JPH01292058A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having excellent heat resistance, moldability, fluidity, hydrolysis resistance and mechanical properties, by blending a liquid crystal polyester having a specific structure with polyphenylene sulfide. CONSTITUTION:A composition comprising (A) 1-99wt.% liquid crystal polyester which consists of structural units shown by formula I-formula III (X is group shown by formula IV, formula V, CH2CH2, etc., CO groups of the formula II and formula III are mutually in para- or meta-position and >=50mol% of the CO groups are in para-position), has 190-280 deg.C heat distortion temperature, <=330 deg.C liquid crystal starting temperature and >=10,000 poise melt viscosity and forms anisotropic melt phase, (B) 99-1wt.% polyphenyl sulfide and preferably further containing 0.1-70 pts.wt. based on 100 pts.wt. total amounts of the components A and B, 0.1-70 pts.wt. olefinic polymer, 5-400 pts.wt. reinforcing agent (fibrous or granular) and 1-5,000 pts.wt. thermoplastic polyester.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a thermoplastic resin composition having excellent heat resistance, moldability, fluidity, hydrolysis resistance, and mechanical properties.

<Conventional technology> In recent years, the demand for higher performance plastics has been increasing, and many polymers with various new performances have been developed and put on the market. Optically anisotropic liquid crystal polymers have attracted attention because of their excellent mechanical properties.

Examples of polymers that form an anisotropic melt phase include liquid crystal polymers obtained by copolymerizing p-hydroxybenzoic acid with polyethylene terephthalate (Japanese Patent Application Laid-open No. 72393/1983);
Liquid crystal polymer copolymerized with p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid
Also known are liquid crystal polymers obtained by copolymerizing p-hydroxybenzoic acid with 4.4°-dihydroxybiphenyl, terephthalic acid, and isophthalic acid (Japanese Patent Publication No. 57-24407).

In addition, an anisotropic melt phase consisting of p-hydroxybenzoic acid, 1,2-bis(phenoxy)ethane-4,4-dicarboxylic acid, terephthalic acid, methylhydroquinone, 2,6-di-hydroxynaphthalene, etc. A composition (JP-A-57-51739) consisting of a fully aromatic polyester and a polyarylene sulfide is known.

<Problem to be solved by the invention> However, the above-mentioned Japanese Patent Application Laid-Open No. 49-72393, Japanese Patent Application Publication No. 54-77691, and Japanese Patent Publication No. 57-24407
The liquid crystal polymer described in the publication and JP-A-57-
The fully aromatic polyester used in the composition described in Publication No. 51739 has a low heat distortion temperature of less than 190°C, and has insufficient heat resistance.
Although it has good heat resistance at 0°C or higher, it cannot be molded unless the liquid crystal start temperature is 400°C or higher, and the melt viscosity is also high. In particular, the fully aromatic polyester used in the composition described in JP-A-57-51739 has a problem of insufficient hydrolysis resistance at high temperatures. For this reason, even if fully aromatic polyester is blended to improve the mechanical properties of polyphenylene sulfide, it is difficult to obtain a composition that has a balance between heat resistance, moldability, and fluidity. Hydrolysis resistance was also insufficient.

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

<Means for solving the problem> That is, the present invention consists of the following structural units whose heat distortion temperature is 1.
1 to 99% by weight of liquid crystal polyester (A) forming an anisotropic melt phase with a liquid crystal initiation temperature of 330°C or less and a melt viscosity of 10,000 poise or less at 90 to 280°C, and polyphenylene sulfide (B) 99 to 1% by weight. % of the thermoplastic resin composition and one or more groups selected from structural units (n),
The carbonyl groups in 1) are in a para- or meta-position relationship with each other, and 50 mol% or more of them are in the para-position.) 1 olefin copolymer (C) is added to 100 parts by weight of the above thermoplastic resin composition. ~70 parts by weight, reinforcing agent (D)
or 1 part by weight of thermoplastic polyester
5,000 parts by weight of the thermoplastic resin composition.

The structural unit (I) of the thermoplastic polyester (A) in the present invention is a structural unit of a polyester produced from p-hydroxybenzoic acid, and the structural unit (n) is 4.4
- The structural unit (III) of a polyester produced from monodihydroxybiphenyl and terephthalic acid and/or isophthalic acid is hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6
- Each of the structural units of a polyester produced from one or more dihydroxy compounds selected from dihydroxynaphthalene and ethylene glycol and terephthalic acid and/or isophthalic acid is shown.

The liquid crystal polyester (A) of the present invention has the m structural unit (I)
, (n) and (1).

The copolymerization amount of the structural units (I), (If) and (I[[) is arbitrary. From the viewpoint of fluidity, the following copolymerization amount is preferable, that is, the structural unit (I> is preferably 40 to 90 mol% of the total, particularly 60 to 90 mol%)
The molar ratio of the structural units (If)/(III) is preferably 9/1 to 1/9, and in the structural unit (I[), -X-10H2
7.5/2.5 to 2.5/7.5 for cases other than CH2-
is preferable, and 7.5/2.5 to 4/6 is particularly preferable.

Among them, the copolymerization ratio of the structural unit (I) is 72 to 78 mol%, the copolymerization ratio of (II) is 5 to 15 mol%, (II
The copolymerization ratio of I) is 10 to 20 mol%, and 70 of -X-
It is most preferred that mol% or more is 10H2CH2-.

The liquid crystal polyester (A) used in the present invention has a heat distortion temperature of 190 to 280°C when no other components are blended,
The temperature is preferably 190 to 220°C.

If the heat distortion temperature is less than 190°C, the heat resistance is insufficient,
If the temperature exceeds 280°C, a problem arises in that the molding temperature of the resulting resin composition becomes high.

Here, the heat distortion temperature is 1 based on ASTM D648.
This is a value measured on a test piece having a thickness of /8" under a stress of 18.6 kg/-.

In addition, the liquid crystal starting temperature of the liquid crystal polyester (A) is 33
It is essential that the temperature is 0°C or less, and from the viewpoint of fluidity and heat resistance, it is preferably 260 to 330°C, and 260 to 330°C.
Particularly preferred is 280°C.

If the liquid crystal start temperature exceeds 330''C, it is necessary to increase the molding temperature, which is not practical from the viewpoint of moldability.

In addition, it is essential that the melt viscosity is 10,000 poise or less, preferably 5,000 poise or less, especially 2
,000 poise or less is more preferable.

Note that this melt viscosity is a value measured using a Koka type flow tester under conditions of (liquid crystal starting temperature +40°C) and a slip rate of 1,000 (1/sec).

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

For example, in the structural unit (III), -X- is -〇H
When -X- is other than -CH2CH2-, the following manufacturing methods (1) to (4) are preferred, and when -CH2CH2- is -CH2CH2-, the following manufacturing methods are preferred.

(1) A method for producing a diacylated aromatic dihydroxy compound such as p-acetoxybenzoic acid, 4.4-monodiacetoxybiphenyl, or paraacetoxybenzene by a deacetic acid polycondensation reaction from an aromatic dicarboxylic acid such as terephthalic acid.

(2) After reacting an aromatic dihydroxy compound such as p-droxybenzoic acid, 4.4-monodihydroxybiphenyl, or hydroquinone, or an aromatic dicarboxylic acid such as terephthalic acid with acetic anhydride to acylate the phenolic hydroxyl group, , a method of producing by deacetic acid polycondensation reaction.

(3) Phenyl ester of P-hydroxybenzoic acid, 4
．． A method for producing by dephenol polycondensation reaction from an aromatic dihydroxy compound such as 4-monodihydroxybiphenyl or hydroquinone and a diphenyl ester of an aromatic dicarboxylic acid such as terephthalic acid.

(4) Aromatic dicarboxylic acids such as p-hydroxybenzoic acid and terephthalic acid are reacted with a desired amount of diphenyl carbonate to form diphenyl esters, and then aromatic dihydroxy compounds such as 4.4-dihydroxybiphenyl and hydroquinone are reacted. In addition, a method of producing by dephenol polycondensation reaction.

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

Since liquid crystal polyester (A) with a high degree of polymerization is obtained, (
It is more preferable to use method 2).

Typical catalysts used in polycondensation reactions include metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate, antimony trioxide, magnesium, sodium acetate, and zinc acetate. It is effective for

Some of the liquid crystalline polyesters (A) of the present invention can be measured for their intrinsic viscosity in pentafluorophenol, and in this case, the value measured at 60°C at the original concentration of 0.5 dl/g or more is preferable, especially 1.0 to
15.0 dl/l is preferred.

In addition, when polycondensing the liquid crystal polyester (A) used in the present invention, in addition to the components constituting the above (I), (n) and (II[), 4,4--diphenyldicarboxylic acid,
3.3-1 diphenyl dicarboxylic acid, 3.4-1 diphenyl dicarboxylic acid, 2゜2-1 diphenyl dicarboxylic acid, 1.2-bis(phenoxy)ethane-4,4-dicarboxylic acid, 1. Aromatic dicarboxylic acids such as 2-bis(2-chlorophenoxy)ethane-4,4-dicarboxylic acid, alicyclic dicarboxylic acids such as hexadroterephthalic acid, resorcinol, talolhydroquinone, methylhydroquinone, 2.7 - Aromatic dihydroxy compounds such as hydroxynaphthalene, m -oxybenzoic acid, 2,6-
Aromatic oxycarboxylic acids such as oxynaphthoic acid, p-amine phenol, p-aminobenzoic acid, etc. can be further copolymerized within a small proportion that does not impair the object of the present invention.

Polyphenylene sulfide (B) used in the present invention is a polymer represented by the general formula +Ph-3-)-n, has a molecular weight to, ooo~50.000, and a melting point of 270~300°C.
are preferably used. Nanato, Q is F,
CI, Br or C [■3, m represents an integer from 1 to 4,
Among them, the general formula Luffite (B) is preferably used.

In order to remove impurities contained in polyphenylene sulfide (B), treatments such as acid treatment or heat treatment can be used. These methods include, for example, acetic acid,
A method of immersing PPS in an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, propylic acid or an aqueous solution thereof, heating and stirring as necessary, a method of hot water treatment in a pressure vessel, or a combination of these methods. Examples include methods. When these treatments are performed, it is preferable to wash with warm water several times in order to remove residual acids, salts, etc.

In the present invention, the amount of liquid crystal polyester (A) is 1
-99 weight%, preferably 5-95 weight%, particularly preferably 10-90 weight%, polyphenylene sulfide (B
) is blended in an amount of 99 to 1% by weight, preferably 95 to 5% by weight, particularly preferably 90 to 10% by weight. If the liquid crystal polyester (A) is less than 1% by weight, the moldability and mechanical properties are insufficient, and if it exceeds 99% by weight, the hydrolysis resistance is insufficient.

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

As olefin polymers, α-olefins and α,
For copolymers consisting of glycidyl esters of β-unsaturated acids, copolymers consisting of ethylene and α-olefins having 3 or more carbon atoms or ethylene, α-olefins having 3 or more carbon atoms, and non-conjugated dienes, unsaturated Preferably used is a modified 5-ethylene polymer which can be obtained by grafting a carboxylic acid or a derivative thereof.

In the above-mentioned copolymer consisting of α-olefins and glycidyl ester of α,β-unsaturated acid, α-olefins preferably have 2 to 4 carbon atoms, and specifically, ethylene, propylene, butene- 1, among others, ethylene can be preferably used. Also, α, β−
The glycidyl ester of an unsaturated acid has the general formula (wherein R is a hydrogen atom or a lower alkyl group).
Specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, etc. are used, and among them, glycidyl methacrylate is preferably used. The amount of copolymerized glycidyl ester of α,β-unsaturated acid is suitably in the range of 1 to 50 mol%. Furthermore, unsaturated monomers that can be copolymerized with the above copolymer in an amount of 40 mol% or less, such as vinyl ethers, vinyl acetate, vinyl esters such as vinyl 10 pionate,
Esters of acrylic acid and methacrylic acid such as methyl, ethyl, and propyl, acrylonitrile, styrene, and the like may be copolymerized.

In addition, the above-mentioned ethylene and an α-olefin having 3 or more carbon atoms or a copolymer consisting of ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated diene (hereinafter both are collectively referred to as unmodified ethylene polymers) On the other hand, 0.01 to 10
In the modified ethylene polymer obtained by grafting % of unsaturated carboxylic acid or its derivative, the α-olefin having 3 or more carbon atoms includes propylene, butene-1,
Pentene-1,3-methylpentene-1, octacene-
1, among others, propylene and butene-1
is preferably used. In addition, as a non-conjugated diene, 5
-Methylidene-2-norbornene, 5-ethylidene-2
-norbornene, 5-vinyl-2-norbornene, 5-
Propenyl-2-norbornene, 5-isopropenyl-
2-norbornene, 5-talotyl-2-norbornene,
Norbornene such as 5-(2-methyl-2-butenyl)-2-norbornene, 5-(2-ethyl-2-butenyl)-2-norbornene, 5-methacrylnorbornene, 5-methyl-5-vinylnorbornene Compound, dicyclopentadiene, methyltetrahydroindene, 4.7,
8.9-tetrahydroindene, 1,5-cyclooctadiene, 1,4-hexadiene, isoprene, 6-methyl-1,5-1-tadiene, 11-ethyl-1,1,l
-tridecadiene, etc., and preferably 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene, 1,4-hexadiene, etc. can be used.

The copolymerization ratio of an unmodified ethylene polymer consisting of ethylene and an α-olefin having 3 or more carbon atoms is 40/60 to 9.
The range of 9 to 1 (molar ratio) is preferable, especially 70/30 to
9515 (molar ratio) is preferred.

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

Specific examples of unmodified ethylene copolymers include ethylene/
Propylene copolymer, ethylene/butene-1 copolymer,
Preferred examples include ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene 15-ethylidene-2-norbornene copolymer, and among others, ethylene/propylene copolymer containing no non-conjugated diene and ethylene/butene-1 copolymer. Copolymers have good heat resistance and can be used more preferably.

The unsaturated carboxylic acid for obtaining a modified ethylene copolymer by grafting onto the unmodified ethylene copolymer is preferably acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, or itaconic acid. , citraconic acid, butenedicarboxylic acid, etc. Examples of derivatives thereof include alkyl esters, glycidyl esters, acid anhydrides, and imides. Among these, glycidyl esters, acid anhydrides, and imides are preferred.

Preferred specific examples of unsaturated carboxylic acids or derivatives thereof include maleic acid, fumaric acid, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate,
Itaconic acid glycidyl ester, citraconic acid diglycidyl ester, butene dicarboxylic acid diglycidyl ester, maleic anhydride, itaconic anhydride, citraconic anhydride, maleic acid imide, itaconic acid imide, citraconic acid imide, especially glycidyl methacrylate, Maleic anhydride, itaconic anhydride, and maleic acid imide can be preferably used. Two or more of these unsaturated carboxylic acids or derivatives thereof may be used in combination.

The graft reaction amount of unsaturated carboxylic acid or its derivative is 0.0 from the viewpoint of improving mechanical properties, especially surface impact resistance.
1 or more, 11 for aromatic polyester (10 from the thermal point of view)
The range is preferably less than heavy duty, especially 0.05 to 5% by weight.
It is preferable that

Note that the graft reaction here means that an unsaturated carboxylic acid or a derivative thereof is chemically bonded to an unmodified ethylene polymer.

The modified ethylene polymer is prepared by adding an unsaturated carboxylic acid or its derivative to an unmodified ethylene polymer and an organic peroxide of 0.001 to 0.1% by weight based on the unmodified ethylene polymer. It can be produced by melt-kneading at ℃. As an apparatus for melt mixing, a screw extruder, a Banbury mixer, etc. can be used.

Specifically, organic peroxides that 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.

Note that two or more of the above olefin polymers (C) may be used in combination.

The amount of the olefin polymer (C) added is usually 0.1 part by weight per 100 parts by weight in total of the liquid crystal polyester (A) and polyphenylene sulfide (B) in order to obtain the effect of improving mechanical properties. From the viewpoint of fluidity, the above is 70 overlapping parts or less, that is, 0. The range is preferably from 1 to 70 parts by weight, particularly preferably from 0.5 to 50 parts by weight.

In addition, the thermoplastic resin composition of the present invention further has heat resistance,
Specific examples of reinforcing agents (D) to which reinforcing agents CD) can be added to improve mechanical properties include fibrous,
Examples include granular and mixtures of both. Examples of fibrous reinforcing agents include glass fiber, shirasu glass fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber,
Examples include inorganic fibers such as gypsum fibers, metal fibers (for example, stainless steel fibers), and carbon fibers.

In addition, granular reinforcing agents include wollastenite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, and metals such as alumina, silicon oxide, magnesium oxide, zirconium oxide, and titanium oxide. Examples include oxides, carbonates such as calcium carbonate, magnesium carbonate, and dolomite, sulfates such as calcium Ta acid and barium li2 acid, glass peas, boron nitride, silicon carbide, and Saroyan.
These may be hollow (e.g., hollow glass fibers, glass microballoons, glass balloons, carbon balloons, etc.), and the reinforcing agent (D) described above may be pre-prepared with coupling agents such as silane-based and titanium-based, if necessary. May be processed and used.

The amount of reinforcing agent (D) to be added is 5 parts by weight or more to obtain a sufficient reinforcing effect, and 400 parts by weight from the viewpoint of fluidity, based on the total ioomi parts of liquid crystal polyester (A) and polyphenylene sulfide (B). part or less, ie, in the range of 5 to 400 parts by weight, particularly preferably in the range of 25 to 150 parts by weight.

Thermoplastic polyester (E) can be added to the thermoplastic resin composition of the present invention in order to further improve mechanical properties. Thermoplastic polyester (E) consists 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 portion (20 mol% or less) of terephthalic acid or its alkyl ester, phenyl ester, etc. is added to isophthalic acid, orthophthalic acid, or 2,6-naphthalene dicarboxylic acid. acid, 1,5-naphthalene dicarboxylic acid,
Bis(p-carboxyphenyl)methaneanthracene dicarboxylic acid, 4,4-diphenyldicarboxylic acid, 1゜2-bis(phenoxy)ethane-4,4-dicarboxylic acid, 1,2-bis(2-chlorophenoxy) Ethane-4
, 4-monodicarboxylic acid, aromatic dicarboxylic acids such as 5-sodium sulfoisophthalic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,
It may be replaced with one or more types of alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid and ester-forming derivatives thereof.

In addition, alkylene glycols include ethylene glycol,
The main component is 1,4-butanediol, 1,6-hexamethylene glycol, etc., preferably ethylene glycol or its ester-forming derivative, and a portion (20 mol% or less) thereof is added to the extent that the effect is not impaired. Carbon number 2
~200 aliphatic and cycloaliphatic glycols, i.e.
It may be replaced with one or more of propylene glycol, neopentyl glycol, 1°5-bentanediol, decamethylene glycol, cyclohexane dimetatool, cyclohexanediol, etc., and ester-forming derivatives thereof.

The method of polymerizing the thermoplastic polyester (E) of the present invention is not particularly limited, but for example, terephthalic acid and ethylene glycol are directly esterified without a catalyst or in the presence of a catalyst (for example, a tin compound or a titanium compound), or, Dimethyl terephthalate and ethylene glycol as catalysts (magnesium compounds, zinc compounds, cobalt compounds,
First, a low polymer is produced by transesterification in the presence of a calcium compound, a manganese compound, etc.), a polymerization reaction catalyst such as antimony, titanium, germanium compound, etc. is added to this, and the polymerization is carried out under reduced pressure to produce a thermoplastic polyester. Here are some ways to obtain it. The timing of adding this polymerization catalyst is not particularly limited, and it may be added at any time before the reaction, directly before the esterification reaction, or before the transesterification reaction.

In addition, when producing thermoplastic polyester (E), phosphoric acid, phosphorous acid,
Hypophosphorous acid and its alkyl or aryl esters, such as monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, methyl diethyl phosphate, triethyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, Tribenzyl phosphate, tricyclohexyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, tri(δ) phosphite
-hydroxybutyl), triphenyl phosphite, etc., especially phosphoric acid, phosphorous acid, trimethyl phosphate, trimethyl phosphite, etc. may be added after the esterification or transesterification reaction.

In addition, the thermoplastic polyester (E) of the present invention is 0.5 g
The logarithmic viscosity of the old orthochlorophenol solution measured at 25°C is preferably in the range of 0.36 to 1.40 dl/1r - particularly 0.52 to 1.18 dl/t, and 0.36 dl/g. sufficient if less than 11
It is difficult to obtain mechanical properties, and if it exceeds 1.40 dl/g, it is difficult to obtain a molded product with good surface gloss.

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

The amount of thermoplastic polyester (E) added is 1 in total of liquid crystal polyester (A) and polyphenylene sulfide (B).
00 parts by weight, 1 part by weight or more to obtain a sufficient effect of improving mechanical properties, and 5.000 parts by weight or less from the viewpoint of heat resistance, that is, 1 to 5.0001 parts by weight! The amount range is preferably from 10 to 1.000 parts by weight.

In the present invention, any one of the three components of the olefin polymer (C), the reinforcing agent (D), and the thermoplastic polyester (E) can be used for the composition consisting of the liquid crystal polyester (A) and polyphenylene sulfide (B). Two or three components may be added.

The composition of the present invention may contain antioxidants, heat stabilizers (for example, hindered phenol, hydroquinone, phosphites, and substituted products thereof), ultraviolet absorbers ( e.g. resorcinol, salicylates, benzotriazoles, benzophenones, etc.), lubricants and mold release agents (e.g. montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene waxes, etc.), dyes (e.g. nitrosine, etc.) and pigments (e.g.
Addition of conventional additives such as colorants, flame retardants, plasticizers, antistatic agents, reinforcing agents and other thermoplastics to impart the desired properties be able to.

The resin composition of the present invention is preferably melt-kneaded, and known methods can be used for melt-kneading. For example, the composition can be prepared by melt-kneading at a temperature of 200 to 400° C. using a Banbury mixer, a rubber roll machine, a kneader 1 single-screw or twin-screw extruder, or the like.

<Example> Hereinafter, the present invention will be explained 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 d.
130 parts by weight of polyethylene terephthalate (l/g) was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and acetic acid depolycondensation was carried out under the following conditions.

First, under a nitrogen gas atmosphere at 100 to 250°C for 5 hours,
After reacting at 50-300℃ for 1.5 hours, 300℃
The pressure was reduced to 0.5 + IQ in 1 hour, and the reaction was further carried out for 2.25 hours to complete the polycondensation, whereupon an almost theoretical amount of acetic acid was distilled out, and a resin having the following theoretical formula was obtained.

1/m/n=75/10/15 Also, place this polyester on the sample stage of a polarizing microscope,
As a result of raising the temperature and checking the optical anisotropy, the liquid crystal start temperature was 264°C, indicating good optical anisotropy. The logarithmic viscosity of this polyester (measured at 60°C in pentafluorophenol at a concentration of 0°Ig/dl) is 1.96.
dl/g, and the melt viscosity at 304° C. and a rubbing speed of 1.000/sec was 910 poise.

Reference Example 2 519 parts by weight of p-acetoxybenzoic acid, 184 parts by weight of 4.4-1 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 were stirred. The mixture was charged into a reaction vessel equipped with blades and a distillation tube, and reacted for 3.0 hours at 250 to 340°C under a nitrogen gas atmosphere. After raising the temperature to 350°C, the pressure inside the system was reduced to 1.5 mm and 11 g, and The mixture was heated for 1.0 hours to perform a polycondensation reaction to obtain a resin (b) having the following theoretical structural formula.

t-Bu.

1/m/n10=72/17/8.5/2.5 Also, when this polyester was placed on the sample stage of a polarizing microscope and the temperature was raised to confirm the optical anisotropy, the liquid crystal initiation temperature was 30
The temperature was 7°C, showing good optical anisotropy. The logarithmic viscosity of this polyester (measured under the same conditions as Reference Example 1) was 4.
3 dl/g, and the melt viscosity at 347° C. and a rubbing speed of 1,000/sec was 4,300 poise.

Reference Example 3 541 parts by weight of p-acetoxybenzoic acid, 184 parts by weight of 4.4-1 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, and reacted in a nitrogen gas atmosphere at 250 to 360°C for 3 hours, then reduced to 1mm1IQ and heated for another 1 hour to undergo polycondensation. was completed to obtain a resin (c) having the following theoretical structural formula.

1/m/n=75/18.75/6.25 When this polyester was placed on the sample stage of a polarizing microscope and the temperature was raised to confirm the optical anisotropy, the liquid crystal initiation temperature was 305 ° C. It showed good optical anisotropy. The logarithmic viscosity of this polyester (measured under the same conditions as Reference Example 1) was 4.1 dl/r.
The melt viscosity at 345° C. and a sliding speed of 1,000/sec was 3.500 poise.

Examples 1 to 13 Liquid crystal polyester (A), polyphenylene sulfide (
B), olefin polymer (C), reinforcing agent (D), and thermoplastic polyester (E) at the ratio shown in the table.
Melt mixing was performed using a twin screw extruder set at ~360°C.

Polyphenylene sulfide (B) should be washed in advance using the following washing method. 5 First, polyphenylene sulfide (B) was immersed in deionized water at 90°C and kept warm for about 30 minutes while stirring (hot water treatment). After cooling, the contents were taken out and filtered, and the operation of immersing in deionized water at 70°C, stirring, and filtering was repeated five times, and then dried under reduced pressure at 120°C for 24 hours.

The obtained resin composition was subjected to a Sumitomo Nestal injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.), and the cylinder temperature was 300 to 360°C and the mold temperature was 100 to 150°C.
Under the conditions of 1/8"Xi/2" x 5" test piece,
Izot impact test specimens and ASTM NQI dumbbells measuring 1/4" x 172" x 2.5" were molded.

Then, the bending strength of the 1/8" thick test piece was measured according to the ASTM D648 standard.
In accordance with the D256 standard, a notch was cut into a 174" thick Izot impact test piece to measure the Izot impact strength. Furthermore, an ASTM NQI dumbbell was placed in water at 80°C x 7.
After treatment for 2 hours, the breaking strength before and after treatment was measured according to AsTM D63B standard, and the ratio of the value after treatment to that before treatment was defined as hydrolysis resistance. These results are also shown in the table.

Comparative Examples 1 to 4 Liquid crystal polyester (A), polyphenylene sulfide (
Injection molding and evaluation were performed in the same manner as in Examples 1 to 13, except that B) was used alone without being melt-mixed. These results are also shown in the table.

In contrast to Comparative Examples 1 to 4, the resin compositions of Examples 1 to 13 of the present invention had better bending strength and Izot? Excellent balance of impact strength and hydrolysis resistance.

<Effects of the Invention> The present invention adds polyphenylene sulfide to a specific liquid crystalline polyester having a limited structure, thereby creating a thermoplastic material with excellent heat resistance, moldability, fluidity, hydrolysis resistance, and mechanical properties. A resin composition is obtained.

Claims (4)

[Claims] (1) Heat deformation temperature consisting of the following structural units is 190-28
0℃, liquid crystal start temperature 330℃ or less, melt viscosity 10,
A thermoplastic resin composition comprising 1 to 99% by weight of a liquid crystal polyester (A) and 99 to 1% by weight of polyphenylene sulfide (B), which form an anisotropic melt phase of 000 poise or less. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (However, X in the formula is ▲Mathematical formula, chemical formula, etc.) There are tables, etc.▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
▼, -CH_2CH_2- Indicates one or more groups selected from structural unit (II), (
The carbonyl groups in III) are in a para- or meta-position relationship with each other, and more than 50 mol% of them are in the para-position) (2) 0.1 to 7 parts of the olefin polymer (C) is added to 100 parts by weight of the thermoplastic resin composition according to claim (1).
A thermoplastic resin composition containing 0 parts by weight. (3) A thermoplastic resin composition containing 5 to 400 parts by weight of a reinforcing agent (D) based on 100 parts by weight of the thermoplastic resin composition according to claim (1). (4) 1 to 5 parts of thermoplastic polyester (E) to 100 parts by weight of the thermoplastic resin composition according to claim (1);
000 parts by weight of a thermoplastic resin composition.