JP2011256359A - Flame-retardant polycarbonate resin composition excellent in antistatic property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant polycarbonate resin composition excellent in an antistatic property to which flame retardancy needed for home electronics application or the like is also given, and to provide a molding comprising the same.SOLUTION: The flame-retardant polycarbonate resin composition excellent in an antistatic property comprises blending 100 pts.wt. of a polycarbonate resin (A), 0.1-5 pts.wt. of a diglycerol fatty acid ester (B), 0.0001-0.01 pt.wt. of an acidic substance (C), 0.001-0.3 pt.wt. of a perfluoroalkanesulfonic acid metal salt (D), and 0.01-0.8 pt.wt. of an ultraviolet absorber (E) depending on request.

Description

  The present invention relates to a polycarbonate resin composition having excellent antistatic properties, thermal stability, transparency, impact resistance and flame retardancy, and, if desired, weather resistance. More specifically, by preventing a decrease in molecular weight due to decomposition of the polycarbonate resin by the antistatic agent, the decrease in impact resistance, thermal stability and transparency is suppressed, and flame retardancy and, if desired, weather resistance are imparted. The present invention relates to a flame retardant polycarbonate resin composition having excellent antistatic properties.

Polycarbonate resins are excellent in impact resistance, heat resistance, and transparency, and are widely used in fields such as electrical / electronic, optical, building materials, medical, food, and vehicles. However, products obtained from polycarbonate resin are easily charged with static electricity, and there are problems associated with static electricity, such as adhesion of dust to packaging materials and molded products, electric shock during molding and use, and malfunction of OA machines. Conventionally, various formulations of antistatic agents have been studied.
Further, office equipment exterior parts such as optical disk cartridges are also required to have transparency so that the inside can be fully visually recognized simultaneously with the antistatic performance.

  In order to impart antistatic performance to the polycarbonate resin, a fatty acid monoglyceride is blended as an antistatic agent. (Patent Document 1) However, this composition cannot satisfy all of the antistatic performance, transparency and thermal stability.

  In addition, a diglycerin fatty acid ester and an antioxidant are blended in a polycarbonate resin. (Patent Document 2) Although this composition improves antistatic performance and transparency to some extent, there is a problem that it is inferior in thermal stability. In particular, since heat is applied in the melt-kneading process for obtaining pellets of this composition and the molding process of the obtained pellets, a reaction occurs between the diglycerin fatty acid ester and the polycarbonate resin. There is a problem that the decomposition is promoted, the molecular weight is lowered, and the impact resistance inherent to the polycarbonate resin is remarkably lowered.

  Patent Document 2 discloses an example of a polycarbonate resin having a relatively high molecular weight of 25000 average molecular weight, but the polycarbonate resin generally used for injection molding has a lower molecular weight (viscosity average molecular weight of 17000 to 21000). Therefore, Patent Document 2 has a fundamental problem in practical use in terms of the reduction in impact resistance.

Japanese Patent Publication No.55-4141 Japanese Patent Laid-Open No. 02-196852

  The present invention prevents the deterioration of the thermal stability, molecular weight and impact resistance of the polycarbonate resin when the above-described diglycerin fatty acid ester is used as an antistatic agent, and is required for home appliance use and the like. The present invention provides a flame retardant polycarbonate resin composition excellent in antistatic property imparted with flame retardancy, and a molded product comprising the same.

  As a result of diligent research in view of the above-mentioned problems, the present inventor has formulated a polycarbonate resin with a combination of a diglycerin fatty acid ester and an acidic substance, thereby improving the thermal stability, molecular weight, and impact resistance of the polycarbonate resin. It has been found that the deterioration can be remarkably prevented and excellent flame resistance can be achieved by adding a perfluoroalkanesulfonic acid metal salt, and if necessary, excellent weather resistance can be achieved by using an ultraviolet absorber together. The invention has been completed.

  That is, the first aspect of the present invention comprises 100 parts by weight of polycarbonate resin (A), 0.1 to 5 parts by weight of diglycerin fatty acid ester (B), 0.0001 to 0.01 parts by weight of acidic substance (C) and The present invention relates to a flame retardant polycarbonate resin composition having excellent antistatic properties, characterized by comprising 0.001 to 0.3 parts by weight of a perfluoroalkanesulfonic acid metal salt (D), and a molded product comprising the same.

  Furthermore, the second aspect of the present invention comprises polycarbonate resin (A) 100 parts by weight, diglycerin fatty acid ester (B) 0.1-5 parts by weight, acidic substance (C) 0.0001-0.01 parts by weight, Flame retardant polycarbonate resin composition having excellent antistatic properties comprising 0.001 to 0.3 parts by weight of perfluoroalkanesulfonic acid metal salt (D) and 0.01 to 0.8 parts by weight of ultraviolet absorber (E) And a molded article comprising the same.

  The flame retardant polycarbonate resin composition having excellent antistatic properties of the present invention is excellent not only in antistatic properties and impact resistance but also in flame retardancy and, if desired, weather resistance, is transparent and adheres to dust. Is suitable for use in office automation equipment and household appliances where flame retardancy is required, for example, light source peripheral members and molded products whose contents can be confirmed.

  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 an aromatic 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 are used individually or in mixture of 2 or more types. 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 17,000 to 21,000. In producing such a polycarbonate resin, a molecular weight regulator, a catalyst and the like can be used as necessary.

  The diglycerin fatty acid ester (B) used in the present invention can be obtained by esterification of diglycerin obtained by polymerizing glycerin and a fatty acid.

  As the diglycerin fatty acid ester (B), an ester compound of a fatty acid having 10 to 18 carbon atoms and diglycerin is preferably used. If the carbon number is less than 10, the sustainability of the antistatic performance may be inferior, and if the carbon number exceeds 18, the antistatic property may be inferior.

Examples of the fatty acid having 10 to 18 carbon atoms include capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, and stearic acid.

Specific examples of the diglycerin fatty acid ester (B) include diglycerin monolaurate, diglycerin monomyristate, and diglycerin monostearate. Diglycerin monolaurate is preferably used.

  The compounding amount of the diglycerin fatty acid ester (B) of the present invention is 0.1 to 5 parts by weight per 100 parts by weight of the polycarbonate resin (A). If the blending amount is less than 0.1 parts by weight, the antistatic property is inferior, and if it exceeds 5 parts by weight, the transparency and the appearance are deteriorated. More preferably, it is the range of 0.5-3 weight part.

  Examples of the acidic substance (C) used in the present invention include compounds such as phosphoric acid and boric acid. In particular, phosphoric acid which is a nonvolatile weak acid is preferably used.

  The compounding amount of the acidic substance (C) is 0.0001 to 0.01 part by weight per 100 parts by weight of the polycarbonate resin (A). If the blending amount is less than 0.0001 part by weight or more than 0.01 part by weight, the thermal stability and impact resistance are inferior. More preferably, it is the range of 0.001-0.005 weight part.

  Examples of the perfluoroalkanesulfonic acid metal salt (D) used in the present invention include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid. And metal salts such as perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, and perfluorooctanesulfonic acid.

  The metal of the perfluoroalkanesulfonic acid metal salt (D) is preferably an alkali metal or alkaline earth metal. Here, examples of the alkali metal and alkaline earth metal include sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like, preferably sodium and potassium.

  Of the above, potassium perfluorobutanesulfonate is particularly preferably used.

  The compounding amount of the perfluoroalkanesulfonic acid metal salt (D) is 0.001 to 0.3 parts by weight per 100 parts by weight of the polycarbonate resin (A). If the blending amount is less than 0.001 part by weight, the flame retardancy is inferior, and if it exceeds 0.3 part by weight, the transparency is inferior. More preferably, it is in the range of 0.05 to 0.2 parts by weight.

  Specific examples of the ultraviolet absorber (E) used in the present invention include 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert- Octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di -Tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chloro Nzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5 -Tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p- Examples include phenylenebis (1,3-benzoxazin-4-one).

  In the triazine series, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine -2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl-1) , 3,5-triazin-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol The

  Among the ultraviolet absorbers, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole is preferable. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

  As for the compounding quantity of a ultraviolet absorber (E), 0.01-0.8 weight part is preferable per 100 weight part of polycarbonate resin (A). If the blending amount is less than 0.01 parts by weight, the weather resistance is inferior, and if it exceeds 0.8 parts by weight, the initial coloring becomes remarkable, which is not preferable. A more preferred range is 0.05 to 0.6 parts by weight.

  The antistatic polycarbonate resin composition of the present invention can be used in combination with other antistatic agents as long as the effects of the present invention are not impaired. As other antistatic agents that can be used in combination, widely known ones can be used, and examples thereof include alkylsulfonates, alkylbenzenesulfonates, ammonium salts, and other phosphonium salts. It is not limited to.

  There are no particular restrictions on the mixing method and mixing order of the polycarbonate resin (A), diglycerin fatty acid ester (B), acidic substance (C) and perfluoroalkanesulfonic acid metal salt (D) and ultraviolet absorber (E), The mixing can be carried out by mixing with a known mixer such as a tumbler, ribbon blender, high speed mixer, etc., and then melt-kneading with a single screw or twin screw extruder.

  Furthermore, you may mix | blend well-known additives, for example, additives, such as a heat stabilizer, a mold release agent, a flame retardant, and a dye / pigment, in the range which does not impair the effect of this invention as needed.

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

  Based on the blending components and blending amounts shown in Tables 2-6, various blending components were mixed using a tumbler and melt kneaded at a cylinder temperature of 250 ° C. using a twin screw extruder (TEX-30α manufactured by Nippon Steel). Various pellets were obtained.

The compounding components used are as follows.
1. Polycarbonate resin:
Polycarbonate resin synthesized from bisphenol A and phosgene (Sumitomo Dow Caliber 200-20, viscosity average molecular weight 19000,
(Hereinafter abbreviated as PC)
2. Diglycerin fatty acid ester:
Diglycerin monolaurate (Poem DL-100 manufactured by Riken Vitamin Co., hereinafter abbreviated as antistatic agent)
3. Acidic substances:
Phosphoric acid (Nacalai Tesque, hereinafter abbreviated as acidic substance)
4). Perfluoroalkanesulfonic acid metal salt:
Potassium perfluorobutanesulfonate (Biowet C-4 manufactured by Bayer AG, hereinafter abbreviated as metal salt)
5). Ultraviolet absorber Tinuvin 329 (Ciba Specialty Chemicals)
Benzotriazole UV absorber (hereinafter abbreviated as UVA1)
Tinvin 1577 (Ciba Specialty Chemicals)
Triazine UV absorber (hereinafter abbreviated as UVA2)

  Using the obtained pellet, an injection molding machine (J100E-C5 manufactured by Nippon Steel Works) was used to prepare various test pieces at a set temperature of the cylinder of 300 ° C. and subjected to each test.

The test method is as follows.
Melt volume rate (MVR):
Measurement was performed at 280 ° C. according to ISO 1133. It was passed 25cm ^3/10 minutes or less.

・ Surface resistivity:
A 70 × 40 × 3 mm flat plate was prepared by injection molding and measured under the following conditions. After the plate test piece was conditioned for 24 hours under conditions of 23 ° C. and 55% relative humidity, a high resistivity meter (Hirester UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation) was used, and the measurement voltage was 1000 V and the sampling time was 30 seconds. The surface resistivity was measured under the conditions.
A surface resistivity of less than 1 × 10 ¹⁴ Ω / sq was accepted.

・ Charpy impact strength:
The notched Charpy impact strength at 23 ° C. was measured according to ISO 179-2.
10 kJ / m ² or more was accepted.

-Total light transmittance It measured based on ASTM D1003. 70% or more was accepted.

-Initial coloring property Yellowness index (hereinafter abbreviated as YI) was used as an index of initial coloring property.
A 70 × 40 × 3 mm flat plate was prepared by injection molding, and YI was measured according to ASTM D-1925. A YI of 5 or less was accepted.

·Heat-resistant:
A 70 × 40 × 3 mm flat plate was molded by injection molding, then retained in a cylinder at a set temperature of 340 ° C. for 30 minutes, and further molded. The yellowness index (YI) of the molded product before residence and the molded product after residence was measured according to ASTM D-1925. The difference between YI before residence and YI after residence was ΔYI (heat resistance), and 2 or less was accepted.

・ Flame retardance After drying the obtained pellets at 125 ° C for 4 hours, using an injection molding machine (Japan Steel Works J100E-C5) at 240 ° C and an injection pressure of 1600 kg / cm ^2, a test for flammability test A piece (3.0 mm) was molded. The above test piece is left in a constant temperature room at 23 ° C. and 50% humidity for 168 hours, and is flame retardant according to UL94 test (flammability test of plastic materials for parts of equipment) established by Under Rutters Laboratory. Evaluation was performed. The classes according to UL94 are shown in Table 1. V-0 and V-1 were accepted (◯), and the others were rejected (x).

-Weather resistance A 70 x 40 x 3 mm flat plate was prepared by injection molding, and irradiation was performed for 300 hours at an irradiance of 150 W / m ² using a Super Xenon Weather Meter SX75 manufactured by Suga Test Instruments Co., Ltd. The YI of the flat plate before and after irradiation was measured in accordance with ASTM D-1925, and the difference was taken as ΔYI. 10 or less was regarded as acceptable.

  The test results are shown in Tables 2-6.

  As shown in Examples 1 to 7, the polycarbonate resin composition having the requirements of the present invention satisfied the required levels of the required performance including the surface resistivity and flame retardancy.

On the other hand, in the case where the requirements of the present invention were not satisfied, each case had some drawbacks.
In Comparative Example 1, the amount of the metal salt was small and the flame retardancy was poor.
In Comparative Example 2, the amount of the metal salt was large and the transparency was poor.
In Comparative Example 3, the amount of the antistatic agent was small, and the surface resistivity did not satisfy the required level.
Comparative Example 4 was a case where the blending amount of the antistatic agent was large, and was inferior in MVR, heat resistance, impact resistance and flame retardancy.
The comparative example 5 was inferior in impact resistance in the case where there are few compounding quantities of an acidic substance.
Comparative Example 6 was a case where the compounding amount of the acidic substance was large and was inferior in heat resistance.

  Tables 5 and 6 show the results when the ultraviolet absorber was added.

  As shown in Examples 8 to 11, the polycarbonate resin composition having the requirements of the present invention satisfies all the required performances including the surface resistivity, flame retardancy, and weather resistance. It was.

On the other hand, in the case where the requirements of the present invention were not satisfied, each case had some drawbacks.
Comparative Examples 7 and 9 were inferior in weather resistance when the blending amount of the ultraviolet absorber was small.
In Comparative Example 8 and Comparative Example 10, the amount of the ultraviolet absorber was large, and the initial colorability and heat resistance were poor.

Claims (11)

  100 parts by weight of polycarbonate resin (A), 0.1 to 5 parts by weight of diglycerin fatty acid ester (B), 0.0001 to 0.01 parts by weight of acidic substance (C) and metal salt of perfluoroalkanesulfonic acid (D) 0 A flame-retardant polycarbonate resin composition having excellent antistatic properties, comprising 0.001 to 0.3 parts by weight.   Polycarbonate resin (A) 100 parts by weight, diglycerin fatty acid ester (B) 0.1-5 parts by weight, acidic substance (C) 0.0001-0.01 parts by weight, perfluoroalkanesulfonic acid metal salt (D) 0 A flame-retardant polycarbonate resin composition having excellent antistatic properties, comprising 0.001 to 0.3 parts by weight and ultraviolet absorber (E) 0.01 to 0.8 parts by weight.   The flame retardant polycarbonate resin composition having excellent antistatic properties according to claim 1 or 2, wherein the diglycerin fatty acid ester (B) is an ester compound of a fatty acid having 10 to 18 carbon atoms and diglycerin.   The flame retardant polycarbonate resin composition having excellent antistatic properties according to claim 1 or 2, wherein the diglycerin fatty acid ester (B) is diglycerin monolaurate.   The blending amount of the diglycerin fatty acid ester (B) is 0.5 to 3 parts by weight per 100 parts by weight of the polycarbonate resin (A), and is excellent in antistatic properties according to claim 1 or 2. Flame retardant polycarbonate resin composition.   The flame retardant polycarbonate resin composition having excellent antistatic properties according to claim 1 or 2, wherein the acidic substance (C) is one or two selected from phosphoric acid and boric acid. .   The blending amount of the acidic substance (C) is 0.001 to 0.005 parts by weight per 100 parts by weight of the polycarbonate resin (A), and has excellent antistatic properties according to claim 1 or 2. Flame retardant polycarbonate resin composition.   The flame retardant polycarbonate resin composition having excellent antistatic properties according to claim 1 or 2, wherein the perfluoroalkanesulfonic acid metal salt (D) is potassium perfluorobutanesulfonate.    The blending amount of the perfluoroalkanesulfonic acid metal salt (D) is 0.05 to 0.2 parts by weight per 100 parts by weight of the polycarbonate resin (A). A flame retardant polycarbonate resin composition having excellent antistatic properties.   The flame retardant polycarbonate resin composition having excellent antistatic properties according to claim 2, wherein the ultraviolet absorber (E) is one or more ultraviolet absorbers selected from benzotriazole and triazine.   A molded article formed by molding the flame-retardant polycarbonate resin composition having excellent antistatic properties according to any one of claims 1 to 10.