JP3353478B2 - Resin composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent color tone, excellent retention stability, excellent mechanical properties and excellent heat resistance having a molded article appearance, and a process for producing the same. .

[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, optics characterized by a parallel arrangement of molecular chains. Attention has been paid to anisotropic liquid crystal polymers for their excellent moldability and mechanical properties, and their applications are expanding to mechanical parts, electric and electronic parts, and the like.

[0003] As the liquid crystal polymer, for example, a liquid crystal polymer obtained by copolymerizing p-hydroxybenzoic acid with 4,4'-dihydroxybiphenyl, terephthalic acid, and isophthalic acid (Japanese Patent Publication No. 57-24407, Japanese Patent Application Laid-Open No. 60-25046) Gazette), 6-hydroxy-2 to p-hydroxybenzoic acid
-Liquid crystal polymer copolymerized with naphthoic acid (JP-A-54-7)
No. 7691).

A liquid crystal polymer obtained by copolymerizing p-hydroxybenzoic acid and polyethylene terephthalate (Japanese Patent Publication No. Sho.
Japanese Patent Application Laid-Open No. 62-164719) and a liquid crystal polymer obtained by copolymerizing 4,4′-dihydroxybiphenyl, t-butylhydroquinone and terephthalic acid with p-hydroxybenzoic acid have been proposed.

However, since these have a higher melting point than ordinary polyesters such as polyethylene terephthalate and polybutylene terephthalate, they have a problem that they are colored at the time of polymerization and molding, and are deteriorated by heat to deteriorate mechanical properties. Was. As a countermeasure, JP-A-2-515
No. 24 proposes a method of improving the long-term heat resistance by adding a heat-resistant agent such as an organic phosphorus compound or a hindered phenol during polymerization.

[0006]

SUMMARY OF THE INVENTION However, Japanese Patent Laid-Open No.
It has been found that the heat-resistant agent described in Japanese Patent No. 51524 does not always have sufficient effects on the thermal stability at the time of stay and the prevention of coloring. Therefore, the present invention solves the above-mentioned problems,
An object of the present invention is to obtain a resin composition having excellent color tone, excellent retention stability, and having excellent mechanical properties and appearance of a molded article and having excellent heat resistance.

[0007]

That is, the present invention relates to (A) 100 parts by weight of a liquid crystal polyester and / or a liquid crystal polyesteramide, and (B) a metal of phosphorous acid, hypophosphorous acid and hypophosphorous acid . An object of the present invention is to provide a resin composition containing 0.001 to 5 parts by weight of at least one compound selected from salts.

The liquid crystal polyester used in the present invention comprises a structural unit selected from an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic dicarbonyl unit, an ethylenedioxy unit and the like, and forms an anisotropic molten phase. Polyester, a liquid crystal polyester amide as the above structural unit and an aromatic iminocarbonyl unit,
Polyester amides comprising a structural unit selected from an aromatic diimino unit, an aromatic iminooxy unit and the like and forming an anisotropic melt phase are mentioned, and among them, those containing an ethylenedioxy unit are preferable.

The liquid crystal polyester used in the present invention and / or
Alternatively, the melting point of the liquid crystal polyesteramide is preferably 300 ° C. or more and 350 ° C. or less.

Particularly preferred are polyesters comprising the following structural units (I), (III), (IV) or (I), (II), (III), (IV), especially (I), (II) ), (III), (IV)
Is preferred.

[0011]

Embedded image (However, R ₁ in the formula is

Embedded image R ₂ represents one or more groups selected from

Embedded image Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit [(II) + (III)]
And the structural units (IV) are substantially equimolar. )

The structural unit (I) is a structural unit of a polyester 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,
The structural unit formed from an aromatic dihydroxy compound selected from 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, and 4,4′-dihydroxydiphenyl ether has the structure The unit (III) is a structural unit formed from ethylene glycol, and the structural unit (IV) is terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy ) Ethane-4,4′-dicarboxylic acid,
2-bis (2-chlorophenoxy) ethane-4,4'-
The structural units generated from aromatic dicarboxylic acids selected from dicarboxylic acids and diphenyl ether dicarboxylic acids are shown below. Of these, R ₁ is

Embedded image And R ₂ is

Embedded image Is particularly preferred. As the liquid crystal polyesteramide, a liquid crystal polyesteramide containing a p-iminophenoxy unit generated from p-aminophenol in addition to the structural units (I) to (IV) is preferable.

The above structural units (I), (II), (III) and (I)
The copolymerization amount of V) is arbitrary. However, the following copolymerization amount is preferred from the viewpoint of fluidity.

That is, the structural units (I), (III) and (I
In the case of a copolymer comprising V), the structural unit (I) is preferably 30 to 95 mol% of [(I) + (III)],
~ 95 mol% is more preferred. The structural unit (IV) is substantially equimolar to the structural unit (III).

The above structural units (I), (II), (III),
In the case of a copolymer comprising (IV), the structural unit [(I) + (II)] is represented by [(I) + (II) + (III) from the viewpoint of heat resistance, flame retardancy and mechanical properties. ] Is preferably 60 to 95 mol%, more preferably 85 to 93 mol%. Also, structural units
(III) is preferably 40 to 5 mol% of [(I) + (II) + (III)], more preferably 15 to 7 mol%. The molar ratio of the structural units (I) / (II) is preferably from 75/25 to 95/5, more preferably from 78/22 to 93/7, from the viewpoint of the balance between heat resistance and fluidity. The structural unit (I
V) is substantially equimolar to the structural unit [(II) + (III)].

In addition to the components constituting the above structural units (I) to (IV), aromatic dicarboxylic acids such as 3,3'-diphenyldicarboxylic acid and 2,2'-diphenyldicarboxylic acid, adipic acid, azelaic acid, sebacine Acids, aliphatic dicarboxylic acids such as dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone,
4,4'-dihydroxydiphenyl sulfone, 4,4 '
Aromatic diols such as dihydroxydiphenyl sulfide and 4,4′-dihydroxybenzophenone,
Butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol,
Aliphatic, alicyclic diols such as 1,4-cyclohexanedimethanol and the like; m-hydroxybenzoic acid, aromatic hydroxycarboxylic acids such as 2,6-hydroxynaphthoic acid, p-aminophenol, p-aminobenzoic acid and the like. The copolymerization can be further carried out in a small proportion that does not impair the object of the present invention.

The liquid crystal polyester used in the present invention and / or
Alternatively, the method for producing the liquid crystal polyester amide is not particularly limited, and can be produced according to a known polyester polycondensation method.

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

(1) p-acetoxybenzoic acid, 4,4 '
-Diacylated aromatic dihydroxy compounds such as diacetoxybiphenyl and diacetoxybenzene, and aromatic dicarboxylic acids such as terephthalic acid; A method for producing from a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid by a deacetic acid polycondensation reaction.

(2) p-hydroxybenzoic acid, 4,4 '
Aromatic dihydroxy compounds such as dihydroxybiphenyl and hydroquinone; aromatic dicarboxylic acids such as acetic anhydride and terephthalic acid; polymers and oligomers of polyesters such as polyethylene terephthalate, oligomers and aromatic dicarboxylic acids such as bis (β-hydroxyethyl) terephthalate And a bis (β-hydroxyethyl) ester by a deacetic acid polycondensation reaction.

As the catalyst used for the polycondensation reaction, those known as polymerization catalysts for liquid crystal polyesters and liquid crystal polyesteramides can be used.

The liquid crystal polyester used in the present invention and / or
Alternatively, the liquid crystal polyesteramide may be capable of measuring the logarithmic viscosity in pentafluorophenol, in which case the value measured at 60 ° C. at a concentration of 0.1 g / dl is preferably 0.3 or more, 0.5 to 3.0 dl / g
Is particularly preferred.

The melt viscosity of the liquid crystal polyester and / or liquid crystal polyester amide in the present invention is 10
~ 20,000 poises is preferred, especially 20 ~ 10,000 poise.
00 poise is more preferred.

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).

[0026] (B) component in the present invention is at least one or more compounds selected from metal salts of phosphorous acid and hypophosphorous acid and hypophosphorous acid, hypophosphorous acid metal salt also in the name or It is preferably used. On the other hand, lithium, sodium, alkali metals such as potassium, magnesium, calcium, alkaline earth metals such as barium preferably about metal species hypophosphorous acid metal salt, more preferably an alkaline earth metal. More specifically, examples include calcium hypophosphite, magnesium hypophosphite, barium hypophosphite, sodium hypophosphite, potassium hypophosphite and the like.

The component (B) is added in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, per 100 parts by weight of the liquid crystal polyester. The effect of improving the properties is insufficient, and when the amount is more than 5 parts by weight, the mechanical properties deteriorate, which is not preferable.

The component (B) may be added at any time, either before or after the completion of the polymerization, or may be added in a plurality of portions before and after the completion of the polymerization. Specifically, it can be added to the reaction product before or after the completion of the polymerization, and (B) after removing the polymerized liquid crystal polyester and / or liquid crystal polyesteramide from the reaction vessel.
The components can be added and melt-kneaded. Known methods 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, or the like, melt-kneading at a temperature of 200 to 370 ° C. to obtain a composition. Can be.

The component (B) can be added as a solid or as a liquid at a temperature equal to or higher than the melting point of the component (B). When the compounding is performed at a low temperature, the component (B) can be added as a solution.

In the present invention, (C) a metal salt other than phosphorous acid and hypophosphorous acid can be added to further improve the retention stability. Organic or inorganic metal salts other than phosphorous acid and hypophosphorous acid can be used, but sulfuric acid, hydrogen halide, nitric acid, boric acid,
It is preferable to use alkali metal salts and alkaline earth metal salts such as phosphoric acid, pyrophosphoric acid, acetic acid, oxalic acid, and benzoic acid. More specifically, metal salts such as potassium sulfate, sodium acetate, barium acetate, magnesium acetate, sodium benzoate and sodium hydrogen phosphate can be used.

The amount of the metal salt other than phosphorous acid and hypophosphorous acid is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, per 100 parts by weight of the liquid crystal polyester.

The metal salt (C) other than phosphorous acid and hypophosphorous acid can be added as a solid or as a liquid at a temperature equal to or higher than its melting point. When the compounding is performed at a low temperature, it can be added as a solution.

In the present invention, (D) an organic bromine compound can be further added for the purpose of imparting flame retardancy.
The organic bromine compound has a bromine atom in the molecule, and particularly preferably has a bromine content in the bromine compound of 20% by weight or more. Specifically, low molecular weight organic bromine compounds such as decabromodiphenyl ether and ethylene bis- (tetrabromophthalimide), brominated polycarbonate (for example, a polycarbonate oligomer produced from brominated bisphenol A or a copolymer thereof with bisphenol A) Products), brominated epoxy compounds (for example, a diepoxy compound produced by reacting brominated bisphenol A with epichlorohydrin or a monoepoxy compound obtained by reacting brominated phenols with epichlorohydrin), poly (brominated benzyl acrylate), Brominated polyphenylene ether, brominated bisphenol A, condensate of cyanuric chloride and brominated phenol, brominated polystyrene, cross-linked brominated polystyrene, cross-linked brominated poly α-methylstyrene Halogenated polymers or oligomers, or mixtures thereof, among which ethylene bis- (tetrabromophthalimide), brominated epoxy oligomers or polymers, brominated polystyrene, cross-linked brominated polystyrene, brominated polyphenylene ether and bromine Brominated polycarbonate is preferred, and ethylene bis- (tetrabromophthalimide), brominated polystyrene, and brominated polycarbonate can be particularly preferably used. More specifically, the preferred organic bromine compound is preferably a brominated epoxy polymer represented by the following general formula (a).

[0034]

Embedded image The polymerization degree n in the general formula (a) is preferably 15 or more,
More preferably, it is 50 to 80. Further, as the brominated polystyrene, those represented by the following formula (b) having a weight average molecular weight of 1 × 10 ^{3 to} 3 × 10 ⁵ produced by brominating polystyrene obtained by radical polymerization or anion polymerization, or Polybrominated styrene having a brominated styrene unit represented by the formula (b) or (c) produced by radical polymerization or anionic polymerization, preferably radical polymerization of a brominated styrene monomer, and the like. Weight average molecular weight of 1 × 10 ^{3 to} 3 × 10 ⁵ having a structural unit represented by the following formula (c) produced from a monomer as a main component:
Is preferred.

[0035]

Embedded image The brominated styrene monomer here is styrene monomer 1
Preferably, each aromatic ring has about two bromine atoms introduced into the aromatic ring by a substitution reaction, and may contain monobrominated styrene, tribrominated styrene and the like in addition to dibrominated styrene. The polybrominated styrene preferably contains dibrominated styrene units in an amount of 60% by weight or more.
Those containing 0% by weight or more are more preferable. 40% by weight or less, preferably 30% by weight of monobrominated styrene and / or tribrominated styrene in addition to dibrominated styrene
The polybrominated styrene copolymerized below may be used. The weight average molecular weight of this polybrominated styrene is from 1 × 10 ³ to
It is preferably 3 × 10 ⁵ , and 1 × 10 ^{4 to} 1.5
× 10 ⁵ is more preferred. The weight average molecular weight is a value measured using a gel permeation chromatograph, and is a relative value based on polystyrene molecular weight. As the cross-linked brominated polystyrene, a polystyrene obtained by brominating a porous polystyrene cross-linked with diphenylbenzene is preferable. As the brominated polycarbonate, those represented by the following general formula (d) are preferable.

[0036]

Embedded image (R ₃ and R _{4 each} represent a substituted or unsubstituted aryl group, most preferably a pt-phenyl group.) In the above formula (d), the polymerization degree n is preferably 4 or more, and 8 or more. Those, especially 8 to 25, can be more preferably used. The amount of the organic bromine compound (D) added is 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the liquid crystal polyester.

The method of adding these is preferably melt kneading, and a known method can be used for melt kneading. For example, Banbury mixer, rubber roll machine,
Using a kneader, single screw or twin screw extruder, etc.
The composition can be melt-kneaded at a temperature of from about 370 ° C. to a composition.

Further, by adding a reinforcing agent and a filler to the resin composition of the present invention, mechanical properties and heat resistance can be further improved.

When a reinforcing agent and a filler are added, the amount is preferably 200 parts by weight or less, more preferably 15 to 150 parts by weight, based on 100 parts by weight of the liquid crystal polyester.

The reinforcing agents and fillers that can be used in the present invention include glass fibers, carbon fibers, aromatic polyamide fibers, potassium titanate fibers, gypsum fibers, brass fibers, stainless steel fibers, steel fibers, ceramic fibers, and boron. Whisker fiber, asbestos fiber, graphite, mica, talc, silica, calcium carbonate, glass beads, glass flake, glass micro balloon,
Fibrous, powdery, granular or plate-like inorganic fillers such as clay, wollastenite, titanium oxide, molybdenum disulfide and the like can be mentioned. Further, as for these reinforcing agents and fillers, those treated with a silane-based, titanate-based coupling agent, or other surface treatment agents may be used.

Further, the resin composition of the present invention contains an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, hydroquinone, etc.) as long as the object of the present invention is not impaired.
Phosphites and substituted products thereof), ultraviolet absorbers (eg, resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and release agents (montanic acid and its salts, esters, half esters, stearyl alcohol) , Stearamide and polyethylene wax, etc.), dyes (eg, nitrosine) and pigments (eg, cadmium sulfide,
Ordinary additives such as a coloring agent containing phthalocyanine, carbon black, etc.), a plasticizer, an antistatic agent, and other thermoplastic resins can be added to impart predetermined characteristics.

The method of adding these is preferably melt kneading, and a known method can be used for melt kneading. For example, Banbury mixer, rubber roll machine,
Using a kneader, single screw or twin screw extruder, etc.
The composition can be melt-kneaded at a temperature of from about 370 ° C. to a composition.

The resin composition thus obtained is injection molded,
It can be used for ordinary molding such as extrusion molding and compression molding, and is extremely useful as various molded products for electric / electronic parts, precision parts, automobile parts and the like. In addition, since a color tone and retention stability are excellent, a colored molded article can be obtained by adding a coloring agent.

[0044]

The present invention will be described in more detail with reference to the following examples.

Example 1 994 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4'-dihydroxybiphenyl, 112 terephthalic acid
216 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, 960 parts by weight of acetic anhydride, 1.3 parts by weight of phosphorous acid (0.1 part by weight based on 100 parts by weight of liquid crystal polyester) ) Was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and subjected to deacetic acid polymerization under the following conditions.

First, 100-250 in a nitrogen gas atmosphere.
After reacting for 5 hours at 250C and 1.5 hours at 250-300C, the pressure was reduced to 0.5 mmHg at 315C for 1 hour.
When the reaction was allowed to proceed for 25 hours to complete the polycondensation, almost the theoretical amount of acetic acid was distilled out, and a liquid crystal polyester having the following theoretical structural formula was obtained.

[0047]

Embedded image k / l / m / n = 80 / 7.5 / 12.5 / 20

The liquid crystal polyester was placed on a sample table of a polarizing microscope, and the temperature was raised to confirm the optical anisotropy. As a result, the liquid crystal onset temperature was 295 ° C., indicating good optical anisotropy. Was. Further, the melting point (Tm) was 316 ° C.
The logarithmic viscosity of this liquid crystalline polyester (measured in pentafluorophenol at a concentration of 0.1 g / dl at 60 ° C.) is 1.96 dl / g, 326 ° C., shear rate 1000
The melt viscosity at / sec was 800 poise. This was supplied to a Sumitomo Nestal injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.), allowed to stay at a cylinder temperature of 340 ° C. for 4 minutes and 30 minutes, and subjected to a bending test piece at a mold temperature of 90 ° C. (1/32 "x 1/2" x 5 ").
The whiteness (W value) of the test piece was measured using an SM color computer device manufactured by Suga Test Instruments Co., Ltd. Further, this test piece was dissolved in pentafluorophenol, and the logarithmic viscosity (60 ° C. at a concentration of 0.1 g / dl) was measured. The results are shown in Table 1.

Example 2 In the same manner as in Example 1 except that 1.3 parts by weight of calcium hypophosphite (0.1 part by weight based on 100 parts by weight of liquid crystal polyester) was added instead of phosphorous acid. Deacetic acid polymerization was performed.

The liquid crystal onset temperature of this liquid crystal polyester is:
294 ° C., showing good optical anisotropy. Further, the melting point (Tm) was 315 ° C. The logarithmic viscosity of this liquid crystal polyester (measured at 60 ° C. in pentafluorophenol at a concentration of 0.1 g / dl) is 1.97 dl / g, and the melt viscosity at 325 ° C. and a shear rate of 1000 / sec is 7
It was 80 poise. Whiteness of this polyester (W
Value) and logarithmic viscosity were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3 The procedure of Example 2 was repeated except that 1.3 parts by weight of potassium sulfate (0.1 part by weight with respect to 100 parts by weight of the liquid crystal polyester) was further added. went.

The liquid crystal onset temperature of this liquid crystal polyester is:
293 ° C., showing good optical anisotropy. Further, the melting point (Tm) was 315 ° C. The logarithmic viscosity of this liquid crystal polyester (measured in pentafluorophenol at a concentration of 0.1 g · dl at 60 ° C.) is 1.97 dl / g, and the melt viscosity at 325 ° C. and a shear rate of 1000 / sec is 7
It was 90 poise. Whiteness of this polyester (W
Value) and logarithmic viscosity were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 Deacetic acid polymerization was carried out in the same manner as in Example 1 except that no phosphorous acid was added.

The liquid crystal onset temperature of this liquid crystal polyester is:
293 ° C., showing good optical anisotropy. Further, the melting point (Tm) was 314 ° C. The logarithmic viscosity of this liquid crystal polyester (measured in pentafluorophenol at a concentration of 0.1 g / dl at 60 ° C.) is 1.98 dl / g, and the melt viscosity at 324 ° C. and a shear rate of 1000 / sec is 7.
It was 80 poise. Whiteness of this polyester (W
Value) and logarithmic viscosity were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 Deacetic acid polymerization was carried out in the same manner as in Example 1 except that 1.3 parts by weight of triphenyl phosphite was added instead of phosphorous acid.

The liquid crystal onset temperature of this liquid crystal polyester is:
291 ° C., showing good optical anisotropy. Further, the melting point (Tm) was 315 ° C. The logarithmic viscosity of this liquid crystal polyester (measured in pentafluorophenol at a concentration of 0.1 g / dl at 60 ° C.) is 1.94 dl / g, and the melt viscosity at 325 ° C. and a shear rate of 1000 / sec is 7.
It was 40 poise. Whiteness of this polyester (W
Value) and logarithmic viscosity were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 Deacetic acid polymerization was carried out in the same manner as in Example 1, except that 1.3 parts by weight of distearyl pentaerythritol diphosphite was added instead of phosphorous acid.

The liquid crystal onset temperature of this liquid crystal polyester is:
290 ° C., showing good optical anisotropy. Further, the melting point (Tm) was 314 ° C. The logarithmic viscosity of this liquid crystalline polyester (measured in pentafluorophenol at a concentration of 0.1 g / dl at 60 ° C.) is 1.92 dl / g, and the melt viscosity at 324 ° C. and a shear rate of 1000 / sec is 7.
It was 50 poise. Whiteness of this polyester (W
Value) and logarithmic viscosity were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0059]

[Table 1]

Example 4 With respect to 100 parts by weight of the liquid crystal polyester of Example 2, 10 parts by weight of polydibrominated styrene (59% bromine content) obtained by polymerizing dibrominated polystyrene monomer and an average diameter of 10 μm
After mixing 45 parts by weight of glass fiber having an average length of 3000 μm with a ribbon blender, the mixture was melt-kneaded at 310 ° C. using a 30 mmφ twin-screw extruder and then pelletized. This was supplied to a Sumitomo Nestal injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.).
And a retention time of 30 minutes, to form a bending test piece (1/32 "x 1/2" x 5 ") under the condition of a mold temperature of 90 ° C. The test piece was dissolved in pentafluorophenol, the insoluble content was filtered, the concentration was adjusted to 0.1 g / dl, and the logarithmic viscosity was measured at 60 ° C. The results were combined. It is shown in Table 2.

Example 5 0.5 part by weight of calcium hypophosphite, 10 parts by weight of polydibrominated styrene used in Example 4 and 45 parts by weight of glass fiber were used for 100 parts by weight of the liquid crystal polyester of Comparative Example 1. Melt kneading, molding and whiteness (W value) in the same manner as in Example 4.
And the logarithmic viscosity were measured. Table 2 shows the results.

Comparative Example 4 Melt kneading and molding were conducted in the same manner as in Example 5 except that 1 part by weight of triphenyl phosphite was added instead of calcium hypophosphite, and whiteness (W value) and logarithmic viscosity were measured. Was measured. Table 2 shows the results.

Comparative Example 5 Melt kneading and molding were conducted in the same manner as in Example 5 except that calcium hypophosphite was not added, and the whiteness (W value) and logarithmic viscosity were measured. Table 2 shows the results.

[0064]

[Table 2]

As is clear from the results of Tables 1 and 2,
The resin composition of the present invention has an excellent color tone, a small decrease in logarithmic viscosity during staying, and an excellent staying stability. Example 3
It can be seen that the addition of a metal salt other than phosphorous acid and a metal salt of hypophosphorous acid, that is, potassium sulfate, further improves the retention stability. On the other hand, those obtained by adding phosphite compounds other than those used in the present invention as in Comparative Examples 2 to 4, or those obtained by adding nothing as in Comparative Examples 1 and 5, were more stable than the Examples in color tone and retention stability. It turns out that it is inferior.

[0066]

According to the present invention, it is possible to obtain a resin composition having excellent color tone, excellent retention stability, and excellent heat resistance having good mechanical properties and appearance of a molded article.

Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 C08L 67/00-67/03 C08L 77/12

Claims (7)

(57) [Claims] (A) a liquid crystal polyester and / or a liquid crystal polyester amide (100 parts by weight);
A resin composition comprising 0.001 to 5 parts by weight of at least one compound selected from phosphorous acid, hypophosphorous acid, and a metal salt of hypophosphorous acid . 2. A method according to claim 1 further resin composition according (C) a resin composition comprising the additional inclusion hypophosphorous acid metal salt other than a metal salt 0.001 parts by weight. 3. A resin composition according to claim 1 or 2, further comprising (D) 0.5 to 30 parts by weight of an organic bromine compound. 4. The resin composition according to claim 1, wherein the liquid crystal polyester and / or the liquid crystal polyesteramide contains an ethylenedioxy unit as an essential component. 5. The liquid crystalline polyester according to claim 1, wherein the structural unit (I)
, (II), (III) and (IV), each having a structural unit [(I)
+ (II)] is 60 to 95 mol% of [(I) + (II) + (III)], and the structural unit (III) is 40 to 95% of [(I) + (II) + (III)].
5 mol%, and the molar ratio of the structural units (I) / (II) is 75/2.
The resin composition according to any one of claims 1 to 3, wherein the ratio is from 5 to 95/5. 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. The structural unit (IV) is substantially equimolar to the structural unit [(II) + (III)]. ) 6. At least one compound selected from (A) phosphorous acid, hypophosphorous acid and a metal salt of hypophosphorous acid before the completion of the polymerization of (A) the liquid crystalline polyester and / or the liquid crystalline polyesteramide. Of 0.001 to 5 parts by weight per 100 parts by weight of component (A). 7. After completion of the polymerization of (A) the liquid crystal polyester and / or the liquid crystal polyester amide, (B) at least one compound selected from the group consisting of phosphorous acid, hypophosphorous acid and a metal salt of hypophosphorous acid. (A) A method for producing a resin composition, wherein 0.001 to 5 parts by weight is added to 100 parts by weight of the component.