JP2671439B2 - Thermoplastic resin composition - Google Patents

Description

The present invention relates to a heat resistant resin composition having excellent heat resistance and plating characteristics.

<Prior 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.

Examples of the polymer forming the anisotropic molten phase include p-
Liquid crystal polyesters obtained by copolymerizing hydroxybenzoic acid with 4,4'-dihydroxybiphenyl, terephthalic acid with t-butylhydroquinone, hydroquinone, 2,6-dihydroxynaphthalene, isophthalic acid, polyethylene terephthalate, and the like are known (Japanese Patent Application Laid-open No. Sho. 62-39622, JP-A-62-164719, JP-A-62-292832, JP-A-63-30523, and JP-A-63-33418.

Further, a heat distortion temperature composed of, for example, p-hydroxybenzoic acid and polyethylene terephthalate is known (West German Patent No. 3,123,954).

<Problems to be Solved by the Invention> p-Hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, terephthalic acid and t-butylhydroquinone, hydroquinone, 2,6-dihydroxynaphthalene, isophthalic acid, polyethylene terephthalate, etc. were copolymerized. Liquid crystal polyester has a good balance between heat resistance and fluidity, but has poor adhesion to metals and is difficult to plate.

On the other hand, p described in West German Patent No. 3,123,954
The composition comprising -hydroxybenzoic acid and polyethylene terephthalate still has a problem of low heat resistance.

Therefore, it is an object of the present invention to solve the above problems and obtain a thermoplastic resin composition having excellent heat resistance and plating characteristics.

<Means for Solving the Problems> That is, the present invention has a heat deformation temperature comprising the following structural units.
190-280 ° C, liquid crystal onset temperature is 330 ° C or less, melt viscosity is 10,
Liquid crystal polyester (A) 99 to 1% by weight and an styrene resin (B) 1 to form an anisotropic melt phase of 000 poise or less
It is a thermoplastic resin composition comprising 99% by weight.

O-X-O (III) (However, X in the formula is —CH ₂ CH ₂ — represents one or more groups selected from carbonyl groups of the structural unit (IV) in a para or meta position with each other, and 50 mol% or more of the carbonyl groups are in the para position. The structural unit [(II) + (III)] and the structural unit (IV) are substantially equimolar. The structural unit (I) of the liquid crystal polyester (A) in the present invention is a structural unit formed from p-hydroxybenzoic acid, and the structural unit (II) is a structural unit formed from 4,4′-dihydroxybiphenyl. The structural unit (III)
Is a structural unit formed from one or more dihydroxy compounds selected from hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene and ethylene glycol, and structural unit (IV) is terephthalic acid and / or isophthalic acid. The structural units generated from are shown below.

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

The structural units (I), (II), (III) and (IV)
Is arbitrary. The following copolymerization amount is preferable from the viewpoint of fluidity. That is, the structural unit (I)
Is preferably 40 to 90 mol% of [(I) + (II) + (III)], and particularly preferably 60 to 78 mol%. The structural unit (II) / (III) has a molar ratio of 9/1.
To 1/9 is preferable, and in the structural unit (III), -X-
There -CH ₂ CH ₂ - otherwise preferably 7.5 / 2.5 to 2.5 / 7.5, particularly preferably 7.5 / 2.5 to 4/6. Also, the structural unit (I
V) is substantially equimolar to the structural unit [(II) + (III)].

It is essential that the liquid crystal polyester (A) used in the present invention has a heat deformation temperature of 190 to 280 ° C. when no filler is blended.

If the heat distortion temperature is less than 190 ° C, the heat resistance of the composition is insufficient, and if it exceeds 280 ° C, 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 33
It is essential that the temperature be 0 ° C or lower, and it is preferable that the temperature be 260 to 330 ° C from the viewpoint of fluidity and heat resistance.

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

The melt viscosity is essential to be 10,000 poise or less, preferably 5,000 poise or less, and more preferably 2,000 poise or less.

The melt viscosity is a value measured by a Koka type flow tester under the condition of (liquid crystal onset temperature + 40 ° C.) and a shear rate of 1,000 (1 / second).

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

For example, in the structural unit (III), -X- is -CH ₂ CH
_In cases other than _{2-, the following} (1) to (4), -X- is -CH ₂ CH
_In the case of _2-, the production method (5) is preferably mentioned.

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

(2) After reacting aromatic dihydroxy compounds such as p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl and hydroquinone, and aromatic dicarboxylic acids such as terephthalic acid with acetic anhydride to acylate the phenolic hydroxyl group, A method of producing by a deacetic acid polycondensation reaction.

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

(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 dihydroxy compound such as 4,4'-dihydroxybiphenyl and hydroquinone is added. In addition, a method of producing by a dephenol polycondensation reaction.

(5) A method according to (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).

As the catalyst used in the polycondensation reaction, stannous acetate, tetrabutyl titanate, potassium acetate, antimony trioxide, magnesium, sodium acetate, zinc acetate and the like metal compounds are typical, especially in the case of dephenol polycondensation. It is valid.

The liquid crystal polyester (A) of the present invention is capable of measuring the intrinsic viscosity in pentafluorophenol, in which case the value measured at 60 ° C. at a concentration of 0.1 g / dl is used.
0.5 dl / g or more is preferable, and 1.0 to 15.0 dl / g is particularly preferable.

When the liquid crystal polyester (A) used in the present invention is polycondensed, the above (I), (II), (III) and (I)
V) In addition to the components constituting, 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 acids, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, resorcinol, chlorohydroquinone, methylhydroquinone, 2,
Aromatic dihydroxy compounds such as 7-dihydroxynaphthalene, aromatic oxycarboxylic acids such as m-oxybenzoic acid and 2,6-oxynaphthoic acid and p-aminophenol and p-aminobenzoic acid impair the purpose of the present invention. Copolymerization can be further performed in a small proportion in a range that is not so large.

As the styrene resin (B) in the present invention, PS
(Polystyrene), HIPS (High Impact Polystyrene), AS
(Acrylonitrile / styrene copolymer), ABS (Acrylonitrile / butadiene / styrene copolymer), MBS
(Methyl methacrylate / butadiene / styrene copolymer) and the like, and ABS and MBS are preferably used from the viewpoint of plating characteristics.

ABS and MBS will be described in more detail. At least one selected from the vinyl compound (b), the acrylic ester (c) and the methacrylic ester (d) is added to the rubbery polymer (a) and a vinyl cyanide compound ( Graft copolymer obtained by graft polymerization of e) (polymer (i))
In addition, optionally, at least one selected from the aromatic vinyl compound (b), the acrylic acid ester (c) and the methacrylic acid ester (d) and a copolymer of the vinyl cyanide compound (e) (polymer (ii )) Is compounded.

Here, examples of the rubber-like polymer (a) in the polymer (i) include polybutadiene rubber, styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), and other diene rubbers, Examples thereof include acrylic rubber such as butyl acrylate and polyolefin rubber such as ethylene-propylene-non-conjugated diene terpolymer rubber (EPDM). The preferred rubbery polymer is polybutadiene.

As the aromatic vinyl compound (b) in the polymer (i) and the polymer (ii), styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, pt-
There are butyl styrene and the like, but styrene and α-methyl styrene are particularly preferable, and these can be used in combination.

Examples of the acrylic acid ester (c) and the methacrylic acid ester (d) in the polymer (i) and the polymer (ii) include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Methyl methocrylate is preferably used. Examples of the vinyl cyanide compound (e) include acrylonitrile and methacrylonitrile.

The copolymerization amount of the rubber-like polymer (a) in the polymer (i) is 5
-80% by weight is preferred. The vinyl cyanide compound has 50 to 97% by weight of one or more selected from the aromatic vinyl compound (b), the acrylic acid ester (c) and the methacrylic acid ester (d) in the graft component. (E) is preferably 3 to 50% by weight.

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

A suitable copolymerization amount of the vinyl cyanide compound (e) in the polymer (ii) is 3 to 50% by weight.

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

ABS and MBS used as the styrene resin (B) can be used by mixing the polymer (i) as an essential component and the polymer (ii) in an arbitrary ratio.

In the present invention, the compounding amount of the liquid crystal polyester (A) is
99 to 1% by weight, preferably 95 to 5% by weight, particularly preferably 90 to 10% by weight, the compounding amount of the styrene resin (B) is 1 to
99% by weight, preferably 5 to 95% by weight, particularly preferably 10
~ 90% by weight. Liquid crystal polyester (A) 99% by weight
If it exceeds 1, the plating characteristics will be insufficient, and if it is less than 1% by weight, the heat resistance will be insufficient.

The composition of the present invention contains an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and substituted products thereof) and an ultraviolet absorber (to the extent that the object of the present invention is not impaired). For example, resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and release agents (such as montanic acid and its salts, esters, half esters thereof, stearyl alcohol, stearamide, and polyethylene wax), dyes (such as nitrosine) and pigments (such as nitrosine) For example, coloring agents containing cadmium sulfide, phthalocyanine, carbon black, etc., flame retardants, plasticizers, antistatic agents, reinforcing agents (eg, glass fiber, talc, clay,
Conventional additives such as mica, silica, wollastonite) and other thermoplastic resins can be added to impart the desired properties.

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

<Example> Hereinafter, the present invention will be described 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 130 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g The reaction vessel was equipped with a stirring blade and a distilling tube, and subjected to deacetic acid polycondensation under the following conditions.

First, under nitrogen gas atmosphere at 100-250 ° C for 5 hours 1,250-3
After reacting at 00 ° C for 1.5 hours, 0.5mmH at 300 ° C for 1 hour
When the pressure was reduced to g and the reaction was further continued for 2.25 hours to complete the polycondensation, an approximately theoretical amount of acetic acid was distilled off, and a resin (A-1) having the following theoretical structural formula was obtained.

OCH ₂ CH ₂ O _n / l / m / n / o = 75/10/15/25 Also, the polyester was placed on the sample stage of a polarizing microscope and the temperature was raised to confirm the optical anisotropy. C., showing good optical anisotropy. The logarithmic viscosity of this polyester (measured at 60 ° C. in pentafluorophenol at a concentration of 0.1 g / dl) is 1.96 dl / g,
The melt viscosity at 304 ° C. and a shear rate of 1,000 / sec was 910 poise.

Reference Example 2 62.44 parts by weight of p-hydroxybenzoic acid, 14.03 parts by weight of 4,4'-dihydroxybiphenyl, 18.40 parts by weight of 2,6-diacetoxynaphthalene, 25.03 parts by weight of terephthalic acid and 67.69 parts by weight of acetic anhydride were stirred with a stirring blade, distilled Charge into a reaction vessel equipped with an outlet tube, and place in a nitrogen gas atmosphere at 130 to 250 ° C for 4.5 hours, 2
After reacting at 50-300 ° C for 2.5 hours, the temperature was raised to 330 ° C and the pressure was reduced to 0.3 mmHg in 1 hour, and the reaction was continued for 2 hours to complete the polycondensation. ,
A resin (A-2) having the following theoretical structural formula was obtained.

l / m / n / o = 75 / 12.5 / 12.5 / 25 This polyester was placed on the sample stage of a polarizing microscope, and the temperature was raised to confirm the optical anisotropy. And showed good optical anisotropy. The logarithmic viscosity of this polyester (measured under the same conditions as in Reference Example 1) was 6.3 dl / g, and the melt viscosity at 303 ° C. and a shear rate of 1,000 / sec was 1,200 poise.

Polyarylene oxide (B) The components and abbreviations of the styrene resin (B) used in the examples and comparative examples are as follows.

Examples 1 to 5 Liquid crystalline polyester (A) and styrene-based resin (B) were melt-mixed with a 30 mmφ twin-screw extruder set at 280 to 290 ° C. in the proportions shown in Table 1 to obtain compositions. Using an injection molding machine having an injection capacity of 5 _OZ , the obtained composition,
Molding temperature 280-290 ℃, mold temperature 50-80 ℃, 1/4 "× 1/2"
A 5 × 5 ″ test piece was molded, and the heat distortion temperature (18.6 kg / cm ² ) was measured according to the ASTM D648 standard.

In addition, 10cm x 4cm 0.5mm thick sheet is melt-formed and electroplated according to the steps of alkali etching → electrolytic copper plating (thickness 30μm) → electrolytic nickel plating (thickness 15μm) → electrolytic chromium plating (thickness 0.2μm). Applied (electroplated sheet). Electroplated sheet for bending test
It was curved 90 ° and the surface condition was visually observed and evaluated.

In the thermal cycle test, exposing the electroplated sheet to an atmosphere of −30 ° C. (1 hr) → 120 ° C. (1 hr) is set as one cycle, and this is continued for four cycles, and then the surface condition of the plating is visually inspected. It was observed and evaluated.

 The results are shown in Table 1.

Comparative Examples 1 to 4 Using liquid crystal polyester (A) and styrene resin (B), molding and evaluation were carried out in the same manner as in Examples 1 to 5.

 The results are shown in Table 1.

As can be seen from Table 1, the thermoplastic resin compositions of the present invention of Examples 1 to 5 have a higher heat distortion temperature and excellent heat resistance than Comparative Examples 3 and 4, and a bending test for Comparative Examples 1 and 2. Good thermal cycleability and excellent plating characteristics.

<Effects of the Invention> In the present invention, a thermoplastic resin composition having excellent heat resistance and plating characteristics can be obtained by blending a liquid crystal polyester having a specific structure with a styrene resin.

Claims (1)

(57) [Claims] 1. A heat distortion temperature of 190 to 2 comprising the following structural units:
From 99 to 1% by weight of liquid crystalline polyester (A) that forms an anisotropic molten phase having a liquid crystal starting temperature of 330 ° C. or less and a melt viscosity of 10,000 poise or less, and 1 to 99% by weight of styrene resin (B). Resin composition. O-X-O (III) (However, X in the formula is —CH ₂ CH ₂ — represents one or more groups selected from carbonyl groups of the structural unit (IV) in a para or meta position with each other, and 50 mol% or more of the carbonyl groups are in the para position. The structural unit [(II) + (III)] and the structural unit (IV) are substantially equimolar. )