JPH07173275A - Polycarbonate resin, production thereof and resin composition - Google Patents

Abstract

PURPOSE:To prepare a polycarbonate resin having improved releasability by copolymerizing polycarbonate with polyorganosiloxane to give a polymer contg. an A-B type block polymer. CONSTITUTION:A polycarbonate resin comprising a polycarbonate/ polyorganosiloxane copolymer represented by the formula I wherein R<1> and R<2> represent each a halogen, a 1-8C alkyl, or a 6-20C aryl; p and q are 0 to 4; m is 1 to 150; R<3> represents a halogen, a 1-20C alkyl, a 6-20C aryl, or a 7-20C arylalkyl; r is 0 to 5; Z represents a single bond, a 1-20C alkyl, a 1-20C alkylene, alkylidene, a 5-20C cycloalkylene, a cycloalkylidene, -O-, -S-, -SO2-, formula II, or formula III; R<4> to R<7> represent each a 1-8C alkyl or a 6-20C aryl; n is 1 to 500; R<8> represents a 1-8C alkyl or a 6-20C aryl; and A represents a single bond, -O-, or -NH-). It has a viscosity-average mol.wt. of 10,000 to 50,000 and a polyorganosiloxane content of 0.1 to 20wt.%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate resin, a method for producing the same, and a resin composition. More specifically, the present invention relates to a polycarbonate resin excellent in mold releasability, impact resistance, fluidity and rigidity, a method for producing the same, and a resin composition.

[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 has excellent releasability, impact resistance, fluidity and rigidity, and a polycarbonate resin, In order to develop a manufacturing method and a resin composition, earnest research was repeated. As a result, by using a polycarbonate resin containing an AB type block polymer which is a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing the polycarbonate (A) and the polyorganosiloxane (B), It has been found that the releasability of the film 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 4]

[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. R ³ is a halogen atom, carbon number 1
To an alkyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, and r is 0 to
It is an integer of 5. Z is a single bond and has 1 to 2 carbon atoms.
0 alkylene group or alkylidene group, 5 to 20 carbon atoms
A cycloalkylene group or a cycloalkylidene group, -O
-, - S -, - SO 2 - bond or the formula (II) or (II ')

[0007]

[Chemical 5]

The bond represented by Also, R ^{4 to} R ⁷
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 1 to 500. R ⁸ represents a divalent organic residue containing aliphatic and / or aromatic,
R ⁹ is an alkyl group having 1 to 8 carbon atoms or 6 to 2 carbon atoms.
The aryl group of 0 is shown. And A shows a single bond, -O-, or -NH-. ] A polycarbonate-based resin containing a polycarbonate-polyorganosiloxane copolymer represented by the following, wherein the viscosity-average molecular weight of the polycarbonate-based resin is from 10,000 to 50,000, and the polycarbonate-based resin is The present invention provides a polycarbonate resin, characterized in that the content of polyorganosiloxane in the resin is 0.1 to 20% by weight. Further, the present invention, in the presence of a dihydric phenol and a monohydric phenol, a polycarbonate oligomer, the general formula (III)

[0009]

[Chemical 6]

[In the formula, each of R ^{4 to} R ⁷ has 1 carbon atom.
To 8 alkyl groups or 6 to 20 carbon aryl groups, which may be the same or different, and n is 1 to 500. R ⁸ represents a divalent organic residue containing aliphatic and / or aromatic, and R ⁹ represents 1 carbon atom
Is an alkyl group having 8 to 8 or an aryl group having 6 to 20 carbon atoms. A represents a single bond, -O- or -NH-,
n is 1 to 500. ] And a reactive polyorganosiloxane of which one end is sealed is reacted,
A monohydric phenol is used in an amount of 5 times or more (molar ratio) with respect to the reactive polyorganosiloxane represented by the general formula (III), the one end of which is blocked. The reactive polyorganosiloxane represented by the formula (III) with one end blocked is 0.12.
The present invention provides a method for producing a polycarbonate-based resin, which comprises using ~ 35 parts by weight. Furthermore, the present invention comprises (A) 10 to 95% by weight of the above polycarbonate resin, (B) 0 to 80% by weight of the polycarbonate resin, and (C) 5 to 60% by weight of an inorganic filler. A resin composition is provided.

First, the polycarbonate resin of the present invention has the general formula (I)

[0012]

[Chemical 7]

It is characterized by containing a polycarbonate-polyorganosiloxane copolymer represented by (hereinafter sometimes abbreviated as PC-PDMS copolymer). 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), a carbon number of 1 to 1.
8 alkyl group (eg, methyl group, ethyl group, propyl group, n-butyl group, isobutyl 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, and p and q are 0
Is an integer of 4 and m is 1 to 150, preferably 3 to 1
40, particularly preferably 5 to 130. And Z
Is a single bond, an alkylene group having 1 to 20 carbon atoms, preferably 2 to 18 carbon atoms, or an alkylden group (for example, a methylene group,
Ethylene group, propylene group, butylene group, penterylene group, hexylene group, ethylidene group, isopropylidene group, etc.), cycloalkylene group having 5 to 20 carbon atoms or cycloalkylidene group (for example, cyclopentylene group, cyclohexylene group, cyclo (Pentylidene group, cyclohexylidene group, etc.), —O—, —S—, —SO ₂ —, —CO
-Bond or general formula (II) or (II ')

[0014]

[Chemical 8]

The bond represented by

Further, R ^{4 to} R ⁷ are each a carbon number of 1 to
8 alkyl group (eg, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group) or an aryl group having 6 to 20 carbon atoms, preferably 6 to 18 carbon atoms ( For example, a phenyl group, a tolyl group, a xylyl group, and a naphthyl group are shown, and they may be the same or different. And n is 1
~ 500, preferably 51-500, more preferably 1
It is 01 to 500. R ⁸ 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 (IV), (IV ') or (IV ")

[0017]

[Chemical 9]

[In the formula, (A) and (Si) represent bonding with 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
⁹ is an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group) or 6 carbon atoms
~ 20, preferably 6-18 aryl groups (eg, phenyl, tolyl, xylyl, naphthyl, 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 (V)

[0020]

[Chemical 10]

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

[0022]

[Chemical 11]

[In the formula, R ^{4 to} R ⁷ , R ⁸ , R ⁹ , A and n are the same as defined above. ] The polyorganosiloxane (PDMS) in which one end of the structural unit II represented by
It is an AB type diblock copolymer composed of a part. And, one end of the polycarbonate (PC) part of the repeating unit I represented by the general formula (V) has the general formula (VII)

[0024]

[Chemical 12]

A terminal group derived from a monohydric phenol represented by is bonded and sealed. Here, in the terminal group represented by the general formula (VII), R ³ is a halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), a carbon number of 1 to 1.
20 alkyl groups (for example, methyl group, ethyl group, propyl group, n-butyl group, tert-butyl group, isobutyl group, tert-amyl group, isoamyl group, n-hexyl group,
tert-octyl group, nonyl group, etc.), aryl group having 6 to 20 carbon atoms (eg, phenyl group, tolyl group, xylyl group, naphthyl group, etc.) or arylalkyl group having 7 to 20 carbon atoms (eg, α, α) -Dimethylbenzyl group, etc.)
Is shown and r is an integer of 0-5.

In the above-mentioned PC-PDMS copolymer, homoPC (that is, a homopolymer having only repeating unit I as a main chain) is usually produced during the production process. Therefore, the polycarbonate resin of the present invention is a blend with homo PC and contains a PC-PDMS copolymer. The viscosity average molecular weight of this polycarbonate resin is from 10,000 to 50,000, preferably from 12,000.
It is 40,000. If the viscosity average molecular weight is less than 10,000, the mechanical strength will decrease. Further, if it exceeds 50,000, the solution viscosity at the time of polymerization becomes high, which is not preferable in production. Also, injection molding becomes difficult. In addition, the polyorganosiloxane content in the polycarbonate resin is 0.1 to
It is 20% by weight, preferably 0.2 to 18% by weight. If the content is less than 0.1% by weight, the releasability is not improved.
Further, if it exceeds 20% by weight, the heat resistance is lowered, which is not preferable.

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

[0028]

[Chemical 13]

[In the formula, R ^{4 to} R ⁷ , R ⁸ , R ⁹ , A and n are the same as described above. ] Reactive polyorganosiloxane having one end blocked (hereinafter referred to as reactive PD
Sometimes abbreviated as MS. ) And the monohydric phenol is used in an amount of 5 times (molar ratio) or more, preferably 10 times, and more preferably 20 times or more of the reactive PDMS represented by the general formula (III). , And the reactive PDMS was 0.12 to 100 parts by weight of PC oligomer.
The PC-PDMS copolymer can be prepared by using 35 parts by weight, preferably 0.2 to 33 parts by weight. According to the above method, the polycarbonate resin of the present invention described above can be efficiently produced. Furthermore, other types of PC-PDMS copolymers can be produced by appropriately selecting PC oligomer, monohydric phenol and dihydric phenol.

Here, various PC oligomers can be used for the production of the PC-PDMS copolymer, but in the production method of the present invention, the repeating unit represented by the general formula (V) is usually used. This PC oligomer has the general formula (VIII) in the solvent method, that is, in the presence of a known acid acceptor and a terminal stopper (monohydric phenol) in an organic solvent such as methylene chloride.

[0031]

[Chemical 14]

[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 (VIII)
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;
3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiarylketones such as 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 (V), which is constituted by a reaction of a dihydric phenol and phosgene in the polycondensation reaction.
That is, the PC oligomer is reacted with 100 of the dihydric phenol in a molar ratio of phosgene 110 to 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, etc. and, if necessary, a catalyst such as triethylamine or trimethylbenzylammonium chloride at a predetermined ratio. It can be produced by stirring, blowing phosgene into the mixture, and advancing the interfacial polycondensation reaction at a reaction temperature of 30 to 70 ° C. for 1 to 3 hours. 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 2,000 or less 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.

Here, 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.

Various types of end terminators can be used. 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
-Bromophenol, tribromophenol, nonylphenol and the like. The PC-PDM of the present invention
To prepare the S copolymer, the general formula (IX)

[0038]

[Chemical 15]

[In the formula, R ³ and r are the same as defined above. ] The terminal stopper (monohydric phenol) represented by the following is preferably used.

Next, the reactive PD represented by the general formula (III)
MS has one end sealed and a reactive group at the other end. Particularly, those having a phenolic OH group as the reactive group are preferably used. This reactive PDMS can be manufactured by various techniques. 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.) in an organic solvent to seal one end with a dimethylalkylsiloxane unit and the other end with a living end with a dimethyllithium siloxane unit. Then, it is reacted with a dialkyl silicon halide such as dimethylchlorosilane or dimethylbromosilane to obtain polydimethylsiloxane having hydrogen at one end. Next, this is reacted with an aliphatic unsaturated phenol [eg, 2-allylphenol, 4-hydroxystyrene, eugenol (2-methoxy-4-allylphenol), etc.] to give a phenolic O-terminal at one end.
Polydimethylsiloxane having H can be obtained.

In the present invention, the PC-PDMS copolymer comprises the above-prepared PC oligomer and a reactive polyorganosiloxane having one end blocked with a reactive group at one end, as an organic solvent. And an aqueous solution of an alkali metal hydroxide of a dihydric phenol or a monohydric phenol (end terminating agent) is added, and various interfaces are used to carry out an interfacial polycondensation reaction. here,
As the dihydric phenol, various ones can be used, but preferably the same dihydric phenol as that used in the production of the PC oligomer can be mentioned.
Also, the monohydric phenol may be the same as that used in the production of the PC oligomer. The total amount of these monohydric phenols needs to be 5 or more, preferably 10 or more, and more preferably a molar ratio with the reactive polyorganosiloxane (monohydric phenol / reactive polyorganosiloxane). 20
That is all. And, in the present invention, as a branching agent, 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; isatin bis (o-cresol)
A compound having three or more equifunctional groups 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 a method for producing a polycarbonate-based resin containing an MS copolymer. That is, first, a dihydric phenol and phosgene are reacted in an organic solvent to produce a PC oligomer in advance. Then, the PC oligomer, the reactive PDMS produced in advance, the monohydric phenol (end-terminating agent) and the dihydric phenol are reacted in an organic solvent. During this reaction, the reactive PDMS is added neat or as a methylene chloride solution. Further, the terminal stopper is added as a methylene chloride solution or an alkaline aqueous 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 preferable to add the dihydric phenol last. The reaction time is 30 minutes to 2 hours, and the reaction temperature is 20 to 40 ° C. PC-
The PDMS copolymer is produced as described above as an example. In the production process, homo PC is also produced,
The reaction product is essentially obtained as a mixture of PC-PDMS copolymer and homoPC. Therefore, the polycarbonate resin of the present invention contains a PC-PDMS copolymer.

Next, the polycarbonate resin composition of the present invention comprises (A) the above polycarbonate resin and (B)
Consisting of polycarbonate resin and (C) inorganic filler,
And 10 to 95% by weight of the component (A) and 0 of the component (B)
-80% by weight and 5-60% by weight of the component (C), preferably 10-50% by weight. 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, the dihydric phenol may be the same as or different from the compound represented by the general formula (VIII). 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. Here, examples of the inorganic filler include potassium titanate whiskers, mineral fibers (for example, rock wool), glass fibers, carbon fibers, metal fibers (for example, stainless fibers), aluminum borate whiskers, silicon nitride whiskers, and boron. Fiber, tetrapod-shaped zinc oxide whiskers, talc, clay, mica, pearl mica, aluminum foil, alumina, glass flakes, glass beads, glass balloons, carbon black, graphite, calcium carbonate,
Examples thereof include calcium sulfate, calcium silicate, 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 0.1-
8 mm, preferably in the range of 0.3 to 6 mm, and the fiber diameter is 0.1 to 30 μm, preferably 0.5 to 25
μm. 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. Examples of the surface treatment agent include silane-based agents such as aminosilane-based, epoxysilane-based, vinylsilane-based, acrylsilane-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 of treating the glass fiber with the 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 using these sizing agents is not particularly limited, and a conventionally used method, for example, dip coating, roller coating, spray coating, flow coating,
Any method such as spray coating can be used.

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 additive, for example, a hindered phenol-based, phosphite-based, phosphoric ester-based, amine-based antioxidant, for example, a benzotriazole-based, benzophenone-based ultraviolet absorber, 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 (A). 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 method usually used, 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.

[0050]

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 Reactive PDMS-A] 1.73 g of butyllithium
(0.027 mol) in tetrahydrofuran (THF) 35
It was dissolved in 0 ml and kept at 0 ° C or lower. Further, 300 g (1.35 mol) of hexamethylcyclotrisiloxane was dissolved in 170 ml of THF and kept at 0 ° C or lower. Both were mixed, kept at 0 ° C. or lower, and stirred for 10 hours. Then, 2.55 g of dimethylchlorosilane (0.02
(7 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. After filtering the obtained precipitate, 1
Vacuum evaporation was carried out at 50 ° C. and 3 torr to remove low-boiling substances to obtain an oil. Then, 60 g of 2-allylphenol and 0.0014 g of platinum as a platinum chloride-alcoholate complex.
294 g of the oil obtained above in a mixture with
Was added at the temperature of. The mixture was stirred for 3 hours while maintaining the temperature of 90 to 115 ° 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 terminal phenol PDMS is NM
By measurement of R, the number of repeating dimethylsilanooxy units was 150.

Production Example 2-2 [Synthesis of Reactive PDMS-B] In Production Example 2-1
Production Example 2-1 except that 1.73 g of butyl lithium was changed to 3.26 g (0.034 mol) of lithium trimethyl silylate and 2.55 g of dimethylchlorosilane was changed to 3.21 g (0.034 mol). It carried out similarly. In the obtained terminal phenol PDMS, the number of repeating dimethylsilanooxy units was 120 as measured by NMR.

Production Example 2-3 [Synthesis of Reactive PDMS-C] In Production Example 2-1
Butyllithium 1.73 g to 3.20 g (0.05 mol),
Also, 2.53 g of dimethylchlorosilane was added to 4.73 g (0.0
The procedure of Production Example 2-1 was repeated, except that the amount was changed to 5 mol. The terminal phenol PDMS thus obtained had a dimethylsilanooxy unit repeating number of 80 by NMR measurement.
Met.

Production Example 2-4 [Synthesis of Reactive PDMS-D] 1,483 g of octamethylcyclotetrasiloxane, 18.1 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% sulfuric acid were mixed, It was 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 at 150 ° C, 3 torr,
Low boilers were removed. 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. Obtained phenol PD at both ends
As for MS, the number of repeating dimethylsilanooxy units was 150 as measured by NMR.

Example 1 [Polycarbonate resin (PC-PDMS copolymer A
Called. Synthesis of)] Reactive PDMS obtained in Production Example 2-1
-A 91 g (0.0081 mol) was dissolved in 2 liters of methylene chloride and mixed with 10 liters of the PC oligomer obtained in Production Example 1. Thereto, 56 g of sodium hydroxide dissolved in 1 liter of water and triethylamine 5.7
cc was added, and the mixture was stirred at 500 rpm for 1 hour at room temperature.
Then, in an alkaline solution of bisphenol A (650 g of bisphenol A, 378 g of sodium hydroxide, 4.5 liters of water), 4 liters of methylene chloride and p-tert.
-Add 119 g (0.793 mol) of butylphenol,
The mixture was stirred at room temperature at 500 rpm for 1 hour. Then, add 8 liters of methylene chloride, wash with 5 liters of water, wash with 5 liters of 0.01N aqueous sodium hydroxide solution with alkali, wash with 5 liters of 0.1N hydrochloric acid and wash with water 5.
It was washed successively with water (twice), and finally methylene chloride was removed to obtain flaky PC-PDMS copolymer A.

Example 2 [Polycarbonate resin (PC-PDMS copolymer B
Called. )] In Example 1, reactive PDMS
-A PC-PD in the form of flakes was prepared in the same manner as in Example 1 except that 91g of A was changed to 185g (0.016mol).
MS copolymer B was obtained. Example 3 [Polycarbonate-based resin (PC-PDMS copolymer C
Called. )] In Example 1, reactive PDMS
A flaky PC-PD was carried out in the same manner as in Example 1, except that 91 g of A was changed to 380 g (0.034 mol).
MS copolymer C was obtained.

Example 4 [Polycarbonate resin (PC-PDMS copolymer D
Called. )] In Example 1, reactive PDMS
-A 91 g to reactive PDMS-B 740 g (0.082 mol) and p-tert-butylphenol 119
Flake-like PC-PDMS copolymer D was obtained in the same manner as in Example 1 except that 103 g (0.485 mol) of p-cumylphenol was used instead of g.

Example 5 [Polycarbonate resin (PC-PDMS copolymer E
Called. )] In Example 1, reactive PDMS
A flaky PC-PDMS copolymer E was obtained in the same manner as in Example 1 except that 91 g of -A was changed to 185 g of reactive PDMS-C (0.030 mol). Example 6 [Polycarbonate-based resin (PC-PDMS copolymer F
Called. )] In Example 1, reactive PDMS
-A flakes of PC-PD were carried out in the same manner as in Example 1 except that the amount of 91 g was changed to 23 g (0.0020 mol).
MS copolymer F was obtained.

Comparative Example 1 [Polycarbonate resin (PC-PDMS copolymer G
Called. )] In Example 1, reactive PDMS
A flaky PC-PDMS copolymer F was obtained in the same manner as in Example 1 except that 91 g of -A was changed to 185 g of reactive PDMS-C (0.030 mol). Examples 1-6
And PC-PDMS copolymers A to F obtained in Comparative Example 1
The viscosity average molecular weight, the PDMS content, and the flow value of the PC-PDMS copolymer G were measured. The results are shown in Table 1.

[0060]

[Table 1]

The PDMS content, viscosity average molecular weight and flow value were measured as follows. 1: PDMS content It was calculated from the intensity ratio of the isopropyl methyl group peak of bisphenol A seen at 1.7 ppm in ¹ HNMR and the dimethylsiloxane methyl group peak seen at 0.2 ppm. 2: Viscosity average molecular weight (Mv) The viscosity of the methylene chloride solution at 20 ° C. was measured using an Ubbelohde type viscosity tube, and the intrinsic viscosity [η] was calculated from this, and then calculated by the following formula. [Η] = 1.23 × 10 ⁻⁵ × Mv ^0.83 3: Flow value Measured in accordance with JIS K-7210.

Examples 7 to 14 and Comparative Examples 2 to 7 PC-PDMS copolymers A to E, G, polycarbonate resin (PC resin) [Taflon A1 manufactured by Idemitsu Petrochemical Co., Ltd.]
500] and an inorganic filler in the proportions shown in Table 2,
Pelletized with a 30 mm vented extruder. As the inorganic filler, GF [MA-409C manufactured by Asahi Fiber Glass Co., Ltd.] and CF [HTA-C6-CS manufactured by Toho Rayon Co., Ltd.] were used, rather than the feed position of the raw material resin of the extruder. It was supplied from the downstream side. Then, to Example 2 and Comparative Example 3, trisnonylphenylphosphite 200 ppm was added as an antioxidant,
Pelletized. In Comparative Example 3, silicone oil [SH2 manufactured by Toray Dow Corning Silicone Co., Ltd.
[00-350] at 5,000 ppm was added and pelletized. The obtained pellets are 280 using an injection molding machine.
A test piece was prepared by molding at a molding temperature of 300 ° C. 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.

[0063]

[Table 2]

[0064]

[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.

[0066]

INDUSTRIAL APPLICABILITY As described above, the polycarbonate resin of the present invention has a sufficient molecular weight of the PC-PDMS copolymer contained therein, has excellent fluidity, and can be efficiently produced. It has excellent releasability, impact resistance, fluidity and rigidity. Therefore, the polycarbonate resin composition of the present invention can be effectively used as a material for various molded products, for example, various molded products widely used in the fields of electric and electronic devices, automobiles and the like.

[Brief description of drawings]

FIG. 1 is a diagram showing a flow of an example of a method for producing a resin composition of the present invention by an interfacial polycondensation method.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area C08L 83/10 LRX

Claims (4)

[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. R ³ is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or 7 to 2 carbon atoms
The arylalkyl group of 0 is shown, r is an integer of 0-5. 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 ₂
-Bond or general formula (II) or (II ') Indicates a bond represented by. R ^{4 to} R ⁷ 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 1 to 500. is there. R ⁸ is aliphatic and /
Alternatively, a divalent organic residue containing an aromatic group is shown, and R ⁹ is an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms. And A shows a single bond, -O-, or -NH-. ] A polycarbonate-based resin containing a polycarbonate-polyorganosiloxane copolymer represented by the following, wherein the viscosity-average molecular weight of the polycarbonate-based resin is from 10,000 to 50,000, and the polycarbonate-based resin is The content of polyorganosiloxane in the product is 0.
A polycarbonate-based resin, which is 1 to 20% by weight. 2. A polycarbonate oligomer and a compound of the general formula (III) in the presence of a dihydric phenol and a monohydric phenol. [In the formula, R ^{4 to} R ⁷ 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 1 to 1 5
00. R ⁸ represents a divalent organic residue containing an aliphatic and / or aromatic, and R ⁹ represents an alkyl group or an aryl group having 6 to 20 carbon atoms having 1 to 8 carbon atoms. And A
Represents a single bond, -O- or -NH-, and n is 1 to 500.
Is. ] The reactive polyorganosiloxane having one end blocked is reacted with, and the monohydric phenol is reacted with the reactive polyorganosiloxane having one end blocked represented by the general formula (III). 0.12 to 35 parts by weight of the reactive polyorganosiloxane represented by the general formula (III) with one end blocked, relative to 100 parts by weight of the polycarbonate oligomer, in an amount of 5 times or more (molar ratio). A method for producing a polycarbonate-based resin, which comprises using the same. 3. The method for producing a polycarbonate resin according to claim 2, wherein the polycarbonate resin is the polycarbonate resin according to claim 1. 4. A composition comprising (A) 10 to 95% by weight of the polycarbonate resin according to claim 1, (B) 0 to 80% by weight of a polycarbonate resin, and (C) 5 to 60% by weight of an inorganic filler. A polycarbonate resin composition.