JPH04146957A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To improve dimensional stability and prevent mol.wt. reduction by compounding an arom. polycarbonate resin or a thermoplastic resin mixture mainly comprising the polycarbonate resin, an aluminum borate whisker, and a specified amt. of an org. acid. CONSTITUTION:100 pts.wt. arom. polycarbonate resin or thermoplastic resin mixture comprising the polycarbonate resin and 70wt.% or lower other thermoplastic resin, at least 1 pt.wt., pref. at least 5 pts.wt., aluminum borate whisker having a mean diameter of 0.5-1mum and a mean length of 10-30mum. and 0.1-10wt.%, pref. 0.5-5wt.%, (of the whisker) org. acid, pref. a 15C or lower arom. carboxylic acid or a 20C or lower aliph. carboxylic acid (e. g. fumaric acid) are compounded to give a thermoplastic resin compsn. suitable for a large part of a precision machine, automobile, etc.

Description

Detailed Description of the Invention Field of Application The present invention provides aromatic polycarbonate resins or aromatic polycarbonate resins and other thermoplastic resins having excellent dimensional stability and retaining their original properties. ! The present invention relates to a thermoplastic resin composition mainly consisting of a mixture with a synthetic resin.

<Prior Art> It has been known to improve dimensional stability by incorporating an inorganic filler into a thermoplastic resin.

However, when glass fiber is blended with an aromatic polycarbonate resin and, for example, injection molded, the resulting molded product has the disadvantage that its appearance deteriorates and its modulus of elasticity also decreases.

In an effort to eliminate these drawbacks, we investigated many inorganic fillers and found that the use of aluminum borate whiskers could greatly improve the above drawbacks. However, when the necessary amount of aluminum borate whisker is added to the aromatic polycarbonate resin, the aluminum borate whisker has an acidic pH (PI15.
5 to 75), aromatic polycarbonate 1
-The molecular ω of the resin was greatly reduced, and the mechanical properties were also deteriorated, making it impossible to put it to practical use.

A known method for solving these drawbacks is to pre-treat the inorganic filler with a silane coupling agent; however, this method requires that the silane coupling agent is expensive;
The complicated processing steps lead to increased costs, and the effects are not fully satisfactory.

<Object of the Invention> The present invention provides a method for improving dimensional stability by adding aluminum borate whiskers to an aromatic polycarbonate resin or a mixture of an aromatic polycarbonate resin and another thermoplastic resin, but with a slight decrease in molecular weight. The object of the present invention is to provide a resin composition that retains the excellent properties inherent to the resin.

As a result of intensive studies aimed at achieving the above object, the inventors of the present invention have found that, when blending aluminum borate whiskers with aromatic polycarbonate resin, if a specific amount of maleic acid is used in combination, the reduction in molecular weight can be greatly suppressed. I learned. The present invention was completed as a result of further studies based on this knowledge.

<Structure of the Invention> The present invention provides 100 parts by weight of an aromatic polycarbonate resin or a thermoplastic resin obtained by adding 70% by weight or less of another thermoplastic resin to an aromatic polycarbonate resin, and 1 part by weight or more of aluminum borate whiskers and the borium. This invention relates to a thermoplastic resin composition containing an organic acid in an amount of 0.1 to 10% by weight based on the acid aluminum whiskers.

The aromatic polycarbonate resin used in the present invention has a viscosity average molecular ω derived from dihydric phenol of 13,00
0~50.000. Preferably 15,000-3500
0 aromatic polycarbonate resin, and is usually produced from a dihydric phenol and a carbonate precursor by a solution method or a melt method. As a dihydric phenol, 22-bis(4
-hydroxyphenyl)propane (commonly known as bisphenol A), but part or all of it may be replaced with other dihydric phenols. Other dihydric phenols include, for example, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2
, 2-bis(4-hydroxy-3-methylphenyl)propane, and the like. As a carbonate precursor,
Examples include carbonyl halides, carbonyl esters, haloformates, etc. Specific examples include phosgene,
Examples include diphenyl carbonate and dihaloformates of dihydric phenols. Furthermore, when producing an aromatic polycarbonate resin, a molecular weight regulator, a branching agent, a catalyst, etc. can be used as necessary.

The thermoplastic resin mixed with aromatic polycarbonate resin is aromatic polycarbonate! Any material that can be mixed with M resin may be used, such as thermoplastic polyester resins, polyarylene ester resins, polystyrene resins, polyethylene resins, polypropylene resins, diene resins, polyamide resins, and polyether resins. Examples include one or a mixture of two or more selected from resins, polysulfone resins, polyphenylene sulfide resins, and the like.

The thermoplastic polyester resin is a polymer or copolymer obtained by condensation reaction using an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof as main raw materials. As the aromatic dicarboxylic acid used here, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid M, etc. are preferable. Diols include alkylene glycols having 2 to 10 carbon atoms, and 6 to 15 carbon atoms.
Preferred are alicyclic diols such as ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, 3-methylbentanediol (2,4), 2-methylbentanediol (1,4), Examples include 2-ethylhexanediol (1,3), diethylene glycol, and cyclohexane dimetatool. Preferred thermoplastic polyester resins include polyethylene terephthalate, polybutylene terephthalate, their acid components and/or
Alternatively, it is a copolyester in which 30 mol% or less of the diol component is replaced with another component.

The polyarylene ester resin is a polymer or copolymer obtained by condensation reaction of dihydric phenol or its ester-forming derivative and aromatic dicarboxylic acid or its ester-forming derivative as main raw materials. As the dihydric phenol used here, those explained in the above-mentioned aromatic polycarbonate resin are preferably used, and its ester-forming derivatives include, for example, diesters with aliphatic or aromatic carboxylic acids. As the aromatic dicarboxylic acid, those explained in connection with the thermoplastic polyester resin are preferably used. Any method such as interfacial polycondensation, solution polycondensation, melt polycondensation, etc. can be used to produce polyarylene ester resin from dihydric phenol or its ester-forming derivative and aromatic dicarboxylic acid or its ester-forming derivative. Adopted.

Examples of polystyrene resins include general purpose polystyrene, impact-resistant polystyrene, AS resin, ABS resin, and A
Examples include ES resin, MBS resin, MAS resin, AAS resin, styrene-butadiene block copolymer, styrene-maleic anhydride copolymer, and the like.

Examples of polyethylene resins include high-density polyethylene resin, low-density polyethylene resin, linear low-density polyethylene resin, ethylene-vinyl acetate copolymer, and ethylene-vinyl acetate copolymer.
Examples include propylene copolymers, ethylene-acrylic acid ester copolymers, ethylene-glycidyl (meth)acrylate copolymers, and the like.

Examples of the polypropylene resin include polypropylene resin, propylene-vinyl acetate copolymer, and propylene-vinyl acetate copolymer.
Examples include vinyl chloride copolymers.

Examples of diene resins include 1,2-polybutadiene resin, trans-1,4-polybutadiene resin, etc. Diene 41! These are intermediate monomers having an i-structure alone, copolymers with monomers copolymerizable with them, and mixtures thereof.

For example, aminocarbon M
Examples thereof include a polymer alone or composed of a dicarboxylic acid and a diamine, and a polymer obtained by ring-opening polymerization of α,ω-caprolactam.

Preferred examples of the polyether resin include polyphenylene ether polymers or copolymers.

The aluminum borate whiskers used in the present invention are white acicular single crystal fibers with a chemical composition of 9/V2O3.28203, an average diameter of 05 to 1μ, and an average length of 10
~30μ is preferred.

The amount of aluminum borate whiskers to be used can vary widely depending on the purpose of use of the resulting composition and is not particularly limited, but the amount that affects the reduction of the molecular weight of the aromatic polycarbonate resin, that is, the aromatic polycarbonate The present invention is effective when the amount is 1 part or more per weight per 100 parts by weight of the resin, and particularly remarkable effects are obtained when the amount is 5 parts by weight or more.

The compound used in the present invention is a carboxylic acid, a sulfonic acid, etc., and aromatic carboxylic acids having 15 or less carbon atoms and aliphatic carboxylic acids having 20 or less carbon atoms are particularly preferred. Specifically, aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, malonic acid, succinic acid, glutaric acid, stearonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, itaconic acid, and benzoic acid. Examples include aromatic carboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid, and terephthalic acid.

By using such an organic acid, it is possible to greatly suppress a decrease in the molecular weight of the aromatic polycarbonate resin due to aluminum borate whiskers.

If the amount of organic acid used is too small, a sufficient effect of suppressing molecular weight reduction cannot be obtained, and if the amount is too large, the effect becomes saturated. The amount used is usually selected from the range of 0.1 to 10% by weight based on the amount of aluminum borate whiskers used, and the optimum amount used is selected from the range of 0.5 to 5% by weight based on the amount of aluminum borate whiskers. Ru.

The composition of the present invention can be produced by mixing the above-mentioned components using any method such as a tumbler, blender, Nauta mixer, Banbury mixer 1 kneading roll, extruder, etc. may contain other additives, such as antioxidants, 81M agents, antistatic agents, mold release agents, ultraviolet absorbers, etc., as necessary within the scope of the purpose.

<Effects of the Invention> The composition of the present invention contains an aromatic polycarbonate resin or a mixture of an aromatic polycarbonate resin and another thermoplastic resin mixed with aluminum borate whiskers in an amount necessary to improve dimensional stability. Even in some cases, the decrease in molecular weight is significantly suppressed and the resin retains its original excellent properties, so it can be applied to any melt molding method such as injection molding, extrusion molding, compression molding, etc., especially when it could not be used conventionally. It has excellent industrial effects, such as being able to be used in large precision machinery parts, large automobile parts, etc.

<Examples> The present invention will be explained in detail below using examples. In addition, parts in the examples mean parts by weight, and the viscosity average molecular weight M is determined by inserting the specific viscosity ηsp obtained from a solution dissolved in methylene chloride at 20 ° C. at a concentration of 0.7 g / dj into the following formula. Ta.

η, p/C=[η ko + 0.45 [η ]2
C[ηko = 1.23 X10-'M However, C=
0.7 In addition, the impact strength was measured using a test piece with a thickness of 1/4" and 1/8" with an isotnotch.The value <Kgf,
cm/an>, and the heat distortion temperature (HDT) is ASTH
I measured at D-648 (18,6'j f/ci)
Indicated by ('C).

Examples 1 to 4 and Comparative Example 7.2 Ammonium borate listed in Table 1 was added to 100 parts by weight of polycarbonate powder obtained from Suphenol A having a viscosity average molecular weight of 22,500 (Panlite L1225 manufactured by Yojin Kasei Corporation). The indicated amounts of whiskers and ammonium omega (parts by weight) were added, and the mixture was extruded using a 30 aw φ vented extruder (VSK-30 manufactured by Nakatani Corporation) at a cylinder temperature of 290° C. to obtain pellets.

The pellets were dried at 120°C for 5 minutes using a hot air circulation dryer.
After drying for a while, use an injection molding machine (J-12 manufactured by Japan Steel Works, Ltd.).
0S^) cylinder temperature 300℃, mold temperature 80℃
Physical property test pieces were prepared at ℃. Table 1 shows the viscosity average molecules @M of the pellets and molded products (physical property test pieces), and the physical properties of the test pieces.

The aluminum borate whiskers used here had a chemical composition of 9AI20s/282o3 and an average diameter of 05 to 1.
μ, average length 10 to 30 μ, white acicular single crystal fiber M (Alborex G manufactured by Shikoku Kasei ■).

(Margin below)

Claims (1)

[Claims] To 100 parts by weight of an aromatic polycarbonate resin or a thermoplastic resin in which 70% by weight or less of another thermoplastic resin is added to an aromatic polycarbonate resin, 1 part by weight or more of aluminum borate whiskers and 0.1 part by weight with respect to the aluminum borate whiskers. A thermoplastic resin composition containing an organic acid in an amount of ~10% by weight.