JPH0912854A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic resin compsn. which is usable as a permanent antistatic material for many applications and gives a molded item having excellent appearance and heat resistance, a good persistence of antistatic properties, and a markedly improved discoloration resistance during heat aging. CONSTITUTION: This compsn. is prepd. by compounding 100 pts.wt. polymer component comprising 50-98 pts.wt. arom. polycarbonate resin, 2-40 pts.wt. block copolyamide resin, and 0-30 pts.wt. impact modifier with 0.01-1 pt.wt. spirocyclic phosphorus compd. and 0.01-1 pt.wt. metal deactivator.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a permanent antistatic resin composition. The present invention relates to a resin composition having heat resistance, impact resistance, and further, the hue change during heat aging is greatly improved, and particularly, since it has permanent antistatic property, durability of antistatic property It can be used in the fields of electrical and electronic equipment or precision machinery, which are required.

[0002]

2. Description of the Related Art Generally, a synthetic polymer material has a high electric resistance value and is easily charged by friction, peeling or the like, adsorbing dust or dust and impairing its appearance. Further, in the electric and electronic fields, troubles due to them often occur, and a new material excellent in permanent antistatic property is required.

Conventionally, various studies have been attempted as means for imparting antistatic properties to synthetic resin products, and generally, a surfactant-based antistatic agent is applied to a molded product,
Alternatively, a method of imparting antistatic properties by kneading an antistatic agent into a resin material is known.

However, such means has a drawback that the antistatic agent in the surface layer is removed and the antistatic property is lost after long-term use. Further, there is a drawback that the antistatic property is lost due to frictional wear and the like.

Among them, examples of the polycarbonate resin composition having a permanent antistatic property include, for example, JP-A-62-6.
No. 23252 has a polyether ester unit of 95 to 1
A resin composition composed of 0% by weight of polyether ester amide and a polycarbonate resin is proposed. Further, JP-A-1-163252 discloses a polyether ester amide having a polyether ester unit content of 90 to 10% by weight, a polycarbonate resin and an aromatic vinyl monomer, a (meth) acrylic acid ester monomer, and vinyl cyanide. A resin composition comprising a polymer of a vinyl monomer selected from a monomer and a bismaleimide monomer and a rubbery polymer is proposed. Further, JP-A-5-43787 discloses that a phosphite-based compound and / or a phenol-based compound is added in order to prevent resin deterioration during kneading of a polycarbonate resin composition containing a polyamide / polyether block copolymer. is suggesting. However, such compositions have not been satisfactory in terms of thermal discoloration during thermal aging of molded articles.

[0006]

DISCLOSURE OF THE INVENTION The object of the present invention is to significantly improve the thermal discoloration during thermal aging, maintain excellent antistatic property even during long-term use, and cause the appearance defect of a molded product. Another object of the present invention is to provide a polycarbonate resin composition which is free of impact strength or heat resistance and is less likely to deteriorate.

[0007]

The present invention has been made to solve the above problems, and its gist is as follows.
(A) 50 to 98 parts by weight of an aromatic polycarbonate resin,
With respect to 100 parts by weight of the polymer component consisting of 2 to 40 parts by weight of the block copolyamide resin (b) and 0 to 30 parts by weight of the impact modifier (d), (d) a phosphorus-containing compound having a spiro ring structure. It exists in the thermoplastic resin composition which mix | blends 01-1 weight part and (e) 0.01-1 weight part of metal deactivators.

The present invention will be described in detail below. The aromatic polycarbonate resin in the present invention is an aromatic dihydroxy or an optionally branched thermoplastic polycarbonate polymer produced by reacting an aromatic dihydroxy with a small amount of a polyhydroxy compound with phosgene or a diester of carbonic acid.

An example of an aromatic dihydroxy compound is 2,
2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, tetrabromobisphenol A, bis (4-hydroxyphenyl) -P-diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, etc. And bisphenol A is particularly preferable.

To obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-
2,4,6-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,
Polyhydroxy compounds represented by 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane, and 3,3-
Bis (4-hydroxyaryl) oxindole (=
Isatin bisphenol), 5-chlorisatin, 5,
7-Dichlorisatin, 5-bromoisatin and the like are partially replaced with the polyhydroxy compound, for example, 0.1 to 2 mol% of the dihydroxy compound.

Further suitable monovalent aromatic hydroxy compounds for controlling the molecular weight are m- and p-methylphenol, m- and p-propylphenol, p-bromophenol, p-tert-butylphenol and p-length. Chain alkyl substituted phenols and the like are preferred.

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

The molecular weight of the aromatic polycarbonate resin is
The viscosity average molecular weight converted from the viscosity of the methylene chloride solution at 25 ° C. is 10,000 to 100,000, preferably 15,000 to 50,000. Those having a more optimal molecular weight are appropriately selected depending on the addition amount or molecular weight of the polyester 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 form an ester bond or an ester amide bond. . The block copolyamide resin in the present invention includes what is generally called a polyether ester amide resin, and the polyether ester amide resin includes a) an aminocarboxylic acid having 6 or more carbon atoms or a lactam, or a carbon atom. It comprises a polyamide block of a salt of a diamine and a dicarboxylic acid having a number of 6 or more, b) a polyether block of a poly (alkylene oxide) glycol having a number average molecular weight of 200 to 6000, and c) a dicarboxylic acid having a carbon number of 4 to 20. It is a resin.

A) an aminocarboxylic acid having 6 or more carbon atoms or a lactam or a salt of a diamine having 6 or more carbon atoms and a dicarboxylic acid, which constitutes an amide block which is a constituent of the block copolyamide resin in the present invention, is ω- Aminocaproic acid, ω-aminoenanthic acid, ω-
Aminocarboxylic acids such as aminocaprylic acid, ω-aminoperconic acid, ω-aminocapric acid and 11-aminoundecanoic acid, 12-aminododecanoic acid, or lactams such as caprolactam, enanthlactam, capryllactam and laurolactam, and hexamethylenediamine- Diamine-dicarboxylic acid salts such as adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate are used, and caprolactam, 12-aminododecanoic acid and hexamethylenediamine-adipate are particularly preferably used. To be

As the b) poly (alkylene oxide) glycol constituting the ether block which is a constituent of the block copolyamide resin, polyethylene glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene) are used. Oxide) glycol,
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 are used. Among these, polyethylene glycol is particularly preferably used because of its excellent antistatic property.

Further, as the c) dicarboxylic acid having 4 to 20 carbon atoms, which is a constituent of the block copolyamide resin, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7- Aromatic dicarboxylic acids such as dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4. And alicyclic dicarboxylic acids such as 4-dicarboxylic acid, and succinic acid, oxalic acid, adipic acid, sebacic acid, and aliphatic dicarboxylic acids such as dodecanedicarboxylic acid (decanedicarboxylic acid), and the like, particularly terephthalic acid, isophthalic acid, 1,4-cyclohexane dica Bon acid, adipic acid, sebacic acid and dodecanedioic acid are polymerizable, preferably used in the color and physical properties viewpoint. The above-mentioned b) poly (alkylene oxide) glycol and c) dicarboxylic acid are usually subjected to the reaction in a molar ratio of 1: 1.

In the resin composition of the present invention, it is important that the block copolyamide resin is selectively unevenly distributed in the surface layer of the molded product from the viewpoint of imparting antistatic properties to the molded product. For this purpose, the length of each segment constituting the block copolyamide resin used and the total molecular weight within a specific range are selected.

That is, the composition ratio of the polyamide block unit, which is a constituent of the block copolyamide resin, and the polyether block and / or polyester block unit is such that the polyether block and / or the polyester block unit is 95 to 10% by weight. Composed of ranges. When the content of the polyether block and / or the polyester block exceeds 95% by weight, the block copolyamide resin can be unevenly distributed in the surface layer of the molded product, but the surface hardness is low, the surface is easily scratched, and the mechanical strength is low. On the other hand, if it is less than 10% by weight, the antistatic property of the obtained resin is insufficient. When the amount of the block copolyamide resin required to satisfy the antistatic effect is added, heat resistance and mechanical strength are significantly reduced.

The method of polymerizing the block copolyamide of this block copolyamide resin is not particularly limited, and for example, (A) (a) aminocarboxylic acid or lactam and (c) dicarboxylic acid are reacted to form carboxylic acid groups at both ends. The method of preparing the polyamide prepolymer of (2) and reacting it with (b) poly (alkylene oxide) glycol under vacuum, charging the reaction product of (B), (b), (b), and (c) into a reaction tank, A method of producing a carboxylic acid-terminated polyamide prepolymer by pressure-reacting at high temperature in the presence or absence of the reaction, and then proceeding the polymerization under normal pressure or reduced pressure, and (C) above (a) (b) ( It is possible to use a known method such as a method in which the compound of (c) is simultaneously charged into a reaction tank, melt-mixed, and then proceeded with polymerization under high vacuum all at once.

As the impact modifier which is another component which is preferably blended in the thermoplastic resin composition of the present invention, for example, an acrylic ester type core-shell graft copolymer and a styrene type core-shell graft copolymer are used. Examples include copolymers, MBS resins, MABS resins, polyester elastomers, SBR, SEBS, polyurethane elastomers, and the like. Among these, an acrylic acid ester-based core-shell graft copolymer is particularly preferably used because of its compatibility with a matrix such as a polycarbonate resin and heat resistance.

As the polyester resin for use in the present invention, those generally known as engineering plastics are used. Among them, polyalkylene terephthalate obtained by a polycondensation reaction of terephthalic acid or its dialkyl ester with an aliphatic glycol or a copolymer mainly composed of polyalkylene terephthalate is preferably used.
As such a polyester resin, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) or the like is preferably used.

As the above-mentioned aliphatic glycol, linear aliphatic glycols such as ethylene glycol, propylene glycol, tetramethylene glycol and hexamethylene glycol are used. These linear aliphatic glycols include, for example, cyclohexanediol, cyclohexanedimethanol, xylene glycol, 2,2-
It can be used in combination with other cycloaliphatic or aromatic diols such as bis (4-hydroxyphenyl) propane, glycerin and pentaerythritol, and polyhydric alcohols. The amount of these aliphatic or aromatic diols or polyhydric alcohols used is preferably within the range of 40 parts by weight or less with respect to 100 parts by weight of the linear aliphatic glycol.

In the production of the polyester resin, terephthalic acid or its dialkyl ester is used together with
Dibasic acids such as phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, adipic acid, sebacic acid and trimellitic acid, tribasic acids, and dialkyl esters thereof can be used. Its usage is
The amount is preferably 40 parts by weight or less with respect to 100 parts by weight of terephthalic acid or its dialkyl ester.

The number average molecular weight of the polyester resin used in the present invention is in the range of 2000 to 60,000, and more preferably in the range of 25,000 to 52,000. The thermoplastic resin composition containing the aromatic polyester resin of the present invention can improve the appearance without lowering the antistatic property, and is effective in eliminating the appearance defects such as pearl luster and peeling of the molded product. Is.

The polymer component in the thermoplastic resin composition of the present invention is an aromatic polycarbonate resin and a block copolyamide resin, and an impact modifier and / or an aromatic polyester are further added, if necessary. .

In the thermoplastic resin composition of the present invention, the composition ratio of the polymer component differs slightly depending on the presence or absence of the aromatic polyester resin. That is, when the aromatic polyester resin is not included, (a) the aromatic polycarbonate resin is 50 to 98 parts by weight, preferably 70 to 95 parts by weight,
The proportion of the block copolyamide resin (b) is 2 to 40 parts by weight, preferably 5 to 15 parts by weight, and (c) the impact modifier is 0 to 30 parts by weight, preferably 1 to 10 parts by weight. When included, (a) 50 to 95 parts by weight of aromatic polycarbonate resin, preferably 70 to 90 parts by weight, (b) 2 to 40 parts by weight of block copolyamide resin, preferably 5 to 15 parts by weight, (f) aromatic 2 to 50 parts by weight, preferably 5 to 30 parts by weight,
(C) Impact modifier 0 to 30 parts by weight, preferably 1 to 10 parts by weight.

In the resin composition of the present invention, when the amount of the aromatic polycarbonate resin (a) is small, the heat resistance is poor, and when it is large, the antistatic property is insufficient, which is not preferable. If the block copolyamide resin (b) is too small, the antistatic property is insufficient, and if it is too large, the resin composition becomes too flexible and the mechanical strength becomes poor, which is not preferable. When the aromatic polyester resin (f) is added, an improvement in the peeling phenomenon is recognized, but if it is too large, the heat resistance is greatly reduced, which is not preferable. If the amount of the impact modifier (c) is too small, the impact resistance is lowered, and if it is too large, the elastic modulus is greatly lowered, which is not preferable.

In the thermoplastic resin composition of the present invention,
A phosphorus-containing compound having a spiro ring structure and a metal deactivator are added to the polymer component. By using a phosphorus-containing compound having a spiro ring structure and a metal deactivator in combination, not only the thermal stability can be improved but also the hue change during thermal aging can be significantly suppressed. Examples of the compound having a spiro ring structure in the present invention include a phosphorus-containing compound having a spiro ring structure represented by the following structural formula (1).

[0030]

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(In the formula, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, an arylalkyl group, an alkylaryl group, a substituted group thereof, a polyvalent phenol residue or a polyvalent phenol residue. A group in which a hydroxyl group remains in a polyhydric alcohol residue or a group in which at least one of the hydroxyl groups in these residues is a phosphite ester is shown.) Having a spiro ring structure represented by the above structural formula (1) The phosphorus-containing compound is preferably a phosphorus-containing compound having a spiro ring structure represented by the following structural formula (2).

[0032]

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In the formula, R ₃ and R ₈ are H or C _{1 to} C ₄
And the alkyl groups R _{4 to} R ₇ each independently represent H or a C _{1 to} C ₄ alkyl group. Examples of such a phosphorus-containing compound having a spiro ring structure include "Adeka Stab PEP-36" and "Adeka Stab PEP-24G" under the trade name of Asahi Denka Kogyo Co., Ltd.

As the metal deactivator in the present invention,
Examples thereof include oxalic acid derivatives, salicylic acid derivatives, hydrazide derivatives, benzotriazoles, tolyltriazoles, and guanidines. As an example of the metal deactivator comprising an oxalic acid derivative, the following structural formula (3),
Examples include (4).

[0035]

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As the compound represented by the structural formula (3), Eastman Inhibi manufactured by Eastman Kodak Company is used.
tor, OABH.

[0037]

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Examples of the compound represented by the structural formula (4) include Naugard XL-1 manufactured by Uniroyal Chemicals. Examples of the metal deactivator comprising a salicylic acid derivative include those having the following structural formulas (5) and (6).

[0039]

[Chemical 6]

R ₉ : H or alkyl residue Examples of the compound represented by the structural formula (5) include ADK STAB CDA-1 manufactured by Asahi Denka Co., Ltd.

[0041]

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R ₁₀ : C _1-20 Hydrocarbon Residue Examples of the compound represented by the structural formula (6) include ADEKA STAB CDA-6 manufactured by Asahi Denka Co., Ltd. Examples of the metal deactivator composed of benzotriazoles include those having the following structural formula (78).

[0043]

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R ₁₁ : H or alkyl residue As the compound represented by the structural formula (7), benzotriazole can be mentioned. Examples of the metal deactivator composed of tolyltriazoles include those represented by the following structural formula (8).

[0045]

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R ₁₂ : H or alkyl residue R ₁₃ : C _1-20 hydrocarbon residue As a compound having the structural formula (8), tolyltriazole can be mentioned. Examples of the metal deactivator composed of a hydrazide derivative include those having the following structural formulas.

[0047]

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R ₁₄ and R ₁₅ : H or alkyl residue R ₁₆ : C _1-20 hydrocarbon residue Examples of the compound represented by the structural formula (9) include Irganox MD1024 manufactured by Ciba-Geigy. Examples of guanidines include guanidine hydrochloride as guanidine hydrochloride, guanidine nitrate, guanidine carbonate, guanidine phosphate, and guanidine sulfamate.
As the metal deactivator in the present invention, as long as it deactivates or deactivates the metal or metal salt contained in the resin composition, for example, potassium or the like, other than those represented by the above structural formula It may be a metal deactivator.

In the thermoplastic resin composition of the present invention,
The compounding amount of the phosphorus-containing compound (c) having a spiro ring structure is 0.01 to 1 part by weight with respect to 100 parts by weight of the polymer component, and the compounding amount of (f) the metal deactivator is 100 parts by weight of the polymer component.
It is 0.01 to 1 part by weight with respect to parts by weight. In the resin composition of the present invention, when the amount of the phosphorus-containing compound (e) having a spiro ring structure is 0.01 part by weight or less, the effect of improving thermal stability is small. Furthermore, if the blending amount is 1 part by weight or more, it is not preferable because it causes mold deposit.

From the viewpoint of improving thermal stability and preventing mold deposit, the amount of the phosphorus-containing compound having a spiro ring structure is preferably 0.0 based on 100 parts by weight of the polymer component.
It is 3 to 0.2 parts by weight. If the compounding amount of the metal deactivator (f) is 0.01 part by weight or less, the effect of suppressing discoloration during heat aging is small, and if the compounding amount is 1 part by weight or more, it causes mold deposit, which is not preferable.

From the viewpoint of suppressing discoloration during heat aging and preventing mold deposit, the content of the metal deactivator is preferably 0.0 based on 100 parts by weight of the polymer component.
It is 3 to 0.2 parts by weight. The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include (A) (a) aromatic polycarbonate resin, (b) block copolyamide resin, (f) aromatic polyester resin, and (c) impact resistance. , A phosphorus-containing compound having (d) a spiro ring structure, and (e) a method of collectively melt-kneading a metal deactivator,
(B) A method in which (a) and (b) are melt-kneaded in advance, and then (c), (f), (d) and (e) are added and melt-kneaded, or (a) and (f) are previously Examples thereof include a method of melt-kneading, and then adding (b), (c), (d) and (e) to melt-kneading.

The resin composition of the present invention contains, in addition to the above-mentioned components, various stabilizers such as ultraviolet absorbers and additives such as pigments, dyes, lubricants, flame retardants, mold release agents and slidability improvers. Alternatively, a reinforcing material such as glass fiber, glass flake, carbon fiber, or a whisker such as potassium titanate or aluminum borate may be added if necessary. further,
The resin composition of the present invention does not deteriorate the intended antistatic effect even when used in combination with a surface property improving agent such as a release agent or a slidability improving agent.

[0053]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The physical properties of the test pieces were evaluated as follows.

Regarding the antistatic property, the surface resistivity and the charging half-life were examined. Surface resistivity is ULTRA
HIGH RESISTANCE METER (ADV
It was measured after adjusting the condition under the conditions of 23 ° C. and 50% humidity. Regarding the charging half-life, a static Honest meter (manufactured by Shishido Electrostatics) was used, and the charging voltage was 10 KV and the charging time was 60 seconds.

The half-life is the time until the amount of charge during printing is halved after the printing voltage is turned off. The smaller the value, the better the antistatic property. It can be said that there is. Regarding heat aging, a gear oven was used, and aging was performed at 120 ° C. for 400 hours, and the color difference from the initial sample and the difference in the yellow index were measured using Suga Test Instruments Co., Ltd. Color Computer SM-3.

ΔE: Color difference after aging the molded product at 120 ° C. for 400 hours ΔYI: Difference from the initial yellow index after aging the molded product at 120 ° C. for 400 hours ΔE (color difference) and ΔYI (YI It can be said that the smaller the numerical value, the smaller the change.

The abbreviations and the details of the raw materials used in the examples and comparative examples are shown below. S-2000: Sales of Mitsubishi Engineering Plastics Co., Ltd., polycarbonate resin "Iupilon S-2"
000 ", poly-4,4'-isopropylidene diphenyl carbonate, viscosity average molecular weight 23,000 PA-200D: Mitsubishi Rayon high viscosity PET resin MV1074SA: Elf Atchem Co., Ltd. polyether block copolyamide resin MG-1011. : Core shell polymer PEP-36 manufactured by Takeda Pharmaceutical Co., Ltd .: Phosphorus-containing compound having a spiro ring structure manufactured by Asahi Denka Co., Ltd.

[0058]

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CDA-1: Asahi Denka metal deactivator

[0060]

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MD1024: N, N'-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyl] hydrazine Metal deactivator manufactured by Ciba Geigy Co., Ltd. BTZ-M: Benzotriazole Metal deactivator manufactured by Sumitomo Chemical Co., Ltd. Ir-1010: Pentaerythrityl-tetrakis [3
-(3,5-Di-t-butyl-4-hydroxyphenyl) propionate] manufactured by Ciba Geigy Ltd. Ir-1098: N, N 'hexamethylene bis (3,5
-Di-t-butyl-4-hydroxy-hydrocinnamamide manufactured by Ciba Geigy Co., Ltd.

[Example 1] 85 parts by weight of an aromatic polycarbonate resin (S-2000), 10 parts by weight of a block copolyamide (MV1074SA), an impact resistance improver (M
G-1011) 5 parts by weight, phosphorus-containing compound (PEP-36)
0.1 part by weight and metal deactivator (CDA-1) 0.0
After blending 5 parts by weight and blending with a tumbler for 20 minutes, extrusion was performed using a twin-screw extruder at a cylinder temperature of 260 ° C. The obtained pellets were dried at 120 ° C. for 5 hours, and then molded into a test piece at a cylinder temperature of 260 ° C. using an injection molding machine, and physical properties were evaluated. The results are shown in Table 1.

Example 2 CDA-1 in Example 1
Extrusion, molding, and evaluation were carried out in the same manner as in Example 1 except that MD was changed to MD1024. The results are shown in Table 1. [Example 3] CDA-1 was replaced with BTZ-M in Example 1.
Extrusion, molding and the same method as in Example 1 except that
An evaluation was performed. The results are shown in Table 1.

Example 4 70 parts by weight of aromatic polycarbonate resin (S-2000), 15 parts by weight of polyethylene terephthalate (PA-200D), 10 parts by weight of block copolyamide (MV1074SA), impact modifier (MG-). 1011) 5 parts by weight, phosphorus-containing compound (PEP-3
6) 0.1 part by weight and metal deactivator (CDA-1)
0.05 part by weight was compounded, and extrusion, molding and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 1.

[Embodiment 5] CDA-1 in Embodiment 4
Extrusion, molding, and evaluation were carried out in the same manner as in Example 4 except that MD was changed to MD1024. The results are shown in Table 1. [Example 6] CDA-1 was replaced with BTZ-M in Example 1.
Extrusion, molding and the same method as in Example 4 except that
An evaluation was performed. The results are shown in Table 1.

Comparative Example 1 CDA-1 in Example 1
Extrusion, molding and evaluation were carried out in the same manner as in Example 1 except that the above was not included. Table 2 shows the results. Compared to Example 1, the half-life is increased, ΔE and ΔYI are increased, and the hue change after aging is large. Comparative Example 2 Extrusion, molding and evaluation were carried out in the same manner as in Example 4 except that CDA-1 was not included in Example 4. Table 2 shows the results. Compared to Example 4, the half-life was good, but an increase in ΔE and ΔYI was observed,
The change in hue after aging is large.

[Comparative Example 3] In Example 1, an antioxidant (Ir-101) was used instead of the metal deactivator (CDA-1).
Extrusion, molding and evaluation were performed in the same manner as in Example 1 except that 0) was used. Table 2 shows the results. Compared with Example 1, the half-life is increased, ΔE and ΔYI are significantly increased, and the hue change after aging is large.

[Comparative Example 4] In Example 4, an antioxidant (Ir-101) was used instead of the metal deactivator (CDA-1).
Extrusion, molding and evaluation were carried out in the same manner as in Example 4 except that 0) was used. Table 2 shows the results. Compared to Example 4, the half-life is increased, ΔE and ΔYI are significantly increased, and the hue change after aging is large.

[Comparative Example 5] In Example 4, instead of the metal deactivator (CDA-1), an antioxidant (Ir-109) was used.
Extrusion, molding and evaluation were performed in the same manner as in Example 4 except that 8) was used. Table 2 shows the results. Compared to Example 4, the half-life is increased, ΔE and ΔYI are significantly increased, and the hue change after aging is large.

Comparative Example 6 Extrusion, molding and evaluation were carried out in the same manner as in Example 4 except that the phosphorus-containing compound (PEP-36) was not used in Example 4. Table 2 shows the results. Compared to Example 4, the half-life is increased, ΔE and ΔYI are significantly increased, and the hue change after aging is large.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

EFFECTS OF THE INVENTION The thermoplastic resin composition of the present invention is not only excellent in appearance and heat resistance when formed into a molded article, but also has good durability of the antistatic agent. The thermal discoloration at the time is remarkably improved, and it can be used in many applications as a permanent antistatic material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/527 KKM C08K 5/527 KKM C08L 51/06 LLE C08L 51/06 LLE 67/02 LPE 67 / 02 LPE 77/00 LQT 77/00 LQT

Claims (9)

[Claims] 1. (a) Aromatic polycarbonate resin 50
To 98 parts by weight, (b) block copolyamide resin 2 to 4
0.01 to 1 part by weight of (d) a phosphorus-containing compound having a spiro ring structure, and (e) to 100 parts by weight of a polymer component consisting of 0 part by weight and (c) an impact resistance improver of 0 to 30 parts by weight. A thermoplastic resin composition containing 0.01 to 1 part by weight of a metal deactivator. 2. The polymer component comprises (a) 50 to 95 parts by weight of an aromatic polycarbonate resin, (b) 2 to 40 parts by weight of a block copolyamide resin, and (f) an aromatic polyester 2.
The thermoplastic resin composition according to claim 1, wherein the amount is from 50 to 50 parts by weight and the impact modifier (c) is from 0 to 30 parts by weight. 3. The aromatic polycarbonate resin is 2,2
A polycarbonate resin derived from -bis (4-hydroxyphenyl) propane, or 2,2-bis (4-
The thermoplastic resin composition according to claim 1 or 2, which is a polycarbonate copolymer derived from hydroxyphenyl) propane and another aromatic dihydroxy compound. 4. The thermoplastic resin composition according to claim 1 or 2, wherein the block copolyamide resin is composed of a polyamide block and a polyether block and / or a polyester block. 5. A block copolyamide resin comprising a) a polyamide block obtained by polymerizing a) an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt of a diamine and dicarboxylic acid having 6 or more carbon atoms, and b) a number average molecular weight. A polyether block of poly (alkylene oxide) glycol of 200 to 6000 and c) a carbon number of 4 to 2
The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin composition is composed of 0 dicarboxylic acid. 6. The impact resistance improver is a polyester elastomer, MBS resin, MAS resin, acrylic ester core-shell graft copolymer, styrene core.
The thermoplastic resin composition according to claim 1 or 2, comprising at least one selected from a shell graft copolymer, SBR, SEBS, and a polyurethane elastomer. 7. A polymer and a copolymer obtained by a polycondensation reaction of an aromatic polyester resin with terephthalic acid, isophthalic acid, or an ester-forming derivative thereof and glycols such as ethylene glycol and 1,4-butanediol. The thermoplastic resin composition according to claim 2, wherein the thermoplastic resin composition is selected from polymers. 8. The thermoplastic resin composition according to claim 1, wherein the phosphorus-containing compound having a spiro ring structure is a compound having the following structural formula (1). Embedded image (Wherein R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, an arylalkyl group, an alkylaryl group, a substituted group thereof, a polyhydric phenol residue or a polyhydric alcohol residue. A group in which a hydroxyl group remains, or a group in which at least one of the hydroxyl groups in these residues is a phosphite ester is shown.) 9. The metal deactivator comprises one or more selected from oxalic acid derivatives, salicylic acid derivatives, hydrazide derivatives, benzotriazoles, tolyltriazoles and guanidines. 9. The thermoplastic resin composition according to any one of 8.