JP2000319467A - Thermoplastic resin composition and molded item - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition having improved flowability and measuring stability during a molding process and gives a product showing improved impact resistance, heat resistance, chemical resistance, fatigue property and anisotropy and to provide a formed item thereof. SOLUTION: A thermoplastic resin composition is a resin composition obtained by mixing 0.5 to 100 pts.wt. of a liquid crystalline resin (B) with 100 pts.wt. of at least one thermoplastic resin (A) selected from a styrene-based resin, a polycarbonate-based resin and a polyphenylene ether-based resin. A change ratio (%) of a glass transition temperature for the thermoplastic resin (A) satisfies the equation, [(TgA-TgT)/TgA]×100<=5 (wherein, TgA is a glass transition temperature for the thermoplastic resin (A) and TgR is a glass transition temperature derived from the thermoplastic resin (A) of the resin composition).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a fluidity during molding,
The present invention relates to a thermoplastic resin composition having improved measurement stability and impact resistance, heat resistance, chemical resistance, fatigue properties, and anisotropy of a molded article obtained, a method for producing the same, and a molded article.

[0002]

2. Description of the Related Art Many thermoplastic resins such as polystyrene, polycarbonate, and polyphenylene ether are being used as injection molding materials in a wide range of fields such as mechanical mechanism parts, electric and electronic parts, and automobile parts by utilizing their excellent properties. is there. On the other hand, the demand for molded products has increased with the progress of technology, and more complicated shapes have been demanded. Therefore, it has been desired to improve fluidity.

Therefore, an optically anisotropic liquid crystalline polymer characterized by a parallel arrangement of molecular chains is attracting attention because of its excellent fluidity and mechanical properties, and improves the fluidity and mechanical properties of a thermoplastic resin. Numerous alloying technologies are being studied for this purpose. These alloying techniques are described in, for example,
102257, JP-A-3-47861, JP-A-5-70700, JP-A-5-112709, JP-A-6-200129, JP-A-7-33
No. 1051 and Japanese Patent Application Laid-Open No. 9-12744. JP-A-2-102257 and JP-A-3-47861 disclose that a liquid crystal resin having a suitably low heat distortion temperature can be compounded at a melting temperature of a thermoplastic resin, and mechanical properties, heat resistance, The present invention relates to a thermoplastic resin composition having improved dimensional stability and the like.
Japanese Patent No. -70700 discloses a liquid crystal resin comprising a thermoplastic resin and a liquid crystal resin which can be molded at a temperature lower than the liquid crystal onset temperature of the liquid crystal resin. The present invention relates to a modified thermoplastic resin composition. Japanese Patent Application Laid-Open No. 5-112709 discloses a molding resin composition in which a liquid crystalline polymer having a higher melting point than that of a polycarbonate resin as a matrix resin is blended to orient dispersed particles to reduce the strength and rigidity of a remolded product. It is about things. Also, JP-A-6-2
[0012] Japanese Patent Publication No. 00129 relates to a plastic resin composition in which a liquid crystal resin is blended with a polycarbonate resin having a large amount of phenolic hydroxyl group terminals, and delamination is improved by the interaction between the two resins. Japanese Patent Application Laid-Open No. 7-331051 relates to a thermoplastic resin composition in which a flame retardant and a liquid crystal resin are mixed with a polycarbonate resin having a large amount of phenolic hydroxyl group terminals to improve the flame retardancy. Japanese Patent Application Laid-Open No. 9-12744 relates to a liquid crystalline polyester resin composition film in which a compounded liquid crystalline resin forms a continuous phase.

[0004]

Although the strength and rigidity can be improved by variously devising the molding method by the above-mentioned method, however, it is described in JP-A-6-200129 and JP-A-7-331051. In the method, since a polycarbonate having a large amount of phenolic hydroxyl group end groups is preferably used, the interaction between the polycarbonate and the liquid crystal resin becomes too strong, the effect of adding the liquid crystal resin is weakened, and the dispersion particle diameter is reduced. Compared to the case of using polycarbonate alone, the impact strength is lowered and the fluidity and chemical resistance are not improved. Further, in the methods described in JP-A-5-70700 and JP-A-5-112709, after the polycarbonate resin and the liquid crystalline resin are once heated to a temperature higher than the melting point of the liquid crystalline polymer and kneaded in a molten state,
Since the liquid crystal resin particles are oriented, the interaction becomes too strong when the resin is melt-kneaded, the polycarbonate resin is denatured, and the mechanical properties are slightly improved. Is reduced. Mechanical mechanism parts,
For applications such as automobile parts, resistance to various chemicals including engine oil, brake oil, mechanical oil such as gear oil, window washer fluid and battery fluid is required. In addition, in electrical and electronic parts and other applications, with the diversification of processing steps and use environment, resistance to detergents and other organic solvents is required, and improvement in chemical resistance has been desired, Such a decrease in chemical resistance is not preferred. In addition, in JP-A-5-112709, JP-A-2-102257, JP-A-3-47861, and JP-A-9-12744, kneading at a temperature equal to or higher than the melting point of the liquid crystalline resin is preferable. However, in this case, the interaction between the liquid crystalline resin and the thermoplastic resin becomes too strong, and the fluidity and the chemical resistance decrease, which is not preferable.

[0005] The present invention solves the above-mentioned problems, and provides fluidity at the time of molding, metering stability and impact resistance of the obtained molded article.
An object of the present invention is to obtain a thermoplastic resin composition having improved heat resistance, chemical resistance, fatigue properties, and anisotropy, and a molded product thereof.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention relates to (1) 100 parts by weight of one or more thermoplastic resins (A) selected from styrene-based resins, polycarbonate-based resins, and polyphenylene ether-based resins, and 0.5 to 0.5 parts by weight of the liquid crystalline resin (B). A thermoplastic resin composition comprising 100 parts by weight, wherein the rate of change of the glass transition temperature of the thermoplastic resin (A) satisfies the following formula 1. ) = | (Tg _A −Tg _T ) / Tg _A | × 100 ≦ 5- [Formula 1] Tg _A : Glass transition temperature of thermoplastic resin (A) Tg _T : Thermoplastic resin (A) in resin composition (2) The thermoplastic resin composition according to the above (1), wherein the number average particle diameter of the liquid crystal resin particles dispersed in the resin composition is 0.5 to 5 μm. (3) Liquid crystalline resin particles dispersed in the resin composition The thermoplastic resin composition according to the above (1) or (2), wherein the aspect ratio (major axis / minor axis) is less than 3; (4) the thermoplastic resin (A) contains a polycarbonate resin. And the equivalent ratio (E _P ) of the phenolic terminal group (E _P ) to the non-phenolic terminal group (E _N ) of the polycarbonate resin.
(E _N ) is 1/20 or less, the thermoplastic resin composition according to any one of the above (1) to (3),
(5) The liquid crystalline resin (B) is composed of the following structural units (I), (II) and (II)
The thermoplastic resin composition according to any one of the above (1) to (4), which is a liquid crystalline polyester comprising I) and (IV),

[0007]

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(Where R ₁ in the formula is

[0009]

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And R ₂ represents one or more groups selected from

[0011]

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And one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. (6) Any one of the above (1) to (5), wherein a filler is further compounded in an amount of 0.5 to 300 parts by weight based on a total of 100 parts by weight of the thermoplastic resin (A) and the liquid crystal resin (B). (7) The thermoplastic resin composition according to the above (6), wherein the filler is a carbon fiber, (8) the thermoplastic resin (A) and the liquid crystal resin (B). In the case of further blending a filler, the filler is melt-kneaded at a temperature not lower than the liquid crystal onset temperature of the liquid crystalline resin (B) and not higher than the melting point, so that the thermoplastic resin according to any one of (1) to (7) above. (9) a method for producing a thermoplastic resin composition, which comprises producing a composition; (9) a composition comprising a thermoplastic resin (A) and a liquid crystal resin (B), and a filler further mixed with a liquid crystal resin. (B) by melting at a temperature not lower than the liquid crystal starting temperature and not higher than the melting point. Serial (1) - (7) The method of manufacturing a molded article, characterized in that to produce a molded article composed of the thermoplastic resin composition according to any one of (10) above (1) to
(7) A molded article composed of the thermoplastic resin composition according to any one of the above, wherein the molded article is a mechanical mechanism part, an electric / electronic part or an automobile part; (7) A molded article comprising the thermoplastic resin composition according to any one of the above, wherein the molded article has a plate-shaped portion or a box-shaped portion, and a thin-walled portion having a thickness of 1.2 mm or less. A molded article characterized by having 10% or more of the total surface area.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The thermoplastic resin (A) used in the present invention is at least one selected from styrene resins, polycarbonate resins and polyphenylene ether resins.

The styrenic resin contains a unit formed from styrene and / or its derivative.

Specific examples of the unit formed from styrene or a derivative thereof (these may be collectively referred to as an aromatic vinyl monomer) include the following structural units.

[0016]

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R _{3 to} R _{7 each} represent a halogen such as hydrogen or chlorine, an aliphatic group having 1 to 10 carbon atoms, an aromatic group, an alicyclic group, a sulfonyl group, a nitro group, etc., each of which is the same. Or different.

Specific examples of R _{3 to} R ₇ include hydrogen, chlorine,
Groups such as methyl, ethyl, propyl, isopropyl, allyl, butyl, phenyl, benzyl, methylbenzyl, chloromethyl, cyanomethyl, cyanomethoxy, ethoxy, phenoxy, nitro, etc., each of which may be the same or different Good.

Preferred examples of styrene and its derivatives include styrene, α-methylstyrene, vinyltoluene,
Examples thereof include p-methylstyrene and pt-butylstyrene, and styrene and α-methylstyrene are particularly preferable. These can be used in combination.

Examples of the styrene resin include a styrene (co) polymer and a rubber-reinforced styrene (co) polymer. Examples of the styrene (co) polymer include polymers obtained by polymerizing one or more aromatic vinyl monomers, and one or more aromatic vinyl monomers that can be copolymerized therewith. And copolymers obtained by copolymerizing one or more monomers. As the rubber-reinforced styrene (co) polymer, a rubber-reinforced polymer obtained by graft-polymerizing one or more aromatic vinyl monomers onto a rubbery polymer;
Graft copolymers obtained by graft-copolymerizing one or more aromatic vinyl monomers and one or more monomers copolymerizable therewith with a rubbery polymer are exemplified.

Examples of the monomer copolymerizable with the above-mentioned aromatic vinyl monomer include (meth) acrylate and vinyl cyanide.

Examples of the (meth) acrylate include methyl methacrylate and ethyl methacrylate, and methyl methacrylate is preferably used.
Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.

Examples of the rubbery polymer include diene rubbers such as butadiene rubber, styrene-butadiene copolymer rubber (SBR) and acrylonitrile-butadiene copolymer rubber (NBR), and acrylic rubbers such as polybutyl acrylate. And polyolefin-based rubbers such as ethylene-propylene-non-conjugated diene terpolymer rubber (EPDM), among which polybutadiene and ethylene-propylene-non-conjugated diene terpolymer rubber (EPDM)
Is preferably used.

The rubber-reinforced styrenic (co) polymer will be described in more detail. The rubbery polymer (a) has at least one aromatic vinyl compound (b) or a methacrylic acid ester which is a comonomer thereof. (C) and a graft (co) polymer (polymer (i)) obtained by graft polymerization of at least one selected from vinyl cyanide compounds (d) and aromatic vinyl compounds (b) and methacrylic acid esters (c) And a (co) polymer (polymer (ii)) obtained by polymerizing at least one vinyl compound selected from the above, or a vinyl cyanide compound (d).

As the polymer (i), with respect to (a),
When (b) and (c) and / or (d) are graft-polymerized, the copolymerization amount of the rubbery polymer (a) is 5 to 5.
80% by weight is preferred. When the graft component contains a vinyl cyanide compound (d), the total of one or two or more vinyl compounds selected from an aromatic vinyl compound (b) and a methacrylic acid ester (c) is 50 to 97.
% By weight, and the content of the vinyl cyanide compound (d) is 3 to 50%.
% By weight is preferred.

The polymerization method of the polymer (i) is not particularly limited, and known methods such as bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization and bulk-suspension polymerization can be used.

On the other hand, the copolymerization amount of the vinyl cyanide compound (d) in the polymer (ii) is suitably from 3 to 50% by weight.

The polymerization method of the polymer (ii) is not particularly limited, and known methods such as bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization and bulk-suspension polymerization can be used.

As the graft (co) polymer, the polymer (i) can be used as an essential component, and the polymer (ii) can be blended and used in an optional ratio.

In the present invention, preferred styrene resins include styrene polymers such as PS (polystyrene) and the like.
Rubber-reinforced styrene-based polymers such as HIPS (high impact polystyrene), styrene-based copolymers such as AS (acrylonitrile / styrene copolymer), AES (acrylonitrile / ethylene-propylene / non-conjugated diene rubber / styrene copolymer), ABS (acrylonitrile / butadiene / styrene copolymer), MBS (methyl methacrylate /
Rubber reinforcement (co) such as butadiene / styrene copolymer)
And styrene-based polymers such as PS (polystyrene), and AS (acrylonitrile /
Styrene copolymers such as styrene copolymer), ABS
(Acrylonitrile / butadiene / styrene copolymer)
Is preferred. Generally, polystyrene resin can be preferably used regardless of the structure and amount of the terminal group, and is used to improve the interaction with the liquid crystalline resin or for other purposes, such as reaction of maleic anhydride or glycidyl methacrylate. Even when modified polystyrene to which a compound having a functional group is added in an appropriate amount is used, if the rate of change of the glass transition temperature when the liquid crystalline resin is blended is within the range satisfying the above formula 1, these can also be preferably used. .

Examples of the polycarbonate resin include an aromatic homo- or copolycarbonate having a carbonate bond and obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. The phenolic terminal group (E _P ) and the non-phenolic terminal group (E _N ) obtained by reacting an aromatic dihydric phenol compound with phosgene so that the rate of change of the glass transition temperature falls within the range of the present invention. It is preferable to use a polycarbonate resin having an equivalent ratio (E _P ) / (E _N ) of 1/20 or less, more preferably 1/20.
It is 40 or less, more preferably 1/70 or less.

The terminal group of the polycarbonate resin can be measured, for example, by dissolving the polycarbonate resin in acetic acid methylene chloride, adding titanium tetrachloride, and photometrically measuring the generated red complex at 546 nm.

The aromatic homo- or copolycarbonate resin is used in methylene chloride at a concentration of 1.0 g / dl and
Those having a logarithmic viscosity measured at 0 ° C. of 0.2 to 3.0 dl / g, particularly 0.3 to 1.5 dl / g are preferably used. Here, as the dihydric phenol compound,
2-bis (4-hydroxyphenyl) propane, 2,2
-Bis (4-hydroxy-3,5-dimethylphenyl)
Propane, bis (4-hydroxyphenyl) methane,
1,1-bis (4-hydroxyphenyl) ethane, 2,
2-bis (4-hydroxyphenyl) butane, 2,2-
Bis (4-hydroxy-3,5-diphenyl) butane,
2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,
5-diethylphenyl) propane, 1,1-bis (4-
(Hydroxyphenyl) cyclohexane, 1-phenyl-
1,1-bis (4-hydroxyphenyl) ethane and the like can be used, and these can be used alone or as a mixture. Among the above, 2,2-bis (4-hydroxyphenyl) propane is preferred.

The polyphenylene ether-based resin is a thermoplastic resin represented by the following structural unit and has an intrinsic viscosity of 0.01 to 0.80 d measured at 30 ° C. in chloroform.
1 / g of polymer is preferably used.

[0035]

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R _{8 to} R ₁₁ represent hydrogen, halogen, carbon number 1
10 to 10 aliphatic groups, aromatic groups, alicyclic, sulfonyl groups,
Examples thereof include groups such as a nitro group, which may be the same or different.

Specific examples of R _{8 to} R ₁₁ include hydrogen, chlorine, methyl, ethyl, propyl, isopropyl, allyl, butyl, phenyl, benzyl, methylbenzyl, chloromethyl, cyanomethyl, cyanomethoxy, ethoxy, phenoxy, nitro and the like. And these may be the same or different.

Specifically, 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. The polyphenylene ether-based resin may have a graft structure, and may be a resin partially modified and modified by adding another third component. The polyphenylene ether-based resin can be preferably used irrespective of the terminal group structure and the amount thereof.For example, polystyrene or a cyclic polyolefin-based resin is added to improve compatibility with them, or for another purpose. Even when a modified polyphenylene ether to which an appropriate amount of a compound having a reactive group such as maleic anhydride or glycidyl methacrylate is added is used, the rate of change of the glass transition temperature when the liquid crystalline resin is blended satisfies the above formula 1. And these can also be preferably used.

Two or more thermoplastic resins (A) may be used in combination, and specific examples include ABS and polycarbonate, polyphenylene ether and polystyrene or high-impact polystyrene. In addition, other characteristics,
For example, a thermoplastic resin (A) for imparting weather resistance and the like
Part (generally, not more than 85% of the component (A), preferably 7%).
0% by weight or less, more preferably 50% by weight or less) can be replaced with a crystalline thermoplastic resin. Examples of such a crystalline thermoplastic resin include polyamide resin and polyester resin. Specific examples include a combination of polycarbonate and polybutylene terephthalate, a combination of polycarbonate and polyethylene terephthalate, a combination of polyphenylene ether and nylon 6, a combination of polyphenylene ether and nylon 66, and the like.

The liquid crystalline resin (B) of the present invention is a polymer capable of forming anisotropy when melted, and includes liquid crystalline polyester, liquid crystalline polyester amide, liquid crystalline polycarbonate, liquid crystalline polyester elastomer, and the like.
Among them, those having an ester bond in the molecular chain are preferable, and liquid crystal polyesters and liquid crystal polyesteramides are particularly preferably used.

The liquid crystalline resin (B) which can be preferably used in the present invention is a liquid crystalline polyester containing a structural unit composed of p-hydroxybenzoic acid as an aromatic oxycarbonyl unit, and an ethylenedioxy unit as a structural unit. Liquid crystalline polyester can also be preferably used. More preferred are polyesters consisting of the following structural units (I), (III) and (IV) or polyesters consisting of the structural units of (I), (II), (III) and (IV), most preferred
It is a polyester comprising the structural units of (I), (II), (III) and (IV).

[0042]

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(Where R ₁ is

[0044]

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R ₂ represents one or more groups selected from

[0046]

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At least one group selected from Also,
In the formula, X represents a hydrogen atom or a chlorine atom. Note that the sum of structural units (II) and (III) and structural unit (IV)
Are desirably substantially equimolar.

The structural unit (I) is a structural unit formed from p-hydroxybenzoic acid, and the structural unit (II) is 4,4
'-Dihydroxybiphenyl, 3,3', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7- Dihydroxynaphthalene,
Structural units formed from one or more aromatic dihydroxy compounds selected from 2,2-bis (4-hydroxyphenyl) propane and 4,4'-dihydroxydiphenyl ether, and structural unit (III) is a structure formed from ethylene glycol. Structural unit (IV) is terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid,
6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,4'- Each of one or more structural units generated from an aromatic dicarboxylic acid selected from diphenyl ether dicarboxylic acids is shown. Of these, R ₁

[0049]

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And R ₂ is

[0051]

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Is particularly preferred.

The above structural units (I), (II), (III) and (IV)
Is arbitrary. However, in order to exhibit the characteristics of the present invention, the following copolymerization amount is preferable.

That is, the structural units (I), (II) and (II)
I), in the case of a copolymer consisting of (IV), the structural unit (I)
The total of (II) and (II) is preferably from 30 to 95 mol%, more preferably from 40 to 93 mol%, based on the total of the structural units (I), (II) and (III). The structural unit (III) is the structural unit
It is preferably from 70 to 5 mol%, more preferably from 60 to 7 mol%, based on the total of (I), (II) and (III). The molar ratio [(I) / (II)] between the structural units (I) and (II) is preferably 75.
/ 25 to 95/5, more preferably 78/22 to
93/7. Further, it is preferable that the structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III).

The term "substantially equimolar" means that the units constituting the polymer main chain excluding the terminal are equimolar, but the units constituting the terminal are not necessarily equimolar.

On the other hand, when the structural unit (II) is not contained, the structural unit (I) should be 40 to 90 mol% based on the total of the structural units (I) and (III) from the viewpoint of fluidity. Is preferably 60 to 88 mol%, and the structural unit (IV) is preferably substantially equimolar to the structural unit (III).

As the liquid crystalline polyesteramide,
Polyesteramides that form an anisotropic molten phase containing p-iminophenoxy units formed from p-aminophenol in addition to the structural units (I) to (IV) are preferred.

The liquid crystalline polyesters and liquid crystalline polyesteramides which can be preferably used include, in addition to the components constituting the structural units (I) to (IV), 3,3'-diphenyldicarboxylic acid and 2,2 ' -Aromatic dicarboxylic acids 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, 3,4'- Dihydroxybiphenyl, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxybenzophenone, 3,4 '
-Aromatic diols such as dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, and aliphatic and fats such as 1,4-cyclohexanedimethanol Cyclic diols, aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, and p-aminobenzoic acid can be further copolymerized to the extent that liquid crystallinity is not impaired.

The melt viscosity of the liquid crystalline resin (B) in the present invention is preferably 0.5 to 200 Pa · s, and particularly preferably 1 to 1 Pa · s.
00 Pa · s is more preferred. In order to obtain a composition having better fluidity, the melt viscosity is preferably set to 50 Pa · s or less.

The melt viscosity is calculated as melting point (Tm) +10
It is a value measured by a Koka type flow tester under the condition of ° C and a shear rate of 1,000 (1 / second).

Here, the melting point (Tm) refers to an endothermic peak temperature (Tm) observed when a polymer that has been polymerized is measured from room temperature under a heating condition of 20 ° C./min.
After observation at m1), the temperature is maintained at a temperature of Tm1 + 20 ° C. for 5 minutes, cooled once to room temperature at a temperature lowering condition of 20 ° C./min, and then measured again at a temperature rising condition of 20 ° C./min. Refers to the endothermic peak temperature (Tm2).

The melting point of the liquid crystalline resin is not particularly limited, but is preferably 3 in order to obtain a liquid crystalline resin (B) having a number average dispersion diameter within which the effect of the present invention is further exhibited.
It is 40 ° C. or lower, more preferably 320 ° C. or lower.

The method for producing the liquid crystalline polyester used in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method.

For example, in the production of the liquid crystalline polyester, the following production method is preferably mentioned.

(1) A polyester obtained from only the components excluding p-hydroxybenzoic acid and p-acetoxybenzoic acid are heated and melted under a stream of dry nitrogen to form a copolymerized polyester fragment by an acidolysis reaction.
Then, the pressure is reduced to increase the viscosity to produce a liquid crystalline polyester.

(2) p-acetoxybenzoic acid and 4,
Diacylated aromatic dihydroxy compounds such as 4'-diacetoxybiphenyl, diacetoxybenzene, and 2,
A method for producing a liquid crystalline polyester from an aromatic dicarboxylic acid such as 6-naphthalenedicarboxylic acid, terephthalic acid, or isophthalic acid by a deacetic acid condensation polymerization reaction.

(3) p-hydroxybenzoic acid and 4,
4′-dihydroxybiphenyl, an aromatic dihydroxy compound such as hydroquinone and an aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, and isophthalic acid are reacted with acetic anhydride to acylate a phenolic hydroxyl group. A method for producing a liquid crystalline polyester by a deacetic acid polycondensation reaction.

(4) Phenyl esters of p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4'-dihydroxybiphenyl, hydroquinone and 2,6
-A method for producing a liquid crystalline polyester from a diphenyl ester of an aromatic dicarboxylic acid such as naphthalenedicarboxylic acid, terephthalic acid, or isophthalic acid by a phenol-elimination polycondensation reaction.

(5) p-hydroxybenzoic acid and 2,
A predetermined amount of diphenyl carbonate is reacted with an aromatic dicarboxylic acid such as 6-naphthalenedicarboxylic acid, terephthalic acid, or isophthalic acid to form diphenyl esters, and aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone And producing a liquid crystalline polyester by a dephenol polycondensation reaction.

(6) Polyester polymers such as polyethylene terephthalate, oligomers or bis (β-
A method for producing a liquid crystalline polyester by the method (2) or (3) in the presence of a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as (hydroxyethyl) terephthalate.

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

The thermoplastic resin (A) 100 used in the present invention
The compounding amount of the liquid crystalline resin (B) is 0.5 to 1 part by weight.
00 parts by weight, preferably 3 to 60 parts by weight, more preferably 5 to 50 parts by weight, and still more preferably 5 to 30 parts by weight.

If the amount of the liquid crystalline resin (B) is too large or too small, the effects of the present invention are improved flowability during molding, measurement stability, impact resistance and anisotropy of the molded product. It is difficult to achieve the effects at the same time. In particular, L
If the CP is too large, the strength of the weld portion where the resin associates during molding tends to be significantly reduced.

When the liquid crystal resin (B) is blended with the thermoplastic resin (A), the glass transition temperature of the resulting resin composition is as follows. Although it changes from the transition temperature, in order to exhibit the effect of the present invention, the change rate of the glass transition temperature of the thermoplastic resin due to the resin composition with respect to the glass transition temperature of the thermoplastic resin (A) (the following [ It is essential that the rate of change represented by the formula 1] is 5% or less, preferably 3% or less, more preferably 0.05 to 3%, and still more preferably 0.1 to 2%. . This is an essential condition when other fillers and additives are blended, and the preferred range is also the same.

The glass transition temperature of the thermoplastic resin (A) is 5
%, The effect of adding the liquid crystalline resin is remarkably reduced, and it is thought that the liquid crystalline resin (B) forms a specific morphology only in the above range. Impact resistance and chemical resistance are well-balanced.

The glass transition temperature can be measured by, for example, a differential scanning calorimeter (DSC). In this case, the temperature is increased from room temperature at a heating rate of 20 ° C./min, and the observed inflection point is measured. Is the glass transition temperature (Tg). In the case of measuring the resin composition, a plurality of inflection points may be observed depending on the blending components, and an inflection point derived from the thermoplastic resin (A) is selected from the inflection points to determine the glass transition. Temperature.
The rate of change of the glass transition temperature is evaluated as an absolute value.

The rate of change of the glass transition temperature refers to the glass transition temperature Tg _A of the thermoplastic resin (A) measured by a differential scanning calorimeter (DSC) and the thermoplastic resin (A) in the resin composition after compounding. From the glass transition temperature Tg _T of
It can be calculated as follows. Note that when blended with other fillers and additives, to calculate the glass transition temperature of from measured thermoplastic resin after incorporation of them all (A) as Tg _T. In a system in which two or more types of thermoplastic resins (A) are blended to form a matrix, the glass transition temperature of the matrix resin derived from each of the thermoplastic resins (A) is measured, and the liquid crystal resin is measured. Measure the glass transition temperature of each thermoplastic resin of the resin composition after blending, calculate the rate of change for each thermoplastic resin, the sum of the rate of change of the glass transition temperature of each matrix resin,
Evaluate as the overall rate of change.

Rate of change (%) = | (Tg _A −Tg _T ) / Tg _A | × 100− [Formula 1] Further, the number average dispersion of the liquid crystalline resin (B) dispersed in the thermoplastic resin (A) The diameter is not particularly limited.
It is preferably in the range of 5 to 5 μm, more preferably 0.7 to 4.0 μm, and still more preferably 1.0 to 2.
5 μm, most preferably 1.0 to 2.0 μm.

When the number average dispersion diameter of the liquid crystalline resin (B) is within the above range, the fluidity and impact resistance, which are the effects of the present invention, are exhibited in a particularly well-balanced manner.

The dispersion shape of the liquid crystalline resin (B) is not particularly limited. However, in order to exhibit more effects on characteristics such as impact resistance, the aspect ratio (major axis / minor axis) of the liquid crystalline resin particles is required. Is preferably less than 3, more preferably 1.05 to 2.7, and particularly preferably 1.1 to 2.5 spherical or elliptical spherical shape.

Liquid crystalline resin (B) in thermoplastic resin (A)
The method for measuring the number average dispersion diameter and the aspect ratio of is not particularly limited. For example, a section obtained by cutting a central portion of a core layer of a molded piece in a flow direction is observed with a TEM (transmission electron microscope), and a photograph is taken. Photographing is performed, and the average value of 50 dispersed particles can be obtained as a number average dispersion diameter and an aspect ratio, respectively. The particle diameter was measured in the major axis direction. The aspect ratio is obtained by measuring the major axis and minor axis of each particle, calculating the aspect ratio of each particle, and averaging the calculated aspect ratio.

In the present invention, a filler can be used for imparting mechanical strength and other properties to the thermoplastic resin composition. The filler is not particularly limited, but may be in the form of fibrous, plate-like, or powdery. A non-fibrous filler such as a granular filler can be used. Specifically, for example, glass fiber, PA
N-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, oxidation Titanium fiber, silicon carbide fiber, rock wool,
Fibrous, whisker-like fillers such as potassium titanate whiskers, barium titanate whiskers, aluminum borate whiskers, silicon nitride whiskers, mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, Molybdenum disulfide, wollastenite, titanium oxide,
Powder, granular or plate-like fillers such as zinc oxide, calcium polyphosphate, graphite and the like can be mentioned. Among the above-mentioned fillers, glass fibers and carbon fibers are preferable. For example, when an electromagnetic wave shielding property or a high elastic modulus is required, carbon fibers are more preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, for example, chopped strand of long fiber type or short fiber type,
It can be used by selecting from a milled fiber or the like. Further, the glass fiber may be covered or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

Examples of the carbon fiber include PAN-based and pitch-based carbon fibers, and it is preferable to use a high-strength and high-elongation type carbon fiber in order to suppress fiber breakage during molding or the like. Those having low strength are brittle, and the fiber length becomes extremely short due to compound and fiber breakage during molding. As a result, it becomes difficult to obtain the conductivity required for electromagnetic wave shielding. Even those with a tensile modulus in the fiber direction exceeding 300 GPa,
Except for special ones with extraordinary strength, breakage tends to break because the elongation at break is small. Desirable carbon fibers have a tensile strength of 3500 MPa or more, a tensile modulus of 300 GPa or less,
It is a carbon fiber having a breaking elongation of 1.4% or more and all or at least one of the properties. PAN-based carbon fibers that can obtain these characteristics are more desirable. The weight average fiber length in the fiber-reinforced thermoplastic resin composition of the fibrous filler used in the present invention is preferably 0.2 mm or more, more preferably 0.2 mm, from the viewpoint of electromagnetic wave shielding properties.
5 mm or more, more preferably 0.3 mm or more.

A method for measuring the weight-average fiber length of the fibrous filler in the composition is, for example, as follows.
After treatment at 0 ° C. × 7 hours for incineration, 100 mg of the remaining filler is collected and dispersed in 100 cc of soapy water. Then, one to two drops of the dispersion are placed on a slide glass using a dropper, observed under a microscope, and photographed. The fiber length of the filler photographed is measured. The measurement is performed for 500 fibers or more, and the weight average fiber length is determined. When determining the fiber length of the carbon fiber, care must be taken because if the ashing conditions are incorrect, the fiber itself may be oxidized and burned, and it is desirable to incinerate in a nitrogen atmosphere. When the thermoplastic resin to be used is soluble, the composition can be dissolved using a solvent, the fiber can be taken out, and the fiber length can be measured.

In the present invention, the electromagnetic wave shielding property is defined as follows. Fibre-reinforced thermoplastic resin composition
It is formed into a 0 mm square, 1 mm thick flat plate, and the attenuation factor when an electromagnetic wave is transmitted through this flat plate is measured in a frequency band of 10 to 1000 MHz. The measurement is performed by a method generally called an Advantest method. Specifically, using a shield material evaluator TR17301A manufactured by Advantest Corporation,
It is possible to measure an electric field wave using a probe antenna. As a composition imparted with electromagnetic wave shielding properties, when used in a housing of a general electric / electronic device, etc., from the viewpoint of preventing malfunction of an electric circuit due to electromagnetic wave noise, using the above molded article, the above method is used. The electric field shielding property (attenuation of the electric field component of the electromagnetic wave) when measured at a frequency of 300 MHz is 30 dB or more, and the more preferable electric field shielding property is 40 dB or more.

The above-mentioned fillers can be used in combination of two or more kinds. The filler used in the present invention may be used after its surface is treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, or the like) or another surface treatment agent. .

The amount of the above-mentioned filler added depends on the resin composition (A +
The total amount is from 0.5 to 300 parts by weight, preferably from 10 to 200 parts by weight, more preferably from 10 to 50 parts by weight, per 100 parts by weight of (B).

Further, the thermoplastic resin composition of the present invention includes:
Phosphorus compounds can be added for the purpose of imparting flame retardancy and other properties. The phosphorus compound is not particularly limited as long as it is an organic or inorganic compound containing phosphorus, and examples thereof include red phosphorus, ammonium polyphosphate, polyphosphazene, phosphate, phosphonate, phosphinate, and phosphine oxide. Among them, red phosphorus and aromatic phosphate can be preferably used. When red phosphorus is added, long-term heat resistance is improved in addition to flame retardancy, and when aromatic phosphate is added, fluidity is slightly improved in addition to flame retardancy.

The red phosphorus used in the present invention is unstable as it is, and has the property of gradually dissolving in water or reacting with water gradually. Used. As a method for treating such red phosphorus, the method of pulverizing red phosphorus described in JP-A-5-229806 is not performed, and a red crushed surface having high reactivity with water and oxygen is not formed on the surface of red phosphorus. A method of finely dividing phosphorus, a method of catalytically suppressing oxidation of red phosphorus by adding a small amount of aluminum hydroxide or magnesium hydroxide to red phosphorus, a method of coating red phosphorus with paraffin or wax to suppress contact with moisture A method of stabilizing by mixing with ε-caprolactam or trioxane, a method of stabilizing by coating red phosphorus with a thermosetting resin such as a phenol-based, melamine-based, epoxy-based, unsaturated polyester-based, A method in which red phosphorus is treated with an aqueous solution of a metal salt such as copper, nickel, silver, iron, aluminum and titanium to precipitate and stabilize a metal phosphorus compound on the red phosphorus surface. Coating with luminium, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc., stabilizing by coating the surface of red phosphorus with iron, cobalt, nickel, manganese, tin, etc. by electroless plating and combining them Examples of the method include, but are not limited to, a method of pulverizing red phosphorus without pulverizing the red phosphorus and forming a crushed surface on the surface of the red phosphorus; A method of stabilizing by coating with a thermosetting resin such as a polyester resin, a method of stabilizing by coating red phosphorus with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc. Preferably, a method of finely dividing red phosphorus without forming a crushed surface on the surface of red phosphorus, and converting red phosphorus to a phenol-based, melamine-based, epoxy-based, unsaturated poly- This is a method of stabilizing by coating with a thermosetting resin such as an ester. Among these thermosetting resins, red phosphorus coated with a phenolic thermosetting resin or an epoxy thermosetting resin can be preferably used from the viewpoint of moisture resistance, and particularly preferably a phenolic thermosetting resin. Red phosphorus coated with resin.

The average particle size of red phosphorus before being blended with the resin is 35 from the viewpoints of flame retardancy, mechanical properties, wet heat resistance, and suppressing chemical and physical deterioration of red phosphorus due to pulverization during recycling. The thickness is preferably from 0.01 to 0.01 μm, and more preferably from 30 to 0.1 μm.

The average particle size of red phosphorus can be measured by a general laser diffraction type particle size distribution analyzer. There are two types of particle size distribution analyzers: wet method and dry method.
Either one may be used. In the case of the wet method, water can be used as a dispersion solvent for red phosphorus. At this time, red phosphorus surface treatment may be performed with an alcohol or a neutral detergent. It is also possible to use phosphates such as sodium hexametaphosphate and sodium pyrophosphate as the dispersant. It is also possible to use an ultrasonic bath as a dispersing device.

The average particle diameter of red phosphorus used in the present invention is as described above. However, red phosphorus having a large particle diameter contained in red phosphorus, that is, red phosphorus having a particle diameter of 75 μm or more is difficult. In order to significantly reduce the flammability, mechanical properties, wet heat resistance, and recyclability, red phosphorus having a particle size of 75 μm or more is preferably removed by classification or the like. The content of red phosphorus having a particle size of 75 μm or more is preferably 10% by weight or less, more preferably 8% by weight or less, particularly preferably 5% by weight or less from the viewpoints of flame retardancy, mechanical properties, wet heat resistance and recyclability. It is. The lower limit is not particularly limited, but is preferably as close to 0 as possible.

Here, the content of red phosphorus having a particle size of 75 μm or more contained in red phosphorus can be measured by classifying with a mesh of 75 μm. That is, 100 g of red phosphorus
From the residual amount Z (g) when classifying with a 5 μm mesh,
The content of red phosphorus having a particle size of 75 μm or more is (Z / 100) × 10
It can be calculated from 0 (%).

The conductivity of the red phosphorus used in the present invention when it is extracted in hot water (the conductivity is determined by adding 100 mL of pure water to 5 g of red phosphorus, for example, in an autoclave to obtain a conductivity of 12 g).
Extraction treatment was performed at 1 ° C for 100 hours.
Measuring the conductivity of the extracted water diluted to 0 mL), the moisture resistance, mechanical strength, tracking resistance,
0.1 to 1000 μS from the viewpoint of recyclability
/ Cm, preferably 0.1-800 μS / cm,
More preferably, it is 0.1 to 500 μS / cm.

The amount of phosphine generated by the red phosphorus used in the present invention (here, the amount of phosphine generated was determined by placing 5 g of red phosphorus in a container such as a test tube having an internal capacity of 500 mL in which nitrogen was replaced with nitrogen, and reducing the pressure to 10 mmHg. Heat treatment at 280 ° C. for 10 minutes, cool to 25 ° C., dilute the gas in the test tube with nitrogen gas, return to 760 mmHg, measure using a phosphine (hydrogen phosphide) detector tube, and use the following formula Ask.
Phosphine emission (ppm) = detector tube reading (ppm)
× dilution ratio) is usually 1 in view of the amount of gas generated from the composition obtained, stability during extrusion and molding, mechanical strength during melt retention, surface appearance of molded products, terminal corrosion by molded products, etc.
00 ppm or less, preferably 50 pp
m or less, more preferably 20 ppm or less.

[0096] Commercial products of such preferred red phosphorus include "NOVA EXCEL" 140 and "NOVA EXCEL" F5 manufactured by Rin Kagaku Kogyo KK.

The aromatic phosphate used in the present invention is represented by the following formula (1).

[0098]

Embedded image

First, the structure of the phosphorus compound represented by the formula (1) will be described. In the formula (1), n is an integer of 0 or more. K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less, preferably, k and m are each an integer of 0 or more and 1 or less;
Particularly preferably, k and m are each 1.

In the formula (1), R ^{7 to} R ¹⁴ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-
Butyl group, n-isopropyl, neopentyl, tert
-Pentyl group, 2 isopropyl, neopentyl, ter
t-pentyl group, 3-isopropyl, neopentyl, t
tert-pentyl group, neoisopropyl, neopentyl, tert-pentyl group and the like.
A methyl group and an ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted by halogen-free organic residues. Specific examples include a phenyl group, a tolyl group, a xylyl group, a cumenyl group,
Examples include a mesityl group, a naphthyl group, an indenyl group, an anthryl group, and the like. A phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable, and a phenyl group, a tolyl group, and a xylyl group are particularly preferable.

Y is a direct bond, O, S, SO ₂ , C
(CH ₃ ) ₂ , CH ₂ , and CHPh, and Ph represents a phenyl group.

Preferred commercially available aromatic phosphates include "PX-200" and "PX-20" manufactured by Daihachi Chemical Co., Ltd.
1 "," CR-733S "," CR-741 "," TP
P "and their equivalents.

In the present invention, the amount of the phosphorus compound to be added is usually 0.01 to 30 parts by weight, preferably 0 to 30 parts by weight, per 100 parts by weight of the resin composition comprising the thermoplastic resin (A) and the liquid crystal resin (B). 0.05 to 20 parts by weight, more preferably 0.0
It is 6 to 15 parts by weight, more preferably 0.08 to 10 parts by weight. If the amount of the phosphorus compound is too small, the effect of improving the flame retardancy will not be exhibited, and if it is too large, the physical properties will be reduced and the composition will tend to act as a combustion accelerator contrary to the flame retardant effect.

When red phosphorus is further added to the thermoplastic resin composition of the present invention, a metal oxide is added as a stabilizer for red phosphorus, thereby obtaining stability, strength and heat resistance during extrusion and molding. In addition, it is possible to improve the terminal corrosion property of the molded product. Specific examples of such a metal oxide include cadmium oxide, zinc oxide, cuprous oxide, cupric oxide, ferrous oxide, ferric oxide, cobalt oxide, manganese oxide,
Molybdenum oxide, tin oxide and titanium oxide, and the like, among which cadmium oxide, cuprous oxide, cupric oxide, metal oxides other than Group I and / or Group II metals such as titanium oxide are preferable, In particular, cuprous oxide, cupric oxide, and titanium oxide are preferred, but Group I and / or
It may be a Group II metal oxide. Titanium oxide is most preferable in order to further improve non-coloring properties in addition to stability and strength during extrusion and molding, heat resistance, and terminal corrosion of molded articles.

The amount of the metal oxide added is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the resin composition comprising the thermoplastic resin (A) and the liquid crystal resin (B) from the viewpoint of mechanical properties and moldability. Preferably, it is particularly preferably 0.1 to 10 parts by weight.

Further, the thermoplastic resin composition of the present invention contains an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and the like) and an ultraviolet absorber (for example, resorcinol, salicylate). , Benzotriazole, benzophenone, etc.), phosphites, hypophosphites, etc., coloring agents, lubricants, dyes (eg, nigrosine, etc.) and pigments (eg, cadmium sulfide, phthalocyanine, etc.), lubricants and release agents (Such as montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax),
As a conductive agent or a colorant, carbon black, a crystal nucleating agent, a plasticizer, and a red phosphorus or an aromatic phosphate are preferably used as a flame retardant, but other flame retardants (for example, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, Add ordinary additives such as magnesium hydroxide, melamine and cyanuric acid or a salt thereof, flame retardant aid, slidability improver (graphite, fluororesin), antistatic agent, etc. Can be granted.

Further, as the need for further property improvement is required, acid-modified olefin-based polymers such as maleic anhydride, ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / propylene / non-conjugated dienes Copolymer, ethylene / ethyl acrylate copolymer, ethylene /
Glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene /
Addition of one or more mixtures selected from elastomers such as olefin copolymers such as propylene-g-maleic anhydride copolymers, polyester polyether elastomers, and polyester polyester elastomers to further impart predetermined properties can do.

In producing the thermoplastic resin composition of the present invention, for example, a single-screw extruder equipped with a "unimelt" type screw, a twin-screw extruder, a kneader of a kneader type, or the like is used. The composition can be melt-kneaded at 350 ° C. to obtain a composition, but it is preferable to control the melt processing conditions in order to more clearly exert the effects of the present invention.

For example, the melt-kneading temperature is set at a temperature lower than the melting point of the liquid crystalline resin (B) to be blended and higher than the liquid crystal onset temperature so that the rate of change of the glass transition temperature which is a feature of the present invention falls within the range of the present invention. Preferably, the melting point of the liquid crystalline resin (B) -5 ° C. ~ liquid crystal onset temperature,
More preferably, the melting point of the liquid crystalline resin (B) is from -10 ° C to the liquid crystal onset temperature. In the present invention, the composition that has been melt-kneaded may be directly molded, but it is also possible to once subject it to molding by pelletizing or the like and then subject it to molding.

The melting temperature at the time of melt-molding the resin composition is not more than the melting point of the liquid crystal resin (B) to be blended in order to keep the rate of change of the glass transition temperature which is a feature of the present invention within the range of the present invention. In addition, it is preferably performed at a temperature equal to or higher than the liquid crystal onset temperature, and more preferably, the melting point of the liquid crystalline resin (B) −5 ° C.
To the liquid crystal onset temperature, more preferably the melting point of the liquid crystalline resin (B) -10 ° C to the liquid crystal onset temperature.

It is particularly preferable that the melt-kneading of each component is performed at the above-mentioned preferable melt-kneading temperature, and the molding is also performed at the above-mentioned preferable melt-kneading temperature.

The melt-kneading temperature and the melt-molding temperature mentioned here indicate the resin temperature. For example, during melt processing such as melt-kneading and melt molding, since the resin temperature generally becomes higher than the cylinder set temperature due to shear heat, it is necessary to set the cylinder set temperature to a slightly lower temperature so as to reach the target resin temperature. Or together with controlling the screw rotation speed and screw arrangement to keep the resin temperature within the above range, or when using an extruder equipped with a side feeder, the total amount of the liquid crystalline resin (B) mixed from the side A method of partially or entirely charging is preferably used. The onset temperature of the liquid crystal was measured using a shear stress heating device (CSS-450) at a shear rate of 1,000 (1/1).
The temperature was measured at a heating rate of 5.0 ° C./min with an objective lens of 60 times, and the temperature at which the entire visual field started to flow was defined as the liquid crystal onset temperature.

The thermoplastic resin composition of the present invention may be extruded, for example, by premixing other necessary additives and fillers in the components of the thermoplastic resin (A) and the liquid crystal resin (B) with or without premixing. It is prepared by sufficiently melting and kneading the mixture in a machine or the like, but preferably, a part of the thermoplastic resin (A) and the liquid crystal resin (B) (for example, (A)) from the viewpoint of handling properties and productivity. Part or all of (B), part or all of component (B), or finally contained (A)
And part of (B)) are melt-kneaded once and liquid crystalline resin (B) to be actually blended into the thermoplastic resin composition
A resin composition (D) having a higher liquid crystal resin concentration than the amount is prepared, and a resin composition (D) having a higher liquid crystal resin concentration in the remaining thermoplastic resin (A) or liquid crystal resin (B) component.
And other optional additives and fillers are prepared by melt-kneading.

When additives that can be used arbitrarily (hereinafter referred to as “other additives”) are blended, a part or all of the thermoplastic resin (A) and a part or all of the liquid crystal resin (B) component are added. Alternatively, a part of (A) and (B) to be finally contained and other additives are once melt-kneaded, so that the amount of the liquid crystal resin to be actually added to the thermoplastic resin composition is smaller than that of the liquid crystal resin. A resin composition (D) having a high liquid crystal resin concentration is produced, and added in the remaining thermoplastic resin (A) or liquid crystal resin (B) component and at the stage of the resin composition (D) having a high liquid crystal resin concentration. It can also be prepared by melt-kneading additives and fillers other than the above-mentioned optional additives.

The resin composition (D) having a high concentration of the liquid crystalline resin is preferably used in the form of a so-called master pellet, but is not limited thereto.
It may be in the form of a powder or a mixture thereof. The thermoplastic resin (A) and the liquid crystal resin (B) to be mixed with the component (D) are preferably in the form of pellets, but are not limited thereto.
It may be in the form of a powder, or a mixture of a chip and a powder, but preferably the thermoplastic resin (A) and the liquid crystalline resin (B) have substantially the same shape, size and shape, or are similar to each other. Are preferred in that they can be uniformly mixed.

The molding method for molding the molded product is a usual molding method (injection molding, extrusion molding, blow molding, press molding, injection press molding, etc.), such as a three-dimensional molded product, sheet, container, pipe, etc. Molded article having a thin wall portion (for example, a plate-shaped molded article or a box-shaped molded article).
It can be preferably applied to a molded product having a thin portion of 2 mm or less. Specifically, a molded article having a portion having a thickness of 1.2 mm or less with respect to the total surface area of the molded article of 10% or more, particularly a molded article having a portion of 1.2 mm or less having a thickness of 15% or more, particularly 1.0 mm It is effective for a molded article having the following portions at 10% or more. As a molding method, injection molding or injection press molding is preferred. Among them, it is particularly suitable for use in injection molded products, and is suitable for various mechanical mechanism parts, electric and electronic parts, or automobile parts. In the injection molding, it is preferable to adjust the conditions such as the injection speed and the injection pressure so that the mold filling time is appropriately long because the effects of the present invention such as impact resistance and chemical resistance are more remarkably exhibited.

Since the thermoplastic resin composition of the present invention thus obtained has good fluidity during molding, defects such as unfilling due to insufficient fluidity can be reduced, and molding can be performed in a wide range of molding conditions. It is possible. In addition, since it has excellent measurement stability, there is no variation in various characteristics. In addition, in terms of impact strength, even when one kind of the thermoplastic resin (A) is a polycarbonate resin, it is a molded product having a thick portion of 1/4 inch or more in thickness compared to the thermoplastic resin (A) alone. And particularly high impact strength. Further, since the heat resistance is improved, it is most suitable for housings, covers, bases, and the like that require heat resistance in electric and electronic equipment applications. In addition, because of its excellent chemical resistance, a highly reliable molded product can be obtained when a member to which a chemical adheres or a surface treatment with the chemical is required. This effect of improving chemical resistance is particularly remarkably exhibited with oils, plasticizers, detergents, electrolytes, and the like. In addition, since the anisotropy is also reduced, dimensional changes due to molding shrinkage and thermal expansion are suppressed, and a molded product having a high reliability can be obtained from molded products of any shape from a bulk molded product to a thin plate.

[0119] The molded article thus obtained is composed of various gears,
Various cases, sensors, LED lamps, connectors, sockets, paper separating claws, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, optical pickup slide bases, oscillators, various terminal boards, transformers, Plug, printed wiring board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FD
D / carriage, FDD chassis, HDD parts, motor brush holder, parabolic antenna, electric and electronic parts represented by computer related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, sound parts Audio equipment parts such as audio, laser disk, compact disk,
Lighting parts, refrigerator parts, washing machine parts, air conditioner parts, typewriter parts, home appliances, office electrical products parts, office computer related parts, telephone related parts, facsimile related parts represented by word processor parts, etc.
Copier-related parts, cleaning jigs, various bearings such as oilless bearings, stern bearings, underwater bearings, etc., motor parts, machine-related parts such as lighters, typewriters, microscopes, binoculars, cameras, watches, etc. Representative optical equipment, precision machinery related parts, alternator terminal, alternator connector, IC regulator, various valves such as exhaust gas valve, various fuel related / exhaust / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine Cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor Over, air conditioner thermostat base, heating warm air flow control valve, radiator motor for the brush holder, water pump impeller, turbine base-in, wiper motor-related parts, du string views coater, a starter switch, starter relay, transmission wire harness,
Window washer nozzles, window washer fluid tanks, oil tanks such as brakes, battery cases, air conditioner panel switch boards, coils for fuel-related electromagnetic valves, connectors for fuses, horn terminals, electrical component insulating plates, step motor rotors, lamp sockets, lamps Automotive and vehicle related parts such as reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, power seat housings, ignition coil parts, etc.
Bottles for shampoo and rinse, tanks for chemicals, containers for oil transfer, oil pans, other toiletries,
It is useful for various uses such as entertainment supplies, medical supplies, medical equipment members, and general equipment. In particular, various cases having a thin portion of 1.2 mm or less and 10% or more of the total surface area of the molded product,
It is particularly useful as switches, bobbins, connectors, socket connectors, housings for mobile phones, personal computer housings, and housings (housings) for various devices.

[0120]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the gist of the present invention is not limited to the following Examples.

Reference Example 1 The following thermoplastic resin was used.

PC "LEXAN" 141 manufactured by General Electric Co. was used as the polycarbonate resin. The equivalent ratio of phenolic terminal groups (E _P) and non-phenolic terminal groups _{(E N) (E P)} / (E N) is the result 1/100 of titanium tetrachloride complex photometric quantification, the results of the DSC measurements The glass transition temperature was 153 ° C. This was designated as PC (a). For comparison, the logarithmic viscosity measured at 20 ° C. at a concentration of 1.0 g / dl in methylene chloride, which was synthesized by melt polymerization of bisphenol A and diphenyl carbonate, was 0.45 dl / g, and (E _P ) / (E _N ) = 1/3, a polycarbonate resin having a glass transition temperature of 146 ° C. was used. This was designated as PC (b).

PC // ABS The above polycarbonate resin “Lexane” 141 was added to 55
ABS resin 45 containing 9% by weight butadiene rubber
Weight% using a twin screw extruder, cylinder temperature 250 ° C,
Kneading was performed at a screw rotation speed of 100 rpm. As a result of DSC measurement, the glass transition temperatures were -72 ° C, 105 ° C, and 152 ° C.
The above two are glass transition temperatures derived from ABS resin (-72 ° C. is a glass transition temperature derived from a rubber component, 105
° C is the glass transition temperature derived from AS), and 152 ° C is the glass transition temperature derived from polycarbonate. The rate of change of the glass transition temperature was calculated for these three glass transition temperatures, and the sum of them was evaluated.

Poly-2,6-dimethyl 1,4 synthesized by oxidative coupling using an amine copper complex salt of PPE 2,6-xylenol
-Polyphenylene ether was used. As a result of DSC measurement, a glass transition temperature was observed at 210 ° C.

PPE // PS "Noryl" 731 manufactured by GE Plastics Japan was used.
As a result of DSC measurement, a glass transition temperature was observed at 153 ° C. Since only one glass transition temperature was observed, this was taken as the glass transition temperature of the matrix resin.

Reference Example 2 The following liquid crystalline resin was polymerized and used.

LCP1 994 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4'-dihydroxybiphenyl, 112 terephthalic acid
Parts by weight, 216 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 960 parts by weight of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distilling tube, and polymerization was carried out. Melting point 314 ° C. consisting of 80 molar equivalents of oxycarbonyl units, 7.5 molar equivalents of aromatic dioxy units, 12.5 molar equivalents of ethylenedioxy units, and 20 molar equivalents of aromatic dicarboxylic acid units; liquid crystal onset temperature of 293 ° C .;
Melt viscosity at 24 ° C. 21 Pa · s (orifice 0.5φ ×
A liquid crystalline resin having a thickness of 10 mm and a shear rate of 1,000 (1 / sec) was obtained.

LCP2 907 parts by weight of p-hydroxybenzoic acid, 457 parts by weight of 6-hydroxy-2-naphthoic acid and 873 parts by weight of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distillation tube, and the polymerization was carried out. A melting point of 283 ° C. consisting of 100 molar equivalents of aromatic oxycarbonyl units, a liquid crystal onset temperature of 233 ° C., 29
The melt viscosity at 3 ° C is 50 Pa · s (orifice 0.5φ ×
A liquid crystalline resin having a thickness of 10 mm and a shear rate of 1,000 (1 / sec) was obtained.

LCP3 994 parts by weight of p-hydroxybenzoic acid, 346 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 809 parts by weight of acetic anhydride were placed in a reaction vessel equipped with stirring blades and a distilling tube. As a result of charging and polymerization, 80 mole equivalents of aromatic oxycarbonyl units and 2 ethylenedioxy units were obtained.
0 mol equivalent, 20 mol equivalent of aromatic dicarboxylic acid unit, melting point 282 ° C., liquid crystal onset temperature 231 ° C., melt viscosity at 292 ° C. 24 Pa · s (orifice 0.5φ × 10 m
m, a liquid crystal resin having a shear rate of 1,000 (1 / second) was obtained.

LCP4 901 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4'-dihydroxybiphenyl, 112 terephthalic acid
Parts by weight, 346 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 960 parts by weight of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distilling tube, and polymerization was carried out. 72.5 molar equivalents of oxycarbonyl units, 7.5 molar equivalents of aromatic dioxy units, 20 molar equivalents of ethylenedioxy units, and 27 dicarboxylic acid units.
Melting point 267 ° C. consisting of 5 molar equivalents, liquid crystal onset temperature 238
277 ° C melt viscosity 34 Pa · s (orifice 0.
A liquid crystalline resin having a diameter of 5 × 10 mm and a shear rate of 1,000 (1 / sec) was obtained.

Examples 1-27, Comparative Examples 1-23 A thermoplastic resin shown in Table 1 was charged from a hopper with a TEX30 type twin screw extruder manufactured by Nippon Steel Works equipped with a side feeder. The reactive resins (LCP1 to LCP4) and the filler are charged from the side, and the heater set temperature of the cylinder is set as shown in Table 1. The resin temperature (the resin temperature is determined by the heat generated by the shearing heat generated by the screw arrangement and the screw rotation speed) The mixture was melt-kneaded while measuring the temperature of the mixture to obtain a pellet. After hot air drying, the pellets are converted to Sumitomo Nestor injection molding machine Promat 4
0/25 (manufactured by Sumitomo Heavy Industries, Ltd.), the resin temperature was set as shown in Table 1, the mold temperature was set to 80 ° C., and 1
The test pieces for measurement described in the following (2) and (4) to (9) were injection-molded under the conditions of one speed (injection speed: 99%, injection pressure: minimum filling pressure + 5 kgf / cm ² ).

Each evaluation was measured according to the method described below.

(1) Change rate of glass transition temperature The glass transition temperature (Tg) of the thermoplastic resin (A)_A)and
(A) is blended with a liquid crystal resin (B) in a predetermined weight part shown in Table 1.
From the thermoplastic resin (A) in the resin composition after the heat treatment
Transition temperature (Tg_T) Is a differential scanning calorimeter (Perkin-L)
It was measured by DSC-7) manufactured by Mer Company. Cutting pellets
About 10 mg of the pieces, at a heating rate of 20 ° C./min from room temperature
When the temperature rises, the inflection point observed is defined as the glass transition temperature (Tg).
did. The rate of change of the glass transition temperature depends on the observed thermoplasticity.
Glass transition temperature Tg of resin (A) _AAnd resin composition after compounding
Transition temperature Tg derived from thermoplastic resin (A) in the product_T
Was calculated according to the following equation 1.

Change rate (%) = | (Tg _A −Tg _T ) / Tg _A | × 100− [Formula 1] (2) Number average dispersion diameter of liquid crystal resin particles, aspect ratio Izod impact prepared according to ASTM D256 A section obtained by cutting the center portion of the 1/8 inch bar for strength measurement in the flow direction was observed and photographed with a TEM (H-7100 transmission electron microscope manufactured by Hitachi, Ltd.), and a photograph was taken.
The average value of the pieces was determined as the number average dispersion diameter and the aspect ratio (major axis / minor axis). The dispersed particle diameter was measured in the major axis direction. The aspect ratio is the major axis of each particle,
The minor axis was measured, the aspect ratio was calculated, and the average was evaluated.

(3) Fluidity Using the above molding machine, the resin temperature when using only the thermoplastic resin shown in Table 1 (PC is 300 ° C., PC // ABS
Is 250 ° C, PPE is 300 ° C, and PPE // PS is 30
0 ° C) at an injection speed of 99% and an injection pressure of 5 at the same resin temperature.
12.7mm width × 0.8m in the conditions of 00kgf / cm ²
The flow length (rod flow length) of a test piece having a thickness of m was measured.

(4) Heat Resistance Using the above molding machine, 127 mm long × 12.7 mm wide ×
Create a 1.2mm thick rod-shaped molded product and place it in a hot air oven,
At a temperature obtained by subtracting 130 ° C. from the resin temperature of each of the thermoplastic resins shown in Comparative Examples 1 to 4 in Table 1, for 30 minutes, a vertical 27 mm was fixed with a clamp, and a heat sag test was performed using 100 mm as a test portion. <Evaluation> ：: Deformation less than 5 mm, ×: Deformation of 5 mm or more (5) Impact strength According to ASTM D256, 1/4 inch (notched) bar Izod impact strength was measured.

(6) Chemical resistance Using the above molding machine, 127 mm long × 12.7 mm wide ×
A 3.2 mm thick bending test piece was prepared, and the test piece was 11
It was curved so as to be 0 mm, and both ends were fixed using a jig. DOP (dioctyl phthalate, manufactured by Daihachi Chemical Co., Ltd.) was applied near the center of the arc, and the time until the test piece was broken was measured.

(7) Measurement Stability (Cushion Amount Variation) In the molding cycle of 5 seconds of injection, 10 seconds of cooling, and 4 seconds of middle, one vertical cycle
A bending test piece of 27 mm x 12.7 mm x 3.2 mm thickness is molded for 50 cycles, and the cushion amount at the time of holding pressure (the cushion amount is a mold used to eliminate defects such as sink in molded products during molding). This is the amount of resin that weighs the resin of the full filling amount + α and leaves an excess of resin at the tip of the molding machine cylinder. At this time, from the cylinder tip position (0 mm) to the screw position corresponding to the mold full filling amount + α The standard deviation of the variation in the distance (mm) was evaluated.

(8) Effect of reducing anisotropy Using the molding machine described above, a square plate-shaped molded product having a length of 70 × 70 × 1 mm was prepared, and cut pieces (70 mm long) in the flow direction and the vertical direction of the square plate were prepared. × width 12.7mm × thickness 1mm, each n = 2
0) was prepared, a bending test was performed in accordance with ASTM D790, and strength anisotropy was calculated by the following equation 2.

Anisotropy = Bending strength in vertical direction / Bending strength in flow direction− [Equation 2] (9) Fatigue characteristics Using the above molding machine, 127 mm long × 12.7 mm wide ×
A 3.2 mm thick bending test piece was prepared and the span was 50 mm.
A stress was applied to the central portion of the test piece in step (1), and the head with the load detector was lowered at a constant speed so that the strain reached １ ／ of the maximum strain in the elastic range of the test piece in 30 seconds. Thereafter, the head was returned to the initial position at the same speed. After repeating this low-speed load application for 10 minutes, ASTM
A bending test was performed according to D790, and the rigidity retention was evaluated. <Evaluation> ：: Rigidity retention of 90% or more, ：: Rigidity retention of 80% or more, ×: Rigidity retention of less than 80% (10) Electromagnetic wave shielding 150 mm × 150 mm × 1 mm thick square plate is injection molded. Then, the shielding property of the electric wave was measured based on the Advantest method using the obtained molded article. Specifically, Advantest's shield material evaluator TR1
Using a 7301A, a spectrum analyzer, and a probe antenna, the attenuation factor when an electromagnetic wave was transmitted through this flat plate was measured in a frequency band of 10 to 1000 MHz, and the electric field shielding property at a frequency of 300 MHz was read from a measurement chart. Was. <Evaluation> ：: Electromagnetic wave shielding property of 40 dB / 1 GHz or more, ：: Electromagnetic wave shielding property of 35 dB /
1 GHz or more, ×: electromagnetic wave shielding property less than 35 dB / 1 GHz As is clear from Table 1, the composition of the present invention is superior in flowability and measurement stability to the comparative example, and the obtained molded article has impact resistance. Improved strength, heat resistance, and chemical resistance, and reduced anisotropy.Thin and thick sections, and boxes with thin sections for use in applications that have opportunities to contact various chemicals. It turns out that it is very excellent in obtaining a molded article.

According to Tables 2 and 3, when the carbon fiber is used as the filler, the fatigue property and the electromagnetic wave shielding property are improved by the effect of the liquid crystalline resin as compared with the case where only the carbon fiber is used. It can be seen that it is most suitable as a housing for mobile and portable electric and electronic equipment such as mobile phones and mobile phones.

[0142]

[Table 1]

[0143]

[Table 2]

[0144]

The thermoplastic resin composition of the present invention has improved fluidity and measurement stability during molding, and has improved impact resistance, heat resistance, chemical resistance, and fatigue properties of molded articles. Since the anisotropy is also reduced, the material is suitable for electrical and electronic equipment, precision equipment, office equipment, automobiles, and other various applications that require these characteristics.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 25/16 C08L 25/16 51/04 51/04 69/00 69/00 71/12 71/12 / / (C08L 25/06 67:03) (C08L 25/12 67:03) (C08L 25/16 67:03) (C08L 51/04 67:03) (C08L 69/00 67:03) (C08L 71 / 12 67:03) F term (reference) 4F071 AA22 AA48 AA50 AA51 AA86 AA88 AB03 AD01 AD06 AE17 AH07 AH12 BB05 BB06 BC03 BC04 BC07 4J002 BC031 BC061 BC081 BC091 BC101 BC121 BN061 BN121 BF1 CF2 CF04 BN151 CF2 CL063 CL082 DA016 DA096 DC006 DE046 DE186 DE236 DG026 DG056 DH056 DJ006 DK006 DL006 DM006 FA016 FA043 FA046 FA086 FA106 FB086 FB276 FD013 FD016 FD030 FD050 FD090 FD130 FD160 GB00 GC00 GL00 GM00 GN00 GQ00

Claims (11)

[Claims] 1. A liquid crystalline resin (B) in an amount of 0.5 to 100 parts by weight based on 100 parts by weight of at least one thermoplastic resin (A) selected from a styrene resin, a polycarbonate resin and a polyphenylene ether resin. Wherein the rate of change of the glass transition temperature of the thermoplastic resin (A) satisfies Formula 1 below. Rate of change (%) = | (Tg _A −Tg _T ) / Tg _A | × 100 ≦ 5− [Formula 1] Tg _A : Glass transition temperature of thermoplastic resin (A) Tg _T : Thermoplastic in resin composition Glass transition temperature derived from resin (A) 2. The thermoplastic resin composition according to claim 1, wherein the number average particle diameter of the liquid crystalline resin particles dispersed in the resin composition is 0.5 to 5 μm. 3. The thermoplastic resin composition according to claim 1, wherein the aspect ratio (major axis / minor axis) of the liquid crystalline resin particles dispersed in the resin composition is less than 3. 4. The thermoplastic resin (A) contains a polycarbonate resin, and the phenolic terminal group (E _P ) and the non-phenolic terminal group (E _N ) of the polycarbonate resin.
The thermoplastic resin composition according to any one of claims 1 to 3, wherein the equivalent ratio (E _P ) / (E _N ) is 1/20 or less. 5. A liquid crystalline resin (B) comprising the following structural units (I) and (I)
The thermoplastic resin composition according to any one of claims 1 to 4, which is a liquid crystalline polyester composed of (I), (III) and (IV). Embedded image (Where R ₁ in the formula is And R ₂ represents one or more groups selected from And at least one group selected from In the formula, X represents a hydrogen atom or a chlorine atom. ) 6. A filler is used in an amount of 0.5 to 3 based on a total of 100 parts by weight of the thermoplastic resin (A) and the liquid crystal resin (B).
The thermoplastic resin composition according to any one of claims 1 to 5, further comprising 00 parts by weight. 7. The thermoplastic resin composition according to claim 6, wherein the filler is carbon fiber. 8. A thermoplastic resin (A) and a liquid crystal resin (B),
When a filler is further compounded, the filler is melt-kneaded at a temperature not lower than the liquid crystal onset temperature of the liquid crystalline resin (B) and not higher than the melting point to produce the thermoplastic resin composition according to any one of claims 1 to 7. A method for producing a thermoplastic resin composition, comprising: 9. A thermoplastic resin (A) and a liquid crystalline resin (B),
A molding comprising the thermoplastic resin composition according to any one of claims 1 to 7, wherein the composition further containing a filler is melt-processed at a temperature from the liquid crystal onset temperature to the melting point of the liquid crystalline resin (B). A method for producing a molded article, characterized by producing an article. 10. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 7, wherein the molded article is a mechanical mechanism part, an electric / electronic part or an automobile part. 11. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 7, wherein the molded article has a plate-like portion or a box-like portion and a thickness of 1. A molded article characterized by having a thin part of 2 mm or less with respect to the total surface area of the molded article by 10% or more.