JPS6317955A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent flexural strength and flexural modulus and high chemical resistance and moldability, etc., by adding potassium titanate fiber having tunnel structure to a composition composed of an aromatic polycarbonate resin and an aromatic polyester resin. CONSTITUTION:100pts.wt. of a composition composed of (A) 10-95wt% aromatic polycarbonate resin and (B) 90-5wt% aromatic saturated polyester resin is compounded with (C) 5-100pts.wt. of potassium titanate fiber having tunnel structure. The component A is preferably a polymer produced by using bisphenol A as a raw material and the component B is preferably a polymer having an intrinsic viscosity of >=0.6, especially 0.7-1.5 in a 6:4 mixed solvent of phenol and tetrachloroethylene at 30 deg.C. The component C has a tunnel structure of titanic acid and contains K component included in the tunnel.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a thermoplastic resin composition that has excellent mechanical properties, particularly flexural strength and flexural modulus, and also exhibits good chemical resistance, moldability, etc. Parts of electronic and electrical equipment that require heat resistance, dimensional accuracy, flexural modulus, and chemical resistance, such as connectors, chassis, camera bodies, and automobile parts that are likely to be contaminated with oil. It provides materials suitable for such applications.

[Conventional technology and its problems]

As is well known, aromatic polycarbonate resin is tough, has excellent impact resistance, electrical properties, and has good dimensional stability.
Since it also has excellent transparency, it is widely used as a useful engineering plastic. However, due to its high melt viscosity, it is difficult to fill molds for office equipment chassis, large molded products for automobiles, and thin-walled molded products, resulting in short molds and crepe patterns, resulting in good molded products. It is difficult to obtain, and because it is an amorphous plastic, it has the disadvantage of poor chemical resistance.

In order to improve these shortcomings, the Special Publication No. 36-14035
In Japanese Patent Publication No. 39-20434, there is a proposal to blend aromatic saturated polyester resin into aromatic polycarbonate resin to improve solvent resistance and moldability. A ternary composition containing a polyester resin and a polyolefin has been proposed, and a method for improving moldability, impact resistance, and chemical resistance is further described in JP-A-48-54150. It is proposed to add methylene tedimetalate to improve chemical resistance and surface hardness. However, although these methods improve chemical resistance and moldability, they are unsuitable for applications that require dimensional accuracy and flexural modulus, and are not suitable for applications such as connectors, chassis, and cameras that require these characteristics. The body and the like have been addressed by adding glass fibers, but this composition also has the drawback that the fibers tend to stand out on the surface of the molded product.

As a solution to this problem, a method has been proposed in which potassium titanate fibers with a diameter of about 2.0 mm are added.

However, conventional potassium titanate fibers with a structural formula of 2TI40!1 have a layered structure and the K component is exposed on the fiber surface, so the polycarbonate resin component is hydrolyzed and a good composition is obtained. I couldn't get anything.

[Means for solving problems]

The present invention was developed as a result of intensive studies aimed at developing a material that has the bending strength, bending elastic modulus, chemical resistance and moldability of polycarbonate resin, and has good appearance of molded products. It was discovered that adding potassium fiber was effective, and the present invention was completed.

That is, the present invention provides C,
This is a thermoplastic resin composition containing 5 to 100 parts by weight of tunnel-structured potassium titanate fibers.

The present invention will be explained in detail below.

A, aromatic polycarbonate resin of the present invention is an optionally branched thermoplastic polycarbonate polymer made by reacting aromatic dihydroxy or a small amount of a polyhydroxy compound with a diester of phosgene or carbonic acid. An example of an aromatic dihydroxy compound is
2,2-bis(4-hydroxyphenyl)propane (=
Bisphenol A), Tetramethylbisphenol A1
Tetrabromobisphenol A1 bis(4-hydroxyphenyl)-P-diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, etc., with bisphenol A being particularly preferred. In addition, to obtain a branched aromatic polycarbonate resin,
Phloroglucin, 4,6-cymethyl-2.4.6-)
IJ (4-hydroxyphenyl)hebutene-2,4
,6-dimethyl-2.4.6-tri(4-hydroxyphenyl)hebutane,2,6-dimethyl-2.4.6-tri(4-hydroxyphenyl)hebutene-3,4,6-
Cymethyl-2.4.6-)su(4-hydroxyphenyl)hebutane, 1,3.5-) IJ (4-hydroxyphenyl)benzene, 1.1.1-) 'J (4-hydroxyphenyl)ethane polyhydroxy compounds exemplified by, and 3,3-bis(4-hydroxyaryl)oxindole (=isatin bisphenol),
5-chloroisatin, 5.7-dichlorisatin, 5-
Some of the dihydroxy compounds, such as bromysatin,
For example, 0.1 to 2 mol% is substituted with a polyhydroxy compound. Furthermore, monovalent aromatic hydroxy compounds suitable for controlling the molecular weight include m- and p-methylphenol, m
Preferred are - and p-propylphenol, p-bromophenol, p-tert-butylphenol and p-long chain alkyl-substituted phenol. Typical aromatic polycarbonate resins include polycarbonates whose main raw material is bis(4-hydroxyphenyl)alkane dihydroxy compounds, particularly bisphenol A, which can be obtained by using two or more aromatic dihydroxy compounds in combination. Branched polycarbonate obtained by using a small amount of a polycarbonate copolymer and a trivalent phenol compound can also be mentioned. Aromatic polycarbonate resins may be used as a mixture of two or more.

B, aromatic saturated polyester resin used in the present invention is a polymer obtained by reacting aromatic dicarboxylic acid or its diester with glycol or alkylene oxide by a known method. Specifically, terephthalic acid Ai is polyethylene tedimetalate, polytetramethylene terephthalate, and cyclohexane dimetalate obtained by reacting dimethyl terephthalate with aromatic dicarboxylic acid as the main component and ethylene glycol, butanediol, cyclohexane dimetatool, ethylene oxide, etc. Mention may be made of copolymers of tool with terephthalic acid and isophthalic acid, cyclohexane dimetatool and copolymers of ethylene glycol with terephthalic acid. The aromatic saturated polyester resin may be a copolymer or may be used in the form of a mixture of two or more types.

The aromatic saturated polyester resin used in the present invention has an intrinsic viscosity (intrinsic viscosity) of 0.6 or more, usually 0.6 or more, as measured at 30°C in a mixed solvent of phenol and tetrachloroethylene in a weight ratio of 6:4. A value of 7 to 1.5 is preferable, and if it is less than 0.6, impact strength and chemical resistance will be insufficiently improved.

The tunnel structure potassium titanate fiber used in the present invention has a structural formula of K2TisO,s, in which titanic acid forms a tunnel structure and the K component is confined inside this tunnel. be.

Specific examples of the properties of this tunnel structure potassium titanate fiber are as follows.

Structural formula: K2Ti-01a Crystal system: Monoclinic space group 'C2/m Lattice constant: a = 15.582 people, b = 3.82 people,
c = 9.112A, β = 99.764° Number of molecules in unit cell = 2 Such tunnel structure potassium titanate fiber is commercially available from Titan Kogyo ■ under the product name r IIT-300J r II
T-300E J rllT-200j is preferably used.

The ratio of the resin components in the thermoplastic resin composition of the present invention is A, and the aromatic polycarbonate resin is 10 to 95 wt%.
, preferably 15-90 wt%, and B, aromatic saturated polyester resin, 90-5 wt%, preferably 85-90 wt%.
It is in the range of 10wt%. Further, the amount of the C0 tunnel structure potassium titanate fiber is in the range of 5 to 100 parts by weight, preferably 50 to 80 parts by weight, based on 100 parts by weight of this composition. A. If the component is less than 10wt%, the heat resistance will not reach the level required for engineering plastics.
Dimensional stability is also poor. B. If the content of component is less than 5 wt%, the effect of improving chemical resistance will be insufficient. Furthermore, if the amount of C0 added is less than 5 parts by weight with respect to 100 parts by weight of this composition, the effect of improving bending strength and flexural modulus will be insufficient. Not enough.

The thermoplastic resin composition of the present invention as described above may contain various additives such as stabilizers, pigments, dyes, flame retardants, and lubricants, reinforcing materials such as inorganic or organic fiber substances, glass beads, etc., as desired. Various fillers may be blended, and other resin components may also be blended within a range that does not impair the characteristics of the present invention. For example, polycarbonate oligomers from bisphenol A or tetrabromobisphenol A can be used to improve moldability, flame retardancy, and surface properties, and heat-resistant polyesters such as polyester carbonates and polyarylates (e.g., trade names: U Polymer, Unitika@) For improving heat resistance, it is possible to incorporate

In preparing the thermoplastic resin composition of the present invention,
Any conventionally known method may be used, and methods of kneading using an extruder, Banbury mixer, rolls, etc. may be selected as appropriate.

〔Example〕

Examples and comparative examples will be described below, and "parts" are based on weight unless otherwise specified.

Example 1.2 and Comparative Examples 1 to 3 Aromatic polycarbonate resin made from bisphenol A (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name Newpiron S-10)
00, molecular weight 28.000, rS-1000j)
, polyethylene terephthalate resin (Nippon Unibet ■
(trade name: RT-580, rPET J) and tunnel structure potassium titanate fiber (manufactured by Titan Kogyo, trade name: IIT-300 and IIT~300B,
rHT-300J rllT-300E J) were added to a blender in the proportions shown in Table 1, and
Mixed for 0 minutes.

The obtained mixture was supplied to a 4 On+m vented extruder and melt-kneaded at a cylinder temperature of 230 to 260°C to form pellets. The pellets were dried in a hot air dryer at a temperature of 110 to 12
After drying at 0° C. for 5 hours or more, test pieces for measuring physical properties were molded by injection molding. The test results are shown in Table 1.

For comparison, polycarbonate resin alone (Comparative Example 1), a composition of polycarbonate resin and polyethylene terephthalate resin (Comparative Example 2), and a layered structure potassium titanate fiber (Otsuka Manufactured by Kagaku◇S, product name: TISMO rJ1
01, rllolJ) (comparative example 3), pellets and test pieces were prepared in the same manner as in the example, and physical properties were measured. Table 1 shows the results.

In addition, the description in the table is as follows.

σ1: Tensile strength unit: kg/c.

ε: Tensile elongation unit %.

σF: Bending strength unit: kg/c.

YF: Flexural modulus unit: X 10” kg/c
nf.

11DT: Heat distortion temperature Load 18.6kg /
ct&unit ℃.

CCl4 medium bending strength: Unit kg/cnl Appearance:
Visually observe the appearance of the molded product.

○: Good, ×: Decomposed, colored brown Table 1 Examples 3 to 6 and Comparative Examples 4 to 6 Aromatic polycarbonate resin made from bisphenol A (manufactured by Mitsubishi Gas Chemical ■, trade name Newpilon S-20)
00, molecular weight 25.000, rS-2000J), polybutylene terephthalate resin (manufactured by Polyplastics ■, product name: DURANEX 2002, rPBT
) and tunnel structure potassium titanate fiber (denoted as J) and tunnel structure potassium titanate fiber (
Titanium Industry 0 grade, product name: HT-300 and IIT
-300B, respectively rllT-300''rllT-
300B) in the proportions shown in Table 2, and mixed for 30 minutes.

The obtained mixture was supplied to a 40m+n vented extruder and melt-kneaded at a cylinder temperature of 230 to 260°C to form pellets. The pellets were dried in a hot air dryer to
After drying at 0° C. for 5 hours or more, test pieces for measuring physical properties were molded by injection molding. The test results are shown in Table 1.

For comparison, compositions of polycarbonate resin and polybutylene terephthalate resin (Comparative Example 4.5) and Example 4
In place of tunnel structure potassium titanate fiber, layered structure potassium titanate fiber (manufactured by Ogaki Chemical Co., Ltd., product name:
Tismo D101, "written as [)IOIJ" (Comparative Example 6
), pellets and test pieces were prepared in the same manner as in the examples, and the physical properties were measured, and the results are shown in Table 2.

Note that the descriptions in Table 2 are the same as those in Table 1 above.

[Operation and effects of the invention]

As is clear from the above detailed description, Examples, and Comparative Examples, the composition of the present invention has aromatic polycarbonate resin.
It is possible to obtain a composition that has improved bending strength and flexural modulus compared to aromatic saturated polyester resin compositions, and, unlike conventional potassium titanate fibers, does not deteriorate in appearance.

Claims (1)

[Claims] A, 10 to 95 wt% aromatic polycarbonate resin and B
A thermoplastic resin composition comprising 5 to 100 parts by weight of C and tunnel structure potassium titanate fibers mixed with 100 parts by weight of a composition containing 90 to 5 wt% of an aromatic saturated polyester resin.