JP2013124278A - Polycarbonate resin composition of excellent chemical resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition capable of improving chemical resistance and solvent resistance remarkably, while holding performance such as excellent transparency, impact resistance, heat resistance, thermal stability imparted inherently to a polycarbonate resin, to restrain trouble such as a crack from being generated, even when various solvents such as a detergent are deposited onto a molding obtained from the resin composition.SOLUTION: The polycarbonate resin composition of excellent chemical resistance includes 100 pts.wt of the polycarbonate resin (A), and 2.8-5.0 pts.wt of polysilane (B).

Description

  The present invention relates to a polycarbonate resin composition having excellent chemical resistance. More specifically, the present invention relates to a polycarbonate resin composition that has remarkably improved chemical resistance while maintaining the characteristics, such as transparency, impact resistance, heat resistance, and thermal stability, of the polycarbonate resin.

  Polycarbonate resin is a thermoplastic resin excellent in transparency, impact resistance, heat resistance, thermal stability, and the like, and is widely used in fields such as electricity, electronics, ITE, machinery, and automobiles. However, there are cases where defects such as cracking may occur due to adhesion of various chemicals and solvents such as hand creams and detergents to molded products obtained from polycarbonate resin, and chemical resistance and solvent resistance so that such defects do not occur. There is a demand for a polycarbonate resin having excellent properties.

A resin composition in which a polyester resin is blended with a polycarbonate resin has been proposed for the purpose of improving the above disadvantages. However, by blending polyester resin,
(1) Although chemical resistance and solvent resistance are slightly improved, it cannot be said that the improvement effect is sufficient, such as the occurrence of defects such as cracking when strong attacking alkaline detergents or machine oils adhere. 2) While greatly reducing the transparency, which is an advantage of polycarbonate resin,
(3) The impact resistance of the polycarbonate resin is impaired.
There was a problem.

In order to improve the impact resistance, a method of blending an impact resistance improving material such as MBS with a resin composition comprising a polycarbonate resin and a polyester resin has been proposed. (Patent Document 1) However, there is a problem that coloring caused by MBS and polyester resin cause degradation due to transesterification, and further improvement has been demanded.

Japanese Patent Publication No.55-9435

  It is an object of the present invention to provide a polycarbonate resin composition having significantly improved chemical resistance and solvent resistance while maintaining the transparency, impact resistance, heat resistance, thermal stability, etc. inherent to the polycarbonate resin. .

  As a result of intensive studies in view of such problems, the present inventors have surprisingly found that chemical resistance and solvent resistance can be remarkably improved by blending a specific amount of a specific polysilane into a polycarbonate resin. It came to complete.

  That is, the present invention provides a polycarbonate resin composition excellent in chemical resistance, characterized by comprising 100 parts by weight of a polycarbonate resin (A) and 2.8 to 5.0 parts by weight of a polysilane (B). is there.

  The polycarbonate resin composition having excellent chemical resistance according to the present invention has chemical resistance and solvent resistance while maintaining the properties such as excellent transparency, impact resistance, heat resistance and thermal stability inherent in the polycarbonate resin. Is significantly improved. Even if various solvents such as detergent adhere to the molded product obtained from such a resin composition, the occurrence of defects such as cracking can be suppressed.

The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. A typical example of the polymer is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.

  These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, and the like may be used in combination.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  The viscosity average molecular weight of the polycarbonate resin (A) is not particularly limited, but is usually in the range of 10,000 to 100,000, more preferably 14,000 to 30,000, and even more preferably 16,000 to 26,000 in terms of moldability and strength. Moreover, when manufacturing this polycarbonate resin, a molecular weight modifier, a catalyst, etc. can be used as needed.

The polysilane (B) used in the present invention is preferably a compound represented by the following general formula.
General formula 1:

  The compounding quantity of polysilane (B) is 2.8-5.0 weight part per 100 weight part of polycarbonate resin (A). If it is less than 2.8 parts by weight, the chemical resistance is inferior, and if it exceeds 5 parts by weight, the transparency is impaired. A preferable compounding amount is 3.0 to 4.5 parts by weight, and more preferably 3.0 to 4.0 parts by weight.

  There are no particular limitations on the blending method of the various blending components (A) and (B) of the present invention, and these are mixed by an optional mixer such as a tumbler, ribbon blender, high-speed mixer, etc. It can be melt-kneaded with an extruder or the like. Moreover, there is no restriction | limiting in particular also about the mixing | blending order of these compounding components, collective mixing, and division | segmentation mixing.

  When mixing, other known additives such as mold release agents, antioxidants, antistatic agents, dyes and pigments, spreading agents (epoxy soybean oil, liquid paraffin, etc.) and reinforcing materials (glass fibers) , Carbon fiber, talc, mica, etc.) and other resins can be blended.

  As a preferable mold release agent, organic compounds such as beeswax, glycerol monostearate, glycerol tristearate, pentaerythritol saturated ester, montanic acid ester wax, and carboxylic acid ester are preferably used. These include, for example, beeswax / golden brand manufactured by Miki Chemical Industry, Rikenmar S-100A and SL-900 manufactured by Riken Vitamin, Roxyol VPG861 manufactured by Emery Oleo Japan, and Ricowax E manufactured by Clariant Japan. The compounding amount of the release agent is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight, still more preferably 0.1 to 0.4 parts by weight per 100 parts by weight of the polycarbonate resin (A). Range.

  As preferred antioxidants, phosphites, phosphanite-based antioxidants, and the like have a great effect of suppressing the increase in yellowing, and can be suitably used. These are commercially available as BASF Japan's Irgafos 168, Clariant Japan's Sandstub P-EPQ, and the like. The blending amount of the antioxidant is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.4 part by weight, still more preferably 0.03 to 0.2 part per 100 parts by weight of the polycarbonate resin (A). The range is parts by weight.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Parts and% are based on weight unless otherwise specified.

The compounding components used are as follows.
Polycarbonate resin:
Polycarbonate resin synthesized from bisphenol A and phosgene (Caliber 200-20 manufactured by Sumika Stylon Polycarbonate Co., Ltd.)
Viscosity average molecular weight: 19000, hereinafter abbreviated as PC)
Polysilane:
Ogsol SI-30-10
(Osaka Gas Chemical Co., Ltd., hereinafter abbreviated as SI)
Release agent:
Natural beeswax golden brand (hereinafter abbreviated as MR) manufactured by Miki Chemical Industry Co., Ltd.
Antioxidant Clariant Japan Sandstub P-EPQ (hereinafter abbreviated as AO)
Polybutyl terephthalate resin:
600FP manufactured by Polyplastics (hereinafter abbreviated as PBT)

  The above-mentioned various blending components are collectively put into a tumbler at the blending ratio shown in Table 1, and after dry mixing for 10 minutes, using a twin screw extruder (KTX37 manufactured by Kobe Steel) at a melting temperature of 280 ° C. It knead | mixed and the pellet of the polycarbonate resin composition was obtained.

(Evaluation of chemical resistance of molded products)
The pellets of the resin compositions obtained above were each dried at 125 ° C. for 4 hours, and then set to a set temperature of 280 ° C. and an injection pressure of 1600 kg / cm 2 using an injection molding machine (Japan Steel Works J-100E-C5). A test piece (127 × 13 × 3.2 mm) was prepared.
The obtained test piece was subjected to an arbitrary strain using a cantilever-resistant chemical-resistant test jig (see FIG. 1), and the following chemicals were respectively applied to the center of the test piece.
Drug for evaluation Strong look around the range made by Lion (hereinafter abbreviated as drug 1)
The test piece after application of the above-mentioned chemicals was allowed to stand for 48 hours in an atmosphere at 85 ° C., and the critical strain (%) was determined from the position of cracks and cracks on the test piece by the following equation.

From the critical strain obtained by the above formula, the chemical resistance was judged according to the following criteria, and the critical strain exceeded 0.7% (◯ to ◎) as acceptable. Determination of chemical resistance:
◎: Critical strain is 1.0% or more ○: Critical strain is 0.7% or more to less than 1.0% △: Critical strain is 0.5% or more to less than 0.7% ×: Critical strain is 0.3 % Or more to less than 0.5% XX: Critical strain is less than 0.3%

(Evaluation of transparency of molded products)
The pellets of the resin compositions obtained above were each dried at 125 ° C. for 4 hours, and then set to a set temperature of 280 ° C. and an injection pressure of 1600 kg / cm 2 using an injection molding machine (Japan Steel Works J-100E-C5). Thus, a test piece for transparency evaluation (150 × 90 × 3.0 mm) was prepared. Transparency evaluated the obtained test piece visually.
Transparent (◯) was accepted and white turbidity (x) was rejected.

(Evaluation of heat resistance of molded products)
The pellets of the resin compositions obtained above were each dried at 125 ° C. for 4 hours, and then set to a set temperature of 280 ° C. and an injection pressure of 1600 kg / cm 2 using an injection molding machine (Japan Steel Works J-100E-C5). Then, a test piece according to the ISO test method was prepared, the deflection temperature under load was measured according to ISO 75-2 using the obtained test piece, and the deflection temperature under load was 110 ° C. or higher.

  In the case where the polycarbonate resin composition satisfies the constituent requirements of the present invention (Examples 1 to 4), good results were exhibited in each of chemical resistance, transparency and heat resistance.

On the other hand, in the case where the polycarbonate resin composition does not satisfy the constituent requirements of the present invention, each case has some drawbacks.
Comparative Example 1 was a case where a polyester resin was blended instead of polysilane, and was inferior in chemical resistance, transparency and heat resistance.
In Comparative Example 2, the amount of polysilane added was less than the range defined by the present invention, and the chemical resistance was poor.
In Comparative Example 3, the amount of polysilane added was larger than the range defined by the present invention, and the transparency was poor.

It is explanatory drawing of the jig | tool for chemical resistance test evaluation of a cantilever.

DESCRIPTION OF SYMBOLS 1 Jig body for chemical resistance test evaluation 2 Test piece 3 Fixing screw for test piece 4 Screw giving distortion to the test piece

Claims (2)

  A polycarbonate resin composition having excellent chemical resistance, comprising 100 parts by weight of a polycarbonate resin (A) and 2.8 to 5.0 parts by weight of a polysilane (B). The polycarbonate resin composition having excellent chemical resistance according to claim 1, wherein the polysilane (B) is a polysilane represented by the following general formula 1.
General formula 1

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