JP2003226803A - Polycarbonate resin composition and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition having excellent solvent resistance, compatibility (without delamination or defective appearance), high fluidity, flame retardance, sliding properties, weld strength, or the like, and to provide a molded product of the resin composition. <P>SOLUTION: The polycarbonate resin composition comprises (1) 60-97 mass% of a polycarbonate resin composed of (A) 10-100 mass% of a polycarbonate resin having molecular terminals blocked with phenoxy groups each having a 10-35C alkyl group and (B) 0-90 mass% of a polycarbonate resin having the molecular terminals blocked with phenoxy groups each having a 1-9C alkyl group and (2) 3-40 mass% of a polyolefinic resin. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polycarbonate resin composition, and more particularly, to a solvent composition which is composed of an aromatic polycarbonate resin and a polyolefin resin, has good compatibility, does not suffer from delamination or poor appearance, and is difficult to obtain. The present invention relates to a polycarbonate resin composition having excellent flammability and sliding properties, and a molded product of the resin composition.

[0002]

2. Description of the Related Art Polycarbonate resins are engineering plastics having excellent transparency and impact resistance, but have the drawback that they are highly hygroscopic and are easily attacked by organic solvents and the like. In order to improve such disadvantages, an invention relating to a blend of a polycarbonate resin and a polyolefin resin has been proposed. For example, Japanese Patent Publication No. 40-1
Japanese Patent Publication No. 3663 discloses a blend of a polycarbonate resin and a polyethylene resin, and Japanese Patent Publication No. 40-13664 discloses a blend of a polycarbonate resin and a polypropylene resin. However, since these two resins have low compatibility with each other, delamination occurs with a simple blend, and the molding appearance is poor, so that they have not been put to practical use.

[0003] In order to improve the compatibility of these two components, attempts have been made to coexist with a compatibilizer.
For example, JP-A-59-223742 discloses a method using a modified polypropylene resin and JP-A-3-2690.
No. 34 proposes a method using a modified polypropylene resin and an oxazoline group-containing resin. JP 6
JP-A-3-215750 discloses a method of using an epoxy-modified polypropylene-based resin and a polycarbonate-based resin having a terminal carboxyl group when blending a bisphenol A-type polycarbonate-based resin and a polypropylene-based resin, and JP-A-6-220262 discloses a polycarbonate-based resin. When blending with polyolefin resin,
A method using a carboxylic acid-modified polycarbonate resin and an epoxy-modified polyolefin resin has been proposed.
However, by imparting a functional group such as carboxylic acid to the terminal of the polycarbonate resin, the compatibility is improved, but conversely, the thermal stability is reduced, which causes a reduction in the molecular weight and coloring of the polycarbonate resin during molding. There is. Japanese Patent Laid-Open No. 7-10216 discloses a technique of adding an inorganic filler to a polycarbonate resin and a polyolefin resin.
Although it is disclosed in JP-A-5, it does not describe compatibilization.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a solvent-resistant,
An object of the present invention is to provide a polycarbonate resin composition having excellent compatibility (no delamination or poor appearance), high fluidity, slidability, flame retardancy, weld strength, and the like, and a molded article of the resin composition. Is what you do.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, the selection of a specific polycarbonate resin and the use of a polyolefin resin, a flame retardant, a fluorine resin, and an inorganic filler have been considered. The present inventors have found that a resin composition comprising the combination is excellent in solvent resistance, sliding properties and flame retardancy without delamination or poor appearance, and completed the present invention.

That is, the present invention provides: (1) (A) 10 to 100% by mass of a polycarbonate resin whose molecular terminal is sealed with a phenoxy group having an alkyl group having 10 to 35 carbon atoms and (B) a molecular terminal having an alkyl group having 1 to 9 carbon atoms. 1. A polycarbonate resin composition comprising 60 to 97% by mass of a polycarbonate resin sealed with a phenoxy group and 0 to 90% by mass, and (2) 3 to 40% by mass of a polyolefin resin. The above-mentioned 1., wherein the polyolefin resin is at least one resin selected from a polyethylene resin and a polypropylene resin. 2. The polycarbonate resin composition according to the above, The above 1. Or 2. 3. A molded article comprising the polycarbonate resin composition according to any one of the above, 2. The molded article is a housing or part of an electric / electronic device. Related to molded articles.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polycarbonate resin composition of the present invention comprises (1) (A)
Polycarbonate resins 10 to 10 having molecular ends capped with a phenoxy group having an alkyl group having 10 to 35 carbon atoms
0-90% by mass of a polycarbonate resin containing 0-90% by mass of 0% by mass and (B) 0-90% by mass of a polycarbonate resin capped with a phenoxy group having an alkyl group having 1-9 carbon atoms, and (2) polyolefin System resin 3 ~
It is composed of 40% by mass.

[0008] The polycarbonate resin composition of the present invention comprises
As the component (A), the molecular terminal was sealed with a phenoxy group having an alkyl group having 10 to 35 carbon atoms (hereinafter, referred to as a “component (A)”).
Abbreviated as "alkylphenoxy modification having 10 to 35 terminal carbon atoms". ) A polycarbonate resin is used, and as a component (B), a molecular terminal is sealed with a phenoxy group having an alkyl group having 1 to 9 carbon atoms (hereinafter, referred to as “terminal carbon number 1 to 1”). 9) is characterized by using a polycarbonate resin.

The (A) alkylphenoxy-modified polycarbonate resin having 10 to 35 carbon atoms is obtained by using an alkylphenol having an alkyl group having 10 to 35 carbon atoms as a terminal stopper in the production of the polycarbonate resin. Can be. These alkylphenols are not particularly limited, and decylphenol, undecylphenol, dodecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol, hexadecylphenol, heptadecylphenol, octadecylphenol, nonadecylphenol, eicosylphenol Phenol and the like.

The alkyl group of these alkylphenols may be at any of o-, m- and p-positions with respect to the hydroxyl group, but is preferably at the p-position. The alkyl group may be linear, branched or a mixture thereof. As this substituent, at least one may be the above-mentioned alkyl group having 10 to 35 carbon atoms, and the other four are not particularly limited, and may be an alkyl group having 1 to 9 carbon atoms, or an aryl group having 6 to 20 carbon atoms. It may be a group, a halogen atom or unsubstituted.

The alkylphenoxy-modified polycarbonate resin having 10 to 35 terminal carbon atoms may be any of the polycarbonate resins described below. For example, in order to control the molecular weight in the reaction of dihydric phenol with phosgene or a carbonate compound. In addition, these carbon number 10
This is obtained by using an alkylphenol having an alkyl group of from 35 to 35 as a terminal blocking agent.

For example, it can be obtained by reacting a dihydric phenol with phosgene or a polycarbonate oligomer in a methylene chloride solvent in the presence of a triethylamine catalyst and the alkylphenol having an alkyl group having 10 to 35 carbon atoms. Here, the alkylphenol having an alkyl group having 10 to 35 carbon atoms seals one end or both ends of the polycarbonate resin to modify the end. In this case, the terminal modification is at least 20%, preferably at least 50%, based on all terminals. That is, the other terminal may be a hydroxyl terminal or a terminal sealed by using another terminal blocking agent described below.

Here, as other terminal blocking agents, phenol, p-tert-butylphenol, p-tert-butyl, which are commonly used in the production of polycarbonate resins, are used.
Phenols such as octylphenol and p-cumylphenol are exemplified.

Further, (B) an alkylphenoxy-modified polycarbonate resin having a terminal carbon number of 1 to 9 is also used as a terminal stopper in the production of the polycarbonate resin.
It can be obtained by using an alkylphenol having 9 alkyl groups. Examples of the alkylphenol having an alkyl group having 1 to 9 carbon atoms include p-tert-
Phenols such as butylphenol, p-tert-octylphenol, p-cumylphenol and the like can be mentioned. However, the other four substituents of the alkylphenol are
It may be an aryl group having 6 to 20 carbon atoms other than an alkyl group, a halogen atom or unsubstituted.

The polycarbonate resin in which the molecular terminal constituting the component (1) of the polycarbonate resin composition of the present invention is capped with a phenoxy group having an alkyl group (hereinafter may be abbreviated as "terminal alkylphenoxy modification"). There is no particular limitation, and various types can be mentioned.
Usually, an aromatic polycarbonate produced by reacting a dihydric phenol with a carbonate precursor can be used. That is, a product produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method, that is, a reaction of a dihydric phenol with phosgene, or a transesterification method of a dihydric phenol with diphenyl carbonate or the like is used. Can be.

As the dihydric phenol, various ones can be mentioned. In particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis ( 4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-
3,5-dimethylphenyl) propane, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl)
Cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis ( 4-hydroxyphenyl) ketone and the like.

Particularly preferred dihydric phenols include:
It is based on bis (hydroxyphenyl) alkane, particularly bisphenol A. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. Specific examples include phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate. In addition, examples of the dihydric phenol include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone or in combination of two or more.

The terminal alkylphenoxy-modified polycarbonate resin may have a branched structure. Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″. -Tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, phloroglucin, trimellitic acid and isatin bis (o-
Cresol).

The polycarbonate resin composition of the present invention comprises:
As this molecular weight regulator, the above-mentioned carbon number 1-9 or 10
It is characterized by being composed of a terminal alkylphenoxy-modified polycarbonate resin obtained by capping the molecular terminal using an alkylphenol having an alkyl group of from 35 to 35.

The terminal alkylphenoxy-modified polycarbonate resin used in the present invention may be a polymer of polycarbonate in the presence of a bifunctional carboxylic acid such as terephthalic acid or polymethylenedicarboxylic acid or an ester precursor such as an ester-forming derivative thereof. Or a polyester-polycarbonate copolymer obtained by performing
It may be a mixture of various terminal alkylphenoxy-modified polycarbonate resins.

Further, as the alkyl-terminated phenoxy-modified polycarbonate-based copolymer, in particular, a polycarbonate-polyorganosiloxane copolymer whose molecular terminal is capped with a phenoxy group having an alkyl group (hereinafter referred to as “terminated-alkyl-phenoxy-modified polycarbonate”) Resin-PD
It may be abbreviated as “MS copolymer”. ). The terminal alkylphenoxy-modified polycarbonate resin-PDMS copolymer is composed of a polycarbonate part and a polyorganosiloxane part. For example, a polyorganosiloxane having a reactive group at a terminal constituting a polycarbonate oligomer and a polyorganosiloxane part ( Polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, etc.) in a solvent such as methylene chloride, add an aqueous sodium hydroxide solution of bisphenol A, and carry out an interfacial polycondensation reaction using a catalyst such as triethylamine. Can be manufactured. These terminal alkylphenoxy-modified polycarbonate resin-PDMS copolymers are described in, for example, JP-A-3-292359, JP-A-4-202465, JP-A-8-81620, and JP-A-8-3021.
No. 78, and Japanese Patent Application Laid-Open No. 10-7897.

The degree of polymerization of the polycarbonate portion of the terminal alkylphenoxy-modified polycarbonate resin-PDMS copolymer is preferably 3 to 100, and the degree of polymerization of the polydimethylsiloxane portion is preferably about 2 to 500.
The content of polydimethylsiloxane in the terminal alkylphenoxy-modified polycarbonate resin-PDMS copolymer (including bisphenol A polycarbonate as a by-product) is generally 0.2 to 30% by mass, preferably 0.3 to 30% by mass. The range is 20% by mass. Alkyl-terminated phenoxy-modified polycarbonate resin used in the present invention, alkyl-terminated phenoxy-modified polycarbonate resin-P
The viscosity average molecular weight of a copolymer such as a DMS copolymer is usually 1
000-100,000, preferably 11,000
~ 40,000, particularly preferably 12,000 ~ 30,
000. Here, these viscosity average molecular weights (M
v) is the viscosity of the methylene chloride solution at 20 ° C. measured using an Ubbelohde viscometer,
[Η] is obtained and calculated by the following equation.

[Η] = 1.23 × 10 ⁻⁵ Mv ^0.83 The polycarbonate resin composition of the present invention includes (1)
As the components (A) and (B), a mixed resin with an alkyl-terminated phenoxy-modified polycarbonate resin, an alkyl-terminated phenoxy-modified polycarbonate-based resin-PDMS copolymer, an alkyl-terminated phenoxy-modified bisphenol A polycarbonate, or the like can also be used. In this case, it is blended so that the content of polydimethylsiloxane in the entire polycarbonate resin in the component (1) is 0.1 to 10% by mass, preferably 0.3 to 5% by mass.

(B) Polyolefin Resin The polyolefin resin as the component (2) of the polycarbonate resin composition of the present invention includes various resins such as polyethylene resin, polypropylene resin and poly-1-butene resin. Polyolefin resins can be mentioned. Here, as the polyethylene resin, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene and ethylene and other α
-Copolymers with olefins and the like. Further, as the polypropylene resin, including crystalline propylene homopolymer, crystalline propylene-ethylene block and random copolymer, crystalline propylene-ethylene-α-olefin copolymer and these crystalline propylene polymers And mixtures of elastomers. These polyolefin resins can be used alone or as a mixture of two or more. The melt flow rate (MFR) (230 ° C., 2.16 kg) of these polyolefin-based resins and a mixture thereof is preferably 0.1 to 70 g / 10 minutes, more preferably 0.1 to 70 g / 10 minutes.
５０50 g / 10 min. If it is 0.1 g / 10 min or less, molding becomes difficult, and if it is 70 g / 10 min or more, mechanical properties such as impact resistance are significantly reduced.

The polycarbonate resin composition of the present invention is prepared by mixing (1) an alkylphenoxy-modified polycarbonate resin with (2) a polyolefin resin to obtain compatibility, solvent resistance and slidability of the resin composition. Is to improve. Here, in the (1) terminal alkylphenoxy-modified polycarbonate resin, (A) the alkylphenoxy-modified polycarbonate resin having 10 to 35 terminal carbon atoms is 10 to 100% by mass, preferably 20 to 1% by mass.
00 mass%, more preferably 30 to 100 mass%,
(B) The alkylphenoxy-modified polycarbonate resin having 1 to 9 terminal carbons is 0 to 90% by mass, preferably 0 to 90% by mass.
80 mass%, more preferably 0 to 70 mass% is blended. If the content of the polycarbonate resin (A) is less than 10% by mass, the compatibility is insufficient, delamination occurs, and the impact strength decreases. In the polycarbonate resin composition of the present invention, the compounding ratio of the component (1) and the component (2) is as follows:
Component (1) the terminal alkylphenoxy-modified polycarbonate resin is 60 to 97% by mass, preferably 70 to 95% by mass, more preferably 75 to 90% by mass, and the polyolefin resin of the component (2) is 3 to 40% by mass, Preferably 5
-30 mass%, more preferably 10-25 mass%. Here, when the terminal alkylphenoxy-modified polycarbonate resin of the component (1) is less than 60% by mass, surface layer peeling and poor appearance occur. If it exceeds 97% by mass, improvement in solvent resistance and fluidity is insufficient. When the content of the polyolefin resin (2) is less than 3% by mass, the solvent resistance is insufficient. In this case, as the polyolefin resin of the component (2), a polyethylene resin or a polypropylene resin is preferably used.

The polycarbonate resin composition of the present invention can contain the following additive components as required. For example, phenol-based, phosphorus-based, sulfur-based antioxidants, antistatic agents, polyamide polyether block copolymers (providing permanent antistatic properties), benzotriazole-based and benzophenone-based ultraviolet absorbers, hindered amine-based light stabilizers (Weathering agent), plasticizer, antibacterial agent, compatibilizer,
Coloring agents (dyes and pigments); The amounts of these components are not particularly limited as long as the characteristics of the polycarbonate resin composition of the present invention are maintained. These compounding ratios are appropriately determined in consideration of the molecular weight of the terminal alkylphenoxy-modified polycarbonate resin, the type of the polyolefin resin, the melt flow rate, the use of the molded product, the size, the thickness, and the like.

Next, a method for producing the polycarbonate resin composition of the present invention will be described. The polycarbonate resin composition of the present invention comprises (1) components (A) and (B),
(2) It is obtained by blending the components in the above-mentioned ratio and, if necessary, the above-mentioned additive components in a predetermined ratio, and kneading them. The compounding and kneading at this time are usually used equipment, for example, premixed with a ribbon blender, a drum tumbler or the like, and a Banbury mixer, a single screw extruder, a twin screw extruder, a multi-screw extruder and It can be performed by a method using a coneder or the like. The heating temperature during kneading is appropriately selected usually in the range of 240 to 300 ° C. As the melt-kneading molding, it is preferable to use an extruder, particularly a vent-type extruder. In addition, the components other than the terminal alkylphenoxy-modified polycarbonate resin can be added as a master batch.

The polycarbonate resin composition of the present invention comprises:
A molded product is directly manufactured using the above-described melt-kneading molding machine, or the obtained pellet is used as a raw material, and is used as an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method. Various molded products can be manufactured by a method and a foam molding method. However, a pellet-shaped molding raw material is produced by the above-mentioned melt-kneading method, and then the pellets can be used particularly suitably for production of an injection-molded article by injection molding or injection compression molding. In addition, as an injection molding method, gas injection molding for preventing sink marks on the appearance or for reducing the weight can be employed.

Examples of molded articles obtained from the polycarbonate resin composition of the present invention include copying machines, fax machines, televisions, radios, tape recorders, video decks, personal computers, printers, telephones, information terminals, refrigerators, microwave ovens and the like. -Used in housings or parts of electronic equipment, and also in other fields such as automobile parts.

[0030]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Production Example 1 A mixture of 1-eicosene, 1-docosene and 1-tetracosene [composition ratio (mol%); 53.3: 40.2: 6.5] was placed in a 260 liter reaction vessel equipped with a stirrer for synthesis of monoalkylphenol (AP2024). ] 57.
A reaction raw material and a catalyst were charged as 3 kg, 70 kg of phenol and 7 kg of galeonite # 136 (manufactured by Mizusawa Kagaku Kogyo KK), and the mixture was reacted at 145 ° C. for 80 minutes with stirring in a nitrogen stream. After completion of the reaction, the catalyst was separated by filtration and then separated from heavy components such as phenol and dialkylphenol by distillation under reduced pressure to purify monoalkylphenol (AP2024). Purified A
As a result of analyzing P2024 by gas chromatography, it contained phenol at 500 ppm and no dialkylphenol peak was detected. A obtained
The composition ratio (%) of the ortho, para and meta isomers of P2024 is 50: 48: 2 (mol%), and APHA
Was 10. In addition, the average carbon number of the alkyl group of AP2024 was 21.

2. Preparation of terminal AP2024-modified polycarbonate resin Synthesis of polycarbonate oligomer Bisphenol A was dissolved in a 5.6% by mass aqueous sodium hydroxide solution so that bisphenol A concentration became 13.5% by mass to prepare a sodium hydroxide aqueous solution of bisphenol A. did. Phosgene was continuously supplied at a flow rate of 40 liters / hr of an aqueous sodium hydroxide solution of bisphenol A and 15 liters / hr of methylene chloride to a tubular reactor having an inner diameter of 6 mm and a length of 30 m at a flow rate of 4.0 kg / hr. The tubular reactor had a jacket portion, and the temperature of the reaction solution was kept at 40 ° C. or lower by passing cooling water through the jacket. The reaction solution exiting the tubular reactor was continuously introduced into a baffled tank reactor having an inner volume of 40 liters equipped with a swept wing, and further, 2.8 liters of an aqueous sodium hydroxide solution of bisphenol A was added thereto. hr, 25% by mass aqueous sodium hydroxide solution 0.07 L / hr, water 17 L / hr, and 1% by mass triethylamine aqueous solution 0.64
The reaction was carried out by supplying 2.15 l / hr of a 10.3 mass methylene chloride solution of the AP2024 described above. The reaction solution overflowing from the tank reactor was continuously withdrawn, and the aqueous phase was separated and removed by standing, and the methylene chloride phase was collected. The concentration of the polycarbonate oligomer thus obtained was 323 g / l, and the concentration of the chloroformate group was 0.69 mol / l.

The oligomer solution 10 was placed in a 50-liter tank reactor equipped with a synthetic baffle of polycarbonate, two paddle-type stirring blades, and a cooling jacket.
Liter, methylene chloride 6.15 liter, AP2
024158 g and 3.84 ml of triethylamine were charged, and sodium 226 dithionite was added thereto.
mg of a 6.4 mass% aqueous sodium hydroxide solution (1,720 g) was added thereto with stirring, and the reaction was carried out for 20 minutes. In this reaction step, the reaction was controlled by cooling so that the reaction temperature did not become 20 ° C. or higher. Next, an aqueous sodium hydroxide solution of bisphenol A (a solution in which 331 g of NaOH and 1.32 g of sodium dithionite are dissolved in 4.8 g of water and 660 g of bisphenol A) is added, and the mixture is stirred at 300 rpm for 40 minutes. A polymerization reaction was performed.

Washing Step To dilute, add 10 liters of methylene chloride and stir for 20 minutes to separate an organic phase containing polycarbonate and an aqueous phase containing excess bisphenol A and sodium hydroxide. It was extracted from the lower part of the vessel and isolated. A solution of the polycarbonate thus obtained in methylene chloride was successively added to 15% by volume of 0.03
Washed with an aqueous solution of sodium hydroxide (mol / liter), hydrochloric acid (0.2 mol / liter) and then twice with pure water,
It was confirmed that the electric conductivity in the aqueous phase after washing was 0.01 μS / m or less.

Flaking Step The methylene chloride solution of polycarbonate obtained by washing is concentrated and pulverized, and the obtained flakes are reduced to 100 ° C. under reduced pressure.
And dried.

Production Example 2 1. Production of Polycarbonate Modified with Terminal p-Dodecylphenoxy Group (PDDP) Synthesis of Polycarbonate Oligomers In 400 liters of a 5% by mass aqueous sodium hydroxide solution,
60 kg of bisphenol A was dissolved to prepare an aqueous sodium hydroxide solution of bisphenol A. Then, the sodium hydroxide aqueous solution of bisphenol A kept at room temperature was passed through an orifice plate at a flow rate of 138 liters / hour and methylene chloride at a flow rate of 69 liters / hour through a tubular reactor having an inner diameter of 10 mm and a length of 10 m. Introduce,
Phosgene was blown into the mixture at a flow rate of 10.7 kg / hour and reacted continuously for 3 hours. The tubular reactor used here was a double tube, and the outlet temperature of the reaction solution was kept at 25 ° C. by passing cooling water through the jacket portion. or,
The pH of the discharged liquid was adjusted to be 10 to 11. The reaction solution thus obtained was allowed to stand, whereby the aqueous phase was separated and removed, and the methylene chloride phase (220 liters) was collected to obtain a polycarbonate resin oligomer (concentration: 3).
17 g / l). The degree of polymerization of the polycarbonate resin oligomer obtained here was 2 to 4, and the concentration of the chloroformate group was 0.7 normal.

Synthesis of Polycarbonate 10 liters of the above-mentioned oligomer solution was placed in a container with a stirring volume of 50 liters in internal volume, and p-dodecylphenol (P
162 g of (DDP) (containing a branched dodecyl group) [manufactured by Yuka Schenectady] was dissolved. Next, an aqueous solution of sodium hydroxide (53 g of sodium hydroxide, 1 liter of water)
And 5.8 cc of triethylamine, and add
The mixture was stirred at rpm and reacted. Thereafter, a sodium hydroxide solution of bisphenol A (720 g of bisphenol A, 412 g of sodium hydroxide, 5.5 liter of water) was mixed with the above system, and 8 liter of methylene chloride was added.
The reaction was stirred at 500 rpm for a time. After the reaction, 7 liters of methylene chloride and 5 liters of water were added, and the mixture was stirred for 10 minutes at 500 rpm. After the stirring was stopped, the mixture was allowed to stand, and the organic phase and the aqueous phase were separated. The obtained organic phase was washed with 5 liters of alkali (0.03 N-NaOH), 5 liters of acid (0.2 N-hydrochloric acid) and 5 liters of water (twice). Thereafter, the methylene chloride was evaporated to obtain a flaky polymer. The viscosity average molecular weight is 17,500
Met.

Examples 1-4 and Comparative Examples 1-3 Each component was blended at the ratios shown in Table 1 and supplied to a vented twin-screw extruder (model name: TEM35, manufactured by Toshiba Machine Co., Ltd.). The mixture was melt-kneaded at 280 ° C and pelletized. In all Examples and Comparative Examples, Irganox 1076 (Ciba Specialty Co., Ltd.) was used as an antioxidant with respect to 100 parts by mass of the total amount of the components (1) and (2).
0.2 parts by mass of Chemicals Co., Ltd.) and 0.1 part by mass of ADK STAB C (manufactured by Asahi Denka Kogyo Co., Ltd.). The obtained pellet was dried at 120 ° C. for 12 hours, and then injection molded at a molding temperature of 270 ° C. and a mold temperature of 80 ° C. to obtain a test piece. The performance was evaluated by the following various tests using the obtained test pieces, and the results are shown in Table 1.

The molding materials used and the method of evaluating the performance are described below. (1) Terminal alkylphenoxy-modified polycarbonate resin PC-1: terminal AP2024 obtained in Production Example 1 above
Modified polycarbonate resin PC-2: p-dodecylphenoxy (PDDP) terminal-modified polycarbonate resin PC-3 obtained in Production Example 2 above: Tafflon A1900 (manufactured by Idemitsu Petrochemical Co., Ltd.): bisphenol A polycarbonate resin, MF
R = 19 g / 10 min (temperature: 300 ° C., load: 11.7)
7N), viscosity average molecular weight: 19,000, terminal p-te
rt-butylphenoxy group-modified polycarbonate resin (B) polyolefin resin PP: homopolypropylene, Idemitsu J-700M (made by Idemitsu Petrochemical Co., Ltd.) PE: low-density polyethylene, Tosoh 291A (made by Tosoh Corporation)

[Performance Evaluation Method] (1) IZOD (Izod Impact Strength) According to ASTM D256, 23 ° C. (wall thickness: 3.2 m)
m), unit: kJ / m ² (2) Weld strength Tensile strength test specimens were molded with a two-point gate using a die, and the tensile strength was measured. (3) Friction coefficient Sliding characteristics A contact surface between a disk and a cylinder when a plate-shaped test piece is rotated under a load of 2 kg in accordance with the method A of JIS K7218 (test method for sliding abrasion of plastic). The average value (kg) of the maximum frictional force generated over 5 minutes was measured. The coefficient of friction was evaluated as friction coefficient (kg) / load 2 kg. (4) Q value (flow value) Measured at a load of 160 kg and a temperature of 280 ° C. in accordance with JIS K7210. (5) Grease resistance The grease resistance was based on the chemical resistance evaluation method (critical distortion due to 1/4 ellipse). A sample piece (thickness: 3 mm) was fixed to a jig (1/4 elliptical surface) shown in FIG. 1 (perspective view), and Albanian grease (manufactured by Showa Shell Sekiyu KK) was applied to the sample piece and held for 48 hours. . The minimum length (X) at which cracks occurred was read, and the critical strain (%) was determined from the following equation. Critical strain (%) = (b / 2a ² ) [1- [1 / a ² − (b ²
/ A ⁴ )] X ² ] ⁻³ / ² · ^t (t: thickness of test piece) (6) Compliant with flame-retardant UL94 combustion test (test piece thickness: 1.5 mm) Note that V-2 and NG are , V-0, V-1, and V-2. (7) The cut surface of the surface layer peeled / appeared molded product was visually observed. 〇: good without surface layer peeling, □: slight surface layer peeling, ×: surface layer peeling

[0040]

[Table 1]

From the results in Table 1, it can be seen that the molded article made of the polycarbonate resin composition of the present invention has a terminal carbon number of 10 to 35.
When the alkylphenoxy-modified polycarbonate resin and the polyolefin-based resin are alloyed, the compatibility is improved (prevention of laminar peeling), and the impact strength and weld strength are also increased. It is also excellent in solvent resistance, slidability and melt fluidity. In addition, if only a phenoxy group-capped polycarbonate resin having an alkyl group having 4 carbon atoms at the molecular end is used, the compatibility is low (lamellar peeling), and the impact strength and the weld strength are reduced. Further, when the polyolefin resin is present in a large amount, impact strength and weld strength decrease.

[0042]

According to the present invention, a polycarbonate resin composition having good compatibility and having excellent solvent resistance, flame retardancy and sliding properties without delamination and poor appearance, and a molded article of the resin composition are provided. Obtainable.

[Brief description of the drawings]

FIG. 1 is a perspective view of a test piece mounting jig for evaluating the grease resistance of the composition of the present invention.

Continuation of front page    F term (reference) 4F071 AA15 AA20 AA50 AE05 AF23                       AF28 AH12 AH19 BA01 BB05                 4J002 BB032 BB033 BB052 BB053                       BB122 BB123 BB142 BB143                       BB152 BB153 CG011 CG012                       CG021 CG022 FD030 FD050                       GC00

Claims (4)

[Claims] (1) (1) (A) a molecular terminal having 10 to 3 carbon atoms
10 to 100% by mass of a polycarbonate resin capped with a phenoxy group having an alkyl group of 5 and (B) 0 to 90% by mass of a polycarbonate resin capped at a molecular terminal by a phenoxy group having an alkyl group having 1 to 9 carbon atoms % Of a polycarbonate resin composed of 60 to 97% by mass and (2) 3 to 40% by mass of a polyolefin resin. 2. The polycarbonate resin composition according to claim 1, wherein the polyolefin resin is at least one resin selected from a polyethylene resin and a polypropylene resin. 3. A molded article comprising the polycarbonate resin composition according to claim 1. 4. The molded article according to claim 3, wherein the molded article is a housing or a part of an electric / electronic device.