JP3393616B2 - Polycarbonate-polyorganosiloxane triblock copolymer and resin composition containing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polycarbonate-polyorganosiloxane triblock copolymer and a resin composition containing the same. More specifically, releasability,
Polycarbonate with excellent impact resistance, fluidity and rigidity-
The present invention relates to a polyorganosiloxane triblock copolymer and a resin composition containing the polycarbonate-polyorganosiloxane triblock copolymer.

[0002]

2. Description of the Related Art Polycarbonate resin (hereinafter sometimes abbreviated as PC) is a polycarbonate resin.
It has excellent mechanical strength, electrical characteristics, transparency, etc., and is widely used as an engineering plastic in various fields such as electric and electronic devices and automobiles.
As a polycarbonate resin having such characteristics, a glass fiber reinforced polycarbonate resin to which glass fiber is added as an inorganic filler is known in order to improve rigidity and dimensional stability. However, the polycarbonate resin has a problem that the releasability at the time of molding is significantly reduced by adding glass fiber. Conventionally, a technique for adding a small amount of polyorganosiloxane (silicone oil) has been developed as a method for improving the mold releasability at the time of molding, which is reduced by adding the glass fiber to a polycarbonate resin. However, with this method, although the releasability is improved, it is not yet sufficiently satisfactory. When a large amount of silicone oil is added, there is a problem that it becomes difficult to knead the resin. Further, for example, Japanese Patent Application Laid-Open No. 2-173061 discloses a technique of blending a glass fiber with a copolymer of polyorganosiloxane and a polycarbonate resin, and the release property is improved. There is a strong demand for the development of technology with improved moldability.

[0003]

In view of the above situation, the present inventor has solved the drawbacks of the conventional method and is excellent in releasability, impact resistance, fluidity and rigidity of polycarbonate-polyorganosiloxane. The inventors have earnestly studied to develop a triblock copolymer and a resin composition containing the triblock copolymer. As a result, by using a Y-XY type triblock polymer which is a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing the polycarbonate (X) and the polyorganosiloxane (Y), It was found that the releasability is further improved. The present invention has been completed based on such findings.

That is, the present invention has the general formula (I)

[0005]

[Chemical 3]

[Wherein R ¹ and R ² are each a halogen atom, an alkyl group having 1 to 8 carbon atoms or 6 to 20 carbon atoms]
Of aryl groups, which may be the same or different, p and q are integers from 0 to 4,
m is 1 to 150. Z is a single bond, an alkylene group having 1 to 20 carbon atoms or an alkylidene group, and 5 carbon atoms.
To 20 cycloalkylene groups or cycloalkylidene groups, —O—, —S—, —SO—, —SO ₂ —, —CO—
Bond or general formula (II) or (II ')

[0007]

[Chemical 4]

The bond represented by Also, R ^{3 to} R ⁶
Are each an alkyl group having 1 to 8 carbon atoms or 6 to 8 carbon atoms.
20 aryl groups may be the same or different, and n is 101 to 500. R
⁷ represents a divalent organic residue containing aliphatic and / or aromatic, and R ⁸ represents an alkyl group having 1 to 20 carbon atoms or 6 to 10 carbon atoms.
20 aryl groups are shown. A is a single bond, -O-
Or it shows -NH-. ] Polycarbonate represented by
A polyorganosiloxane triblock copolymer is provided. The present invention also provides (A) the above polycarbonate-polyorganosiloxane triblock copolymer.
0.5 to 30 wt%, (B) Polycarbonate resin 10
94.5 wt% and (C) 5 to 60 wt% inorganic filler, and the content of polyorganosiloxane is 0.1 to 2
The resin composition is 0% by weight.

First, the polycarbonate-polyorganosiloxane triblock copolymer of the present invention (hereinafter referred to as PC-
It may be abbreviated as PDMS copolymer. ) Is the general formula (I)

[0010]

[Chemical 5]

It is characterized in that Here, in the PC-PDMS copolymer represented by the general formula (I), R ¹
And R ² are each a halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, n-
Butyl group, isobutyl group, tert-butyl group, amyl group,
An isoamyl group, a hexyl group, etc.) or a carbon number of 6 to 20,
It is preferably an aryl group of 6 to 18 (for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group), which may be the same or different, and p and q are integers of 0 to 4 And m is 1 to 150, preferably 3 to 140, and particularly preferably 5 to 130. Z is a single bond, having 1 to 20 carbon atoms, preferably 2-1
8 alkylene group or alkylidene group (for example, methylene group, ethylene group, propylene group, butylene group, penterylene group, hexylene group, ethylidene group, isopropylidene group, etc.), cycloalkylene group or cycloalkylidene group having 5 to 20 carbon atoms (For example, a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, a cyclohexylidene group, etc.), -O-, -S-, -SO-,
-SO ₂ -, - CO- bond or general formula (II) or
(II ')

[0012]

[Chemical 6]

The bond represented by

R ^{3 to} R ⁶ are each a carbon number of 1 to
8 alkyl groups (eg, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, tert-butyl group,
Amyl group, isoamyl group, hexyl group) or an aryl group having 6 to 20 carbon atoms, preferably 6 to 18 carbon atoms (eg,
Phenyl group, tolyl group, xylyl group, naphthyl group), which may be the same or different.
n is 101 to 500, preferably 110 to 400, and more preferably 115 to 350. R ⁷ is a divalent organic residue containing an aliphatic and / or aromatic group (for example, methylene group, ethylene group, propylene group, butylene group, penterylene group, hexylene group, ethylidene group, isopropylidene group, cyclopentyl group. Len group, cyclohexylene group, cyclopentylidene group, cyclohexylidene group, etc.) or the general formula (III), (III ') or (III ")

[0015]

[Chemical 7]

[In the formula, (A) and (Si) indicate that they are bonded to A and Si in the general formula (I), respectively. ]
Represents an o-allylphenol residue, a p-vinylphenol residue, an eugenol residue and the like. Furthermore, R
⁸ is an alkyl group having 1 to 20 carbon atoms (for example, a methyl group,
Ethyl group, propyl group, n-butyl group, isobutyl group,
tert-butyl group, amyl group, isoamyl group, hexyl group) or an aryl group having 6 to 20 carbon atoms (eg, phenyl group, tolyl group, xylyl group, naphthyl group, etc.). And A shows a single bond, -O-, or -NH-.

PC-PDM represented by the general formula (I)
The main chain of the S copolymer has the general formula (IV)

[0018]

[Chemical 8]

[In the formula, R ¹ , R ² , Z, p and q are the same as above. ] The polycarbonate (PC) part (X) of the repeating unit I represented by the general formula (V)

[0020]

[Chemical 9]

[In the formula, R ^{3 to} R ⁶ , R ⁷ , R ⁸ , A and n are the same as described above. ] The polyorganosiloxane (PDMS) in which one end of the structural unit II represented by
It is a Y-X-Y type triblock polymer in which a part (Y) is bonded.

Such a PC-PDMS copolymer can be produced by various methods. The following method is mentioned as a preferable manufacturing method. In this preferred method, a polycarbonate oligomer (hereinafter sometimes abbreviated as PC oligomer) and a general formula (VI) in the presence of a dihydric phenol and a terminal stopper are used.

[0023]

[Chemical 10]

[In the formula, R ^{3 to} R ⁶ , R ⁷ , R ⁸ , A and n are the same as described above. ] One end reactive polyorganosiloxane represented by the following (hereinafter sometimes abbreviated as one end reactive PDMS) is reacted, and PC oligomer 1
70 parts by weight of the above-mentioned PDMS having one end reactive with
The PC-PDMS copolymer can be produced by using about 190 parts by weight, preferably 80 to 160 parts by weight. In the above preferable range, PC-
A PDMS copolymer can be obtained. According to the above method, the above-mentioned polycarbonate resin of the present invention can be efficiently produced, and by properly selecting the PC oligomer, the terminal terminator and the dihydric phenol, it is possible to use other types of PC-PDMS copolymers. Coalescence can also be produced.

Here, the PC oligomer used for producing the PC-PDMS copolymer has the repeating unit I represented by the general formula (IV) and is subjected to the solvent method (interfacial polycondensation method), that is, methylene chloride and the like. In the presence of a known acid acceptor and a terminal stopper in the organic solvent of the general formula (VII)

[0026]

[Chemical 11]

[In the formula, R ¹ , R ² , Z, p and q are the same as described above. ] It can manufacture by the reaction of the dihydric phenol and carbonate precursor like phosgene represented by these, or the transesterification reaction of dihydric phenol and carbonic acid diester (For example, carbonate precursor like diphenyl carbonate). The above general formula (VII)
There are various dihydric phenols represented by. Specifically, as the bis (4-hydroxyphenyl) alkane, for example, bis (4-hydroxyphenyl)
Methane [bisphenol F]; 2,2-bis (4-hydroxyphenyl) phenylmethane; bis (4-hydroxyphenyl) naphthylmethane; bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane; bis (3,3 5-dichloro-4-hydroxyphenyl) methane; bis (3,5-dimethyl-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl)
Ethane; 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane; 1-phenyl-1,1-bis (4-
Hydroxyphenyl) ethane; 1,2-bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A]; 2
-Methyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl-1-)
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (3,5) -Dichloro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis (3-chloro-4-hydroxyphenyl) propane;
2,2-bis (3-methyl-4-hydroxyphenyl)
Propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) butane; 1,1-bis (4-hydroxyphenyl) butane; 2,2-bis (4-Hydroxyphenyl) butane [bisphenol B]; 1,4-bis (4-
2,2-bis (4-hydroxyphenyl) pentane; 3,3-bis (4-hydroxyphenyl) pentane; 4-methyl-2,2-bis (4-hydroxyphenyl) pentane; 2-bis (4-hydroxyphenyl) hexane; 3,3-bis (4-hydroxyphenyl) hexane; 4,4-bis (4-hydroxyphenyl) heptane; 2,2-bis (4-hydroxyphenyl) octane; 2,2-bis (4-hydroxyphenyl) nonane; 1,10-bis (4-hydroxyphenyl) decane and the like.

Examples of the bis (4-hydroxyphenyl) cycloalkane include 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane. 1,1-bis (4-hydroxyphenyl) cyclodecane and the like can be mentioned. And bis (4-hydroxyphenyl) sulfone; bis (3,5-dimethyl-
4-hydroxyphenyl) sulfone; dihydroxydiarylsulfones such as bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ether; bis (3,5-dimethyl-4-hydroxyphenyl) ether, etc. Dihydroxydiaryl ethers, 4,4′-dihydroxybenzophenone;
Dihydroxy diaryl ketones such as 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide;
Bis (3-methyl-4-hydroxyphenyl) sulfide; dihydroxydiaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide;
Dihydroxydiaryl sulfoxides such as bis (3-methyl-4-hydroxyphenyl) sulfoxide,
Examples thereof include dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl, bisphenolfluorene such as 9,9-bis (4-hydroxyphenyl) fluorene, and thiobisphenol. Further, examples of the tetrahalogenobisphenols include tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, tetraiodobisphenol A, tetrabromobisphenol F, tetrachlorobisphenol F, tetrachlorobisphenol B and the like. Among these, bisphenol A is particularly preferably used. And these dihydric phenol may be used individually, and may be used in combination of 2 or more type.

As the carbonic acid diester, a carbonic acid diaryl compound, a carbonic acid dialkyl compound or a carbonic acid alkylaryl compound can be used. Here, examples of the diaryl carbonate compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, and bisphenol A bisphenyl carbonate. Examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A bismethyl carbonate and the like. And as the alkyl aryl carbonate compound, for example,
Methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, bisphenol A methyl phenyl carbonate, etc. are mentioned.

When the PC oligomer is produced by the solvent method, that is, the interfacial polycondensation method, the dihydric phenol and phosgene are reacted with each other so that substantially all the phosgene in the reaction system is reacted to obtain the PC oligomer. it can. This PC oligomer has a repeating unit I represented by the general formula (IV), which is constituted by a reaction between a dihydric phenol and phosgene in the above polycondensation reaction. That is, the PC oligomer is a dihydric phenol (for example,
For bisphenol A) 100, phosgene 110-110
The reaction is carried out at a molar ratio of 150. In this reaction, dihydric phenol is usually added in an alkaline aqueous solution and mixed with a solvent such as methylene chloride, chlorobenzene, chloroform, carbon tetrachloride and, if necessary, a catalyst such as triethylamine or trimethylbenzylammonium chloride in a predetermined amount ratio. Stir and bubble phosgene into it for 1 min-3
It can be produced by proceeding the interfacial polycondensation reaction at a reaction temperature of 30 to 70 ° C. for a time. At this time, the reaction system generates heat, so it is preferable to cool with water or ice.
Moreover, since the reaction system shifts to the acidic side as the reaction progresses, it is preferable to maintain the pH at 10 or more by adding an alkaline compound while measuring with a pH meter. The PC oligomer thus obtained has a number average molecular weight of 2,
It is less than 000 and is a 1-10-mer. At the time of the above polycondensation reaction, a terminal terminator usually used in the production of PC may be added.

There are various kinds of organic solvents. For example, dichloromethane (methylene chloride); chloroform; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane; 1,1,2-
Examples include chlorinated hydrocarbons such as trichloroethane; 1,1,1,2-tetrachloroethane; 1,1,2,2-tetrachloroethane; pentachloroethane and chlorobenzene; and acetophenone. These organic solvents are
They may be used alone or in combination of two or more. Of these, methylene chloride is particularly preferable. Examples of alkali metal hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide. Of these, sodium hydroxide and potassium hydroxide are preferred.
As the catalyst, various kinds can be used. Specifically, it is a quaternary ammonium salt, a quaternary phosphonium salt, a tertiary amine, or the like. Examples of the quaternary ammonium salt include trimethylbenzylammonium chloride, triethylbenzylammonium chloride,
Examples thereof include tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride and tetrabutylammonium bromide. Further, as the quaternary phosphonium salt, for example, tetrabutylphosphonium chloride,
Such as tetrabutylphosphonium bromide, and
Examples of the tertiary amine include triethylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine, dimethylaniline and the like.

Next, in the present invention, the one-end reactive PDMS represented by the general formula (VI) used for producing the PC-PDMS copolymer has a reactive group at one end and The end is sealed. Particularly, those having a phenolic OH group as the reactive group are preferably used. This one-end reactive PDMS can be produced by various methods. The following method is mentioned as a preferable manufacturing method. That is, first, an alkyllithium reagent (eg, n-butyllithium, tert-butyllithium, lithium trimethylsilylate, etc.) and a cyclic dimethylsiloxane (eg, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, etc.) are used. The reaction is carried out in an organic solvent, and one end is sealed with a dimethylalkylsiloxane unit and the other end is made a living end with a dimethyllithiumsiloxane unit.
Then, it is reacted with a dialkyl silicon halide such as dimethylchlorosilane or dimethylbromosilane to obtain polydimethylsiloxane having hydrogen at one end. Then, this is reacted with an aliphatic unsaturated phenol [for example, 2-allylphenol, 4-hydroxystyrene, eugenol (2-methoxy-4-allylphenol), etc.] to have one-end reactivity with one-end phenolic OH. PDMS can be obtained.

In the present invention, the PC-PDMS copolymer is preferably the previously prepared PC oligomer,
It can be produced by dissolving the one-end reactive PDMS in an organic solvent, adding an aqueous solution of an alkali metal hydroxide of a dihydric phenol, and using an interfacial polycondensation reaction using various catalysts. As the dihydric phenol, various ones can be used, but the same dihydric phenol as that used when the PC oligomer is produced is preferable. And in the present invention,
Various compounds can be used as the terminal terminator.
Usually, it is used for polymerization of polycarbonate, and monohydric phenol is used. For example, phenol, p-cresol, p-tert-butylphenol, p
-Tert-amylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol,
Examples include bromophenol, tribromophenol, pentabromophenol and the like. However, the terminal stopper should be 1 (molar ratio) or less, preferably 0.2 or less, based on PDMS having one end reactive. In addition, as a branching agent, if necessary, for example, phloroglucin; trimellitic acid; 1,1,1-tris (4-hydroxyphenyl) ethane; 1- [α-methyl-α- (4′-hydroxyphenyl) Ethyl] -4- [α ', α'-bis (4 "
-Hydroxyphenyl) ethyl] benzene; α, α ′,
α ″ -tris (4-hydroxyphenyl) -1,3,5
-Triisopropylbenzene; a compound having three or more functional groups such as isatin bis (o-cresol) can also be used.

The PC-PD of the present invention is prepared by the interfacial polycondensation method.
FIG. 1 is a flow chart showing an example of the method for producing the MS copolymer. That is, for example, in the case of the interfacial polycondensation method, first in an organic solvent,
A PC oligomer is prepared in advance by reacting a dihydric phenol with phosgene. Then, in an organic solvent, the PC oligomer, the one-end reactive PDMS prepared in advance and the dihydric phenol are reacted. During this reaction, the one-end reactive PDMS is added as it is or as a methylene chloride solution. Then, the dihydric phenol is added as an alkaline aqueous solution. The order of addition of these is not particularly limited, but it is desirable to add the dihydric phenol last. The reaction time is 30 minutes to 2 hours, and the reaction temperature is 20 to 40 ° C.

Next, the resin composition of the present invention comprises (A) the above-mentioned PC-PDMS copolymer, (B) a polycarbonate resin and (C) an inorganic filler, and comprises the component (A).
0.5 to 30% by weight, preferably 1.0 to 28% by weight, 10 to 94.5% by weight of the component (B), preferably 12 to 90% by weight, and 5 to 60% by weight of the component (C). , Preferably 1
It is composed of 0 to 50% by weight. Within the preferable range of the components (A) and (B), the effects of further improving the mechanical strength such as rigidity and impact resistance can be obtained.
Here, the polycarbonate resin (PC) of the component (B) constituting the resin composition of the present invention can be easily prepared by reacting a dihydric phenol with phosgene or a carbonic acid diester compound in the same manner as in the case of the PC oligomer. Can be manufactured. That is, for example, by reacting a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or a molecular weight modifier, or by dihydric phenol and a carbonic acid diester (diphenyl). It is produced by a transesterification reaction with a carbonate precursor such as carbonate). Here, as the dihydric phenol, the above-mentioned PC
It may be the same as or different from the compound represented by the general formula (VII) used for producing the oligomer. Examples of the carbonic acid diester include the above-mentioned diaryl carbonate such as diphenyl carbonate and dialkyl carbonate such as dimethyl carbonate and diethyl carbonate. Of course, a commercially available polycarbonate resin can be used.

There are various kinds of inorganic fillers as the component (C) constituting the resin composition of the present invention.
It is used for the purpose of improving the mechanical strength or dimensional stability of the polycarbonate resin composition and for increasing the amount. As described above, this inorganic filler is added to the resin composition in a proportion of 5 to 60% by weight, preferably 10 to 50% by weight. If the blending ratio is less than 5% by weight, the rigidity is insufficient and the dimensional stability is reduced. Further, if it exceeds 60% by weight, kneading becomes difficult or impossible, which is not preferable. Further, in the above preferable range, the effect of further improving the impact resistance can be obtained. Here, as the inorganic filler, for example, potassium titanate whiskers, mineral fibers (for example,
Rock wool), glass fiber, carbon fiber, metal fiber (for example, stainless fiber), aluminum borate whiskers, silicon nitride whiskers, boron fibers, tetrapod-shaped zinc oxide whiskers, talc, clay, mica, pearl mica, aluminum foil, Alumina, glass flakes, glass beads, glass balloons, carbon black, graphite,
Calcium carbonate, calcium sulfate, calcium silicate,
Examples thereof include titanium oxide, zinc sulfide, zinc oxide, silica, asbestos, and quartz powder. These inorganic fillers may be surface-treated in advance or may be untreated. Examples of the surface treatment agent include chemical treatments with various treatment agents such as silane coupling agent type, higher fatty acid type, fatty acid metal salt type, unsaturated organic acid type, organic titanate type, resin acid type and polyethylene glycol type. Alternatively, physical surface treatment may be mentioned.

Among these, as the glass fiber as the fibrous filler, any of alkali-containing glass, low-alkali glass, non-alkali glass and the like can be preferably used. The length of this glass fiber is preferably in the range of 0.1 to 8 mm, more preferably 0.3 to 6 mm, and the fiber diameter is 0.1 to 30 μm, preferably 0.5 to 25 μm. is there. The form of these glass fibers is not particularly limited, and any form such as roving, milled fiber and chopped strand can be used. These glass fibers may be used alone or in combination of two or more. Further, for the purpose of improving the adhesiveness with the polycarbonate resin, it is desirable to use those glass fibers which have been surface-treated with a surface-treating agent and then subjected to bundling treatment with an appropriate bundling agent. Here, as the surface treatment agent,
Examples thereof include silane-based coupling agents such as aminosilane-based, epoxysilane-based, vinylsilane-based, acrylic silane-based, titanate-based, aluminum-based, chromium-based, zirconium-based, and boron-based coupling agents. Among these, silane coupling agents and titanate coupling agents, particularly silane coupling agents are preferable. The method for treating the glass fiber with the above-mentioned surface treatment agent is not particularly limited, and any conventionally used method such as an aqueous solution method, an organic solvent method, or a spray method can be used. Further, examples of the sizing agent include urethane type, acrylic type, acrylonitrile-styrene type copolymer type, and epoxy type, and any of them can be used. The method for bundling the glass fibers with these sizing agents is not particularly limited, and any conventionally used method, for example, dip coating, roller coating, spray coating, flow coating, spray coating, or any other method is used. be able to.

The carbon fiber is generally produced by firing using cellulose fiber, acrylic fiber, lignin, petroleum or coal-based special pitch as a raw material, and various carbon fibers such as flame resistance, carbonaceous or graphite are used. There are types. The length of carbon fiber is usually in the range of 0.01 to 10 mm in the pellet, and the fiber diameter is 5 to 15 μm.
m. The form of the carbon fiber is not particularly limited, and examples thereof include various types such as roving, milled fiber, chopped strand, and strand. The surface of the carbon fiber may be surface-treated with an epoxy resin, a urethane resin or the like in order to enhance the affinity with the above copolymer.

In addition to the components (A), (B) and (C), the resin composition of the present invention may optionally contain
As the component (D), as long as the object of the present invention is not impaired,
Various additives or other synthetic resins, elastomers, etc. can be blended. First, as the additives, for example, hindered phenol-based, phosphite-based, phosphoric ester-based, amine-based antioxidants, for example, benzotriazole-based, benzophenone-based ultraviolet absorbers, for example, hindered amine -Based light stabilizers such as aliphatic carboxylic acid ester-based, paraffin-based, internal lubricants such as silicone oil and polyethylene wax, release agents, commonly used flame retardants, flame retardant aids, antistatic agents, colorants, etc. Is mentioned.

Other synthetic resins include, for example, polyester (polyethylene terephthalate, folybutylene terephthalate, etc.), polyamide, polyarylate, polyethylene, polypropylene, polymethylmethacrylate, polystyrene, AS resin, ABS resin and the above (B). Examples of the resin include polycarbonates other than the component polycarbonate. And
Examples of the elastomer include isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, acrylic elastomer, polyester elastomer, holamide elastomer, and core-shell type MBS and MAS.

The resin composition of the present invention can be obtained by blending the above-mentioned components (A), (B) and (C) with (D) if necessary and kneading. Then, for the compounding and kneading, a commonly used method, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a co-kneader, a multi-screw extruder, etc. Can be done using. The heating temperature for kneading is usually selected in the range of 250 to 300 ° C. The resin composition thus obtained can be subjected to various known molding methods, for example, injection molding, blow molding, extrusion molding, compression molding, calender molding, rotational molding, etc., to produce various molded articles. Can be offered.

[0042]

The present invention will be further described in detail with reference to production examples, examples and comparative examples. Production Example 1 [Production of PC oligomer] 60 kg of bisphenol A was added to 400 liters of a 5 wt% sodium hydroxide aqueous solution.
Was dissolved and a sodium hydroxide aqueous solution of bisphenol A was prepared. Then, the aqueous sodium hydroxide solution of bisphenol A kept at room temperature was flown at a flow rate of 138 liters / hour, and methylene chloride was flown at a flow rate of 69 liters / hour through an orifice plate into a tubular reactor having an inner diameter of 10 mm and a tube length of 10 m. Introduce phosgene into this and co-flow 1
It was blown in at a flow rate of 0.7 kg / hour and continuously reacted for 3 hours. The tubular reactor used here was a double tube, and cooling water was passed through the jacket to keep the discharge temperature of the reaction solution at 25 ° C. The pH of the discharged liquid is 10 to 11
Was adjusted as shown. The reaction liquid thus obtained was allowed to stand, the aqueous phase was separated and removed, and the methylene chloride phase (220 liters) was collected to obtain a PC oligomer (concentration 317 g / liter). P obtained here
The degree of polymerization of the C oligomer was 2 to 4, and the concentration of the chloroformate group was 0.7N.

Production Example 2-1 [Synthesis of PDMS-A Reactive with One Terminal] Butyllithium 1.
73 g (0.027 mol) of tetrahydrofuran (TH
F) It was dissolved in 350 ml and kept at 0 ° C or lower.
In addition, 300 g of hexamethylcyclotrisiloxane (1.
35 mol) in 170 ml of THF and dissolved at 0 ° C.
Kept below. Both were mixed, kept at 0 ° C. or lower, and stirred for 10 hours. After that, 2.55g of dimethylchlorosilane
(0.027 mol) and 320 ml of cyclohexane were added, and the mixture was further stirred for 10 hours. The solvent was evaporated off and an oily precipitate was obtained. The resulting precipitate was filtered and then vacuum evaporated at 150 ° C. and 3 torr to remove low-boiling substances to obtain an oil. Then 2-allylphenol 60
g and platinum as a platinum chloride-alcoholate complex 0.0
294 g of the oil obtained above in a mixture with 014 g
Was added at a temperature of 90 ° C. 90-115 this mixture
The mixture was stirred for 3 hours while maintaining the temperature of ° C. The product was extracted with methylene chloride and washed 3 times with 80% aqueous methanol to remove excess 2-allylphenol. The product was dried over anhydrous sodium sulphate and evaporated in vacuo to a temperature of 115 ° C. The obtained one-end phenol PD
As for MS, the number of repeating dimethylsilanooxy units was 150 as measured by NMR.

Production Example 2-2 [Synthesis of PDMS-B Reactive with One Terminal] In Production Example 2-1, 1.73 g of butyllithium was replaced with 3.26 g (0.034 mol) of lithium trimethylsilylate, and dimethyl was added. The procedure of Production Example 2-1 was repeated, except that 2.55 g of chlorosilane was changed to 3.21 g (0.034 mol). In the obtained one-terminal phenol PDMS, the number of repeating dimethylsilanooxy units was 120 as measured by NMR.

Production Example 2-3 [Synthesis of PDMS-C Reactive with One Terminal] In Production Example 2-1, 1.73 g of butyllithium was added to 3.20 g (0.05 mol) and 2.55 g of dimethylchlorosilane was added. To 4.73
The procedure of Production Example 2-1 was repeated, except that the amount was changed to g (0.05 mol). The obtained one-end phenol PDMS is N
According to the measurement of MR, the number of repeating dimethylsilanooxy units was 80.

Production Example 2-4 [Synthesis of PDMS-D Reactive with One Terminal] In Production Example 2-1, 1.73 g of butyllithium was added to 21.8 g (0.34 mol), and 2.55 g of dimethylchlorosilane was added. To 32.2
The procedure of Production Example 2-1 was repeated, except that the amount was changed to g (0.34 mol). The obtained one-end phenol PDMS is N
According to the measurement of MR, the number of repeating dimethylsilanooxy units was 12.

Production Example 2-5 [Synthesis of PDMS-E Reactive with Both Terminals] 1,483 g of octamethylcyclotetrasiloxane, 18.1 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% sulfuric acid were mixed. And stirred at room temperature for 17 hours. Then, the oil phase was separated, 25 g of sodium hydrogen carbonate was added, and the mixture was stirred for 1 hour. After filtration, vacuum distillation was performed at 150 ° C. and 3 torr to remove low-boiling substances. Then 60 g of 2-allylphenol and platinum as platinum chloride-alcoholate complex
To a mixture with 0.0014 g of oil 29 obtained above
4 g were added at a temperature of 90 ° C. 90 to 1 of this mixture
The mixture was stirred for 3 hours while maintaining the temperature of 15 ° C. The product was extracted with methylene chloride and washed 3 times with 80% aqueous methanol to remove excess 2-allylphenol. The product was dried over anhydrous sodium sulphate and evaporated in vacuo to a temperature of 115 ° C. Obtained phenol P at both ends
In the DMS, the number of repeating dimethylsilanooxy units was 150 as measured by NMR.

Example 1 [Synthesis of Polycarbonate-Polyorganosiloxane Triblock Copolymer (referred to as PC-PDMS Copolymer A)] One end reactive PDMS-A3, obtained in Production Example 2-1
954 g (0.35 mol) was dissolved in 9 liters of methylene chloride and mixed with 10 liters of the PC oligomer obtained in Production Example 1. To this, 56 g of sodium hydroxide dissolved in 1 liter of water and 5.7 cc of triethylamine were added, and the mixture was stirred at 500 rpm for 1 hour at room temperature. Then, an alkaline solution of bisphenol A (650 g of bisphenol A, 378 g of sodium hydroxide, 4.5 liters of water) was added, and the mixture was stirred at 500 rpm for 1 hour at room temperature.
Then, add 6 liters of methylene chloride and add 5 more water.
Rinse with water, 0.01N sodium hydroxide solution 5
Alkali washing with liter, acid washing with 5 liters of 0.1N hydrochloric acid and water washing with 5 liters of water (twice) are carried out in order, and finally methylene chloride is removed to give flaky PC-PDMS.
A copolymer A was obtained.

Example 2 [Synthesis of Polycarbonate-Polyorganosiloxane Triblock Copolymer (referred to as PC-PDMS Copolymer B)] In Example 1, one end-reactive PDMS-A3,
954 g of PDMS-B reactive with one end was 5,421 g (0.6
Flake-like PC-PDMS copolymer B was obtained in the same manner as in Example 1 except that the amount was changed to 0 mol).

Comparative Example 1 [Synthesis of Polycarbonate-Polyorganosiloxane Triblock Copolymer (referred to as PC-PDMS Copolymer C)] In Example 1, one end reactive PDMS-A3,
One-terminal reactive PDMS-C2 (138 g, 954 g) (0.3 g)
A flake PC-PDMS copolymer C was obtained in the same manner as in Example 1 except that the amount was changed to 5 mol).

Comparative Example 2 [Synthesis of Polycarbonate-Polyorganosiloxane Triblock Copolymer (referred to as PC-PDMS Copolymer D)] In Example 1, one end reactive PDMS-A3,
954 g of PDMS-D having one end reactive with 627 g (0.60 g)
A flake PC-PDMS copolymer D was obtained in the same manner as in Example 1 except that the amount was changed to mol.

Comparative Example 3 Synthesis of Polycarbonate-Polyorganosiloxane Triblock Copolymer (referred to as PC-PDMS Copolymer E) In Example 1, one end reactive PDMS-A3,
954 g is PDMS-E3 reactive with both ends, 954 g (0.3
5 mol) and p-tert-butylphenol 52.7 g
A flake PC-PDMS copolymer E was obtained in the same manner as in Example 1 except that (0.35 mol) was used.

Example 3 [Synthesis of Polycarbonate-Polyorganosiloxane Triblock Copolymer (referred to as PC-PDMS Copolymer F)] In Example 1, one end reactive PDMS-A3,
954 g was changed to 3,163 g (0.28 mol) and p-tert
-Flake-shaped PC-P was carried out in the same manner as in Example 1 except that 10.5 g (0.07 mol) of butylphenol was used.
DMS copolymer F was obtained.

PC-PDMS copolymers A, B and F obtained in Examples 1 to 3 and PC-P obtained in Comparative Examples 1 to 3.
For DMS copolymers C to E, PDMS content, m
(Number of repetitions of polycarbonate part) and n (PDMS
The number of repetitions was measured. The results are shown in Table 1.

[0055]

[Table 1]

The PDMS content and m were measured as follows. 1) PDMS content It was calculated from the intensity ratio of the isopropyl methyl group peak of bisphenol A found at 1.7 ppm and the dimethylsiloxane methyl group peak found at 0.2 ppm in ¹ H NMR. 2) Repeating unit of polycarbonate part (m) Calculated from the composition ratio of the copolymer by ¹ HNMR.

Examples 4 to 11 and Comparative Examples 4 to 12 PC-PDMS copolymers A to F, polycarbonate resin (PC resin) [Taflon A150 manufactured by Idemitsu Petrochemical Co., Ltd.]
0] and an inorganic filler in the proportions shown in Table 2,
Pelletized by extruder with mm vent. In addition,
As the inorganic filler, GF [Asahi Fiber Glass Co., Ltd.
MA-409C] and CF [H from Toho Rayon Co., Ltd.]
TA-C6-CS] was used to supply the raw material resin of the extruder from the downstream side of the hopper supply position. Then, in Example 4 and Comparative Example 7, trisnonylphenyl phosphite (200 ppm) was added as an antioxidant and pelletized. Further, in Comparative Example 8, silicone oil [Toray
SH200-35 made by Dow Corning Silicone Co., Ltd.
0] of 5,000 ppm was added and pelletized. The obtained pellets are 280 to 300 ° C. using an injection molding machine.
A test piece was prepared by molding at the molding temperature of. The flow value and the mold release pressure were measured for each pellet, and the breaking strength was measured for each test piece. The results are shown in Table 3.

[0058]

[Table 2]

[0059]

[Table 3]

The flow value, mold release pressure and breaking strength were measured as follows. 1: Flow value Measured according to JIS K-7210. 2: Mold release pressure Using a cylindrical mold, the mold release resistance at the time of protrusion (mold release) was measured. 3: Breaking strength Measured according to JIS K-7113.

[0061]

INDUSTRIAL APPLICABILITY As described above, the polycarbonate-polyorganosiloxane triblock copolymer of the present invention has excellent fluidity and can be produced efficiently, and the resin composition has excellent releasability, impact resistance, and It has excellent fluidity and rigidity. Therefore, the polycarbonate-polyorganosiloxane triblock copolymer and the resin composition of the present invention are used as materials for various molded products, for example, various molded products widely used in the fields of electric / electronic devices and automobiles. It is effectively used.

[Brief description of drawings]

FIG. 1 is a diagram showing a flow of an example of a method for producing a polycarbonate-polyorganosiloxane triblock copolymer of the present invention by an interfacial polycondensation method.

Claims (2)

(57) [Claims] 1. A compound represented by the general formula (I): [In the formula, R ¹ and R ² each represent a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may be the same or different, p And q are integers of 0 to 4, and m is 1 to 15.
It is 0. Z is a single bond, an alkylene group having 1 to 20 carbon atoms or an alkylidene group, a cycloalkylene group having 5 to 20 carbon atoms or a cycloalkylidene group, -O-,-.
S -, - SO -, - SO 2 -, - CO- bond or general formula (II) or (II ') ## STR2 ## Indicates a bond represented by. R ^{3 to} R ⁶ each represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may be the same or different, and n is 101 to 500. is there. R ⁷ represents an aliphatic and / or aromatic divalent organic residue, and R ⁸ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. A is a single bond, -O- or -NH-.
Indicates. ] The polycarbonate-polyorganosiloxane triblock copolymer represented by these. 2. Polycarbonate-polyorganosiloxane triblock copolymer (A) according to claim 1, 0.5 to
30% by weight, (B) Polycarbonate resin 10-94.5
Wt% and (C) 5 to 60 wt% inorganic filler,
A resin composition having a polyorganosiloxane content of 0.1 to 20% by weight.