JP2012056973A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition whose molding has remarkably excellent designability because the molding obtained has remarkably good hue, exhibits deep iridescent luster which is conventionally unachievable, and has excellent three-dimensional appearance while maintaining various characteristics of a polycarbonate resin, such as impact resistance, heat resistance, transparency, and heat stability.SOLUTION: The polycarbonate resin composition includes: 100 pts.wt. of a polycarbonate resin (A); 0.01-0.2 pt.wt. of a phosphorus-based antioxidant (B); and 0.1-10 pts.wt. of pulverized artificial opal. The molding obtained by molding the polycarbonate resin composition has excellent designability and appearance and also has excellent impact resistance, heat resistance, transparency, and heat stability, so that the molding can be suitably used in applications, such as housings or internal parts of cameras, game machines, household electrical appliances, IT devices, and the like, or extrusion moldings, such as sheets and films.

Description

  The present invention relates to a polycarbonate resin composition having various opal-like shines. More specifically, the present invention relates to a polycarbonate resin composition having excellent design and appearance while maintaining the impact resistance, heat resistance, transparency, thermal stability, etc., which are characteristics of the polycarbonate resin.

  Polycarbonate resin is a thermoplastic resin excellent in impact resistance, heat resistance, transparency, thermal stability and the like, and is widely used in fields such as electricity, electronics, ITE, machinery, and automobiles. On the other hand, in addition to these excellent performances of the resin, materials having excellent design properties and appearance are required in the above-mentioned fields from the viewpoint of design.

  As means for satisfying the above-mentioned demand, in the prior art, a method of applying a metallic paint on the surface of a polycarbonate resin molded article, aluminum fine powder, glass flake coated with a metal film or mica and titanium dioxide is used. A method of blending a multilayered pigment or the like with the resin and melt-molding them has been adopted. However, although these methods can achieve a certain level of design and appearance, they cannot be obtained with a deep rainbow luster and full of three-dimensional appearance, and the need for improvement has been advocated. .

Japanese Patent No. 2651058 Special table 2003-525319 gazette

  In the present invention, while maintaining various properties such as impact resistance, heat resistance, transparency, and thermal stability of the polycarbonate resin, the hue of the obtained molded product is extremely good and has not been obtained conventionally. An object of the present invention is to provide a polycarbonate resin composition that exhibits a deep rainbow luster and has an excellent appearance with a three-dimensional appearance.

  As a result of earnest research to achieve the above object, the present inventor has confirmed that the above object can be achieved by blending a specific amount of not only pulverized artificial opal but also a specific phosphorus-based antioxidant into the polycarbonate resin. The headline and the present invention were completed.

  That is, the present invention comprises 100 parts by weight of the polycarbonate resin (A), 0.01 to 0.2 parts by weight of the phosphorus-based antioxidant (B) and 0.1 to 10 parts by weight of the pulverized artificial opal (C). A polycarbonate resin composition is provided.

  A molded product formed by molding the polycarbonate resin composition of the present invention is excellent in design and appearance, and also in impact resistance, heat resistance, transparency, and thermal stability. It can be suitably used for applications such as casings and internal parts of household electrical appliances and IT equipment, or extruded products such as sheets and films.

  The polycarbonate resin (A) used in the present invention is a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted or a transesterification method obtained by reacting a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate. A typical example is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (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 can be used alone or in admixture of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be mixed and used.

  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 usually 10,000 to 100,000, preferably 15,000 to 35,000, and more preferably 18000 to 22,000. In producing such an aromatic polycarbonate resin, a molecular weight regulator, a catalyst, and the like can be used as necessary.

As phosphorus antioxidant (B) used by this invention, well-known phosphorus antioxidant used for polycarbonate resin, for example, Sandstub P-EPQ by Clariant Japan, Sumitizer by Sumitomo Chemical Co., Ltd. P-168 etc. are mentioned. Especially, the compound shown in the following general formula 1 can be used conveniently.
General formula 1:

（一般式１において、Ｒ１、Ｒ２は炭素数１〜２０のアルキル基、またはアルキル基で置換されてもよいアリール基を、ａ、ｂは整数０〜３を示す。）

(In General Formula 1, R1 and R2 represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group, and a and b represent integers 0 to 3.)

  Examples of the compound of the general formula 1 include Adeka Stab PEP-36 manufactured by Adeka Corporation as a commercially available one.

  The compounding quantity of phosphorus antioxidant (B) is 0.01-0.2 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is less than 0.01 parts by weight, the heat stability is poor, and if it exceeds 0.2 parts by weight, the hue is inferior. More preferably, it is 0.03-0.15 weight part, More preferably, it is 0.05-0.10 weight part.

  The pulverized artificial opal (B) used in the present invention is a pulverized plate-like opal made of fine silicon dioxide particles. In this production method, fine particles of silicon dioxide are uniformly precipitated in a liquid such as water to form a state in which the particles are closely arranged, and then the water is slowly removed by removing the water from the precipitated layer. Examples of the method include forming an opal layer and pulverizing the same. The pulverized artificial opal (B) is commercially available, for example, as Kyoto Opal manufactured by Kyocera Corporation.

  The blending amount of the pulverized artificial opal (B) is 0.1 to 10 parts by weight per 100 parts by weight of the polycarbonate resin (A). A blending amount of less than 0.1 part by weight is not preferable because a high-quality appearance cannot be obtained. Moreover, since the impact strength will fall remarkably when the compounding quantity exceeds 10 weight part, it is unpreferable. More preferably, it is 0.5-6 weight part, More preferably, it is the range of 1-3 weight part.

  As an average particle diameter of a pulverization artificial opal (B), a 50-3000 micrometer thing can be used conveniently. If it is out of this range, the quality of the molded product may be inferior. A more preferable average particle diameter is 250 to 2000 μm.

  Regarding the blending method of the polycarbonate resin (A), the phosphorus antioxidant (B) and the pulverized artificial opal (C) of the present invention, the pulverized artificial opal (C) may be pulverized during mixing and melt kneading. Therefore, melt blending by hand blending and full flight screw is desirable. Moreover, there is no restriction | limiting also about the mixing | blending order of said (A), (B) and (C).

  Furthermore, various resins, heat stabilizers, fluorescent brighteners, pigments, dyes, carbon black, fillers, mold release agents, UV absorbers are added to the polycarbonate resin composition of the present invention within the range not impairing the effects of the present invention , Antistatic agent, rubber, softener, spreader (liquid paraffin, epoxy soybean oil, etc.), flame retardant, organic metal salt additives, flame retardant anti-dripping polytetrafluoroethylene resin, etc. Also good.

  Examples of the various resins include polystyrene, high impact polystyrene, ABS, AES, AAS, AS, acrylic resin, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polysulfone, and polyphenylene sulfide resin. Or you may use together by 2 or more types.

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

Details of the raw materials used are as follows.
Polycarbonate resin (A):
Polycarbonate resin synthesized from bisphenol A and phosgene (Caliber 200-20 manufactured by Sumitomo Dow, viscosity average molecular weight 19000
Hereinafter abbreviated as “PC”)
Phosphorous antioxidant (B):
ADEKA ADK STAB PEP-36
(Hereafter abbreviated as “AO”)
Ground artificial opal (C):
Kyoto Opal manufactured by Kyocera (white opal powder (blue))
(Particle diameter 350-500 μm, hereinafter abbreviated as “OP”)

(Preparation of resin composition pellets)
The above-mentioned various raw materials are hand-blended at the blending ratios shown in Tables 1 and 2, and melt-kneaded at a melting temperature of 270 ° C. using a single-screw extruder (VS-40 manufactured by Tanabe Plastics Co., Ltd.) Various pellets of the product were obtained.

(Creation of test specimen for evaluation)
The pellets obtained were dried at 120 ° C. for 4 hours, and then dried with an injection molding machine (J100EII-P, manufactured by Nippon Steel Co., Ltd.) under the condition of a melting temperature of 300 ° C. X width 10 mm x thickness 4 mm) and color chips (size: 60 x 60 x 3 mm) were prepared.

(Evaluation items and evaluation methods)
Impact strength:
Using the obtained dumbbell test piece, the notched Charpy impact strength at 23 ° C. was measured according to ISO 179-2. A numerical value of 4 KJ / m2 or more was considered acceptable. The results are shown in Tables 1 and 2.

Hue:
The hue of the obtained color chip was measured using a spectrophotometer CMS35-SP manufactured by Murakami Color Research Laboratory under the conditions of a D65 light source and a viewing angle of 10 °. When the yellowness was 5.5 or less, the hue was determined to be good. The results are shown in Tables 1 and 2.

Appearance:
Using the resulting color chip, the appearance was visually determined. Judgment criteria are as follows.
Various shines of the pulverized artificial opal (B) could be confirmed, and when the color chip had no dullness, it was judged that there was a high-class feeling and excellent appearance.
The results are shown in Tables 1 and 2.

色相の判定： ○： 合格 ×：不合格

Judgment of hue: ○: Pass ×: Fail

色相の判定： ○： 合格 ×：不合格

Judgment of hue: ○: Pass ×: Fail

As shown in Examples 1 to 4, those satisfying the constituent requirements of the present invention satisfied the required performance.
On the other hand, as shown in Comparative Examples 1 to 4, those that do not satisfy the constituent requirements of the present invention have the following drawbacks.
In Comparative Example 1, the blending amount of the antioxidant was less than the specified amount, and the hue was not acceptable.
In Comparative Example 2, the amount of the antioxidant was greater than the specified amount, and the hue was not acceptable.
Comparative Example 3 was a case where the blending amount of the pulverized artificial opal was less than the specified amount, and was inferior in a high-class feeling.
Comparative Example 4 was a case where the blended amount of the pulverized artificial opal was larger than the specified amount, and was inferior in luxury.

Claims (5)

  A polycarbonate resin composition comprising 100 parts by weight of a polycarbonate resin (A), 0.01 to 0.2 parts by weight of a phosphorous antioxidant (B) and 0.1 to 10 parts by weight of a pulverized artificial opal (C). object. The polycarbonate resin composition according to claim 1, wherein the phosphorus-based antioxidant (B) is a compound represented by the following general formula 1.
General formula 1

(In General Formula 1, R1 and R2 represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group, and a and b represent integers 0 to 3.)   2. The polycarbonate resin composition according to claim 1, wherein the amount of the phosphorus-based antioxidant (B) is 0.03 to 0.15 parts by weight per 100 parts by weight of the polycarbonate resin (A).   The polycarbonate resin composition according to any one of claims 1 to 3, wherein the pulverized artificial opal (C) has an average particle size of 50 to 3000 µm.   The compounding quantity of a pulverization artificial opal (C) is 0.5-6 weight part per 100 weight part of polycarbonate resin (A), The polycarbonate as described in any one of Claims 1-4 characterized by the above-mentioned. Resin composition.