JP2980054B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to heat resistance, moldability,
The present invention relates to a thermoplastic resin composition having excellent fluidity, hydrolysis resistance, and mechanical properties.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for higher performance of plastics, and a number of polymers having various new properties have been developed and marketed. Among them, the polymer is characterized by a parallel arrangement of molecular chains. Optically anisotropic liquid crystal polymers have attracted attention because of their excellent mechanical properties.

As a polymer forming an anisotropic molten phase, for example, a liquid crystal polymer obtained by copolymerizing polyethylene terephthalate with p-hydroxybenzoic acid (JP-A-49-7239)
No. 3), a liquid crystal polymer obtained by copolymerizing p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid (Japanese Patent Laid-Open No.
And a liquid crystal polymer obtained by copolymerizing p-hydroxybenzoic acid with 4,4'-dihydroxybiphenyl, terephthalic acid and isophthalic acid (Japanese Patent Publication No. 57-24).
No. 407) is known.

Also, p-hydroxybenzoic acid, 1,2-
Bis (phenoxy) ethane-4,4′-dicarboxylic acid,
There is known a composition comprising a wholly aromatic polyester which forms an anisotropic molten phase composed of terephthalic acid, methylhydroquinone, 2,6-dihydroxynaphthalene and the like, and polyarylene sulfide (JP-A-57-51739). .

[0005]

However, Japanese Patent Application Laid-Open Nos. Sho 49-72393 and 54-77691 describe the above.
The liquid crystalline polymer described in JP-A-57-24407 and the completely aromatic polyester used in the composition described in JP-A-57-51739 have a low thermal deformation temperature of less than 190 ° C. , Heat resistance is insufficient and heat distortion temperature is 190 ° C or higher, which is good heat resistance. However, the liquid crystal starting temperature is too high and molding cannot be performed at 400 ° C or higher, and the melt viscosity is high. It does not have a balance between moldability and fluidity, and among them, the wholly aromatic polyester used in the composition described in JP-A-57-51739 is insufficient in hydrolysis resistance at high temperatures. There was a problem. For this reason, even if a completely aromatic polyester is blended to improve the mechanical properties of polyphenylene sulfide, heat resistance and moldability,
It was difficult to obtain a composition having a balance with fluidity, and the hydrolysis resistance was insufficient.

Accordingly, an object of the present invention is to solve the above-mentioned problems and to provide a thermoplastic resin composition having excellent heat resistance, moldability, fluidity, hydrolysis resistance, and mechanical properties.

That is, in the present invention, the heat distortion temperature comprising the following structural units is 190 to 280 ° C., and the liquid crystal onset temperature is 330 ° C.
Hereinafter, 70 to 99% by weight of a liquid crystal polyester (A) which forms an anisotropic molten phase having a melt viscosity of 10,000 poise or less.
When, the acid treatment and / or hot water treatment and polyphenylene sulfide comprising (B) 1~ 3 0 thermoplastic resin composition comprising by weight%,

Embedded image (However, X in the formula is

Embedded image —CH ₂ CH ₂ — represents at least one group selected from the group consisting of carbonyl groups of the structural unit (IV) in a para or meta position, and 50 mol% or more of the carbonyl groups are in the para position.
A thermoplastic resin composition comprising 1 to 70 parts by weight of the olefin polymer (C) based on 100 parts by weight of the thermoplastic resin composition, and reinforced with 100 parts by weight of the thermoplastic resin composition The thermoplastic polyester (E) is contained in an amount of 1 to 5,000 parts by weight based on 100 parts by weight of the thermoplastic resin composition containing the agent (D) in an amount of 5 to 400 parts by weight. Is a thermoplastic resin composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The structural unit (I) of the thermoplastic polyester (A) in the present invention is a structural unit formed from p-hydroxybenzoic acid, and the structural unit (II) is 4,4'-dihydroxyl. Structural units generated from biphenyl, wherein the structural unit (III) is hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6-
A structural unit generated from one or more dihydroxy compounds selected from dihydroxynaphthalene and ethylene glycol, and a structural unit (IV) indicates a structural unit generated from terephthalic acid and / or isophthalic acid.

The liquid crystal polyester (A) of the present invention is a copolymer comprising the structural units (I), (II), (III) and (IV).

The copolymerization amount of the structural units (I), (II), (III) and (IV) is arbitrary. The following copolymerization amount is preferable from the viewpoint of fluidity. That is, the content of the structural unit (I) is preferably 40 to 90 mol% based on the total of the structural units (I), (II) and (III). Also,
The molar ratio of the structural units (II) and (III) [(II) / (II
I)] is preferably 90 / 10-10 / 90, in the structural unit (III) -X- is -CH ₂ CH ₂ - otherwise preferably 75 / 25-25 / 75, 75/25
~ 40/60 is particularly preferred.

On the other hand, in (III), X- is -CH ₂ CH
_In the case of _2- , the structural unit (III) is the structural unit (I) or (II)
And 23 to 5 mol% with respect to the total of (III) and (III), and the molar ratio of the structural units (I) and (II) [(I)
/ (II)] is preferably from 75/25 to 95/5.

The structural unit (IV) is a structural unit (I
It is substantially equimolar to the sum of I) and (III).

The liquid crystal polyester (A) used in the present invention
Has a heat distortion temperature of 190 to 2 when no other component is blended.
80 ° C.

When the heat distortion temperature is less than 190 ° C., the heat resistance is insufficient, and when it exceeds 280 ° C., there arises a problem that the molding temperature of the obtained resin composition becomes high.

Here, the heat distortion temperature is a value obtained by measuring a 1/8 ″ thick test piece at a stress of 18.6 kg / cm ² based on ASTM D648.

The liquid crystal onset temperature of the liquid crystal polyester (A) is essential to be 330 ° C. or lower, and is preferably 260 to 330 ° C. in view of fluidity and heat resistance. It is particularly preferred that there is.

If the liquid crystal onset temperature exceeds 330 ° C., the molding temperature must be increased, which is not practical in terms of moldability.

It is essential that the melt viscosity be 10,000 poise or less, preferably 5,000 poise or less, and more preferably 2,000 poise or less.

Note that this melt viscosity is (liquid crystal onset temperature + 4
0 ° C.) and a shear rate of 1,000 (1 / second) under the conditions of a Koka flow tester.

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

For example, in the structural unit (III), -X
- otherwise the following (1) to (4), - is -CH ₂ CH ₂ -
X- is -CH ₂ CH ₂ - in the case of the production method of (5) are preferred.

(1) p-acetoxybenzoic acid, 4,4 '
-A method of producing from a diacylated aromatic dihydroxy compound such as diacetoxybiphenyl or paraacetoxybenzene and an aromatic dicarboxylic acid such as terephthalic acid by a deacetic acid polycondensation reaction.

(2) p-hydroxybenzoic acid, 4,4 '
A method of reacting an aromatic dihydroxy compound such as dihydroxybiphenyl or hydroquinone, or an aromatic dicarboxylic acid such as terephthalic acid with acetic anhydride to acylate a phenolic hydroxyl group, followed by a deacetic acid polycondensation reaction.

(3) Manufactured by a dephenol polycondensation reaction from an aromatic dihydroxy compound such as phenyl ester of p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl or hydroquinone and a diphenyl ester of aromatic dicarboxylic acid such as terephthalic acid. how to.

(4) A desired amount of diphenyl carbonate is reacted with an aromatic dicarboxylic acid such as p-hydroxybenzoic acid and terephthalic acid to form a diphenyl ester, and then an aromatic dicarboxylic acid such as 4,4'-dihydroxybiphenyl and hydroquinone is obtained. Add a dihydroxy compound,
A method of producing by a dephenol polycondensation reaction.

(5) A method of producing by the method of (1) or (2) in the presence of polyethylene terephthalate.

Since a liquid crystal polyester (A) having a high degree of polymerization can be obtained, it is more preferable to use the method (2).
Typical catalysts used in the polycondensation reaction include metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate, antimony trioxide, magnesium, sodium acetate, and zinc acetate. It is effective for

Some liquid crystal polyesters (A) of the present invention can be measured for intrinsic viscosity in pentafluorophenol.
It is preferably 0.5 dl / g or more, more preferably 1.0 to 15.0 dl / g, as measured at ° C. When the liquid crystal polyester (A) used in the present invention is polycondensed, in addition to the components constituting (I), (II), (III) and (IV), 4,4'-diphenyldicarboxylic acid, 3,3'-
Diphenyldicarboxylic acid, 3,4'-diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid, 1,2-
Bis (phenoxy) ethane-4,4′-dicarboxylic acid,
1,2-bis (2-chlorophenoxy) ethane-4,4
Aromatic dicarboxylic acids such as' -dicarboxylic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, resorcinol, chlorohydroquinone, methylhydroquinone,
Aromatic dihydroxy compounds such as 2,7-dihydroxynaphthalene, aromatic oxycarboxylic acids such as m-oxybenzoic acid and 2,6-oxynaphthoic acid, p-aminophenol, p-aminobenzoic acid and the like are objects of the present invention. Can be further copolymerized in a small proportion that does not impair the above.

The polyphenylene sulfide (B) used in the present invention is a polymer represented by the general formula (Ph-S) n, having a molecular weight of 10,000 to 50,000 and a melting point of 270 to 270.
Those having a temperature of 300 ° C. are preferably used. In the above general formula, -Ph-

Embedded image Q is F, Cl, Br or CH ₃ , m is 1
Shows an integer of ~ 4. General formula

Embedded image The polyphenylene sulfide (B) represented by is preferably used.

It is important to carry out an acid treatment and / or a heat treatment in order to remove impurities contained in the polyphenylene sulfide (B). These methods include, for example, a method of immersing PPS in an acid such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, or propyl acid or an aqueous solution thereof, heating and stirring as necessary, Examples of the method include a method of water treatment, a method of combining these, and the like. When these treatments are performed, it is preferable to wash with warm water several times in order to remove remaining acids, salts and the like.

In the present invention, the liquid crystal polyester (A)
Is 70 to 99% by weight, preferably 70 to 95% by weight, particularly preferably 70 to 90% by weight, and the amount of polyphenylene sulfide (B) is 30 to 1% by weight, preferably 30 to 90% by weight. 5% by weight, particularly preferably from 3 0 to 10 wt%
It is. When the content of the liquid crystal polyester (A) exceeds 99% by weight, the hydrolysis resistance is insufficient.

In order to further improve the mechanical properties, the thermoplastic resin composition of the present invention contains an olefin polymer (C).
Can be added.

Examples of the olefin polymer include a copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid, an ethylene and an α-olefin having 3 or more carbon atoms or ethylene, A modified ethylene polymer obtained by grafting an unsaturated carboxylic acid or a derivative thereof to a copolymer comprising an α-olefin and a non-conjugated diene is preferably used.

In the copolymer comprising the α-olefins and the glycidyl ester of an α, β-unsaturated acid,
-As the olefins, those having 2 to 4 carbon atoms are preferable, and specific examples thereof include ethylene, propylene, and butene-1. Among them, ethylene can be preferably used.
Glycidyl esters of α, β-unsaturated acids are represented by the general formula

Embedded image (In the formula, R is a hydrogen atom or a lower alkyl group.)
And specific examples thereof include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferably used. The copolymerization amount of the glycidyl ester of α, β-unsaturated acid is suitably in the range of 1 to 50 mol%. Further, if it is 40 mol% or less, unsaturated monomers copolymerizable with the above copolymers, that is, vinyl esters such as vinyl ethers, vinyl acetate, and vinyl propionate;
Esters of acrylic acid and methacrylic acid such as methyl, ethyl and propyl, acrylonitrile, styrene and the like may be copolymerized. The ethylene and carbon number 3
The copolymer of the above α-olefin or ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated diene (hereinafter, both are collectively referred to as an unmodified ethylene polymer) is used in an amount of 0.01 to 10%. In the modified ethylene polymer obtained by grafting an unsaturated carboxylic acid or a derivative thereof in an amount of 3% by weight, propylene, butene-1, pentene-1, and 3-methylpentene-1 are used as α-olefins having 3 or more carbon atoms. And octacene-1. Among them, propylene and butene-1 are preferably used.
Examples of the non-conjugated diene include 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-isopropenyl-2-norbornene, and
Crotyl-2-norbornene, 5- (2-methyl-2-
Butenyl) -2-norbornene, 5- (2-ethyl-2)
-Butenyl) -2-norbornene, 5-methacrylnorbornene, norbornene compounds such as 5-methyl-5-vinylnorbornene, dicyclopentadiene, methyltetrahydroindene, 4,7,8,9-tetrahydroindene, 1,5 -Cyclooctadiene, 1,4-hexadiene, isoprene, 6-methyl-1,5-heptadiene, 11-ethyl-1,1,1-tridecadiene and the like, preferably 5-methylidene-2-norbornene;
5-ethylidene-2-norbornene, dicyclopentadiene, 1,4-hexadiene and the like can be used.

The copolymerization ratio of an unmodified ethylene polymer comprising ethylene and an α-olefin having 3 or more carbon atoms is 4
The range is preferably from 0/60 to 99 to 1 (molar ratio), and particularly preferably from 70/30 to 95/5 (molar ratio).

The copolymerization amount of the α-olefin having 3 or more carbon atoms in the unmodified ethylene copolymer comprising ethylene, α-olefin having 3 or more carbon atoms and a non-conjugated diene is 5
Is preferably from 80 to 80 mol%, particularly preferably from 20 to 60 mol%, and the copolymerization amount of the non-conjugated diene is from 0.1 to 20 mol%
Is preferably used, and particularly preferably 0.5 to 10 mol% is used.

Specific examples of the unmodified ethylene copolymer include ethylene / propylene copolymer and ethylene / butene-
1 copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer and the like are preferably exemplified.
Among them, ethylene / propylene copolymers and ethylene / butene-1 copolymers containing no non-conjugated diene have good heat resistance and can be used more preferably.

As the unsaturated carboxylic acid obtained by performing a graft reaction on the unmodified ethylene-based copolymer to obtain a modified ethylene-based copolymer, acrylic acid, methacrylic acid, or the like is preferable.
Ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, butenedicarboxylic acid and the like. In addition, as their derivatives, alkyl esters,
Glycidyl esters, acid anhydrides, imides and the like are mentioned, and among these, glycidyl esters, acid anhydrides and imides are preferable.

Preferred specific examples of the unsaturated carboxylic acids or derivatives thereof include maleic acid, fumaric acid, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, diglycidyl citraconic ester, and butenedicarboxylic acid diester. Glycidyl esters, maleic anhydride, itaconic anhydride, citraconic anhydride, maleic imide, itaconic imide, and citraconic imide, and particularly, glycidyl methacrylate, maleic anhydride, itaconic anhydride, and maleic imide can be preferably used. . Two or more of these unsaturated carboxylic acids or derivatives thereof may be used in combination.

The amount of the grafting reaction of the unsaturated carboxylic acid or a derivative thereof is preferably 0.01 or more from the viewpoint of the effect of improving the mechanical properties, particularly the surface impact, and 10% by weight or less from the viewpoint of the heat resistance of the aromatic polyester. , Especially 0.05-
Preferably it is 5% by weight. Here, the graft reaction means that an unsaturated carboxylic acid or a derivative thereof is chemically bonded to an unmodified ethylene polymer.

The modified ethylene polymer is present in an unmodified ethylene polymer in an amount of 0.001 to 0.1% by weight based on the unsaturated carboxylic acid or its derivative and the unmodified ethylene polymer.
And then melt-kneaded at 150 to 300 ° C. A screw extruder, a Banbury mixer, or the like can be used as an apparatus for the melt mixing.

Specific examples of the organic peroxide which can be preferably used in this graft reaction include tert-butylcumyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- Di (tert-
Butylperoxy) hexane, 2,5-dimethyl-2,
5-di (tert-butylperoxy) hexyne-3, α,
α'-di- (tert-butylperoxy) diisopropylbenzene and the like.

The olefin polymer (C) may be used in combination of two or more.

The amount of the olefin polymer (C) is usually 0.1 to 100 parts by weight of the total of the liquid crystal polyester (A) and the polyphenylene sulfide (B) in order to obtain the effect of improving the mechanical properties. The amount is preferably 1 part by weight or more and 70 parts by weight or less from the viewpoint of fluidity, that is, 0.1 to 70 parts by weight, and particularly preferably 0.5 to 50 parts by weight.

The thermoplastic resin composition of the present invention may further comprise a reinforcing agent (D) for further improving heat resistance and mechanical properties.
Can be added. Specific examples of the reinforcing agent (D) include fibrous, granular, and a mixture of both. As the fibrous reinforcing agent, glass fiber, shirasu glass fiber,
Examples include inorganic fibers such as alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, and metal fibers (eg, stainless steel fibers) and carbon fibers. In addition, as a granular fortifying agent, walastenite, sericite, kaolin, mica, clay, bentonite,
Asbestos, talc, silicates such as alumina silicate, alumina, metal oxides such as silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, carbonates such as calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, etc. Examples thereof include sulfate, glass beads, boron nitride, silicon carbide, and Saroyan, which may be hollow (eg, hollow glass fiber, glass microballoon, shirasu balloon, carbon balloon, and the like). The above-mentioned reinforcing agent (D) may be used after pretreatment with a silane-based or titanium-based coupling agent if necessary.

The amount of the reinforcing agent (D) to be added was 10% in total of the liquid crystal polyester (A) and the polyphenylene sulfide (B).
In order to obtain a sufficient reinforcing effect with respect to 0 parts by weight, the range is preferably 5 parts by weight or more and 400 parts by weight or less from the viewpoint of fluidity, that is, a range of 5 to 400 parts by weight, particularly 25 to 150 parts by weight.
A range of parts by weight is preferred. In order to further improve the mechanical properties, a thermoplastic polyester (E) can be added to the thermoplastic resin composition of the present invention. The thermoplastic polyester (E) is composed of terephthalic acid and alkylene glycol.

Terephthalic acid is an ester-forming derivative such as terephthalic acid or its alkyl ester or phenyl ester, and a part (20 mol% or less) of isophthalic acid, orthophthalic acid,
2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methaneanthracenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4
Aromatic dicarboxylic acids such as' -dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid, 5-sodium sulfoisophthalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedione It may be replaced with one or more of aliphatic dicarboxylic acids such as acids, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

The alkylene glycol is preferably composed mainly of ethylene glycol or its ester-forming derivative such as ethylene glycol, 1,4-butanediol, and 1,6-hexamethylene glycol, and its effect is not impaired. A part (20 mol% or less) of aliphatic and alicyclic glycols having 2 to 200 carbon atoms, that is, propylene glycol, neopentyl glycol, 1,5-pentanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexane It may be replaced by one or more of diols and the like, and their ester-forming derivatives.

The method for polymerizing the thermoplastic polyester (E) of the present invention is not particularly limited. For example, terephthalic acid and ethylene glycol may be esterified without a catalyst or directly in the presence of a catalyst (eg, a tin compound or a titanium compound). Alternatively, dimethyl terephthalate and ethylene glycol are transesterified in the presence of a catalyst (such as a magnesium compound, a zinc compound, a cobalt compound, a calcium compound, or a manganese compound) to first produce a low polymer, which is then treated with antimony, titanium And a method of adding a polymerization reaction catalyst such as a germanium compound and polymerizing under reduced pressure to obtain a thermoplastic polyester. The timing of adding the polymerization catalyst is not particularly limited, and may be any time before the polymerization reaction, and may be added before the direct esterification reaction or before the transesterification reaction.

In the production of the thermoplastic polyester (E), phosphoric acid, phosphorous acid, hypophosphorous acid and their alkyl or aryl esters such as phosphoric acid are used to further improve the color tone of the polymer. Monomethyl, dimethyl phosphate, trimethyl phosphate, methyl diethyl phosphate, triethyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, tribenzyl phosphate, tricyclohexyl phosphate, trimethyl phosphite, triethyl phosphite , Phosphite, tri (δ-hydroxybutyl) phosphite, triphenyl phosphite, etc., especially phosphoric acid, phosphorous acid, trimethyl phosphate, trimethyl phosphite, etc. are added after the esterification reaction or transesterification reaction. May be. The thermoplastic polyester (E) of the present invention has a logarithmic viscosity of 0.36 to 1.40 dl / g, particularly 0.52 to 1.18, as measured at 25 ° C. in a 0.5 g / dl orthochlorophenol solution.
dl / g is preferable, and when it is less than 0.36 dl / g, it is difficult to obtain sufficient mechanical properties.
If it exceeds 1.40 dl / g, it is difficult to obtain a molded product having good surface gloss.

Preferred specific examples of the thermoplastic polyester (E) include polyethylene terephthalate and polybutylene terephthalate.

The addition amount of the thermoplastic polyester (E)
1 part by weight or more based on 100 parts by weight of the total of the liquid crystal polyester (A) and the polyphenylene sulfide (B), and 5,000 parts by weight or less from the viewpoint of heat resistance, in order to sufficiently obtain the effect of improving mechanical properties. , 1 to 5,000 parts by weight, particularly preferably 10 to 1,000 parts by weight.

In the present invention, the liquid crystal polyester (A)
Of the olefin polymer (C), the reinforcing agent (D), and the thermoplastic polyester (E), to the composition consisting of styrene and polyphenylene sulfide (B). Is also good.

The composition of the present invention contains an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and their substitutes) as long as the object of the present invention is not impaired. Absorbents (eg, resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and release agents (eg, montanic acid and its salts, esters, half-esters, stearyl alcohol, stearamide, and polyethylene wax), dyes (eg, nitrosine) And colorants, including pigments (eg, cadmium sulfide, phthalocyanine, carbon black), flame retardants,
Ordinary additives such as a plasticizer, an antistatic agent, and a toughening agent and other thermoplastic resins can be added to impart predetermined characteristics.

The resin composition of the present invention is preferably melt-kneaded, and a known method can be used for melt-kneading. For example, using a Banbury mixer, a rubber roll machine, a kneader, a single-screw or twin-screw extruder,
The composition can be melt-kneaded at a temperature of 400 ° C. to obtain a composition.

[0056]

The present invention will be described below in detail with reference to examples.

Reference Example 1 466 parts by weight of p-hydroxybenzoic acid, 84 parts by weight of 4,4'-dihydroxybiphenyl, 480 parts by weight of acetic anhydride, 75 parts by weight of terephthalic acid and an intrinsic viscosity of about 0.6
130 parts by weight of dl / g polyethylene terephthalate was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and subjected to deacetic acid polycondensation under the following conditions.

First, at 100 to 250 ° C. in a nitrogen gas atmosphere.
After 5 hours at 250-300 ° C for 1.5 hours, the pressure was reduced to 0.5 mmHg at 300 ° C for 1 hour and further reacted for 2.25 hours to complete the polycondensation. Of acetic acid was distilled off to obtain a resin having the following theoretical formula.

[0059]

Embedded image 1 / m / n / o = 75/10/15/25 Moreover, this polyester was placed on a sample stage of a polarizing microscope,
As a result of raising the temperature and confirming the optical anisotropy, the liquid crystal onset temperature was 264 ° C., indicating good optical anisotropy. The logarithmic viscosity of this polyester (measured in pentafluorophenol at a concentration of 0.1 g / dl at 60 ° C.) is 1.96 dl /
The melt viscosity at 304 ° C. and a shear rate of 1,000 / sec was 910 poise.

Reference Example 2 519 parts by weight of p-acetoxybenzoic acid, 184 parts by weight of 4,4'-diacetoxybiphenyl, 85 parts by weight of t-butylhydroquinone diacetate, 19.4 parts by weight of hydroquinone diacetate and 186 parts by weight of terephthalic acid The reactor was charged into a reaction vessel equipped with a stirring blade and a distillation tube, reacted under a nitrogen gas atmosphere at 250 to 340 ° C. for 3.0 hours, heated to 350 ° C., and then depressurized to 1.5 mmHg. The mixture was further heated for 1.0 hour to carry out a polycondensation reaction to obtain a resin (b) having the following theoretical structural formula.

[0061]

Embedded image 1 / m / n / o / p = 72/17 / 8.5 / 2.5 / 2
8 Place this polyester on the sample stage of a polarizing microscope.
When the temperature was raised and the optical anisotropy was confirmed, the liquid crystal onset temperature was 307 ° C., indicating good optical anisotropy. The logarithmic viscosity of the polyester (measured under the same conditions as in Reference Example 1) was 4.3 dl / g, 347 ° C., shear rate 1,0
The melt viscosity at 00 / sec was 4,300 poise.

Reference Example 3 541 parts by weight of p-acetoxybenzoic acid, 184 parts by weight of 4,4'-diacetoxybiphenyl, 62 parts by weight of hydroquinone diacetate and 124 parts by weight of terephthalic acid,
42 parts by weight of isophthalic acid was charged into a reaction vessel equipped with a stirring blade and a distillation tube, reacted under a nitrogen gas atmosphere at 250 to 360 ° C. for 3 hours, reduced to 1 mmHg, and further heated for 1 hour to perform polycondensation. Was completed to obtain a resin (c) having the following theoretical structural formula.

[0063]

Embedded image 1 / m / n / o / p = 72/17/25 / 18.75 /
6.25 This polyester was placed on a sample stage of a polarizing microscope, and the temperature was raised to confirm the optical anisotropy.
The temperature was 05 ° C., indicating good optical anisotropy. The logarithmic viscosity of this polyester (measured under the same conditions as in Reference Example 1) was 4.1 dl / g, 345 ° C., shear rate 1,000 /
The melt viscosity in seconds was 3,500 poise.

Examples 1 to 5 The liquid crystal polyester (A), the polyphenylene sulfide (B) and the thermoplastic polyester (E) were melt-mixed at a ratio shown in the table by a twin-screw extruder set at 300 to 360 ° C.

The polyphenylene sulfide (B) used had been previously washed by the following washing method. First, the polyphenylene sulfide (B) was immersed in deionized water at 90 ° C., heated for about 30 minutes with stirring (hot water treatment), and then cooled. Next, the contents are taken out and filtered.
The operation of immersing in 0 ° C. deionized water, stirring and filtering was repeated 5 times, and then dried under reduced pressure at 120 ° C. for 24 hours.

The obtained resin composition was applied to Sumitomo Nestal injection molding machine Promat 40/25 (Sumitomo Heavy Industries, Ltd.)
) At a cylinder temperature of 300 to 360 ° C and a mold temperature of 100 to 150 ° C.
A 5 "test piece, a 1/4" x 1/2 "x 2.5" Izod impact test piece and an ASTM No. 1 dumbbell were molded.

According to the ASTM D648 standard, 1
The bending strength of a / 8 ″ thick test piece was measured.
In accordance with the STM D256 standard, a notch was cut into a 1/4 ″ thick Izod impact test piece to measure the Izod impact strength.
After treating at 0 ° C. for 72 hours, the breaking strength before and after the treatment was measured according to ASTM D638 standard, and the ratio of the value after the treatment to the value before the treatment was defined as the hydrolysis resistance. The results are shown in the table.

Comparative Examples 1 to 4 Injection molding and evaluation were performed in the same manner as in Examples 1 to 6, except that the liquid crystal polyester (A) and the polyphenylene sulfide (B) were used alone without melting and mixing. The results are shown in the table.

The resin compositions of the present invention of Examples 1 to 6 are superior to Comparative Examples 1 to 4 in the balance of flexural strength, Izod impact strength and hydrolysis resistance.

[0070]

[Table 1]

[0071]

According to the present invention, a thermoplastic resin having excellent heat resistance, moldability, fluidity, hydrolysis resistance and mechanical properties is obtained by adding polyphenylene sulfide to a specific liquid crystal polyester having a limited structure. A resin composition is obtained.

Continuation of the front page (56) References JP-A-1-252657 (JP, A) JP-A-1-204926 (JP, A) JP-A-62-141064 (JP, A) JP-A-62-549 (JP) JP-A-62-48728 (JP, A) JP-A-54-155300 (JP, A) Patent 2700127 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 67 / 00-67/08 C08L 81/02 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A heat distortion temperature comprising the following structural unit: 190
To 280 ° C, a liquid crystal onset temperature of 330 ° C or lower, and a melt viscosity of 70 to 99% by weight of a liquid crystal polyester (A) forming an anisotropic molten phase of 10,000 poise or lower, and acid treatment and / or
Alternatively, a thermoplastic resin composition comprising 1 to 30 % by weight of polyphenylene sulfide (B) obtained by hot water treatment. Embedded image (Where X in the formula is —CH ₂ CH ₂ — represents at least one group selected from the group consisting of carbonyl groups of the structural unit (IV) in a para or meta position, and 50 mol% or more of the carbonyl groups are in the para position. 2. The thermoplastic resin composition 100 according to claim 1.
0.1 to 0.1 parts by weight of the olefin polymer (C)
A thermoplastic resin composition containing 70 parts by weight. 3. The thermoplastic resin composition 100 according to claim 1,
A thermoplastic resin composition containing 5-400 parts by weight of a reinforcing agent (D) based on parts by weight. 4. The thermoplastic resin composition 100 according to claim 1,
1 part by weight of the thermoplastic polyester (E)
A thermoplastic resin composition containing 5,000 parts by weight.