JP3332056B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a permanent antistatic resin composition. The resin composition of the present invention has excellent heat resistance and impact resistance, and further relates to a resin composition having excellent heat stability and antistatic properties. It can be used in electrical and electronic equipment requiring high durability or precision machinery.

[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, various studies have been made as a means for imparting antistatic properties to synthetic resin products. Generally, a surfactant-based antistatic agent is applied to a molded article, or an antistatic agent is added to a resin material. There is a method of imparting an antistatic property to a molded article by kneading the compound.

[0004] However, such means has a drawback that the antistatic agent in the surface layer is removed and the antistatic property is lost due to long-term use. Further, there is a disadvantage that the antistatic property is lost due to frictional wear and the like.

Further, as a polycarbonate resin composition for imparting permanent chargeability, for example, a resin composition comprising a polyetheresteramide having 95 to 10% by weight of a polyetherester unit and a polycarbonate resin has been known (Japanese Patent Laid-Open Publication No. Hei 9 (1994)). 1987-623252). A polyetherester amide, a polycarbonate resin and an aromatic vinyl monomer, a (meth) acrylate monomer, a vinyl cyanide monomer and a bismaleimide monomer having a polyetherester unit content of 90 to 10% by weight; A resin composition comprising a polymer of a vinyl monomer selected from a polymer and a rubbery polymer (JP-A-1-163252) is known.

[0006]

The antistatic properties of the above-mentioned conventionally known resin compositions are improved to some extent, but may cause poor appearance of polycarbonate resin molded articles, and are not yet satisfactory. . In view of these circumstances, the present invention provides a polycarbonate resin composition which is excellent in chargeability, particularly maintains excellent antistatic properties even when used for a long period of time, and does not cause appearance defects of molded articles.

[0007]

Means for Solving the Problems The present inventors have conducted various studies in view of the above problems, and as a result, by blending a block copolyamide resin with a polycarbonate resin, the durability of the antistatic property has been improved. It has been found that heat stability can be improved by adding a phosphorus compound having a specific structure, and the appearance of a molded article can be improved by adding an aromatic polyester.

That is, the present invention relates to ( A ) 50 to 95 parts by weight of an aromatic polycarbonate resin, and ( B ) a polyethylene resin.
The block copolyamide resins derived from glycol to 2 to 40 parts by weight (C) Polyester resin 2 to 50 parts by weight will by blending phosphorus-containing compound having a (D) spiro ring structure, (A), ( A total of 1 of the components B ) and ( C )
The present invention relates to a thermoplastic resin composition obtained by adding 0.01 to 1 part by weight of ( D ) to 00 parts by weight.

The present invention uses a block copolyamide resin having a specific structure, that is, a polyamide block and a polyether block and / or a polyether block, and these blocks are connected by an ester bond or an ester amide bond. Further, the addition of a polyester resin promotes the development of antistatic properties, and does not impair the desired antistatic properties even if other release agents or slidability improvers are added, and furthermore, pearl luster, peeling phenomena, etc. Improved the appearance defect phenomenon. In addition, the addition of a phosphorus-containing compound having a spiro ring structure significantly improves the thermal stability as compared with the conventional one.

Japanese Patent Application Laid-Open No. 63-199750 discloses a method for improving the impact resistance of a molding material mainly composed of an aromatic polyester, comprising an aromatic polyester (A) and an aromatic polycarbonate resin (B). ) And (B), a resin composition in which a block copolyamide elastomer is blended in an amount of 2 to 80 parts by weight based on 100 parts by weight in total. However, in the present invention, no consideration is given to the problem of the antistatic property, and no description is given. Moreover, there is no description about blending a phosphorus-containing compound having a spiro ring structure, which is one of the essential components in the present invention.

Hereinafter, the present invention will be described specifically. The aromatic polycarbonate resin of the present invention is an optionally branched thermoplastic polycarbonate polymer produced by reacting aromatic dihydroxy or a small amount thereof with a phosgene or carbonic acid diester.

One example of the aromatic dihydroxy compound is 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, and bisphenol A is particularly preferable.

In order 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
A polyhydroxy compound such as -bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol, 5,7-dichloroisatin bisphenol, or 5-bromoisatin bisphenol, Parts, for example from 0.1 to 2 mol% are used.

Further, as molecular weight regulators, monovalent aromatic hydroxy compounds include m- and p-methylphenol, m- and p-propylphenol, p-bromophenol, p-bromophenol,
-Tert-butylphenol and p-long-chain alkyl-substituted phenols and the like are used.

The molecular weight of the aromatic polycarbonate resin is
Those having a viscosity average molecular weight of 16,000 to 30,000, preferably 17500 to 23,000 in terms of a methylene chloride solution viscosity at 25 ° C are used.
Those having a further optimum molecular weight are appropriately selected depending on the amount of the polyester resin added or the molecular weight.

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

As the polyester resin used 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 a dialkyl ester thereof with an aliphatic glycol, or a copolymer based on polyalkylene terephthalate is preferably used. As such a polyester resin, for example, polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) is preferably used.

As the above aliphatic glycol, for example, ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol and the like are used. These aliphatic glycols may be used in combination with other diols or polyhydric alcohols such as cyclohexanediol, cyclohexanedimethanol, xylene glycol, 2,2-bis (4-hydroxyphenyl) propane, glycerin and pentaerythritol. Can be. The amount of these diols or polyhydric alcohols used is preferably in the range of 40 parts by weight or less based on 100 parts by weight of the aliphatic glycol.

In the production of the polyester resin, terephthalic acid or its dialkyl ester is
Phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, adipic acid, sebacic acid, trimellitic acid and dibasic acids such as dialkyl esters thereof, tribasic acids and the like, and also the use of dialkyl esters thereof it can. The amount used 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 number average molecular weight of the polyester resin used in the present invention is in the range of 20,000 to 60,000.
Are preferred.

In the present invention, polyethylene glycol
The block polyamide resin derived from
What is called ether ester amide resin
You.

The polyetherester amide resin is (a)
An aminocarboxylic acid or lactam having 6 or more carbon atoms,
Alternatively, a polyamide block of a salt of a diamine and a dicarboxylic acid having 6 or more carbon atoms, and (b) a number average molecular weight of 200
A resin composed of a polyether block of polyethynylene glycol having a molecular weight of up to 6000 and (c) a dicarboxylic acid having 4 to 20 carbon atoms.

The (a) aminocarboxylic acid having 6 or more carbon atoms or lactam or the salt of diamine and dicarboxylic acid having 6 or more carbon atoms constituting the amide block which is a constituent component of the block copolyamide resin in the present invention includes: ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω
-Aminocapric acid and 11-aminoundecanoic acid, 1
Aminocarboxylic acids such as 2-aminododecanoic acid; lactams such as caprolactam, enantholactam, caprylactam and laurolactam; and hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate And a salt of diamine-dicarboxylic acid of the formula (1), and particularly preferably caprolactam, 12-aminododecanoic acid and hexamethylenediamine-adipate.

The poly (alkylene oxide) glycol (b) constituting the ether block, which is a constituent component of the block copolyamide resin, has excellent antistatic properties.
In particular, polyethylene glycol is used.

The number average molecular weight of polyethylene glycol is used in the range of 200 to 6000, particularly 250 to 4000. When the number average molecular weight is less than 200, the mechanical strength of the obtained block copolyamide is inferior and the number average molecular weight is 60.
If it exceeds 00, it is not preferable because the antistatic property is insufficient.

Further, (c) terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7 as dicarboxylic acids having 4 to 20 carbon atoms which are constituents of the block copolyamide resin. Aromatic dicarboxylic acids, such as dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, diphenoxyethane dicarboxylic acid and sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl- Alicyclic dicarboxylic acids such as 4,4-dicarboxylic acid and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanediacid (decanedicarboxylic acid), and especially terephthalic acid and isophthalic acid 1,4-cyclohexanedical Phosphate, adipic acid, sebacic acid and dodecanedioic acid are polymerizable, preferably used in the color and physical properties viewpoint. The poly (alkylene oxide) glycol as the component (b) and the dicarboxylic acid as the component (c) are usually used in the reaction at a molar ratio of 1: 1.

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

That is, the composition ratio of the polyamide block unit and the polyether block and / or polyester block unit, which are constituent components of the block copolyamide resin, is such that the polyether block and / or polyester block unit is 95 to 10% by weight. Consists of a range. If the polyether block and / or polyester block unit exceeds 95% by weight, the block copolyamide resin can be unevenly distributed on the surface layer of the molded product, but the surface hardness is low, the surface is easily damaged, and the mechanical strength is low. On the other hand, if it is less than 10 parts by weight, the antistatic effect is insufficient.
Addition of the block copolyamide resin in an amount necessary to satisfy the antistatic effect significantly reduces heat resistance and mechanical strength.

The block copolyamide resin has a weight average molecular weight of 50,000 to 200,000, more preferably 7000.
Those having a range of 0 to 120,000 are preferred. When the molecular weight of the block copolyamide resin is lower than 50,000, the dispersibility of the block copolyamide resin is not sufficient, and problems such as influence on the antistatic property of the molded article due to molding conditions may occur. Absent. On the other hand ,
In the case of a resin having a high molecular weight exceeding 200,000, it is difficult to cause the block copolyamide resin to be unevenly distributed on the surface layer of the molded article, and as a result, the antistatic property becomes insufficient. In the resin composition of the present invention, in order to reduce the difference in melt viscosity between the aromatic polycarbonate resin and the polyester resin and the block copolyamide resin at the time of melting, the respective molecular weights, the composition ratios, and the like are appropriately selected to obtain severe conditions. Thus, it is possible to obtain a molded article having no peeling phenomenon and exhibiting more stable antistatic properties.

[0030] is not particularly limited with respect to the polymerization method of block copolyamide resin, for example a (i) (a) polyamide prepolymer aminocarboxylic acid or a lactam and (c) both ends carboxylic acid group by reacting a dicarboxylic acid making, a method of reacting under vacuum (b) polyethylene glycol to (b) (a), (b) and the respective reaction components (c) were charged to a reaction vessel, the presence of water or in the absence A method of producing a carboxylic acid-terminated polyamide prepolymer by pressure reaction at a high temperature, and then proceeding the polymerization under normal pressure or reduced pressure; and ( c ) the method (a),
A known method such as a method in which the respective reaction components (b) and (c) are simultaneously charged into a reaction vessel and melt-mixed, and then the polymerization is allowed to proceed at once in a high vacuum can be used.

When the block copolyamide resin is polymerized,
A phenolic stabilizer is generally added for the purpose of suppressing oxidative deterioration and coloration at a temperature of 200 ° C. or higher, which are suppressed. In the present invention, a block copolyamide resin containing such a stabilizer is preferably used. Commercial products usually contain a stabilizer, but when no stabilizer is used, it is preferable to use a phenol-based stabilizer with appropriate addition.

In the resin composition of the present invention, a phosphorus-containing compound having a spiro ring structure represented by the following formula is added. The thermal stability is further improved by adding such a specific compound.

Embedded image ( Wherein , R _{1 and} R ₆ are H or C ₁ -C ₄ alkyl groups, and R ₂ -R ₅ are each independently H or C ₁ -C ₄
Represents an alkyl group. )

Examples of such a phosphorus-containing compound having a spiro ring structure include “ADK STAB PEP-36” or “ADK STAB PEP-24” (trade name, manufactured by Asahi Denka Kogyo KK).
G "and the like. Such a compound is known as a stabilizer having an effect of suppressing a decrease in the molecular weight of the aromatic polycarbonate resin accompanying the transesterification reaction between the aromatic polycarbonate resin and the polyester resin, but in the present invention, When used in combination with a block copolyamide resin, the thermal stability of the resin composition can be further improved, and even when an impact resistance improver is added, heat resistance during molding is not impaired.

The resin composition of the present invention further contains an impact modifier. Examples of the impact modifier include a polyester elastomer, MBS resin, and MAS.
Resin, acrylate-based core-shell graft copolymer, styrene-based core-shell graft copolymer, SB
R, SEBS, polyurethane elastomers and the like are exemplified. Among them, acrylate-based core-shell graft copolymers are particularly preferably used in view of compatibility with resin components such as aromatic polycarbonate resin, polyester resin, polyamide resin, and the like, heat resistance, and the like. The acrylate-based core-shell graft copolymer described in JP-A-5-222140 is preferably used. This acrylate-based core-shell graft copolymer has a remarkable effect on improving appearance defects such as pearl luster of molded articles. In the present invention, the amount of the impact modifier used is 10% in total of the components (a), (b) and (c).
1 to 30 parts by weight, more preferably 3 parts by weight, per 0 parts by weight
To 10 parts by weight.

In the resin composition of the present invention, 50 to 95 parts by weight of an aromatic polycarbonate resin, 2 to 40 parts by weight of a block copolyamide resin, and 2 to 40 parts by weight of a polyester resin
50 parts by weight are used. (A) The aromatic polycarbonate resin is used in the range of 50 to 95 parts by weight, and if it exceeds 95 parts by weight, the antistatic property of the resin composition is insufficient, and
If the amount is less than 0 parts by weight, heat resistance is inferior, which is not preferable.

The block copolyamide resin is 2 to 4
When the amount is less than 2 parts by weight, the antistatic property is insufficient. When the amount exceeds 40 parts by weight, the resin composition becomes too flexible, and the mechanical strength is poor, which is not preferable.

The polyester resin is used in an amount of 2 to 50 parts by weight. If the amount is less than 2 parts by weight, the effect of improving the peeling phenomenon is insufficient, and if it exceeds 50 parts by weight, the heat resistance is insufficient, which is not preferable.

The method for producing the resin composition of the present invention is not particularly limited. For example, (1) a method in which an aromatic polycarbonate resin, a block copolyamide resin, and a polyester resin are melt-kneaded together; There is a method in which a polycarbonate resin and a block copolyamide resin or an aromatic polycarbonate resin and a polyester resin are melt-kneaded in advance, and then a polyester resin or a block copolyamide resin is added and melt-kneaded.

The resin composition of the present invention may further contain, if necessary, various stabilizers such as an ultraviolet absorber, and additives such as pigments, dyes, lubricants, flame retardants, mold release agents, and slidability improvers. Reinforcing agents such as glass fibers, glass flakes and carbon fibers or whiskers such as potassium titanate and aluminum borate can be added. Furthermore, 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 improver such as a release agent or a sliding property improver.

In the present invention, as one of the evaluations of the antistatic property, the relative value of charge and the half-life of charge were examined. The charging half-life (hereinafter simply referred to as half-life) is measured by the following method, and it can be said that the shorter the half-life, the better the antistatic property. As one measure of the antistatic property, the half-life is preferably within 60 seconds, more preferably within 30 seconds. Particularly, in the field of electronics and electric machinery, if the half-life exceeds 60 seconds, an error or the like is likely to occur, which is not preferable.

[0041]

The present invention will be specifically described below with reference to examples and the like. In addition, physical property evaluation was performed as follows.

The specific surface resistance is ULTRA HIGH RESISTANC.
It measured using E METER (made by ADVANTEST).

With respect to the antistatic property, a rectangular molded product of 50 mm × 90 mm × 2 mm was used to examine the relative charging value and the charging half-life. The relative charge value and half-life were measured using a static honest meter under the conditions of an imprint voltage of 7 KV and an imprint time of 30 seconds. Here, the relative charge value indicates the amount of charge when the imprint voltage is applied to the sample for a certain period of time, and the half-life indicates the time until the relative value is reduced to half after the imprint voltage is turned off. In each case, the smaller the value, the better the antistatic property.

The deflection temperature under load was measured under a high load condition in accordance with ASTM D-648.

The appearance was visually determined.

Example 1 Aromatic polycarbonate resin (manufactured by Mitsubishi Gas Chemical, trade name “Iupilon E-2000”, hereinafter simply referred to as “E-2000”) 85
Polyethylene terephthalate (PET)
(Mitsubishi Rayon, product name "Diapet PA-20
0 ", hereinafter simply referred to as" PA-200 ").
Block copolyamide (trade name “PAS-40” manufactured by Toray
As a phosphorus-containing compound having a spiro ring structure, 0.1 part by weight of "Adeka Stab PEP-36" (hereinafter simply referred to as "PEP-36") as a phosphorus-containing compound having a spiro ring structure. After adding and blending in a tumbler for 20 minutes, the mixture was extruded and pelletized in a twin-screw extruder at a cylinder temperature of 260 ° C. After drying the pellets at 120 ° C. for 5 hours, test pieces were molded at 260 ° C. cylinder temperature by an injection molding machine, and the physical properties were evaluated. The results are shown in Table-1.

Example 2 As shown in Table 1, the amount of the polycarbonate resin in Example 1 was 80 parts by weight, and polyethylene terephthalate (PE) was used.
T) 10 parts by weight of PA-200, block copolyamide resin (PA
S-40T) 10 parts by weight, and 0.1 part by weight of PEP-36 were further added, and pelletized in the same manner as in Example 1 to prepare a test piece.
Physical properties were evaluated. Table 1 shows the results.

Example 3 In place of PAS-40T of Example 2, 10 parts by weight of Pebax MX-1723 (a system manufactured by Atochem with an additive Irganox 1010) was added, and pelletized in the same manner as in Example 1 to obtain a test piece. Was prepared and physical properties were evaluated. Table 1 shows the results.

Example 4 60 parts by weight of an aromatic polycarbonate resin, PET (PA-20
0) 0.1 part by weight of PEP-36 was added to 10 parts by weight of PAS-40T and 30 parts by weight of PAS-40T, and pelletized in the same manner as in Example 1 to prepare a test piece, which was evaluated for physical properties. Table 1 shows the results.

Example 5 50 parts by weight of an aromatic polycarbonate resin, PET (PA-20
0) Test pieces were prepared using pellets obtained by adding 0.1 parts by weight of PEP-36 to 40 parts by weight and 10 parts by weight of PAS-40T in the same manner as in Example 1, and the physical properties were evaluated. Table 1
Shown in

Example 6 75 parts by weight of an aromatic polycarbonate resin, PET (PA-20
0) 10 parts by weight, PAS-40T 10 parts by weight, acrylic acid core /
Shell Elastomer MG-1011 (Takeda Pharmaceutical Co., Ltd.) Pellets were pelletized in the same manner as in Example 1 using a resin composition containing 5 parts by weight of “Staphyroid” and 0.1 part by weight of PEP-36. Table 2 shows the results of the fabrication and physical property evaluation.

Example 7 70 parts by weight of the aromatic polycarbonate resin of Example 6 was added to MG
Same as Example 6 except that -1011 was changed to 10 parts by weight. Table 2 shows the results of the physical property evaluation.

Example 8 As a phosphorus-containing compound having a spiro ring structure, "ADK STAB PEP-24G" (trade name, manufactured by Asahi Denka Kogyo Co., Ltd., manufactured by Asahi Denka Kogyo Co., Ltd .; ") Was used in the same manner as in Example 6. Table-Physical property evaluation
It is shown in FIG.

Comparative Example 1 The procedure of Example 1 was repeated, except that the resin composition to which the phosphorus-containing compound PEP-36 was not added was used. Table 2 shows the evaluation results. As compared with Example 2, the half-life is increased, the load deflection temperature is reduced, and the Izod impact strength is reduced. Silver streaks (silver strips) were also observed in appearance.

Comparative Example 2 The same procedure as in Example 2 was carried out except that PEP-36 of Example 2 was changed to ADK STAB 2112 (manufactured by Asahi Denka, Tris (2,4-di-tert-butylphenyl) phosphite). . Table-Evaluation results
It is shown in FIG. As compared with Example 2, the half-life was increased, the load deflection temperature was decreased, and the Izod impact strength was decreased.

Comparative Example 3 PAS-40T was added to 90 parts by weight of an aromatic polycarbonate resin.
10 parts by weight and 0.1 part by weight of PEP-36 were added, and the same procedure as in Example 1 was carried out without using a polyester resin. Table 2 shows the evaluation results. Compared with Example 2, the half-life was increased and pearl luster was observed.

Block copolyamide resin (polyamide block / polyethylene glycol (number average molecular weight 100
Example 9 Caprolactam 500 parts (parts by weight), number average molecular weight 10
Of polyethylene glycol of Example No. 00 and 450 parts (parts by weight) of terephthalic acid were mixed with N, N′-hexamethylenebis (3,5-di-tert.-butyl-4-butyl).
Hydroxy-hydroxycinnamide (trade name “Irganox 1098” manufactured by Ciba Geigy) 5 parts (parts by weight)
Was charged into a polymerization apparatus equipped with a helical ribbon stirring blade, and stirred at 260 ° C. for 1 hour under a nitrogen atmosphere, and then 1.0 part (part by weight) of antimony trioxide was added. afterwards,
The reaction was performed under reduced pressure for 3 hours to obtain a block copolyamide resin. (A-1) Compounded according to the composition shown in Table-3, pelletized by the same method as in Example 1, prepared a test piece, and evaluated for physical properties. The results are shown in Table-3.

Block copolyamide resin (polyamide block / polyethylene glycol (number average molecular weight 400
Example 10: Synthesis of 50/50) Example 10 Polyethylene glycol 484 having a number average molecular weight of 4000
Parts (parts by weight) and 20 parts (parts by weight) of terephthalic acid were obtained in the same manner as in Example 8 to obtain a block copolyamide resin (referred to as A-2). Formulated with the composition shown in Table-3,
Table 3 shows the results obtained by pelletizing by the same method as in Example 1 to prepare a test piece and evaluating physical properties.

Block copolyamide resin (polyamide block / polyethylene glycol (number average molecular weight 100
Comparative Example 4 Caprolactam 950 parts (parts by weight), number average molecular weight 10
A block copolyamide resin was obtained in the same manner as in Example 8 except that 44.3 parts (parts by weight) of polyethylene glycol and 7.3 parts (parts by weight) of terephthalic acid were used (A).
-3). Example 1 formulated with the composition shown in Table-3
Table 3 shows the results of pelletizing by the same method as described above, producing test pieces and evaluating the physical properties.

Example 11 Physical properties were the same as in Example 6 except that the aromatic polycarbonate resin of Example 6 was changed to a low-viscosity polycarbonate "H-3000" (trade name "Iupilon H-3000" manufactured by Mitsubishi Gas Chemical). Table 4 shows the results of the evaluation.

Example 12 The procedure of Example 6 was repeated, except that PA-200 of Example 6 was changed to low-viscosity polyethylene glycol “PA-500” (trade name “Diapet PA-500” manufactured by Mitsubishi Rayon). Table 4 shows the results of the evaluation of the physical properties.

[0062]

From the above results, the present invention has good thermal stability, heat resistance and durability of antistatic properties as a permanent antistatic material of a polycarbonate resin, and can be used in many applications.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

────────────────────────────────────────────────── (5) References JP-A-62-223257 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 67/00-67/02 C08L 69 / 00 C08L 77/00-77/12

Claims (5)

(57) [Claims] ( A ) Aromatic polycarbonate resin 50
~ 95 parts by weight, derived from ( B ) polyethylene glycol
The block copolyamide resin 2 to 40 parts by weight is (C)
A polyester resin is blended with 2 to 50 parts by weight and the following phosphorus-containing compound having a ( D ) spiro ring structure, ( A )
(D) based on a total of 100 parts by weight of the components ( B ) and ( C )
A thermoplastic resin composition comprising 0.01 to 1 part by weight of Embedded image ( Wherein , R _{1 and} R ₆ are H or C ₁ -C ₄ alkyl groups, and R ₂ -R ₅ are each independently H or C ₁ -C ₄
Represents an alkyl group. ) 2. A total of 100 parts by weight of the components ( A ), ( B ) and ( C ) according to claim 1 is added with an impact modifier in an amount of 1 to 100 parts by weight.
The thermoplastic resin composition according to claim 1, which is added by 30 parts by weight. 3. A block copolyamide resin, (a) a carboxylic acid or lactam having 6 or more carbon atoms of the amino or polyamide blocks of salt having 6 or more carbon atoms of the diamine and dicarboxylic acid,, (b) a number average Molecular weight 200-
The resin composition according to claim 1 or 2, which is a polyamide comprising 6000 polyethylene glycol polyether blocks and ( c) a dicarboxylic acid having 4 to 20 carbon atoms. 4. An aromatic polycarbonate resin comprising 2,2
Polycarbonate resin derived from -bis (4-hydroxyphenyl) propane, or 2,2-bis (4-
3. The resin composition according to claim 1, which is a polycarbonate copolymer of (hydroxyphenyl) propane and another dihydroxy compound. 5. A polyester resin comprising a polymer and a copolymer obtained from terephthalic acid, isophthalic acid, or an ester-forming derivative thereof, and ethylene glycol, 1,4-butanediol, or an ester-forming derivative thereof. 3. The resin composition according to claim 1, which is selected.