WO2010101041A1

WO2010101041A1 - Polycarbonate resin composition and molded articles using same

Info

Publication number: WO2010101041A1
Application number: PCT/JP2010/052658
Authority: WO
Inventors: 佑介青木; 中江　貢
Original assignee: 出光興産株式会社
Priority date: 2009-03-04
Filing date: 2010-02-22
Publication date: 2010-09-10
Also published as: JP2010202806A; TW201038666A; JP5431751B2; TWI443150B

Abstract

Provided is a polycarbonate resin composition which improves in sliding properties without undergoing the deterioration of mechanical properties. Also provided are molded articles using the polycarbonate resin composition. Disclosed is a polycarbonate resin composition characterized by: comprising 30 to 100 parts by mass of (A) polycarbonate/ polyorganosiloxane copolymer having a specific structure and 70 to 0 parts by mass of (B) an aromatic polycarbonate resin in a sum total of 100 parts by mass; and further containing (C) a silicone oil which exhibits a dynamic viscosity of 500 to 9000 mm²/s at 25 °C in an amount of 0.5 to 5 parts by mass per 100 parts by mass of the sum total of the components (A) and (B). Also disclosed are molded articles using the polycarbonate resin composition.

Description

Polycarbonate resin composition and molded product using the same

The present invention relates to a polycarbonate resin composition and a molded product using the same. More specifically, a polycarbonate resin composition having improved slidability while maintaining excellent mechanical strength by incorporating a silicone oil having a specific kinematic viscosity into the polycarbonate-polyorganosiloxane copolymer, and an OA using the same The present invention relates to molded products used for equipment, information / communication equipment, electrical / electronic equipment, home appliances, various parts of automobiles, and the like.

Polycarbonate resins produced from bisphenol A and the like are excellent in heat resistance and mechanical properties, and thus are used as materials for various parts in the electric / electronic field, automobile field, and the like. However, slidability may be required depending on the location where it is used, and when a polycarbonate resin obtained from bisphenol A is used alone, the slidability is inferior. ing. For example, a resin composition with PTFE (polytetrafluoroethylene) (see Patent Document 1), a resin composition with silicone oil (see Patent Documents 2 and 3), a polyolefin resin to improve the compatibility between a polycarbonate resin and silicone oil, etc. A resin composition containing other resins (see Patent Document 4), a resin composition with a polyolefin wax or the like (see Patent Document 5), a resin composition with a polyphenylene resin (see Patent Document 6), and a sliding polycarbonate resin Known as a composition.
In these resin compositions, the effect of improving the slidability is insufficient when a small amount of the slidable material is added, and when the addition amount is increased, the mechanical properties such as tensile properties, which are the original properties of the polycarbonate resin, are lowered. For long-term use, there arises a problem that the slidability deteriorates due to wear and dropout.

On the other hand, a polycarbonate-polydimethylsiloxane copolymer (PC-PDMS) is known as a polycarbonate excellent in impact resistance and flame retardancy (see Patent Document 7).
However, regarding the slidability of PC-PDMS itself, a method of blending PTFE as a slidability improver (see Patent Document 8), a method of adding silicone oil having a specific viscosity or higher (see Patent Document 9), etc. are reported. However, in any case, the slidability is insufficient.
For example, in Patent Document 3, silicone oil in which a part or all of methyl groups of polydimethylsiloxane are substituted with phenyl groups is added, but moldability, long-term slidability, abrasion resistance are added. Insufficient sex.
In Patent Document 4, in order to improve the compatibility between polycarbonate and silicone oil, other resins such as polyolefin resin are added, but mechanical properties and long-term slidability are insufficient.
In Patent Document 9, silicone oil is added to a polycarbonate-polydimethylsiloxane copolymer, but the viscosity is high when the number of siloxane repeats n in the copolymer is 50 in the examples. Even if this silicone oil is added, the slidability, particularly the long-term slidability, is insufficient.

JP-A-7-228763 Japanese Patent Publication No. 36-7641 JP 2000-248165 A JP-A-9-255864 JP 2005-320367 A Japanese Patent Application Laid-Open No. 2007-23309 Japanese Patent No. 2663210 Japanese Patent No. 3026613 JP 2000-302962 A

An object of the present invention is to provide a polycarbonate resin composition having improved slidability without deteriorating mechanical properties and a molded product using the same.

As a result of diligent investigations, the present inventors have been able to achieve the above object by including a specific proportion of silicone oil having a specific kinematic viscosity in a polycarbonate-polyorganosiloxane copolymer having a specific structure. The present invention was completed.

That is, this invention provides the following polycarbonate-type resin composition and a molded article using the same.
1. (A) Containing a polyorganosiloxane block portion having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) and including the structural unit represented by the general formula (II) 30 to 100 parts by mass of a polycarbonate-polyorganosiloxane copolymer having an amount of 1 to 30% by mass and an average repeating number of the structural unit represented by the general formula (II) of 70 to 200, and (B) 70 to 0 parts by mass of the aromatic polycarbonate resin in a proportion of 100 parts by mass in total, and (C) kinematic viscosity at 25 ° C. with respect to 100 parts by mass in total of the components (A) and (B). A polycarbonate-based resin composition comprising 0.5 to 5 parts by mass of silicone oil of 500 to 9000 mm ² / s:

[Wherein, R ¹ and R ² each independently represents an alkyl group or alkoxy group having 1 to 6 carbon atoms, and X represents a single bond, an alkylene group having 1 to 8 carbon atoms, or an alkylidene group having 2 to 8 carbon atoms. , A cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO—, —SO ₂ —, —O— or —CO—, wherein R ³ and R ⁴ are And each independently represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group or aryl group, and a and b each represent an integer of 0 to 4.]

2. (C) The polycarbonate resin composition as described in 1 above, wherein the silicone oil is dimethyl silicone oil.
3. (A) The polycarbonate resin composition as described in 1 or 2 above, wherein the polycarbonate-polyorganosiloxane copolymer has a viscosity average molecular weight of 13,000 to 50,000.
4). 4. A molded article comprising the polycarbonate resin composition as described in any one of 1 to 3 above.
5). 5. The molded product according to 4 above, which is a sliding part.

According to the present invention, it is possible to provide a polycarbonate resin composition having improved slidability without deteriorating mechanical properties and a molded product using the same.

[Polycarbonate resin composition]
The polycarbonate resin composition of the present invention contains (A) 30 to 100 parts by mass of a polycarbonate-polyorganosiloxane copolymer and (B) 70 to 0 parts by mass of an aromatic polycarbonate resin in a total amount of 100 parts by mass. Furthermore, (C) 0.5 to 5 parts by mass of silicone oil is added to 100 parts by mass of the total of components (A) and (B).
Hereinafter, (A) a polycarbonate-polyorganosiloxane copolymer, (B) an aromatic polycarbonate resin, (C) a silicone oil, and additives that can be added as necessary will be described.

[(A) Polycarbonate-polyorganosiloxane copolymer]
The (A) polycarbonate-polyorganosiloxane copolymer used in the present invention has a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II). The content of the polyorganosiloxane block part containing the structural unit represented by II) is 1 to 30% by mass, preferably 1 to 20% by mass, and the average of the structural units represented by the general formula (II) The number of repetitions is 70 to 200.

In the above formulas (I) and (II), R ¹ and R ² each independently represents an alkyl group or alkoxy group having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 8 carbon atoms, carbon Represents an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO—, —SO ₂ —, —O— or —CO—. , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group or aryl group, and a and b each represents an integer of 0 to 4.

Component (A) is, for example, a copolymer of a dihydric phenol represented by the following general formula (1), a polyorganosiloxane represented by the general formula (2), and phosgene, carbonate ester or chloroformate. Can be obtained.

In the above formula (1), X, R ¹ , R ² , a and b are the same as in the general formula (I), and n represents an integer of 70 to 200 in terms of the average number of repeating units of the organosiloxane constituent unit. In the general formula (2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an optionally substituted alkyl group or aryl group, Y is a halogen atom, R ⁷ OH, —R ⁷ COOH, —R ⁷ NH ₂ or —SH, wherein R ⁷ represents a linear, branched or cyclic alkylidene group, an alkylene group, an aryl-substituted alkylidene group, an aryl-substituted alkylene group or an arylene group; M represents 0 or 1;

In the polycarbonate resin composition of the present invention, there are various dihydric phenols represented by the above general formula (1) used as the raw material for the component (A). (4-Hydroxyphenyl) propane [common name: bisphenol A] is preferred. Examples of bisphenols other than bisphenol A include bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) butane; (4-hydroxyphenyl) octane; 2,2-bis (4-hydroxyphenyl) phenylmethane; 2,2-bis (4-hydroxy-3-methylphenyl) propane; bis (4-hydroxyphenyl) naphthylmethane; 1 1,2-bis (4-hydroxy-t-butylphenyl) propane; 2,2-bis (4-hydroxy-3-bromophenyl) propane; 2,2-bis (4-hydroxy-3,5-tetramethylphenyl) ) Propane; 2,2-bis (4-hydroxy-3-chlorophenyl) propane; 2,2-bis (4-hydro) Bis-3,5-tetrachlorophenyl) propane; bis (hydroxyaryl) alkanes such as 2,2-bis (4-hydroxy-3,5-tetrabromophenyl) propane, 1,1-bis (4-hydroxyphenyl) ) Cyclopentane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane; 2,2′-bis (4-hydroxyphenyl) Bis (hydroxyaryl) cycloalkanes such as norbornene, 4,4′-dihydroxyphenyl ether; dihydroxyaryl ethers such as 4,4′-dihydroxy-3,3′-dimethylphenyl ether,

4,4'-dihydroxydiphenyl sulfide; dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; 4,4'-dihydroxydiphenyl sulfoxide; 4,4'-dihydroxy-3,3 Dihydroxy diaryl sulfoxides such as' -dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone; Dihydroxy diaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, 4,4'-dihydroxy Dihydroxydiphenyls such as diphenyl, 9,9-bis (4-hydroxyphenyl) fluorene; dihydroxydiarylfluorenes such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, bis (4-hydroxy) Phenyl) diphenylmethane, 1,3-bis (4-hydroxyphenyl) adamantane; 2,2-bis (4-hydroxyphenyl) adamantane; 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, etc. Dihydroxydiaryladamantanes, bis (4-hydroxyphenyl) diphenylmethane, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4-hydroxyphenyl) -9-anthrone 1,5-bis (4-hydroxyphenylthio) -2,3-dioxapentaene and the like. These dihydric phenols may be used alone or in combination of two or more.

Examples of the polyorganosiloxane of the general formula (2) include the following formulas (3) to (11).

In the above formulas (3) to (11), R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom or an alkyl which may have a substituent, as in the general formula (1). R ⁸ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group, n represents an integer of 70 to 200 in terms of the average number of repeating units of the organosiloxane, and c is usually 1 to 20 Indicates a positive integer.
Among the above formulas (3) to (11), the phenol-modified polyorganosiloxane represented by the formula (3) is preferable from the viewpoint of ease of polymerization, and moreover, α, ω which is one of the compounds represented by the formula (4) -Bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane or α, ω-bis [3- (4-hydroxy-3-methoxyphenyl) propyl] poly, which is one of the compounds represented by formula (5) Dimethylsiloxane is preferred from the viewpoint of availability.

The polyorganosiloxane represented by the general formula (2) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, allylphenol, eugenol, isopropenylphenol or the like having a predetermined polymerization degree n. It can be easily produced by hydrosilation reaction at the end of the polyorganosiloxane chain having the following.

The viscosity average molecular weight of the (A) polycarbonate-polyorganosiloxane copolymer is preferably from 1,3000 to 50,000, more preferably from 15,000 to 30,000, and even more preferably from 15,000 to 26,000. 000. If the viscosity average molecular weight is 13,000 or more, the strength of the molded article is sufficient, and if it is 50,000 or less, the productivity does not decrease.

[(B) Aromatic polycarbonate resin]
The polycarbonate resin composition of the present invention can contain (B) an aromatic polycarbonate resin for the purpose of adjusting the amount of the polyorganosiloxane block portion in the component (A).
The components (A) and (B) are contained in the polycarbonate resin composition of the present invention in such a proportion that 30 to 100 parts by mass of the component (A) and 70 to 0 parts by mass of the component (B) are 100 parts by mass in total. The component (A) is preferably 50 to 100 parts by mass, and the component (B) is 50 to 0 parts by mass.

The component (B) is reacted with a dihydric phenol compound and phosgene in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, and then added with a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt. It can be obtained by conventional methods for producing aromatic polycarbonates, such as the interfacial polymerization method for polymerization and the pyridine method in which a dihydric phenol compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent and phosgene is introduced directly. . In the above reaction, a molecular weight regulator, a branching agent and the like may be used as necessary.

(B) As a dihydric phenol type compound used for manufacture of a component, the thing similar to the illustration of the dihydric phenol in description of the said (A) component is mentioned, for example.
Moreover, as a molecular weight regulator, various things can be used if it is normally used for superposition | polymerization of polycarbonate resin. Specifically, as monohydric phenol, for example, phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot -Butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexylphenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol M-nonylphenol, pn-nonylphenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol; 2,5-di -T-butylphenol; 2,4-di-t-butylphenol; 3,5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-dicumylphenol; p-cresol, bromophenol, tribromo Phenol, monoalkylphenol having a linear or branched alkyl group having an average carbon number of 12 to 35 in the ortho, meta or para position; 9- (4-hydroxyphenyl) -9- (4-methoxyphenyl) fluorene 9- (4-hydroxy-3-methylphenyl) -9- (4-methoxy-3-methylphenyl); Le) fluorene; 4- (1-adamantyl) phenol, and the like.
Of these monohydric phenols, pt-butylphenol, p-cumylphenol, and p-phenylphenol are preferably used. This molecular weight regulator may be used individually by 1 type, and may be used in combination of 2 or more type.

Further, a branched polycarbonate can be obtained by using a branching agent in combination in the range of about 0.01 to 3 mol%, particularly 0.1 to 1 mol% with respect to the dihydric phenol compound.
Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane; 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl ] Ethylidene] bisphenol; α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl]- A compound having three or more functional groups such as 4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; phloroglysin, trimellitic acid, and isatin bis (o-cresol) can be used.

[(C) Silicone oil]
The silicone oil (C) used in the present invention is blended for the purpose of expanding the size of the siloxane domain consisting of the general formula (II) in the component (A). The slidability can be improved while maintaining the excellent impact resistance.
Component (C) has a kinematic viscosity at 25 ° C. of 500 to 9,000 mm ² / s, and is preferably dimethyl silicone oil (polydimethylsiloxane).
If the kinematic viscosity at 25 ° C. is less than 500 mm ² / s, the slidability is insufficient, and if it exceeds 9,000 mm ² / s, the specific wear increases. The thickness is preferably 500 to 5000 mm ² / s, more preferably 500 to 3000 mm ² / s. The kinematic viscosity can be measured according to JIS K 2283.
The component (C) is available as a commercial product, and examples thereof include a trade name “KF96” series (manufactured by Shin-Etsu Chemical Co., Ltd.).

〔Additive〕
In addition to the components (A) to (C), additives such as antioxidants usually used for polycarbonate resins can be added to the polycarbonate resin composition of the present invention as desired. In addition to antioxidants, for example, reinforcing materials, fillers, stabilizers, UV absorbers, antistatic agents, lubricants, mold release agents, dyes, pigments, other flame retardants and elastomers for improving impact resistance, etc. Is mentioned.
As the antioxidant, a hindered phenol-based antioxidant, an aromatic amine-based antioxidant, a hindered amine-based antioxidant, a sulfide-based antioxidant, an organic phosphate-based antioxidant, and the like are preferable. Inhibitors and organophosphate antioxidants are particularly preferred.

These antioxidants are available as commercial products. Examples of organophosphorus antioxidants include tris (2,4-di-t-butylphenyl) phosphite, trade name “IRGAFOS168” (Ciba Specialty). Chemicals), bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol di-phosphite, and trade name “Adeka Stab PEP-36” (manufactured by ADEKA) are preferably used.
In addition, as a hindered phenol-based antioxidant, a trade name “IRGANOX 1076” (manufactured by Ciba Specialty Chemicals), a trade name “IRGANOX 1010” (manufactured by Ciba Specialty Chemicals), and a trade name “Sumilyzer GM” (Sumitomo) Chemical Co., Ltd.) is preferably used. Further, a blend product of IRGANOX 1076 and IRGAFOS 168 and a blend product of IRGANOX 1010 and IRGAFOS 168 are also commercially available.

〔Molding〕
The present invention provides a molded article comprising the above polycarbonate resin composition. This molded product is particularly useful as a sliding part. There are no particular limitations on the method for producing the molded article of the present invention, and various conventionally known molding methods such as injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, and foam molding. Etc. can be used.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the following examples, performance evaluation was performed by the following method about the obtained molded article.
The obtained results are shown in Tables 1 and 2.
(1) Sliding test (dynamic friction coefficient, specific wear)
In accordance with JIS K7218-A method, a sliding test was performed under the conditions of a normal pressure of SUS304, a surface pressure of 250 kPa, a speed of 0.5 m / sec, and a test distance of 3 km at normal temperature.
(2) Impact test (impact strength)
A notched Izod impact test was conducted at 23 ° C. according to ASTM D256.
(3) Flexural modulus It was performed according to ASTM D790.
(4) Appearance of molded product The presence or absence of silver on the ring surface for sliding test was visually evaluated.

[Production example of polycarbonate oligomer]
2,000 ppm of sodium dithionite is added to 5.6 mass% sodium hydroxide aqueous solution to bisphenol A (BPA) which is later dissolved, and BPA is dissolved so that the BPA concentration becomes 13.5 mass%. A sodium hydroxide aqueous solution of BPA was prepared. Phosgene was continuously passed through a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m at a flow rate of 4.0 kg / hour at a flow rate of 40 liters / hour of sodium hydroxide aqueous solution of BPA and 15 liters / hour of methylene chloride. 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 internal volume of 40 liters equipped with a receding blade, and further 2.8 liters / hour of sodium hydroxide aqueous solution of BPA, The reaction was carried out by adding 25 mass% aqueous sodium hydroxide solution 0.07 liter / hour, water 17 liter / hour, and 1 mass% triethylamine aqueous solution at a rate of 0.64 liter / hour.
The reaction liquid overflowing from the tank reactor was continuously extracted and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected.
The polycarbonate oligomer solution thus obtained had a concentration of 329 g / liter and a chloroformate group concentration of 0.74 mol / liter.

[Example 1]
Allyl having 15 liters of polycarbonate oligomer solution prepared above, 9.0 liters of methylene chloride, 90 average dimethylsiloxane unit repeats in a 50 liter tank reactor equipped with baffle plate, paddle type stirring blades and cooling jacket 205 g of phenol-terminated polydimethylsiloxane (hereinafter referred to as “PDMS-90”) and 8.8 ml of triethylamine were added, and 1389 g of a 6.4% by mass aqueous sodium hydroxide solution was added thereto with stirring, and the polycarbonate oligomer for 10 minutes. And an allylphenol terminal-modified PDMS were reacted to obtain a polymerization solution.
In this polymerization solution, methylene chloride solution of pt-butylphenol (PTBP) (126 g of PTBP dissolved in 2.0 liters of methylene chloride), sodium hydroxide aqueous solution of BPA (577 g of NaOH and 2.0 g of sodium dithionite) A solution obtained by dissolving 1012 g of BPA in an aqueous solution dissolved in 8.4 liters of water) was added, and the polymerization reaction was carried out for 50 minutes.
For dilution, 10 liters of methylene chloride was added and stirred for 10 minutes, and then separated into an organic phase containing polycarbonate and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated.
The polycarbonate methylene chloride solution thus obtained was washed successively with 15% by volume of 0.03 mol / liter NaOH aqueous solution and 0.2 mol / liter hydrochloric acid, and then in the aqueous phase after washing. Washing was repeated with pure water until the electric conductivity reached 0.01 μS / m or less.
The methylene chloride solution of polycarbonate obtained by washing was concentrated and pulverized, and the obtained flakes were dried at 120 ° C. under reduced pressure.
The amount of the PDMS block portion determined by NMR was 3.5% by mass, the viscosity number measured in accordance with ISO 1628-4 (1999) (hereinafter simply referred to as viscosity number) was 46.8, and the viscosity average molecular weight (hereinafter referred to as “viscosity number”). , Unit Mv) = 17400.

Polydimethylsiloxane having a kinematic viscosity of 1000 mm ² / s at 25 ° C. with respect to 100 parts by mass of the copolymer (component (A)) (component (C)), trade name “KF96-1000cs”, Shin-Etsu Chemical Co., Ltd. Company] 1 part by mass and tris (2,4-di-t-butylphenyl) phosphite (trade name “IRGAFOS168”, manufactured by Ciba Specialty Chemicals) as an antioxidant at a high speed of 0.05 part by mass The mixture was uniformly mixed with a mixer and granulated at a resin temperature of 280 ° C. using a 50 mmφ single screw extruder with a vent to obtain pellets.
The obtained pellets were injection molded using an injection molding machine under molding conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. to obtain a molded product.

[Example 2]
A molded product was obtained in the same manner as in Example 1 except that 2 parts by mass of “KF96-1000cs” was used.

[Comparative Example 1]
Instead of “KF96-1000cs”, 1 part by weight of polydimethylsiloxane (trade name “KF96H-1 million cs”, manufactured by Shin-Etsu Chemical Co., Ltd.) with a kinematic viscosity at 25 ° C. of 1,000,000 mm ² / s is used. A molded product was obtained in the same manner as in Example 1 except that.

[Example 3]
A molded product was obtained in the same manner as in Example 1 except that 575 g of PDMS-90 was used (the amount of the PDMS block portion was 10% by mass).

[Comparative Example 2]
Copolymer flakes were obtained in the same manner as in Example 1 except that 575 g of allylphenol-terminated polydimethylsiloxane (hereinafter referred to as PDMS-50) having an average number of dimethylsiloxane units of 50 was used instead of PDMS-90. (The amount of the PDMS block portion was 10% by mass). Others were carried out in the same manner as in Example 1 to obtain a molded product.

[Example 4]
A molded article was obtained in the same manner as in Example 1 except that 205 g of allylphenol-terminated polydimethylsiloxane (hereinafter referred to as PDMS-150) having an average number of repeating dimethylsiloxane units of 150 was used instead of PDMS-90. Got.
The amount of the PDMS block portion determined by NMR of the obtained flakes was 3.5% by mass, the viscosity number was 46.4, and Mv = 17200.

[Comparative Example 3]
Copolymer flakes were produced in the same manner as in Example 1 except that 205 g of PDMS-50 was used instead of PDMS-90.
The amount of the PDMS block portion was 3.5% by mass, the viscosity number was 46.8, and Mv = 17400. Others were carried out in the same manner as in Example 1 to obtain a molded product.

[Example 5]
A copolymer flake was produced in the same manner as in Example 1 except that 575 g of PDMS-90 was used (the amount of the PDMS block portion was 10% by mass).
BPA polycarbonate having PTBP as a terminal group with respect to 50 parts by mass of this copolymer, [trade name “Taflon FN1700A”, manufactured by Idemitsu Kosan Co., Ltd., viscosity number 46.9, viscosity average molecular weight Mv = 17400] 50 parts by mass , 1 part by weight of “KF96-1000cs” and 0.05 part by weight of “IRGAFOS168” were uniformly mixed with a high-speed mixer, and granulated at a resin temperature of 280 ° C. using a 50 mmφ single-screw extruder with a vent. Except having obtained, it implemented similarly to Example 1 and obtained the molded article.

[Comparative Example 4]
1 part by weight of “KF96-1000cs” and 0.05 part by weight of “IRGAFOS168” are uniformly mixed with 100 parts by weight of “Taflon FN1700A” using a high-speed mixer, and resin is produced using a 50 mmφ single screw extruder with a vent. A molded product was obtained in the same manner as in Example 1 except that pellets were obtained by granulation at a temperature of 280 ° C.

[Comparative Example 5]
1 part by weight of “KF96H-1 million cs” and 0.05 part by weight of “IRGAFOS168” are uniformly mixed with 100 parts by weight of “Taflon FN1700A” using a high-speed mixer, and a 50 mmφ single screw extruder with a vent is used. A molded product was obtained in the same manner as in Example 1 except that the pellet was obtained by granulation at a resin temperature of 280 ° C.

[Comparative Example 6]
A molded product was obtained in the same manner as in Example 1 except that “KF96-1000cs” was not added.

[Comparative Example 7]
Example except that kinematic viscosity at 25 ° C. using a 100 mm ² / s polydimethylsiloxane [trade name "KF96-100cs", manufactured by Shin-Etsu Chemical Co., Ltd.] 1 part by weight in place of the "KF96-1000cs" 1 The molded product was obtained in the same manner.

[Comparative Example 8]
Copolymer flakes were produced in the same manner as in Example 1 except that 205 g of PDMS-50 was used instead of PDMS-90.
The amount of the PDMS block portion was 3.5% by mass, the viscosity number was 46.8, and Mv = 17400. A molded product was obtained in the same manner as in Example 1 except that “KF96-1000cs” was not added.

[Comparative Example 9]
Copolymer flakes were produced in the same manner as in Example 1 except that 205 g of PDMS-50 was used instead of PDMS-90.
The amount of the PDMS block portion was 3.5% by mass, the viscosity number was 46.8, and Mv = 17400. A molded product was obtained in the same manner as in Example 1 except that 1 part by weight of “KF96-100cs” was used instead of “KF96-1000cs”.

[Comparative Example 10]
Copolymer flakes were produced in the same manner as in Example 1 except that 205 g of PDMS-50 was used instead of PDMS-90.
A molded product was obtained in the same manner as in Example 1 except that 1 part by weight of “KF96H-1 million cs” was used instead of “KF96-1000 cs”.

Tables 1 and 2 show the following.
From a comparison between Examples 1 and 2 and Comparative Example 1, if the kinematic viscosity of (C) silicone oil is too large, the specific wear amount increases and the slidability deteriorates.
From the comparison between Example 3 and Comparative Example 2, and the comparison between Example 4 and Comparative Example 3, the average number of repeating units of the structural unit represented by formula (II) in the copolymer (A) is small. As a result, the dynamic friction coefficient and the specific wear amount increase and the slidability is inferior. Moreover, silver is observed in the molded product of Comparative Example 2, and the molded appearance is inferior.
From the comparison between Example 5 and Comparative Examples 4 and 5, it was found that (A) the copolymer was not contained, and (B) the aromatic polycarbonate resin alone increased the dynamic friction coefficient and specific wear amount, resulting in poor slidability and impact. Strength is also reduced and mechanical properties are inferior. Moreover, silver is observed in the molded articles of Comparative Examples 4 and 5, and the molded appearance is inferior.
From Comparative Examples 6 and 7, when (C) silicone oil is not contained or the kinematic viscosity is small, the dynamic friction coefficient is increased, and from Comparative Examples 8 to 10, the average number of repetitions is small, and no silicone oil is contained or the kinematic viscosity is specified. Even outside the range, the dynamic friction coefficient or both the dynamic friction coefficient and the specific wear amount increase and the slidability decreases.

Since a molded product using the polycarbonate resin composition of the present invention has excellent slidability without deteriorating mechanical properties, it can be suitably used in fields requiring such characteristics.

Claims

(A) Containing a polyorganosiloxane block portion having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) and including the structural unit represented by the general formula (II) 30 to 100 parts by mass of a polycarbonate-polyorganosiloxane copolymer having an amount of 1 to 30% by mass and an average repeating number of the structural unit represented by the general formula (II) of 70 to 200, and (B) 70 to 0 parts by mass of the aromatic polycarbonate resin in a proportion of 100 parts by mass in total, and (C) kinematic viscosity at 25 ° C. with respect to 100 parts by mass in total of the components (A) and (B). A polycarbonate-based resin composition comprising 0.5 to 5 parts by mass of silicone oil of 500 to 9000 mm 2 / s:

[Wherein, R 1 and R 2 each independently represents an alkyl group or alkoxy group having 1 to 6 carbon atoms, and X represents a single bond, an alkylene group having 1 to 8 carbon atoms, or an alkylidene group having 2 to 8 carbon atoms. , A cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO—, —SO 2 —, —O— or —CO—, wherein R 3 and R 4 are And each independently represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group or aryl group, and a and b each represent an integer of 0 to 4.]
(C) The polycarbonate resin composition according to claim 1, wherein the silicone oil is dimethyl silicone oil.
The polycarbonate resin composition according to claim 1 or 2, wherein (A) the polycarbonate-polyorganosiloxane copolymer has a viscosity average molecular weight of 13,000 to 50,000.
A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 3.
The molded article according to claim 4, which is a sliding part.