JPH0598143A - Thermpolastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in electrical conductivity and antistatic nature, colorable in any color by incorporating a specific thermoplastic polycarbonate resin with a specified amount of ultrafine metal oxide powder. CONSTITUTION:The objective composition suitable as a material for injection molding, films and sheets can be obtained by incorporating (A) 100 pts.wt. of a polycarbonate resin made up of constituent unit of the formula (A is 1-10C straight chain, branched chain or cyclic alkylidene, aryl-substituted alkylidene, 1-4C alkyl or alkenyl) with (B) 1-300 pts.wt. of halogen, 1-4C alkyl or alkenyl) with (B) 1-300 pts.wt. of ultrafine metal oxide powder consisting of pref. titanium dioxide, indium oxide, zinc oxide, tin oxide and/or antimony oxide. The component B is pref. treated, in advance, with an organic silicate or titanate and/or organic polysiloxane.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic polycarbonate resin composition. More specifically, it is made by blending a polycarbonate resin with an ultrafine powder of a conductive metal oxide, which is excellent in conductivity and antistatic property and can be arbitrarily colored. And a polycarbonate resin composition.

[0002]

2. Description of the Related Art A conductive polymer prepared by mixing a conductive powder with a resin is used not only for replacing conventional metal-based conductive materials such as conductors, electrodes, electromagnetic wave shields and antistatics, but also for batteries, catalysts,
It is used or expected to be used in applications such as recording and display devices and sensors. However, since the resin composition obtained by adding the conductive carbon black to the polycarbonate resin is black, it cannot be colored other than black, which limits the range of use.

[0003]

SUMMARY OF THE INVENTION The present invention overcomes these deficiencies by using conductive metal oxide ultrafine powder. That is, the present invention provides (a) a polycarbonate resin having one or more structural units represented by the following general formula (1).

[0004]

[Chemical 2]

(A is a linear, branched or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylidene group, an arylenedialkylidene group, or -O-, -S-, -CO
-, -SO ₂ -is shown, and R ¹ , R ² , R ³ and R ⁴ are hydrogen, halogen or an alkyl group having 1 to 4 carbon atoms or an alkenyl group.)
And (b) an ultrafine powder of a metal oxide, and the blending amount of (b) is 1 to 300 parts by weight with respect to 100 parts by weight of (a).

The structure of the present invention will be described below. The polycarbonate resin of the present invention is a dihydric phenol represented by the following general formula (2):

[0007]

[Chemical 3]

(Wherein R ¹ , R ² , R ³ , R ⁴ and A are represented by the general formula (1)
(The same as the above) is reacted with phosgene, a carbonic acid ester, or a chloroformate, and has the general formula (1) as a structural unit. The viscosity average molecular weight is usually 10,000-5
It is 0,000, preferably 20,000-40,000.

The dihydric phenol compound represented by the general formula (2) used as a raw material for the polycarbonate resin in the present invention includes bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2 -Bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-
3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 1,1-bis (4-hydroxy) Phenyl) -1-phenylethane and bis (4-hydroxyphenyl) diphenylmethane are exemplified, and 2,2-bis
(4-Hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are preferable from the viewpoint of thermal stability.

Further, a terminal stopper or a molecular weight modifier is usually used. Examples of these include compounds having a monovalent phenolic hydroxyl group, in addition to ordinary phenol, p-tertiary butylphenol, tribromophenol, etc., long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxy. Benzoic acid alkyl ester, hydroxyphenyl alkyl ester,
An alkyl ether phenol etc. are illustrated. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, based on 100 mol of all dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination. Further, a branching agent can be used in the range of 0.01 to 3 mol%, particularly 0.1 to 1.0 mol% with respect to the above dihydric phenol compound to form a branched polycarbonate. Glycine, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,4,
6-Dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2,1,3,5-tri (2-hydroxyphenyl) benzol, 1,1,1-tri (4-hydroxyphenyl) ethane , 2,6-
Polyhydroxy compounds exemplified by bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, α, α ′, α ″ -tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene And 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin, 5,7-dichlorisatin, 5-bromoisatin and the like.

The conductive metal oxide ultrafine powder is a particle which is invisible under an optical microscope but is observed by an electron microscope and has a diameter of 1 μm or less, preferably 0.5 μm or less,
It is preferable that the powder resistance value is 100 Ωcm or less, particularly 70 Ωcm or less. Examples of the conductive metal oxide ultrafine powder include titanium oxide, indium oxide, zinc oxide, tin oxide, antimony oxide, and the like. The conductive metal oxide ultrafine powder is added in an amount of 1 to 300 parts by weight, preferably 30 to 100 parts by weight, based on 100 parts by weight of the thermoplastic polycarbonate resin. The electrically conductive metal oxide ultrafine powder can be compounded by a method known per se, for example, the polycarbonate powder and the electrically conductive metal oxide ultrafine powder can be simply blended. Melt kneading can be carried out batchwise or continuously. The conductive metal oxide ultrafine powder is an organic silicate,
It is also possible to treat with titanate or polyorganosiloxane, and the treatment method may be either a dry method or a wet method. In the wet treatment, the powder is usually immersed in a solution of a low boiling point solvent of the treating agent and then the solvent is removed. .. In the case of the dry type, usually, the powder and the treating agent are mixed in a mixer such as a Henschel mixer, a super mixer, a V-type blender or the like, or an organic solution of the treating agent is sprayed for adhesion, and if necessary, further. After adhesion, heat treatment is performed at a temperature of 100 to 250 ° C. The treatment can mitigate the decrease in the molecular weight of the polycarbonate resin during melting.

If desired, the thermoplastic resin composition of the present invention may be blended with various conventionally known additives to a polycarbonate resin. These include a reinforcing material, a filler, a stabilizer, and an ultraviolet absorber. Examples include agents, antistatic agents, lubricants, release agents, dyes, pigments, other flame retardants, and elastomers for improving impact resistance. For example, phosphorous acid or phosphite is particularly suitable as the stabilizer. Further, examples of the releasing agent include mono- or polyhydric alcohol esters of saturated fatty acids, and stearyl stearate, behenyl behenate, pentaerythritol tetrastearate, dipentaerythritol hexaoctoate and the like are exemplified as preferable examples. To be done. Glass powder, glass beads, synthetic mica or fluorinated mica, zinc oxide, carbon fiber, especially glass fiber having a fiber diameter of 2 μm or less,
Examples include organic or inorganic fillers and reinforcing agents such as zinc oxide whiskers, stainless fibers, and Kevlar fibers, and MBS, MABS, MAS, and the like as elastomers. Further, ordinary resins such as polycarbonate, polyester carbonate, polyarylate and the like can naturally be suitably used according to the purpose.

[0013]

【Example】

Example 1 Polycarbonate resin consisting only of BPA (Mitsubishi Gas Chemical Co., Ltd.
Co., Ltd .; Iupilon S-2000, viscosity average molecular weight 24,000,
Hereinafter referred to as "PC") and titanium oxide (0.2 [mu] m, Mitsubishi Materials Corp., conductive powder W-1, hereinafter referred to as "TiO _2")
Were blended in the proportions (wt%) shown in Examples 1-1 and 1-2 in Table 1, mixed in a tumbler, and extruded into pellets at 270 to 280 ° C by a twin-screw extruder with a 35 mmφ vent. The obtained pellets were dried by a hot air circulation dryer at 120 ° C. for 5 hours and then compression-molded to obtain a molded product having a thickness of 200 μm. The resistance value of the obtained molded product was measured. The results are shown in Table 1.

Comparative Example 1 Same as Example 1 except that only PC was extruded and pelletized. The results are also shown in Table 1.

Table 1 Example 1 Comparative Example 1 1-1 1-2 Composition component (wt%) PC 70 50 100 TiO ₂ 30 50 ─ Resistance value (Ωcm) ^* 7.5 × 10 ¹⁴ 1.4 × 10 ⁷ 1.9 × 10 ^{16 * By} the method according to JIS K6911 (The following resistance values are the same).

Production Example 1 TiO ₂ was immersed in a methylene chloride solution (prepared to have a concentration of 2%) of γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .; KBE903, hereinafter referred to as “aminosilane”), and then the solvent. Removed, dried, aminosilane treated TiO ₂
(Hereinafter referred to as “TiO ₂ —S”) was obtained.

Example 2 Example 1 was repeated except that PC and TiO ₂ -S were blended in the ratios shown in Examples 2-1 and 2-2 in Table 2. The results are shown in Table 2.

[0018]

Example 3 PC and indium oxide (0.02 μm, Mitsubishi Materials
Co., Ltd .; conductive powder ITO, hereinafter referred to as "ITO") was used in the same manner as in Example 1 except that the proportions shown in Examples 3-1 and 3-2 in Table 3 were added. The results are shown in Table 3.

[0020]

Production Example 2 An aminosilane-treated ITO (hereinafter referred to as “ITO-S”) was obtained in the same manner as in Production Example 1 except that ITO was used instead of TiO ₂ .

Example 4 Example 4 was repeated except that PC and ITO-S were mixed in the proportions shown in Examples 4-1 and 4-2 in Table 4. The results are shown in Table 4.

[0023]

Example 5 PC and zinc oxide (0.2 μm, manufactured by Mitsui Kinzoku Co., Ltd .; zinc oxide type conductive powder, hereinafter referred to as “ZnO 2”)
The same procedure was performed as in Example 1 except that the proportions shown in 1 and 5-2 were used. The results are shown in Table 5.

[0025]

Production Example 3 Aminosilane-treated ZnO (hereinafter referred to as "ZnO-S") was obtained in the same manner as in Production Example 1 except that ZnO was used instead of TiO ₂ .

Example 6 The same as Example 1 except that PC and ZnO—S were compounded in the ratios shown in Table 6. The results are shown in Table 6.

[0028]

[0029]

EFFECTS OF THE INVENTION According to the present invention, a polycarbonate resin having excellent conductivity, antistatic performance and mechanical properties, which can be arbitrarily colored, is obtained by blending a conductive metal oxide ultrafine powder with the polycarbonate resin. A composition is obtained. The resin composition of the present invention is suitable as an injection molding material, a film or a sheet material.

Claims (3)

[Claims] 1. A polycarbonate resin having one or more kinds of structural units represented by the following general formula (1): (A represents a linear, branched or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylidene group, an arylenedialkylidene group, or -O-, -S-, -CO-, -SO _2- , R ¹ , R ² , R ³ and R ⁴ are hydrogen, halogen or 1 to 1 carbon atoms.
4 represents an alkyl group or an alkenyl group) and (b) a metal oxide ultrafine powder is blended, and the blending amount of (b) is 1 to 300 parts by weight relative to 100 parts by weight of (a). Thermoplastic resin composition 2. The composition according to claim 1, wherein the ultrafine powder of metal oxide (b) is one or more of titanium oxide, indium oxide, zinc oxide, tin oxide and antimony oxide. 3. The ultrafine metal oxide powder of (b) is one or two of organic silicate, titanate, and polyorganosiloxane.
The composition according to claim 1, which has been treated with one or more species.