manufactured by Toray Industries, Inc. was used.

Reference Example 1 870 parts by weight of p-hydroxybenzoic acid 168 parts by weight of 4,4'-dihydroxybiphenyl, 914 parts by weight of acetic anhydride, 150 parts by weight of terephthalic acid and 2.5 mol% of sodium sulfoisophthalate were copolymerized. 346 parts by weight of polyethylene terephthalate was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and deacetic acid polycondensation was carried out under the following reaction conditions.

After reacting at 100 to 250 ° C. for 1.5 hours in a nitrogen gas atmosphere, 290 ° C. and 0.5 m in 2 hours
When the pressure was reduced to mHg and the reaction was further continued for 1.0 hour to complete the polycondensation, almost the theoretical amount of acetic acid was distilled out, and 0.5
A liquid crystal polyester (B-1) copolymerized with 0 mol% of sodium sulfoisophthalate was obtained. The liquid crystal starting temperature was 243 ° C., and the melting point was 273 ° C.

Reference Example 2 870 parts by weight of p-hydroxybenzoic acid, 168 parts by weight of 4,4'-dihydroxybiphenyl, 914 parts by weight of acetic anhydride, 150 parts by weight of terephthalic acid, 346 parts by weight of polyethylene terephthalate, 4-hydroxybenzenesulfonic acid 9.5 parts by weight of sodium (0.44 mol% with respect to the total of carboxyl groups and carboxy group residues) was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and deacetic acid polymerization was conducted under the same conditions as in Reference Example 1. Liquid crystal polyester (B-2)
Got The liquid crystal starting temperature was 236 ° C., and the melting point was 267 ° C.

Reference Example 3 7.7 parts by weight of sodium 4-hydroxybenzoate instead of sodium 4-hydroxybenzenesulfonate in Reference Example 2 (0.44 mol% relative to the total of carboxyl group and carboxy group residue) Was added and polymerized to obtain liquid crystal polyester (B-3). The liquid crystal starting temperature was 238 ° C., and the melting point was 268 ° C.

Examples 1-9, Comparative Examples 1-4, Example 10
-12, Comparative Examples 5-7 Non-liquid crystalline thermoplastic resin (A) (PBT, nylon 6)
The liquid crystalline resins (B) polymerized in Reference Examples 1 to 3 were weighed in predetermined amounts as shown in Table 1 and Table 2, and dry blended. 3 set to 280 ° C (resin temperature 290 ° C)
The mixture was melt-kneaded with a 0 mmφ extruder, and the obtained gut was chopped with a strand cutter. After hot air drying, the mold temperature is 80 ℃
And the resin temperature is 270 ° C. under ASTM No.
4 Dumbbells were injection molded using both a normal mold with the gate at one end of the dumbbell (Dumbbell I) and a weld mold with the gate at both ends of the dumbbell (Dumbbell II).
Using these test pieces, the tensile strength of dumbbell was measured according to the ASTM D638 standard, and the tensile strength of dumbbell II with respect to dumbbell I was determined as the weld strength retention rate.

[0051]

[Table 1]

[Table 2]

From the results shown in Tables 1 and 2 above, when comparing the case where the metal salt compound was copolymerized at the terminal and the case where the metal salt compound was copolymerized in the molecular chain, no significant difference was observed between the two in terms of non-weld strength. However, regarding the weld strength, it is found that the copolymerization at the terminal is higher, and the weld strength retention rate is also higher.

[0053]

The molded article obtained from the thermoplastic resin composition according to the present invention is excellent in mechanical properties and weld strength, and thus can be widely used in applications such as electric and electronic device parts and automobile parts. Is.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-5-1179 (JP, A) JP-A-6-157733 (JP, A) JP-A-5-140431 (JP, A) JP-A-8- 53543 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (6)

(57) [Claims] 1. Anisotropy containing (A) 99 to 1% by weight of one or more non-liquid crystalline thermoplastic resins and (B) units represented by the following (I) and / or (II). A thermoplastic resin composition comprising 1 to 99% by weight of a liquid crystalline resin that forms a molten phase. —X—Y—SO ₃ M (I) —X—Y—COOM (II) (wherein, X represents —O— and / or —CO—, and Y represents a divalent organic group. , M represents an alkali metal.) 2. The thermoplastic resin composition according to claim 1, wherein the units represented by (I) and / or (II) are bonded as terminal groups of the molecular chain of the liquid crystalline resin (B). . 3. The thermoplastic resin composition according to claim 1, wherein the unit represented by (I) is a unit represented by the following (III) and / or (IV). [Chemical 1] 4. The content of the units represented by (I) and / or (II) in the liquid crystalline resin (B) is such that when X is --O--, the carboxyl group and the residual carboxyl group in the liquid crystalline polyester. 0.01 to 2 mol% relative to the total of the groups, X is -CO-
In the case of, the thermoplastic resin composition according to any one of claims 1 to 4 , which is 0.01 to 2 mol% with respect to the total of hydroxyl groups and hydroxyl group residues in the liquid crystal polyester. 5. The thermoplastic resin composition according to claim 1, wherein the liquid crystalline resin (B) is a liquid crystalline polyester further containing the following structural units (V) to (VIII). [Chemical 2] (However, R ₁ in the formula is R ₁ represents one or more groups selected from Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit [(VI) + (VII)]
And structural unit (VIII) are equimolar. ) 6. A non-liquid crystalline thermoplastic resin (A) is a thermoplastic resin composition according to any one of claims 1 to 5, which is a non-liquid crystalline polyester resin or a polyamide resin.