JP3270147B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent permanent antistatic properties and good mechanical properties and thermal stability during molding. The present invention relates to a polycarbonate-based resin composition suitable as a material capable of preventing electrostatic charging of a part.

[0002]

2. Description of the Related Art Polycarbonate resins, which have excellent impact resistance and heat resistance, have been widely used as materials for various parts in electronic products, home appliances, OA equipment and the like. However, molded products made of polycarbonate resin have high surface resistivity and are easily charged with static electricity due to friction or the like. It has the disadvantage that it can cause obstacles. Therefore, it has been desired to impart an antistatic property to the polycarbonate resin without deteriorating the excellent properties of the polycarbonate resin as described above.

As a method for imparting antistatic properties to a polycarbonate resin, it has been well known that, for example, a surfactant is kneaded into the resin at the stage of pellet production or applied to the surface of a molded article. I have. However,
In such a method, the surfactant existing on the surface is easily removed by washing with water, friction, or the like, and it has been difficult to impart a permanent antistatic property to the molded article made of the polycarbonate resin.

[0004] Further, a method of blending a polyamide elastomer has been proposed in order to impart permanent antistatic properties to a polycarbonate resin. That is, JP-A-62-273252 discloses a method of blending a polycarbonate-based resin with a polyamide elastomer and, if necessary, a styrene-based resin. JP-A-1-163252 discloses a polyamide resin and a modified vinyl polymer containing at least one reactive functional group such as a carboxyl group, an epoxy group, an amino group, and a hydroxyl group in a polycarbonate resin. Also disclosed is a composition blended with a rubber graft copolymer as required.

[0005]

However, the method disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 62-273252 is disadvantageous in that the compatibility between the polycarbonate-based resin and the polyamide elastomer is not good, so that delamination occurs in the molded product. was there. Further, in the method of JP-A-1-163252, although the delamination of the molded article can be eliminated, the molded article is gelated by heating during molding to lower the fluidity, or is contained in the modified vinyl polymer. Depending on the type of the functional group, the polyamide has a drawback that the molecular weight is reduced, and is not practical.

The present invention has been made to solve such a problem and has excellent antistatic properties.
An object of the present invention is to provide a polycarbonate resin composition which has good thermal stability and does not cause delamination when formed into a molded article.

[0007]

Means for Solving the Problems To achieve the above object, the composition of claim 1 comprises (A) 60 to 95% by weight of a polycarbonate resin component, and (B) (a) the following formula (1) Polyamide (1) represented by
Polyamide segments of, - [C (= O) -R 1 -C (= O) -NH-R 2 -NH] n 1 - ...... (1) ( where, R _1, R ₂ are each a divalent Wherein at least one of R ₁ and R ₂ is an aromatic hydrocarbon residue, and the average value of n _{1 in} all polyamide segments is 1 to 20.) (b) 50 weight % Or more polyoxyethylene,
A polyoxyalkylene segment having a number average molecular weight of 500 to 6000, and (c) a dicarboxylic acid, a diamine, or a diisocyanate linking the polyamide segment and the polyoxyalkylene segment,
The polyamide elastomer component has a total content of (a) and (c) of 20 to 70% by weight and 5 to 40% by weight.

Further, the composition of claim 2 comprises: (A) 60 to 95% by weight of a polycarbonate resin component; and (B) (a) a polyamide (1) represented by the following formula (1).
And a polyamide segment comprising a polyamide (2) represented by the following formula (2) and having a molar ratio of the polyamide (2) to the polyamide (1) of 10 or less:-[C (= O) -R _{1 -C (= O) -NH-} R 2 -NH] n 1 - ...... (1) - [C (= O) -R 3 -NH] n 2 - ...... (2) ( where, R _1, R ₂ is a divalent hydrocarbon residue, at least one of R ₁ and R ₂ is an aromatic hydrocarbon residue, and R ₃ is a divalent hydrocarbon residue having 5 to 11 carbon atoms. And the average value of n ₁ and n ₂ in all the polyamide segments is 1 to 20.) (b) contains 50% by weight or more of polyoxyethylene;
A polyoxyalkylene segment having a number average molecular weight of 500 to 6000, and (c) a dicarboxylic acid, a diamine, or a diisocyanate linking the polyamide segment and the polyoxyalkylene segment,
The polyamide elastomer component has a total content of (a) and (c) of 20 to 70% by weight and 5 to 40% by weight.

The composition according to claim 3 is the composition according to claim 1 or 2, wherein R _{1 in the} formula (1) representing the polyamide (1) in (a) of the component (B) is divalent. An aliphatic hydrocarbon residue, wherein R ₂ is a divalent aromatic hydrocarbon residue. The polycarbonate resin as the component (A) in the composition according to claim 1 or 2, which is a polycarbonate resin or a blend with another thermoplastic resin and contains at least 50% by weight of the polycarbonate resin. Is used.

That is, as the polycarbonate resin, 2,2-bis (4-oxyphenyl) alkane-based resin,
Bis (4-oxyphenyl) ether-based, bis (4-oxyphenyl) sulfone-based, bis (4-oxyphenyl) sulfide-based, bis (4-oxyphenyl) sulfoxide-based polymers or the like comprising bisphenols A polymer or a polymer comprising a halogen-substituted bisphenol is exemplified.

Further, such a polycarbonate resin may contain a reactive functional group such as a carboxyl group, an acid anhydride group and an epoxy group as long as the thermal stability is not impaired. These polycarbonate resins can be used alone or in combination of two or more. The production method is not particularly limited, and one obtained by a known polymerization method such as a phosgene method or a transesterification method can be used.

The thermoplastic resin which can be blended with such a polycarbonate resin includes a styrene resin, an acrylic resin, a polyester resin and the like. Examples of the styrene resin include polystyrene (PSt), rubber-reinforced polystyrene (HIPS), poly (styrene-acrylonitrile) copolymer (AS resin), and rubber-reinforced poly (styrene-acrylonitrile) copolymer (ABS resin). No. Further, styrene constituting these styrene resins may be partially substituted with α-methylstyrene, or acrylonitrile may be partially or entirely substituted with acrylate or methacrylate. These styrene resins can be used alone or in combination of two or more.

Examples of the acrylic resin include a homopolymer or a copolymer of a methacrylic acid ester, and a copolymer partially substituted with an acrylic acid ester. Examples of the polyester resin include a polyethylene terephthalate resin and a polybutylene terephthalate resin. The polyamide elastomer of the component (B) in each of the compositions according to claims 1 to 3, wherein the polyamide segment of (a) and the polyoxyalkylene segment of (b) are a linking agent of (c), and an ester bond, an amide bond, It is a multi-block copolymer linked by urethane bonds or urea bonds.

As the polyamide segment (a),
The polyamide (1) represented by the following formula (1) is an essential component. — [C (＝ O) —R ₁ —C (＝ O) —NH—R ₂ —NH] n ₁ — (1) (where R ₁ and R ₂ are each a divalent hydrocarbon residue And at least one of R ₁ and R ₂ is an aromatic hydrocarbon residue, and the average value of n _{1 in} all polyamide segments is 1 to 20.) In the formula (1), R ₁ and R ₂ Are each a divalent hydrocarbon residue, and at least one of them must be an aromatic hydrocarbon residue. When both R ₁ and R ₂ are aliphatic hydrocarbon residues, the compatibility with the polycarbonate resin is deteriorated, which causes delamination when the composition is molded.

[0015] Such polyamide (1), by polycondensation of diisocyanate and a dicarboxylic acid, or readily obtained by polycondensation of a diamine and a dicarboxylic acid.
For example 6, by polycondensation of aliphatic diamine and an aromatic dicarboxylic acid as T- nylon, or by polycondensation of an aliphatic diisocyanate and an aromatic dicarboxylic acid, polycondensation of an aromatic diisocyanate and an aliphatic dicarboxylic acid the <br/>, by polycondensation of an aromatic diamine and an aliphatic dicarboxylic acid, obtained by polycondensation of the polycondensation of an aromatic diisocyanate and an aromatic dicarboxylic acid, or an aromatic diamine and an aromatic dicarboxylic acid .

Examples of the diisocyanate to form the polyamides (1), hexamethylene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and naphthylene diisocyanate and the like,
These halogen-substituted products are exemplified, and diphenylmethane diisocyanate is particularly preferably used.

Examples of the diamine forming the polyamide (1) include hexamethylenediamine, diaminodiphenylmethane, diaminodiphenylether, xylylenediamine, naphthylenediamine, and halogen-substituted products thereof. Diaminodiphenylmethane and diaminodiphenylether are particularly preferable. It is preferably used. Examples of the dicarboxylic acid forming the polyamide (1) include adipic acid,
Azelaic acid, sebacic acid, aliphatic dicarboxylic acids such as decanedicarboxylic acid, terephthalic acid, isophthalic acid, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and these dicarboxylic acids. Ester compounds, acid chlorides and the like, among these, azelaic acid,
Sebacic acid or decanedicarboxylic acid is particularly preferably used.

Preferred polyamides (1) include:
A polyamide obtained from an aromatic diisocyanate or an aromatic diamine and an aliphatic dicarboxylic acid, particularly preferably a polyamide obtained from an aromatic diisocyanate and an aliphatic dicarboxylic acid. Here, (a) in claim 2
Is composed of the above polyamide (1) and a polyamide (2) represented by the following formula (2).

-[C (= O) -R ₃ -NH] n _2- (2) (where R ₃ is a divalent hydrocarbon residue having 5 to 11 carbon atoms, and in all polyamide segments, 1 the average value of n ₂ is
20. ) In this polyamide (2), R ₃ has 5 to 1 carbon atoms.
If it is outside the range of 1, the molecular weight of the polyamide elastomer may not be sufficiently large, or the antistatic performance of the composition obtained by mixing with the polycarbonate resin may not be sufficient.

Examples of the polyamide (2) include 6-nylon, 7-nylon, 8-nylon, 9-nylon
Nylon, 10-nylon, 11-nylon, 12-nylon and the like can be mentioned, but 6-nylon, 11-nylon and 12-nylon are particularly preferably used. These polyamides can be easily obtained by polymerizing an aminocarboxylic acid or a lactam.

In the polyamide segment (a) in the composition of the second aspect, the molar ratio of the polyamide (2) to the polyamide (1) is 10 or less. The molar ratio is 1
If it exceeds 0, the component (B) (polyamide elastomer)
The compatibility with the polycarbonate-based resin is deteriorated, and when the composition is formed into a molded product, delamination is likely to occur. Although it depends on the kind and content of the aromatic component constituting the polyamide (1), the molar ratio of the polyamide (2) to the polyamide (1) is preferably 5 or less, particularly preferably 0.1 to 3.

The polymerization degree (n ₁ , n ₂ ) of the polyamide (1) and the polyamide ( ₂ ) has an average value of 1 to 20 in all the polyamide segments. When this value exceeds 20, it becomes difficult to obtain a polyamide elastomer having a high molecular weight, and the mechanical strength of a molded article formed of a composition with a polycarbonate resin component is reduced. This value is preferably 1 to 10, and particularly preferably 1 to 5.

The polyoxyalkylene segment (b) is obtained from a polyoxyalkylene having a hydroxyl, amino or carboxyl group at the end. Here, as the polyamide elastomer of the component (B),
From the viewpoint of thermal stability, a polyetheresteramide linked by an ester bond or a polyetheramide linked by an amide bond is preferable.

When the polyoxyalkylene segment of (b) and the polyamide segment of (a) are connected by an ester bond by the connecting agent of (c) to form a polyetheresteramide as the component (B). Uses a compound whose terminal is a hydroxyl group. That is, polyoxyethylene glycol (50% by weight or more) and another polyoxyalkylene glycol, for example, polyoxypropylene glycol, polyoxytetramethylene glycol, glycol obtained by block copolymerizing ethylene oxide and propylene oxide, and the like are used. Used. Also, low molecular weight diols such as ethylene oxide adducts of bisphenol-A and bisphenol-S and ethylene oxide of dihydroxynaphthalene can be used together.

When the polyoxyalkylene segment (b) and the polyamide segment (a) are linked by an amide bond by the linking agent (c) to form a polyetheramide as the component (B), Those having an amino group or a carboxyl group at the end are used. That is,
Polyoxyethylene (50% by weight or more) having an amino group or a carboxyl group at the end, polypropylene oxide or polytetramethylene oxide having an amino group or a carboxyl group at the end, or a block copolymer of ethylene oxide and propylene oxide is used.

In the polyoxyalkylene segment (b), it is necessary to contain 50% by weight or more of polyoxyethylene. If the amount is less than 50% by weight, the antistatic performance of the composition is reduced. It is particularly preferable that polyoxyethylene is contained in an amount of 70% by weight or more. The number average molecular weight of the polyoxyalkylene segment (b) is 500 to 60.
00 range. If it is less than 500, the melting point of the elastomer will be low and it will be difficult to harden, and the physical properties of the composition will be reduced. When the number average molecular weight exceeds 6000, it becomes difficult to synthesize a high molecular weight elastomer, and the mechanical properties when the composition is formed into a molded product are reduced. The preferred range of the number average molecular weight is 600 to 4000,
3000 is particularly preferred.

(C) is a linking agent for linking the polyamide segment and the polyoxyalkylene segment,
Dicarboxylic acids, diamines or diisocyanates are used. As described above, when the polyoxyalkylene segment (b) and the polyamide segment (a) are linked by an ester bond to form a polyetheresteramide as the component (B), a dicarboxylic acid is used. . Such a dicarboxylic acid may be any of an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, and an aromatic dicarboxylic acid, and a dicarboxylic acid having 4 to 20 carbon atoms is preferable from the viewpoint of polymerizability and physical properties. That is, for example,
Examples include succinic acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid. These may be used alone or in combination of two or more. Of these, aliphatic dicarboxylic acids are particularly preferably used.

In the case where the polyoxyalkylene segment of (b) and the polyamide segment of (a) are linked by an amide bond to form a polyetheramide as the component (B), the polyoxyalkylene segment of (b) When an alkylene segment having an amino group at the end is used, the same dicarboxylic acid as described above is used. When a polyoxyalkylene segment having a carboxyl group at the end is used as (b), diamine or diisocyanate is used.

As such a diamine or diisocyanate, hexamethylene diamine, hexamethylene diisocyanate, diaminodiphenylmethane, diaminodiphenyl ether, diphenylmethane diisocyanate and the like are preferably used. (C)
By using the polyoxyalkylene segment (b) substantially equimolarly, a polyamide elastomer having a high molecular weight can be obtained as the component (B).

The polyamide elastomer (B) is a polyamide elastomer obtained by linking the polyoxyalkylene segment (b) and the polyamide segment (a) by an ester bond with the dicarboxylic acid (c). Particular preference is given to using teresteramides. Further, in the composition according to claim 2, the polyamide elastomer of the component (B) is obtained by separating the polyamide (1) and the polyamide (2) of the component (a) separately and independently with the coupling agent of the component (c). The polyoxyalkylene segment may be bonded to the polyoxyalkylene segment, or the copolymer of the polyamide (1) and the polyamide (2) of (a) may be combined with the polyoxyalkylene segment of (b) by the coupling agent of (c). It may be bonded, but the latter, in which the copolymerized polyamide segment is bonded to the polyoxyalkylene segment of (b), is more preferable. Furthermore, if the amount is small, other polyamide-forming monomers may be copolymerized with the polyamide (a).

In the polyamide elastomer of the component (B), each structural unit of the polyamide segment (a) and the coupling agent (c) contributes to the heat resistance and strength of the elastomer and the compatibility with the polycarbonate resin. And the total content in the elastomer is 20
It must be in the range of 70 to 70% by weight, preferably 30 to 60% by weight, particularly preferably 35 to 60% by weight. When the content is less than 20% by weight or more than 70% by weight,
The antistatic performance of the composition is reduced.

As a method for producing the polyamide elastomer of the component (B), any method can be adopted as long as a uniform elastomer can be obtained. For example, the polyetheresteramide is prepared by previously reacting a monomer capable of forming a polyamide segment (a) with a dicarboxylic acid (c) to synthesize a polyamide having a carboxyl group at the end. The polyoxyalkylene segment having a hydroxyl group at the terminal as the polyoxyalkylene segment of the above) can be obtained by heating in the presence or absence of a solvent to homogenize the mixture, and then increasing the degree of polymerization under reduced pressure.

Further, the polyamide-forming monomer, dicarboxylic acid and polyoxyalkylene are charged together,
It can also be obtained by a method of increasing the degree of polymerization under reduced pressure after homogenization by heating. In this reaction, synthesis can be performed in a short time by using an esterification catalyst. The degree of polymerization of the polyamide elastomer (B) is
Although it can be changed as needed, it is preferable that the melt viscosity under kneading conditions is close to that of the polycarbonate resin.
That is, a solution prepared by dissolving 0.5 g of an elastomer in meta-cresol to make 100 ml has a temperature of 30 ° C.
The relative viscosity measured in the above is preferably 1.5 or more, and more preferably the relative viscosity is 1.6 or more.

Further, in order to enhance the thermal stability of the obtained polyamide elastomer, various heat-resistant stabilizers such as a heat-resistant anti-aging agent and an antioxidant can be used. Such a heat stabilizer can be added at the time of polymerization of the polyamide elastomer, and the initial stage, the middle stage, and the
Alternatively, it may be added at any stage of the final stage. The heat stabilizer can be added when the polyamide elastomer is kneaded with the polycarbonate resin.

Examples of such heat stabilizers include N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxycinnamic acid amide) and 4,4'-bis (2, 6-di-t-butylphenol), 2,2′-methylenebis- (4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, etc. Hindered phenols; N,
N′-bis (β-naphthyl) -p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine,
Aromatic amines such as poly (2,2,4-trimethyl-1,2-dihydroquinoline); sulfur compounds and phosphorus compounds such as dilaurylthiodipropionate are used.

The composition according to any one of claims 1 to 3 comprises 60 to 95% by weight of the polycarbonate resin (A) and 5 to 40% by weight of the polyamide elastomer (B). That is, in the composition consisting of the component [A] and the component [B], the polyamide elastomer of the component [B] is blended at a ratio of 5 to 40% by weight. When the proportion of the component (B) is less than 5% by weight, the antistatic effect of the composition is insufficient, and when it exceeds 40% by weight, the rigidity of the composition as a molded article tends to decrease. The preferred range of the ratio of the component (B) is 5 to 25% by weight, and the more preferred range is 6 to 20% by weight.

The compositions according to claims 1 to 3 can be prepared by mixing a polycarbonate resin as the component (A) and a polyamide elastomer as the component [B] in a known manner, for example, using a Banbury mixer.
It can be obtained by kneading with a mixing roll, a single-screw or twin-screw extruder, or the like. The kneading temperature at this time is preferably in the range of 230 to 290 ° C.

In order to further enhance the antistatic performance, a surfactant or an inorganic alkali metal salt can be added to the compositions of claims 1 to 3. As such a surfactant, a nonionic surfactant such as an aliphatic ester or polyoxyethylene alkyl allyl ether, or an anionic surfactant such as an organic sulfonate or an organic phosphate is preferably used. As the inorganic alkali metal salts, lithium,
Examples thereof include halides such as sodium, potassium, and cesium, and sulfates, nitrates, and phosphates.

These surfactants and inorganic alkali metal salts may be used alone or in combination of two or more, and the total amount thereof is 5% by weight based on the whole composition. The following is assumed. If the amount is more than 5% by weight, the surface of the molded article becomes rough, or is colored during molding, which is not preferable. The amount is preferably 0.1 to 3% by weight, particularly preferably 0.3 to 1% by weight.

The composition according to any one of claims 1 to 3, further comprises other components,
For example, a dye, an ultraviolet absorber, a weathering agent, a heat stabilizer, an antioxidant, a lubricant, a light scattering agent, a plasticizer, a release agent, or another polymer in any process such as a kneading process or a molding process. It can be contained. Claim 1 obtained in this way
The compositions (3) to (3) can be molded by a known method employed for forming a general thermoplastic resin, for example, a method such as injection molding, extrusion molding, blow molding, or vacuum molding.

[0041]

According to the compositions of claims 1 and 2, the aforementioned (a)
Specific polyamide segments defined by (b)
A polyamide elastomer containing a specific polyoxyalkylene segment defined by the formula (1) is satisfactorily kneaded with the polycarbonate resin. Thereby, the molded articles obtained from the compositions of claims 1 and 2 have excellent antistatic properties, good thermal stability, and are unlikely to cause delamination.

In the composition according to the third aspect, R ₁ and R ₂ constituting the polyamide (1) in the polyamide elastomer are limited, so that the action imparted to the compositions according to the first and second aspects is achieved. Can be noticeable.

[0043]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. First, preparation methods of various polyamide elastomers (B1 to B7) used in the following Examples and Comparative Examples will be described. The relative viscosity of the elastomer was measured at 30 ° C. using a solution prepared by dissolving 0.5 g of the elastomer in meta-cresol to make 100 ml. <Polyamide elastomer B-1> 112.0 g (75.2 mmol) of polyoxyethylene glycol having a number average molecular weight of 1490 was placed in a 500 ml reactor equipped with a stirrer, a nitrogen inlet, and a distillation tube, and sebacic acid. 46.1 g (228 mmol), caprolactam 3
6.5 g (323 mmol) and 0.4 g of 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene were charged and heated to 120 ° C. After melting by heating, 37.6 g (150 mmol) of 4,4'-diphenylmethane diisocyanate was added and reacted at 250 ° C. for 3 hours while flowing nitrogen gas at 100 ml / min.

Then, the pressure was gradually reduced to distill off unreacted caprolactam, the pressure was returned to normal pressure, 0.4 g of zirconium tetrabutoxide was added, and the reaction was carried out at 260 ° C. and 1 torr for 2.0 hours. Was. The molten polymer was made into a strand from the reactor, drawn out into water, cooled, and cut with a pelletizer to obtain a transparent polyamide elastomer chip.

This elastomer had a polyamide segment content of 44% by weight, polyamide (2) / polyamide (1) = 1.2, and a relative viscosity of 1.9. <Polyamide elastomer B-2> In the same reactor as described above, 88.0 g (59.1 mmol) of polyoxyethylene glycol having a number average molecular weight of 1490 and 5.6 g (17.1 mmol) of an ethylene oxide adduct of bisphenol-A were added. ), 62.3 g (308 mmol) of sebacic acid,
13.0 g (115 mmol) of caprolactam, 50 g of 2-pyrrolidone, and 1,3,5-trimethyl-2,
0.4 g of 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene was charged, heated to 120 ° C. and melted, and then 57.2 g of 4,4′-diphenylmethane diisocyanate (229 g) Mmol)
While flowing nitrogen gas at 100 ml / min.
The reaction was carried out at 3 ° C. for 3 hours.

Then, the pressure was gradually reduced to distill off the caprolactam unreacted with 2-pyrrolidone. After returning to normal pressure, 0.4 g of zirconium tetrabutoxide was added. The reaction was performed for 0 hours. Thereafter, a transparent polyamide elastomer chip was obtained in the same manner as described above. This elastomer had a polyamide segment content of 53% by weight, polyamide (2) / polyamide (1) = 0.4, and a relative viscosity of 1.7. <Polyamide elastomer B-3> In the same reactor as above, 82.0 g (55.1 mmol) of polyoxyethylene glycol having a number average molecular weight of 1490, 51.7 g (225 mmol) of 1,10-decanedicarboxylic acid, and caprolactam 18 2.0 g (159 mmol), 2-pyrrolidone 50 g, and 1,3,5-trimethyl-2,4,6-
After charging 0.4 g of tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and heating at 120 ° C. to melt, 41.3 g (165 mmol) of 4,4′-diphenylmethane diisocyanate was added. And said B2
In the same manner as in the above, the same treatment was carried out to obtain a transparent polyamide elastomer chip.

This elastomer had a polyamide segment content of 52% by weight, polyamide (2) / polyamide (1) = 0.7, and a relative viscosity of 1.9. <Polyamide elastomer B-4> In a reactor similar to the above, 112.0 g (113 mmol) of polyoxyethylene glycol having a number average molecular weight of 990, and sebacic acid 46.
1 g (228 mmol), 50.0 g N-methyl-ε-caprolactam, and 1,3,5-trimethyl-2,
0.4 g of 4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene was charged, heated to 120 ° C. and melted, and then 28.3 g of 4,4′-diphenylmethane diisocyanate (113 g) Mmol)
While flowing nitrogen gas at 100 ml / min.
The reaction was carried out at 3 ° C. for 3 hours.

Then, the temperature was raised to 280 ° C., and the pressure was gradually reduced to distill off unreacted N-methyl-ε-caprolactam. Thereafter, a transparent polyamide elastomer chip was obtained in the same manner as in the method of B1. This elastomer had a polyamide segment content of 35% by weight, polyamide (2) / polyamide (1) = 0, and a relative viscosity of 1.8. <Polyamide elastomer B-5> In a reactor similar to the above, 114.0 g (76.5 mmol) of polyoxyethylene glycol having a number average molecular weight of 1490, sebacic acid 4
6.9 g (232 mmol), caprolactam 45.0
g (398 mmol), 30.6 g (153 mmol) of 4,4'-diaminodiphenyl ether, and 1,
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene
After charging 4 g and heating to 120 ° C. to melt, 3 g at 260 ° C. while flowing nitrogen gas at 100 ml / min.
Allowed to react for hours. Hereinafter, in the same manner as in the method of B1,
A transparent polyamide elastomer chip was obtained.

This elastomer had a polyamide segment content of 43% by weight, polyamide (2) / polyamide (1) = 1.5, and a relative viscosity of 1.9. <Polyamide elastomer B-6> A 1-liter reactor equipped with a stirrer and a nitrogen inlet was charged with a number-average molecular weight of 1
Polyoxyethylene 13 whose diamine is a diamine 13
0.0 g (129 mmol), 54.0 g sebacic acid
(267 mmol), 200 g of sulfolane and 1,
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene
After charging 4 g and heating to 120 ° C. to melt,
32.5 g of 4'-diphenylmethane diisocyanate
(130 mmol), and reacted at 200 ° C. for 2 hours while flowing nitrogen gas at 100 ml / min.

Next, after the temperature was raised to 260 ° C. and the reaction was further performed for 2 hours, the molten polymer was taken out of the reactor and recovered, washed with water and dried to obtain a transparent polyamide elastomer chip. This elastomer has a polyamide segment content of 35% by weight, polyamide (2) / polyamide (1) = 0, and a relative viscosity of 2.
It was one. <Polyamide elastomer B-7> 100.0 g (67.1 mmol) of polyoxyethylene glycol having a number average molecular weight of 1490 was charged into the same reactor as in the case of B-1.
9.90 g (67.8 mmol) of adipic acid, 62.0 g (549 mmol) of caprolactam, and 1,3,3
5-trimethyl-2,4,6-tris (3,5-di-t
-Butyl-4-hydroxybenzyl) benzene 0.4 g
And reacted at 250 ° C. for 3 hours while flowing nitrogen gas at 50 ml / min.

Then, the pressure was gradually reduced to remove unreacted caprolactam, the pressure was returned to normal pressure, 0.4 g of zirconium tetrabutoxide was added, and the reaction was carried out at 260 ° C. and 1 Torr for 2.5 hours. Was. Thereafter, a transparent polyamide elastomer chip was obtained in the same manner as in the case of B1. This elastomer had a polyamide segment content of 50% by weight, did not contain polyamide (1), and had a relative viscosity of 2.1. That is, this elastomer is out of the range of the component [B] in the present invention.

The polyamide elastomers thus obtained, the following polycarbonate resins, thermoplastic resins, surfactants, and other additives are shown in Table 1 below.
The composition mixed with the composition of
C., and the resulting strand was cooled with water and pelletized. After drying the obtained pellets, injection molding was performed under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 120 ° C.

<Polycarbonate resin> Trade name "Panlite L-1285" (Teijin Chemical Co., Ltd.)
<Thermoplastic resin> C-1: ABS resin Trade name "Stylac ABS A-4130" (manufactured by Asahi Kasei Corporation) C-2: Polyester resin Trade name "Mitsui PET J125" (Mitsui Pet Resin Co., Ltd.) C- 3 ): Carboxyl group-containing polystyrene (polystyrene obtained by copolymerizing 8% by weight of methacrylic acid) <Surfactant> D-1: Sodium dodecylbenzenesulfonate (manufactured by Takemoto Yushi Co., Ltd.) D-2: Polystyrene Oxyethylene alkyl allyl ether (manufactured by Kao Corporation) <Additive (heat-resistant stabilizer)> Tris (2,4-di-t-butylphenyl) phosphate trade name "Irgafos 168" (Ciba Geigy Corporation)
Made)

[0054]

[Table 1]

The sample molded as described above was
After standing for 2 days at 55 ° C. and 55% RH, each physical property was measured as follows. <Surface resistivity> A sample molded to a size of 50 × 50 × 2 mm was washed with running water for 1 minute, and then the attached water was wiped off.
The surface resistivity was determined by measuring the resistance value when a voltage of 500 V was applied using a 651 electrode and a shield box and an electrode holder manufactured by Ando Electric Co., Ltd.

<Izod impact strength> ASTM D-2
According to No. 56, a 1 / 8-inch-thick notched test piece was used in an environment at 23 ° C. and 55% RH. <Flexural modulus> 1 according to ASTM D-790
Using a / 8 inch test piece, the measurement was performed in an environment of 23 ° C. and 55% RH.

<Surface Condition> A JIS No. 1 test piece was pulled on a tensile tester at a speed of 50 mm / min.
The state at the time of breakage was visually observed, and it was examined whether or not delamination occurred. <Thermal stability> The pellet before injection molding and the pellet obtained by heating the pellet at a temperature of 280 ° C. for 10 minutes in an inert gas stream, then cooling to room temperature, and then pulverizing the pellet were 1 mm in diameter and 10 mm in length. Temperature 280
The melt flow rate (MFR) was measured at a temperature of 2.6 ° C. and a load of 2.6 kg, and the respective values were compared.

The results are shown in Table 2 below.

[0059]

[Table 2]

As can be seen from Table 2, in each of the examples of the present invention, it was found that the values of the Izod impact strength and the flexural modulus were well maintained while the surface resistivity was kept low. . That is, the molded article obtained from the polycarbonate resin composition of the present invention has sufficient mechanical properties while having excellent antistatic properties. In addition, these molded products have good surface conditions, and it is understood from the MFR values that they have excellent thermal stability during molding.

On the other hand, in Comparative Example 1, since the content of the polyamide elastomer was as small as 3.0% by weight, the surface resistivity was large and the antistatic performance was poor. In Comparative Example 2, the content of the polyamide elastomer was 40.
Since it is as large as 0% by weight, the flexural modulus becomes small, and the mechanical strength of the molded body decreases. In Comparative Examples 3 and 4, the polyamide elastomer was out of the range of the component [B] in the present invention (B-7 containing no amide (1)). In Comparative Example 3, delamination occurred. In Comparative Example 4, After the heat treatment, the MFR value is greatly reduced.

[0062]

As described above, according to the present invention, a polycarbonate elastomer containing a specific polyamide segment and a specific polyoxyalkylene segment is contained in a polycarbonate resin.
It is possible to provide a polycarbonate resin composition which is excellent in antistatic properties when formed into a molded article, has good thermal stability, and hardly causes delamination.

In the composition according to the third aspect, the polyamide segment is further limited by the first aspect.
The effect given to the compositions of the above and 2 can be remarkable. As a result, it is suitably used as an antistatic material for various components such as electronic products, home appliances, and OA equipment.

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Claims (3)

(57) [Claims] 1. [A] polycarbonate resin component 60
And (B) (a) a polyamide (1) represented by the following formula (1):
Polyamide segments of, - [C (= O) -R 1 -C (= O) -NH-R 2 -NH] n 1 - ...... (1) ( where, R _1, R ₂ are each a divalent Wherein at least one of R ₁ and R ₂ is an aromatic hydrocarbon residue, and the average value of n _{1 in} all polyamide segments is 1 to 20.) (b) 50 weight % Or more polyoxyethylene,
A polyoxyalkylene segment having a number average molecular weight of 500 to 6000, and (c) a dicarboxylic acid, a diamine, or a diisocyanate linking the polyamide segment and the polyoxyalkylene segment,
A polycarbonate resin composition comprising 5 to 40% by weight of a polyamide elastomer component having a total content of (A) and (C) of 20 to 70% by weight. 2. [A] polycarbonate resin component 60
And (B) (a) a polyamide (1) represented by the following formula (1):
And a polyamide segment comprising a polyamide (2) represented by the following formula (2) and having a molar ratio of the polyamide (2) to the polyamide (1) of 10 or less:-[C (= O) -R _{1 -C (= O) -NH-} R 2 -NH] n 1 - ...... (1) - [C (= O) -R 3 -NH] n 2 - ...... (2) ( where, R _1, R ₂ is a divalent hydrocarbon residue, at least one of R ₁ and R ₂ is an aromatic hydrocarbon residue, and R ₃ is a divalent hydrocarbon residue having 5 to 11 carbon atoms. And the average value of n ₁ and n ₂ in all the polyamide segments is 1 to 20.) (b) contains 50% by weight or more of polyoxyethylene;
A polyoxyalkylene segment having a number average molecular weight of 500 to 6000, and (c) a dicarboxylic acid, a diamine, or a diisocyanate linking the polyamide segment and the polyoxyalkylene segment,
A polycarbonate resin composition comprising 5 to 40% by weight of a polyamide elastomer component having a total content of (A) and (C) of 20 to 70% by weight. 3. The component (B) wherein R _{1 in the} formula (1) representing the polyamide (1) in the component (A) is a divalent aliphatic hydrocarbon residue, and R ₂ is a divalent aromatic hydrocarbon residue. The polycarbonate resin composition according to claim 1, wherein the composition is a hydrogen residue.