JP2002020605A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which is excellent in antistatic properties and in heat stability during molding and gives a molded article free from external appearance defects. SOLUTION: This resin composition is prepared by compounding (a) 100 pts.wt. aromatic polycarbonate resin with (b) 1-50 pts.wt. polyester resin, (c) 1-50 pts.wt. block copolyamide resin, and (d) 0.01-3 pts.wt. phosphoric ester represented by formula (1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition, and more particularly to a permanent antistatic polycarbonate resin composition.

[0002]

2. Description of the Related Art In general, a synthetic polymer material has a high electric resistance and is easily charged by friction or abrasion, etc., adsorbs dirt and dust, and impairs the appearance. Further, in the electric and electronic fields, troubles due to charging often occur, and new materials having excellent permanent antistatic properties are required.

Conventionally, as a means for imparting the antistatic property of a synthetic resin product, a molded article is coated with a surfactant-based antistatic agent or kneaded with an antistatic agent into a resin material to prevent the molded article from being charged. There is a method of imparting properties. However, such a method has a drawback that the antistatic agent in the surface layer is removed by long-term use and the antistatic property is lost. Further, there is a disadvantage that the antistatic property is lost due to frictional wear and the like.

[0004] As a polycarbonate resin composition for imparting permanent charging properties, for example, a resin composition comprising a polyetheresteramide and a polycarbonate resin is known. Japanese Patent Application Laid-Open No. Hei 7-224217 discloses an aromatic polycarbonate resin composition. Resin, block copolyamide resin,
Polyester resin, a resin composition containing a phosphorus-containing compound having a spiro ring is disclosed, but a molded article from such a resin composition may cause poor appearance, and a necessarily satisfactory antistatic resin composition. I couldn't say.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an excellent antistatic property, and in particular, to maintain excellent antistatic properties even when used for a long period of time, and to have excellent thermal stability during molding and appearance of a molded article. An object of the present invention is to provide a polycarbonate resin composition free from defects.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and its gist is as follows.
(B) 1 to 50 parts by weight of a polyester resin, (c) 1 to 50 parts by weight of a block copolyamide resin, and (d) with respect to 100 parts by weight of an aromatic polycarbonate resin.
It is present in a polycarbonate resin composition containing 0.01 to 3 parts by weight of a phosphoric ester represented by the following formula (1).

[0007]

Embedded image (Wherein, R represents an alkyl group having 8 to 30 carbon atoms,
n represents an integer of 1 or 2)

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The aromatic polycarbonate resin (a) in the present invention can be obtained by an interfacial polymerization method of aromatic dihydroxy or a small amount of a polyhydroxy compound and phosgene.
Or, it is a thermoplastic polycarbonate polymer which may be branched by the transesterification reaction between the aromatic dihydroxy compound and the carbonic acid diester.

The aromatic dihydroxy compounds include 2,2.
2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (4-hydroxy-3,
5-dimethylphenyl) propane (= tetramethylbisphenol A), 2,2-bis (4-hydroxy-3,
5-dibromophenyl) propane (= tetrabromobisphenol A), 2,2-bis (4-hydroxy-3,
5-dichlorophenyl) propane (= tetrachlorobisphenol A), 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl)
-P-diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, and the like are preferable, and bisphenol A is preferable.

In order to obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,4
6-tri (4-hydroxyphenyl) heptene-2,
4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-
Tri (4-hydroxyphenylheptene-3,1,3,
5-tri (4-hydroxyphenyl) benzene, 1,
Polyhydroxy compounds represented by 1,1-tri (4-hydroxyphenyl) ethane and the like, and 3,3-bis (4
Polyhydroxy compounds such as -hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol, 5,7-dichlorisatin bisphenol, and 5-bromoisatin bisphenol are used as a part of the dihydroxy compound. . The amount of the polyhydroxy compound used is, for example, about 0.1 to 2 mol% of the dihydroxy compound.

Further, a monovalent aromatic hydroxy compound or the like can be used as a molecular weight regulator. Examples of the molecular weight modifier include m- and p-methylphenol, m- and p-propylphenol, p-bromophenol, p-tert-butylphenol and p-long-chain alkyl-substituted phenol.

The molecular weight of the aromatic polycarbonate resin is as follows:
The viscosity average molecular weight measured from the methylene chloride solution viscosity at 25 ° C., preferably 16,000 to 38,
000, more preferably 18,000 to 35.0.
00. Those having a further optimum molecular weight are appropriately selected depending on the amount of the polyester resin added or the molecular weight.

Examples of the aromatic polycarbonate resin include bis (4-hydroxyphenyl) alkane-based dihydroxy compounds, particularly polycarbonates containing bisphenol A as a main material, and the use of bisphenol containing halogen such as tetrabromobisphenol A. Can also. Furthermore, a polycarbonate copolymer obtained by using two or more kinds of aromatic dihydroxy compounds in combination and a branched polycarbonate obtained by using a small amount of trivalent or more polyhydroxy compounds in combination can also be mentioned. The aromatic polycarbonate resin may be a mixture of two or more kinds.

The (b) polyester resin in the present invention is a thermoplastic polyester resin obtained by a polycondensation reaction between a polybasic acid and a polyhydric alcohol, and is preferably a terephthalic acid or a dialkyl ester thereof and an aliphatic glycol. Examples thereof include polyalkylene terephthalate obtained by a polycondensation reaction, and specific examples include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).

Examples of the aliphatic glycol include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol and the like. In the polycondensation reaction, other diols such as cyclohexanediol, cyclohexanedimethanol, xylene glycol, 2,2-bis (4-hydroxyphenyl) propane, glycerin, pentaerythritol and polyhydric alcohols besides aliphatic glycols Can be used together. The use amount of these diols or polyhydric alcohols is preferably within a range of 40 parts by weight or less based on 100 parts by weight of the aliphatic glycol.

In the polycondensation reaction, terephthalic acid or a dialkyl ester thereof may be used together with phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, or dialkyl esters thereof. Basic acids, tribasic acids and the like, and dialkyl esters thereof can be used. The use amount of these is preferably in the range of 40 parts by weight or less based on 100 parts by weight of terephthalic acid or its dialkyl ester. The molecular weight of the polyester resin is an intrinsic viscosity measured at 30 ° C. in a mixed solvent of phenol and tetrachloroethane (weight ratio = 50/50), preferably 0.5 to 1.8, more preferably 0.7 to 1.5.

The amount of the polyester resin is 1 to 50 parts by weight based on 100 parts by weight of the polycarbonate resin. If the blending amount of the polyester resin is less than 1 part by weight, the improvement of the peeling phenomenon is insufficient, and if it exceeds 50 parts by weight, the heat resistance tends to decrease. The blending amount of polyester resin is
The amount is preferably 2 to 40 parts by weight, more preferably 3 to 30 parts by weight, based on 100 parts by weight of the polycarbonate resin.

The block copolyamide resin in the present invention comprises a polyamide block and a polyether block and / or a polyester block, and the polyamide block and the polyether block and / or the polyester block are linked by an ester bond or an ester amide bond. .

Examples of the block copolyamide resin include a polyetheresteramide resin. The polyetheresteramide resin is a polymer obtained by reacting a component forming a polyamide block, a component forming a polyether block, and a dicarboxylic acid. The component forming the polyamide block preferably includes a salt of an aminocarboxylic acid or lactam having 6 or more carbon atoms or a salt of a dicarboxylic acid with a diamine having 6 or more carbon atoms, and the component forming the polyether block is preferably Is a polyalkylene oxide glycol, and the dicarboxylic acid is preferably a dicarboxylic acid having 4 to 20 carbon atoms.

As salts of aminocarboxylic acids or lactams having 6 or more carbon atoms or diamines and dicarboxylic acids having 6 or more carbon atoms, ω-aminocaproic acid, ω
-Aminoenanoic acids, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid and aminocarboxylic acids such as 11-aminoundecanoic acid, 12-aminododecanoic acid; caprolactam, enantholactam, caprylactam and laurolactam, etc. Lactams; and salts of diamine-dicarboxylic acids such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate, preferably caprolactam, 12-aminododecanoic acid, Methylene diamine-adipate.

Examples of the polyalkylene oxide glycol include polyethylene glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, and poly (tetramethylene oxide).
Glycol, poly (hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran.

The polyalkylene oxide glycol is preferably polyethylene glycol from the viewpoint of antistatic properties. The number average molecular weight of the polyalkylene oxide glycol is preferably 200 to 6000,
More preferably, it is 250-4000. If the number average molecular weight is less than 200, the mechanical strength tends to decrease, and
If it exceeds 00, the antistatic property tends to be insufficient.

The dicarboxylic acids having 4 to 20 carbon atoms include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid Dicarboxylic acids such as diphenyloxyethane dicarboxylic acid and sodium 3-sulfoisophthalate, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4-dicarboxylic acid Examples thereof include acids and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecandioic acid (decanedicarboxylic acid), and preferably terephthalic acid and isophthalic acid from the viewpoint of polymerizability, color tone and physical properties. 1,4-cyclohexanedicarboxylic acid, adipic acid Sebacic acid and dodecanedioic acid. The polyalkylene oxide glycol and the dicarboxylic acid are usually used in the reaction at a molar ratio of 1: 1.

The composition ratio of the polyamide block unit and the polyether block and / or polyester block unit, which are constituents of the block copolyamide resin, is preferably such that the polyether block and / or polyester block unit is 95 to 10% by weight. is there. When the polyether block and / or polyester block unit exceeds 95% by weight, the surface hardness of the molded product is low, the material is easily damaged, the mechanical strength is also low, and if it is less than 10 parts by weight, the antistatic property is liable to decrease. .

The weight average molecular weight of the block copolyamide resin is preferably from 50,000 to 200,000, more preferably from 70,000 to 120,000. The weight average molecular weight of the block copolyamide resin is 5
If it is less than 000, the dispersibility of the block copolyamide resin is not sufficient and the antistatic properties of the molded article are easily affected by molding conditions and the like. If it exceeds 200,000, the block copolyamide resin is used as the surface layer of the molded article. It is difficult to unevenly disperse the antistatic property in the portion, and the antistatic property tends to be insufficient. In the polycarbonate resin composition of the present invention, in order to reduce the respective melt viscosity difference of the aromatic polycarbonate resin, polyester resin and block copolyamide resin at the time of melting, by appropriately selecting each molecular weight, composition ratio and the like, severe A molded article having no anti-peeling phenomenon and exhibiting a more stable antistatic property even under a suitable condition can be obtained.

The method of polymerizing the block copolyamide resin is not particularly limited. For example, an aminocarboxylic acid or a lactam is reacted with a dicarboxylic acid to form a polyamide prepolymer having carboxylic acid groups at both ends, and the poly (alkylene oxide) is added thereto. A) A method of reacting glycol under vacuum, charging each reaction component of aminocarboxylic acid or lactam, dicarboxylic acid and poly (alkylene oxide) glycol into a reaction tank, and performing pressure reaction at a high temperature in the presence or absence of water. A method of producing a carboxylic acid-terminated polyamide prepolymer and then proceeding with polymerization under normal pressure or reduced pressure, and simultaneously reacting each reaction component of aminocarboxylic acid or lactam, dicarboxylic acid and poly (alkylene oxide) glycol into a reaction vessel. After mixing and mixing, all at once under high vacuum Known method such as a method of advancing the polymerization can be used.

The compounding amount of the block copolyamide resin is 1 to 50 parts by weight based on 100 parts by weight of the polycarbonate resin. If the amount of the block copolyamide resin is less than 1 part by weight, the antistatic property is insufficient, and if it exceeds 50 parts by weight, heat resistance and mechanical strength are liable to decrease. The compounding amount of the block copolyamide resin is preferably 2 to 40 parts by weight, more preferably 3 to 30 parts by weight, based on 100 parts by weight of the polycarbonate resin.

The phosphate in the present invention is a phosphorus compound represented by the following formula (1).

[0029]

Embedded image

In the formula, R represents an alkyl group having 8 to 30 carbon atoms, and n represents an integer of 1 or 2. Examples of the alkyl group having 8 to 30 carbon atoms include octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl,
Isodecyl, dodecyl, tridecyl, isotridecyl,
Examples include tetradecyl, hexadecyl, octadecyl, eicosyl, triacontyl and the like.

The phosphate represented by the above formula (1) is
For example, synthesized by a known method such as a method of hydrolyzing a corresponding trialkyl phosphate, a method of reacting phosphorus oxychloride with a corresponding alkanol and then a hydrolysis, or a method of reacting phosphorus pentoxide with a corresponding alkanol. can do.

The amount of the phosphate represented by the above formula (1) is based on 100 parts by weight of the polycarbonate resin.
0.005 to 3 parts by weight. When the amount of the phosphate represented by the above formula (1) is less than 0.005 parts by weight, the thermal stability of the resin composition is insufficient, and when it exceeds 3 parts by weight, the appearance becomes insufficient. The amount of the phosphoric acid ester represented by the above formula (1) is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin.

Examples of the phosphoric ester represented by the above formula (1) include “ADK STAB AX-71” (trade name of Asahi Denka Kogyo KK). By incorporating such a phosphorus compound, the heat stability of the polycarbonate resin composition of the present invention containing the block copolyamide resin can be further improved, and even when the composition further contains an impact resistance improver, Thermal stability is satisfied.

In the polycarbonate resin composition of the present invention, it is preferable to incorporate an impact resistance improver. Examples of the impact resistance improver include polyether-based elastomer, MBS resin, MAS resin, acrylate-based core-shell graft copolymer, styrene-based core-shell graft copolymer, SBR, SEBS, polyurethane-based elastomer, and the like. No. Among these, acrylate-based core-shell graft copolymers improve appearance defects such as pearl luster from the viewpoint of compatibility and heat resistance with aromatic resin such as aromatic polycarbonate resin, polyester resin and polyamide resin. In view of the above, specific examples include acrylate-based core-shell graft copolymers described in JP-A-5-222140.

The compounding amount of the impact resistance improving agent is preferably 1 to 30 parts by weight based on 100 parts by weight of the polycarbonate resin. By incorporating an impact resistance improver, the impact strength is improved, but if it exceeds 30 parts by weight, the rigidity tends to decrease. The compounding amount of the impact resistance improving agent is more preferably 2 to 20 parts by weight, most preferably 3 to 15 parts by weight, based on 100 parts by weight of the polycarbonate resin.

The method for producing the polycarbonate resin composition of the present invention is not particularly limited. For example, (1) an aromatic polycarbonate resin, a block copolyamide resin,
A method in which a polyester resin and, if necessary, an impact modifier are melt-kneaded together; (2) an aromatic polycarbonate resin and a block copolyamide resin or an aromatic polycarbonate resin and a polyester resin are melt-kneaded in advance, and then the polyester resin or For example, a method of adding a block copolyamide resin and, if necessary, an impact resistance improver and melt-kneading the mixture may be used.

The polycarbonate resin composition of the present invention comprises
If necessary, various stabilizers such as UV absorbers, additives such as pigments, dyes, lubricants, flame retardants, mold release agents, slidability improvers, etc., and reinforcement of glass fibers, glass flakes, carbon fibers, etc. Materials or whiskers such as potassium titanate and aluminum borate can be added. further,
The resin composition of the present invention does not cause a reduction in the intended antistatic effect even when used in combination with a surface property improving agent such as a release agent or a sliding property improving agent.

[0038]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, physical property evaluation was performed as follows.

(1) The surface specific resistance value is ULTRA HIGH RES
ASTM D using ISTANCE METER (ADVANTEST)
It measured according to -257. (2) Izod impact strength was measured according to ASTM D-256. (3) The appearance of the molded product was visually judged for color tone and silver generation. The evaluation was evaluated as ○ when no silver was generated and the color tone was good, X when silver was generated, and XX when silver was significantly generated and the color tone was yellowed.

In the examples and comparative examples, the following raw materials were used. (4) Aromatic polycarbonate resin: manufactured by Mitsubishi Engineering-Plastics Corporation, trade name: Iupilon E
−2000, viscosity average molecular weight 27,000, hereinafter referred to as “P
C ". (5) Polyethylene terephthalate: manufactured by Mitsubishi Rayon,
Product name: Diapet PA-200, intrinsic viscosity 1.2,
Hereinafter, it is also referred to as “PES”. (6) Block copolyamide: manufactured by Toray, trade name: PAS
-40T, block copolyamide resin composed of caprolactam polymerized polyamide block (weight average molecular weight 90,000), polyethylene glycol block (number average molecular weight 1000) and terephthalic acid (weight ratio of polyamide block / polyether block and polyester block is 50/50), hereinafter also referred to as “CPA”. (7) Impact modifier: acrylic acid-based core / shell elastomer MG-1011 manufactured by Takeda Pharmaceutical Co., Ltd., trade name: Staphyloid. (8) Phosphate ester 1: manufactured by Asahi Denka Kogyo Co., Ltd., trade name: ADK STAB AX-71, a mixture of a compound represented by the following formula (2) and a compound represented by the following formula (3).

[0041]

Embedded image

(9) Phosphate ester 2: Adekastab 21
12 (manufactured by Asahi Denka, tris (2,4-di-tert-butylphenyl) phosphite) (10) Phosphate ester 3: Spiro ring-containing phosphite ester, trade name: ADK STAB PEP36, manufactured by Asahi Denka.

Example 1 6 parts by weight of a polyester, 12 parts by weight of a block copolyamide and 0.1 part of a phosphoric ester 1 were added to 100 parts by weight of an aromatic polycarbonate resin.
2 parts by weight were blended, blended by a tumbler for 20 minutes, and extruded at a cylinder temperature of 260 ° C. into a pellet using a twin screw extruder. After drying the pellets at 120 ° C. for 5 hours, test pieces were molded by an injection molding machine at a cylinder temperature of 260 ° C. and a molding cycle of 1 minute, and physical properties were evaluated. Further, as an evaluation of the thermal stability during molding, molding was performed at a cylinder temperature of a molding machine of 280 ° C. and a molding cycle of 3 minutes, and physical properties were evaluated. Table 1 shows the results.

Example 2 A pellet was prepared in the same manner as in Example 1 except that the amount of the phosphoric acid ester 1 was changed to 0.04 parts by weight, a test piece was prepared, and physical properties were evaluated. Table 1 shows the results.

Example 3 The amount of the polyester was 20
A pellet was prepared in the same manner as in Example 2 except that the blending amount of the copolyamide was changed to 13 parts by weight, and a test piece was prepared. Table 1 shows the results.

Example 4 13 parts by weight of a polyester, 13 parts by weight of a block copolyamide, 7 parts by weight of an impact modifier and 0.12 parts by weight of a phosphoric ester 1 were mixed with 100 parts by weight of an aromatic polycarbonate resin. Example 1
As in the above, pelletization, preparation of test pieces and evaluation of physical properties were performed. Table 1 shows the evaluation results.

Comparative Example 1 The procedure of Example 1 was repeated except that the phosphoric acid ester 1 was not used. Table 1 shows the evaluation results. Comparative Example 2 Phosphate ester 2 instead of Phosphate ester 1
The procedure was performed in the same manner as in Example 1 except for using. Table 1 shows the evaluation results.

[Comparative Example 3] The procedure of Example 1 was repeated, except that the phosphoric acid ester 3 was used instead of the phosphoric acid ester 1. Table 1 shows the evaluation results.

[0049]

[Table 1]

[0050]

Industrial Applicability The polycarbonate resin composition of the present invention has excellent permanent antistatic properties, excellent heat resistance and impact resistance, and also excellent thermal stability during molding. Further, even when a release agent or a slidability improving agent is added, the antistatic property is hardly reduced, and phenomena of poor appearance such as pearl luster and peeling phenomenon are improved. A molded article obtained by molding the polycarbonate resin composition of the present invention is useful in the field of electric / electronic equipment or precision machinery which requires durability of antistatic property.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) C08L 101: 00) C08L 101: 00) F term (Reference) 4J002 AC08Z BC05Z BC06Z BG04Z CF03X CF05X CF06X CF07X CF10Z CF17Z CG001 CG011 CG031 CK02Z CL07Y CL08Y EW046 FD066 GM00 GQ00

Claims (6)

[Claims] (A) Aromatic polycarbonate resin 10
(B) 1 to 50 parts by weight of a polyester resin, (c) 1 to 50 parts by weight of a block copolyamide resin,
And (d) a polycarbonate resin composition comprising 0.01 to 3 parts by weight of a phosphoric ester represented by the following formula (1). Embedded image (Wherein, R represents an alkyl group having 8 to 30 carbon atoms,
n represents an integer of 1 or 2) 2. An aromatic polycarbonate resin 10
2. The polycarbonate resin composition according to claim 1, wherein (e) 1 to 30 parts by weight of an impact modifier is blended with respect to 0 parts by weight. 3. The method according to claim 1, wherein (a) the aromatic polycarbonate resin is
The polycarbonate resin composition according to any one of claims 1 to 3, which is a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane. 4. The polycarbonate resin composition according to claim 1, wherein (a) the aromatic polycarbonate resin has a viscosity average molecular weight of 16,000 to 38,000. 5. The polycarbonate according to claim 1, wherein the polyester resin is a polyalkylene terephthalate obtained by a polycondensation reaction between terephthalic acid or a dialkyl ester thereof and an aliphatic glycol. Resin composition. 6. The polycarbonate according to claim 1, wherein (b) the block copolyamide resin is a block copolyamide resin composed of a polyamide block, a polyether block, and a polyester block. Resin composition.