JPH06329781A - Polycarbonate/polyorganosiloxane copolymer and resin composition - Google Patents

Abstract

PURPOSE:To obtain the title copolymer which has a main chain made up of specific repeating units and a specific structural unit, has a given viscosity- average mol.wt., and is excellent in flame retardancy, impact resistance, transparency, and releasability. CONSTITUTION:The copolymer has a main chain made up of the repeating units represented by formula I wherein R<1> and R<2> are each a 1-6C alkyl or a 6-12C aryl; m and n are each 0-4; and Z is a single bond, a 1-6C alkylene or alkylidene, a 5-20C cycloalkylene or cycloalkylidene, fluorenylidene, O, S, SO, SO2, or CO, the repeating units represented by formula II wherein X<1> to X<4> are each a halogen and Y has the same meaning as Z, and the structural unit represented by formula III wherein R<3> to R<6> are each H, a 1-6C alkyl, or phenyl; R<7> and R<8> are each an organic group containing an aliphatic or aromatic group; A is O, NH, or a single bond; and j is 100-500, in the amount of the units II being 1-10mol% based on the sum of the units I and II and that of the unit III being 0.01-10wt.% based on the sum of the units I, II, and III. The copolymer has a viscosity-average mol.wt. of 10,000-50,000.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polycarbonate-polyorganosiloxane copolymer and a resin composition.
More specifically, the present invention relates to a polycarbonate-polyorganosiloxane copolymer excellent in flame retardancy, impact resistance and releasability, and a resin composition containing the copolymer and the like.

[0002]

2. Description of the Related Art Conventionally, various flame-retardant halogen-containing copolycarbonates have been proposed. For example, Japanese Patent Publication No. 46-40715 and Japanese Patent Publication No. 47-24660.
Japanese Patent Publication [Tetrabromobisphenol A (TBA) and Bisphenol A (BPA) Copolymer], JP-A-51
-123294 (copolymer of tetrabromobisphenol sulfone (TBS) and BPA), JP-A-51
No. 136796 [Copolymer of statistical mixture of halogenated bisphenol and BPA], JP-A-52-14
No. 0597, JP-A-54-50065 [Copolymer of thiodiphenol (TDP) and BPA, tetrabromobisphenol A (TBA) and bisphenol A]
Blend with (BPA) Copolymer], JP-A-56-
No. 99226 [Tetrabromothiodiphenol (T
BTDP) and BPA copolymer] and the like are known. These copolymers are obtained by copolymerizing halogenated bisphenols in which a benzene nucleus of bisphenols is substituted with halogen. However, both of them have a problem that these halogenated bisphenols must be used in a relatively large amount, and accordingly, the mechanical strength (particularly impact resistance strength) of the polycarbonate must be sacrificed. Other halogen-containing polycarbonates are also known in Japanese Examined Patent Publication No. 46-40715 [using halogenated phenols as terminal terminators]. However, also in this case, it is not possible to impart both flame retardancy and mechanical strength. As a method for improving the above-mentioned drawbacks, a method in which polyhalogenophenol is used as a terminal terminating agent and BPA and a halogenated bisphenol are copolymerized [eg, JP-A-64-79227].
JP-A-64-79228, JP-A-3-2
[00833] and the like] are known, and flame retardancy and impact resistance can be imparted at the same time by these methods. As a result of further research, the present inventors succeeded in exhibiting excellent flame retardancy and impact resistance by copolymerizing a dihydric phenol, a halogenated bisphenol and a polyorganosiloxane.

[0003]

[Means for Solving the Problems] That is, a polycarbonate-polyorganosiloxane copolymer comprising a specific polycarbonate polymer composed of a dihydric phenol and a halogenated bisphenol, and a specific polyorganosiloxane polymer, and the copolymer. It was found that the resin composition containing the above has the desired properties. The present invention has been completed based on such findings.

In the present invention, the main chain is (a) general formula (I)

[0005]

[Chemical 11]

[In the formula, R ¹ and R ² each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may be the same or different, m And n are integers of 0 to 4, respectively. Z is
Single bond, C1-C6 alkylene group or alkylden group, C5-C20 cycloalkylene group, cycloalkylidene group, fluorenylidene group, or -O-, -S
-, - SO -, - indicating the or -CO- bond - SO _2. ] The repeating unit I represented by the formula (b) general formula (II)

[0007]

[Chemical 12]

[In the formula, X ^{1 to} X ⁴ each represent a halogen atom. Y is a single bond, an alkylene group having 1 to 6 carbon atoms or an alkylden group, a cycloalkylene group having 5 to 20 carbon atoms, a cycloalkylidene group, a fluorenylidene group,
Or -O -, - S -, - SO -, - SO 2 - or -CO
-Indicating binding. ] The repeating unit II and (c) the general formula (III)

[0009]

[Chemical 13]

[In the formula, R ^{3 to} R ⁶ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group,
They may be the same or different. R ⁷ and R ⁸ each represent an organic residue containing an aliphatic or aromatic group, and A represents —O—, —NH— or a single bond. j is an integer of 101 to 500. ] A repeating unit I and a repeating unit having a content of repeating unit II in the main chain
1 to 10 mol% relative to the total amount of II,
The content of structural unit III is such that repeating unit I and repeating unit II
And 0.01 to 10% by weight with respect to the total amount of the structural unit III, and the viscosity average molecular weight thereof is 10,000 to 50,0.
And a polycarbonate-polyorganosiloxane copolymer I.

In the present invention, the main chain (A) is (a) the general formula (I).

[0012]

[Chemical 14]

[Wherein R ¹ and R ² each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may be the same or different, m And n are integers of 0 to 4, respectively. Z
Is a single bond, an alkylene group having 1 to 6 carbon atoms or an alkylden group, a cycloalkylene group having 5 to 20 carbon atoms, a cycloalkylidene group, a fluorenylidene group, or -O-,-.
S -, - SO -, - indicating the or -CO- bond - SO _2. ] The repeating unit I represented by the formula (b) general formula (II)

[0014]

[Chemical 15]

[In the formula, X ^{1 to} X ⁴ each represent a halogen atom. Y is a single bond, an alkylene group having 1 to 6 carbon atoms or an alkylden group, a cycloalkylene group having 5 to 20 carbon atoms, a cycloalkylidene group, a fluorenylidene group,
Or -O -, - S -, - SO -, - SO 2 - or -CO
-Indicating binding. ] The repeating unit II and (c) the general formula (III ')

[0016]

[Chemical 16]

[Wherein R³~ R⁶Is the hydrogen source
Child, an alkyl group having 1 to 6 carbon atoms or a phenyl group
But they may be the same or different
Yes. Also, R ⁷And R⁸Are respectively aliphatic or aromatic
Represents an organic residue containing, A is -O-, -NH-
Indicates binding. p is an integer of 1 to 500. ]]
Having a structural unit III ′ having the general formula (IV)

[0018]

[Chemical 17]

[In the formula, X ⁵ represents a halogen atom, and k is an integer of 1 to 5. When k is plural, plural X
Each ⁵ may be the same or different. ] The end group IV of the polyhalogenophenoxy group represented by
Polycarbonate-polyorganosiloxane copolymer II 85-99.99% by weight and (B) pigment 15-0.
The present invention also provides a resin composition characterized by comprising 01% by weight.

First, the polycarbonate-polyorganosiloxane copolymer I (hereinafter abbreviated as PC-PDMS copolymer I) of the present invention is represented by the general formula (I) in which the main chain is the component (a). The repeating unit I is represented by the formula (II), which is the component (b), and the structural unit III represented by the formula (III), which is the component (c). Here, R ¹ and R ² in the repeating unit I represented by the general formula (I) are each an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, n-butyl group, Isobutyl group, amyl group, isoamyl group, hexyl group, etc.) or aryl group having 6 to 12 carbon atoms (eg,
(Phenyl group, tolyl group, xylyl group, naphthyl group, etc.)
May be the same or different, and m and n are each an integer of 0 to 4. Z is a single bond, an alkylene group having 1 to 6 carbon atoms or an alkylidene group (for example, methylene group, ethylene group, propylene group, butylene group, penterylene group, hexylene group, ethylidene group, isopropylidene group, etc.), carbon A cycloalkylene group or a cycloalkylidene group (for example, a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, a cyclohexylidene group, etc.) having a number of 5 to 20, a fluorenylidene group, or -O-, -S-, -S
O -, - indicating the or -CO- bond - SO _2. Here, the fluorenylidene group has the formula

[0021]

[Chemical 18]

It is represented by Also represented by the general formula (II)
X in repeating unit II¹~ X^FourAre bromine atom and salt, respectively
Shows halogen atoms such as elementary atoms, fluorine atoms, and iodine atoms
You This X¹~ X ^FourAre different even if they are the same
May be, but is usually the same
There are many. Y is a single bond, an alkylene group having 1 to 6 carbon atoms, or
Is an alkylidene group (eg, methylene group, ethylene group,
Propylene group, Butylene group, Pentylene group, Hexile
Group, ethylidene group, isopropylidene group, etc.), carbon
Cycloalkylene group or cycloalkylide of the number 5 to 20
Group (eg cyclopentylene group, cyclohexylene
Group, cyclopentylidene group, cyclohexylidene group
), Fluorenylidene group, or -O-, -S-, -S
O-, -SO₂-Or -CO- bond is shown. Furthermore,
R in the structural unit III represented by the general formula (III)³~ R
⁶Are a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, respectively.
(For example, methyl group, ethyl group, propyl group, n-butyl
Group, isobutyl group, amyl group, isoamyl group, hex
Group) or a phenyl group. This R³~ R⁶Is
They may be the same or different. Well
R⁷And R⁸Include aliphatic or aromatic, respectively
Represents an organic residue, A represents -O-, -NH- or a single bond
And j is 101 to 500, preferably 101 to 400
It is an integer. If j exceeds 500, both PC-PDMS
The polymer becomes difficult to manufacture. And this PC-PDM
S-copolymer I is generally used at both terminal positions of the molecule, especially at both terminal positions.
The terminal group IV represented by the formula (IV), that is, polyhalogenofe
Those having a noxyl group bonded thereto are preferable. This general formula (I
X in the terminal group IV represented by V)^FiveIs the above X¹~ X^FourPlace
Bromine atom, chlorine atom, fluorine atom
Child, halogen atom such as iodine atom, k is 1 to 5
It is an integer. When k is multiple, multiple X ^FiveAre the same
It may be the same or different. Or this
PC-PDMS copolymer I of
In both terminal positions, the general formula (IV ')

[0023]

[Chemical 19]

An end group IV 'represented by is bound. That is, a non-halogenophenoxy group (that is, a phenoxy group containing no halogen atom as a substituent) is bonded. Here, R in the terminal group IV ′ represented by the general formula (IV ′)
¹³ is an alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, octyl group, nonyl group, tert-butyl group , Tert-amyl group, tert
-Octyl group), an aryl group having 6 to 20 carbon atoms (eg, phenyl group, tolyl group, xylyl group, naphthyl group, etc.) or an arylalkyl group having 7 to 20 carbon atoms (eg, benzyl group, phenethyl group, 9 -Anthrylmethyl group, α, α-dimethylbenzyl group, etc.), and q is 0
Is an integer of ~ 5. When q is plural, plural R ¹³
May be the same or different.
This PC-PDMS copolymer I has the above repeating unit I,
II and a structural unit III, and has a constitution in which a polyhalogenophenoxy group of the terminal group IV or a non-halogenophenoxy group of the terminal group IV ′ is bonded at the terminal positions (preferably both terminal positions). , II and structural units
There are various types such as III random copolymers, block copolymers, and alternating copolymers.

In this PC-PDMS copolymer I,
The proportion of the repeating unit II represented by the general formula (II), which is the component (b), is 1 to 10 mol%, preferably 4 to 9 mol% based on the total amount of the repeating unit I and the repeating unit II. Is. If the proportion of the repeating unit II is less than 1 mol%, the flame retardancy-improving effect is not observed. Further, if it exceeds 10 mol%, mechanical strength such as impact resistance decreases. In addition, the structural unit represented by the general formula (III) which is the component (c)
The proportion of III is 0.01 to 10% by weight, preferably 0.02 to 8% by weight, based on the total amount of repeating unit I, repeating unit II and structural unit III. The proportion of structural units III is
If it is less than 0.01% by weight, mechanical strength such as impact resistance is lowered and excellent flame retardancy is not exhibited. Also, 10
If it exceeds 5% by weight, heat resistance is lowered, which is not preferable. The viscosity average molecular weight is 1,000,000 to 5,000,000, preferably 12,000 to 40,000. When the viscosity average molecular weight is less than 10,000, the mechanical strength such as impact resistance decreases. On the other hand, when it exceeds 50,000, the fluidity is lowered and the moldability is deteriorated, which is not preferable. Also, this PC-
The content of halogen atoms in PDMS copolymer I is usually 4 to 15% by weight, preferably 4.5 to 10% by weight. If the content is less than 4% by weight, 1/32 inch V-2
Becomes Further, if it exceeds 15% by weight, mechanical strength such as impact resistance decreases, which is not preferable.

Next, the resin composition of the present invention is constituted.
Component (A) Polycarbonate-Polyorganosiloxa
Copolymer II (hereinafter abbreviated as PC-PDMS Copolymer II
You ) Is represented by the general formula (I) in which the main chain is the component (a).
Represented by the general formula (II), which is the repeating unit I and the component (b)
General formula (III ') which is the repeating unit II and the component (c)
In addition to having a structural unit III ′ represented by the general formula (IV)
The end group IV of the polyhalogenophenoxy group represented by
It is something. Here, the repetition represented by the general formula (I)
R in unit I¹And R²Are hydrogen atom or charcoal, respectively
Alkyl groups of prime number 1 to 4 (methyl group, ethyl group, propyl group
Group, butyl group), even if they are the same
It may be one. Further, the repeating represented by the general formula (II)
X in return unit II¹~ X^FourAre bromine atom and chlorine, respectively
Indicates a halogen atom such as atom, fluorine atom, iodine atom, etc.
You This X¹~ X ^FourAre different even if they are the same
May be, but is usually the same
There are many. And in the repeating unit II represented by the general formula (II)
R³And R^FourFor the above R¹And R²alike
Each is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (
(Cyl group, ethyl group, propyl group, butyl group)
They may be the same or different. Change
And R in the structural unit III ′ represented by the general formula (III ′)^Five~ R
⁸Are a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, respectively.
Or a phenyl group. This R^Five~ R⁸Are the same
It may be the same or different. Also, R⁹Over
And R^TenIs an organic residue containing aliphatic or aromatic, respectively
And A represents -O-, -NH- or a single bond. k
Is an integer of 1 to 500, preferably 5 to 400. This
PC-PDMS copolymer II of is a terminal position of a molecule, in particular,
At both terminal positions, the terminal group IV represented by the general formula (IV), that is,
A rehalogenophenoxy group is attached. This general formula (I
X in the terminal group IV represented by V)^FiveIs the above X¹~ X^FourPlace
Bromine atom, chlorine atom, fluorine atom
And a halogen atom such as iodine atom, m is 1 to 5
It is an integer. When m is plural, plural X^FiveAre the same
It may be the same or different. In addition, the above
X in the repeating unit II represented by the general formula (II)¹~ X^FourAnd general
X in the terminal group IV represented by the formula (IV)^FiveIs the same
Or it may be different. This PC-PDMS
Polymer II has the above repeating unit I, repeating unit II and structure
Has unit III and has terminal positions (preferably both terminal positions)
End) the polyhalogenophenoxy group of terminal group IV was bound to
The repeating unit I, the repeating unit II and the structure
Random copolymer, block copolymer, copolymer of building block III
There are various types such as mutual copolymers.

In this PC-PDMS copolymer II,
The proportion of the repeating unit II represented by the general formula (II), which is the component (b), is 1 to 10 mol%, preferably 2 to 8 mol%, based on the total amount of the repeating unit I and the repeating unit II. Is. If the proportion of the repeating unit II is less than 1 mol%, the flame retardancy-improving effect is not observed. Further, if it exceeds 10 mol%, mechanical strength such as impact resistance decreases. At the same time, the proportion of the structural unit III ′ represented by the general formula (III ′), which is the component (c), is from 0.01 to about 0.01 to the total amount of the repeating unit I, the repeating unit II and the structural unit III ′. It is 10% by weight, preferably 0.02 to 8% by weight. If the proportion of the structural unit III 'is less than 0.01% by weight, the mechanical strength such as flame retardancy and impact resistance will decrease. Further, if it exceeds 10% by weight, the heat resistance is deteriorated, which is not preferable. And its viscosity average molecular weight is 10000 to 50000, preferably 12.0.
It is from 00 to 40,000. Viscosity average molecular weight is 10,000
If it is less than 100%, mechanical strength such as impact resistance decreases. On the other hand, when it exceeds 50,000, the fluidity is lowered and the moldability is deteriorated, which is not preferable. The content of halogen atoms in this PC-PDMS copolymer II is preferably 4% by weight or more, and more preferably 4.5% by weight or more. If the content of halogen atoms is less than 4% by weight, the flame retardancy is lowered, which is not preferable.

The PC-supplied to the resin composition of the present invention
Specific examples of the PDMS copolymer II include, for example, P
The repeating unit I of the C-PDMS copolymer II has the general formula (V)

[0029]

[Chemical 20]

[In the formula, R ⁹ and R ¹⁰ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different. ], The repeating unit II is represented by the general formula (VI)

[Chemical 21] [In the formula, R ¹¹ and R ¹² each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different. Further, X ^{1 to} X ⁴ each represent a halogen atom. ] PC-PDMS copolymer II represented by these is mentioned.

The PC-PDMS copolymer I and the PC-PDMS copolymer II used in the resin composition of the present invention can be produced by the same method. First, PC-P
Examples of an efficient and preferable method for producing the DMS copolymer I include, but are not limited to, the following methods. (Refer to the production flow of PC-PDMS copolymer in FIG. 1) First, in a solvent such as methylene chloride, if necessary, in the presence of a known acid acceptor and molecular weight modifier, the following general formula (VI
I)

[0032]

[Chemical formula 22]

[In the formula, R ¹ , R ² , m, n and Z are the same as defined above. ] The bisphenol represented by phosgene is reacted with phosgene in the reaction system to substantially all react to give a polycarbonate oligomer (hereinafter, referred to as PC
Abbreviated as oligomer. ) Is manufactured. This PC oligomer has a repeating unit I represented by the general formula (I) which is formed by the reaction of bisphenols and phosgene in the polycondensation reaction. That is, this general formula (I)
The PC oligomer having the repeating unit I represented by
The reaction is carried out at a molar ratio of 0. Usually, in this reaction, bisphenols are added in an alkaline aqueous solution, and the mixture is stirred 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. Then, phosgene is blown into this and the interfacial polycondensation reaction is allowed to proceed for 1 to 3 hours at a reaction temperature of 30 to 70 ° C. At this time, the reaction system generates heat, so it is preferable to cool with water or ice. In addition, since the reaction system shifts to the acidic side as the reaction progresses, p
It is preferable to maintain the pH at 10 or more by adding an alkaline compound while measuring with an H meter. The thus-obtained PC oligomer has a number average molecular weight of 2000 or less and is a 1-10 monomer.

Then, after substantially all the phosgene in the reaction system is reacted, the PC oligomer having the repeating unit I represented by the general formula (I) is added to the following general formula (VIII).

[0035]

[Chemical formula 23]

[In the formula, X ^{1 to} X ⁴ and Y are the same as defined above. ] An alkaline aqueous solution of tetrahalogenobisphenols represented by the following general formula (IX)

[0037]

[Chemical formula 24]

[In the formula, X ⁵ and k are the same as defined above. ] Or a polyhalogenophenol represented by the following general formula (IX ')

[0039]

[Chemical 25]

[In the formula, R ¹³ and q are the same as defined above. ] A non-halogenophenol alkaline aqueous solution represented by the following formula and a catalyst such as triethylamine and trimethylbenzylammonium chloride are mixed and stirred at a predetermined ratio to perform polymerization, and a polycarbonate copolymer oligomer (hereinafter abbreviated as PC copolymer oligomer). To manufacture.
Here, the non-halogenophenol represented by the general formula (IX ′) does not contain a halogen atom as a substituent. This PC copolymer oligomer is prepared by reacting 100 bisphenol units in the PC oligomer in a molar ratio of tetrahalogenobisphenols 1.2 to 14 and polyhalogenophenol or non-halogenophenol 0.3 to 6.0. can get. The PC copolymer oligomer obtained has a repeating unit II represented by the general formula (II) and a repeating unit I represented by the general formula (I), which are formed by the reaction with tetrahalogenobisphenols in the above reaction. Have.

The bisphenols represented by the general formula (VII) are specifically bis (4-hydroxyphenyl) alkanes such as bis (4-hydroxyphenyl) methane [bisphenol F]. ; 2
2-bis (4-hydroxyphenyl) phenylmethane;
Bis (4-hydroxyphenyl) naphthylmethane; Bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane; Bis (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-methylphenyl) propane; 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-hydroxyphenyl) butane; 2,2-
Bis (4-hydroxyphenyl) pentane; 3,3-bis (4-hydroxyphenyl) pentane; 4-methyl-
2,2-bis (4-hydroxyphenyl) pentane;
2,2-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 can be mentioned.

Examples of bis (4-hydroxyphenyl) cycloalkanes 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, thiobisphenol, bisphenol Z, and tetrabromobisphenol A. Among these, bisphenol A is particularly preferably used. These bisphenols may be used alone or in combination of two or more.

The tetrahalogenobisphenols represented by the general formula (VIII) include, for example, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, tetraiodobisphenol A, tetrabromobisphenol F and tetrabromobisphenol A. Examples thereof include chlorobisphenol F and tetrachlorobisphenol B, and particularly tetrabromobisphenol A is preferably used. And, as the polyhalogenophenol represented by the general formula (IX), for example, bromophenol, chlorophenol, fluorophenol, dibromophenol, dichlorophenol, difluorophenol, tribromophenol, trichlorophenol, trifluorophenol, tetra Examples thereof include bromophenol, tetrachlorophenol, tetrafluorophenol, pentabromophenol, pentachlorophenol and pentafluorophenol, with tribromophenol being particularly preferred. In addition, a part (50 mol% or less) of polyhalogenophenol is added to p-ter
You may change to monohydric phenols, such as t-butylphenol and phenol. Examples of the non-halogenophenol represented by the general formula (IX ') include phenol,
Examples thereof include p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol and p-tert-amylphenol. Further, other examples of the catalyst include tributylamine, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylphenylammonium chloride, triethylphenylammonium chloride, tetrabutylammonium bromide, and the like. Triethylamine is preferred. As the alkaline aqueous solution, an aqueous solution of an alkaline compound such as sodium hydroxide, potassium hydroxide or sodium carbonate can be used.

After completion of the reaction, the reaction mixture thus obtained is allowed to stand or separate by centrifugation to separate an aqueous phase and an organic phase containing the PC copolymerized oligomer into an organic phase containing the PC copolymerized oligomer. The phase may be taken out or the next step may be performed without phase separation. The PC copolymerized oligomer contained in the reaction mixture or the separated organic phase is then treated with a polyorganosiloxane (PDMS) corresponding to the structural unit III represented by the general formula (III).
It is possible to produce a PC-PDMS copolymer by mixing and under the condition that substantially no alkaline compound is present, and further reacting bisphenols in the presence of the alkaline compound. Here, there are various polyorganosiloxanes corresponding to the structural unit III, but preferably the general formula (X)

[0045]

[Chemical formula 26]

It is represented by and is highly reactive PDMS.
Where R³~ R⁶Are hydrogen and C1-6, respectively.
Alkyl groups (eg methyl, ethyl, propyl
Group, n-butyl group, isobutyl group, amyl group, isoamido
Group, hexyl group, etc.) or phenyl group,
These may be the same or different. Also, 1
J R in the molecule³And j R ^FourIs that
These may be the same or different. And
R⁷And R⁸Is an organic residue containing aliphatic or aromatic
Z is hydroxyl group, amino group, carboxyl group, acid chloride
Id or phenolic hydroxyl group. j is 101 to
It is an integer of 500, preferably 101-400. here
When j exceeds 500, the production of PC-PDMS copolymer
Difficult to make. For the production of PC-PDMS copolymer I
Alternatively, the above PDMS is the PC copolymer oligomer.
In a weight ratio of 0.01 to 14 with respect to (solid amount) 100,
The reaction is preferably carried out at a ratio of 0.02-12. Also,
Sphenols are bisphenols in PC oligomers
10 to 30 mol of bisphenols based on 100 units
React in a ratio. In addition, tetrahalogenobisphenol
, Non-halogenophenols and bisphenols
It is added as an aqueous solution of Lucari, and PDMS is unchanged.
Or, it is added as a methylene chloride solution.
There is no particular limitation. However, bisphenols are
It is desirable to add it later. Reaction time is 30 minutes to 2:00
During, the reaction temperature is 20 to 40 ° C.

In the PC-PDMS copolymer I of the present invention, the PC copolymer oligomer having the repeating units I and II and the PDMS corresponding to the structural unit III are substantially present as an alkaline compound. It is prepared by mixing under non-existing conditions, reacting in the presence of an alkaline compound and a catalyst, and then reacting with bisphenols. That is, in order to produce the PC-PDMS copolymer I of the present invention, first, a PC copolymer oligomer and PD
MS is mixed with MS using an organic solvent (eg methylene chloride) in a mixer under conditions substantially free of alkaline compounds. Here, the mixer is not particularly limited as long as it can mix fluids, and may be a vertical type or a horizontal type, and may be a dynamic mixer or a static mixer. It may also be an orifice or a centrifugal pump. Specific examples of the dynamic mixer include a multi-line mixer [manufactured by Satake Chemical Industry Co., Ltd.], Komatsu Through The Disintegrator [Komatsu Zenoa Co., Ltd.]
Made], Pipeline Homo Mixer [Special Kika Kogyo Co., Ltd.
Manufactured] and the like. Also, as a static mixer,
Specific examples thereof include a Kenix type static mixer, a Sulzer type static mixer, and a Toray type static mixer.

The mixture of PC copolymerized oligomer and PDMS mixed in this mixer is then reacted with bisphenols in the presence of an alkaline compound and a catalyst in a reactor to form PC-PDMS copolymer I. A reaction product can be obtained. Alternatively, the mixture of PC copolymerized oligomer and PDMS mixed in this mixer is then reacted in the reactor in the presence of an alkaline compound and a catalyst to form a PC-PDMS copolymerized oligomer. Furthermore, this PC-PDMS
PC-by reacting the copolymer oligomer with bisphenols in the presence of an alkaline compound and a catalyst.
It is also possible to obtain the reaction product of PDMS copolymer I.
Here, tetrahalogenobisphenols represented by the general formula (VIII) can be used as a part of the bisphenols. This PC copolymer oligomer and PD
The reaction product of PC-PDMS copolymer I obtained by the reaction with MS has an excess amount of PC copolymerized oligomer in a molar amount. Therefore, PC-PDMS copolymerization in which the PC copolymerized oligomer is reacted at both ends of PDMS Oligomer and PC
It is a mixture of copolymerized oligomers. Here, the reactor is not particularly limited as long as it can stir the fluid, and may be a vertical type or a horizontal type. For example, there is a pipeline homomixer [made by Tokushu Kika Kogyo Co., Ltd.]. The reaction temperature in this reactor is 0 to 60 ° C, preferably 10 to 50 ° C. The reaction residence time may be 1 second or longer.

Examples of the alkaline compound used to obtain the above-mentioned PC-PDMS copolymer I or PC-PDMS copolymer oligomer include NaOH and KOH.
And so on. This alkaline compound is PDMS
1 to 20, preferably 1.1 in molar ratio with respect to the terminal groups of
-10 is added. If the alkaline compound is less than 1, P
It is not preferable because the reaction between the C copolymer oligomer and PDMS does not proceed completely. In addition, the alkaline compound is 2
When it exceeds 0, decomposition of the chloroformate group of the PC copolymer oligomer increases, and the molecular weight of the resulting PC-PDMS copolymer I is not improved, which is not preferable.

The catalyst may be a tertiary amine or
Can use a quaternary ammonium salt. concrete
Examples of the tertiary amine include trimethylamido.
And triethylamine, tripropylamine, etc.
Be done. Further, as the quaternary ammonium salt, for example,
Trimethylbenzylammonium chloride, triethyl
And rubenzyl ammonium chloride. This
The amount of the catalyst added is equal to that of the PC copolymer oligomer chlorophore.
The molar ratio to the mate group is 1.0 × 10^-Four~ 5.0 x 1
0^-2, Preferably 5.0 × 10^-Four~ 1.0 x 10 ^-2Is.
Addition amount is 1.0 × 10^-FourWhen the value is less than 1, the reaction progresses slowly and
It was 5.0 × 10^-2If it exceeds, the effect will be
No fruit is seen and it is not necessary to add more than this.

Next, the PC used for the resin composition of the present invention
The -PDMS copolymer II can be produced by the same method as the PC-PDMS copolymer I. That is, in the method for producing the PC-PDMS copolymer I, in place of the polyorganosiloxane represented by the general formula (X), a general formula corresponding to the structural unit III ′ represented by the general formula (III ′) is used. (X ')

[0052]

[Chemical 27]

A polyorganosiloxane having a high reactivity represented by and a polyhalogenophenol represented by the general formula (IX) corresponding to the terminal group (IV) can be used for the same production. Here, R ^{5 to} R ⁸ , R ⁹ , R
¹⁰ and Z are the same as above. And p is 1 to 50
It is an integer of 0, preferably 5 to 400. The copolymers I and II obtained here are substantially a mixture of a PDMS-containing copolymer and a PDMS-free copolymer, and the smaller the PDMS content is, the larger k is. The higher the proportion of the PDMS-free copolymer.
In the present invention, the resulting mixture is referred to as a PC-PDMS copolymer.

The molded product using the PC-PDMS copolymer I of the present invention can be obtained by molding the PC-PDMS copolymer I alone by a conventional molding method. It can also be obtained by, for example, preparing and molding a PC-PDMS copolymer composition containing PC-PDMS copolymer I, glass fiber and polycarbonate resin as main components. That is, in this case
The PC-PDMS copolymer composition is usually PC-PDM.
S-copolymer I 5 to 95% by weight, preferably 10 to 90% by weight, glass 5 to 60% by weight, preferably 10 to 55% by weight and polycarbonate resin 0 to 90% by weight, preferably 0 to 85% by weight. Is prepared in. Here, as the glass used in the preparation of the PC-PDMS copolymer composition, various kinds or forms can be applied. For example, glass fibers, glass beads, glass flakes, glass powder and the like can be used, and these may be used alone or in combination of two or more kinds. Among these, the glass fibers widely used for resin reinforcement may be any of alkali-containing glass, low-alkali glass and non-alkali glass. Also,
The fiber length is 0.1 to 8 mm, preferably 0.3 to 6 mm, and the fiber diameter is 0.3 to 30 μm, preferably 0.5 to 25 μm.
m. The form of the glass fiber is not particularly limited, and various forms such as roving, milled fiber, chopped strand, etc. can be mentioned. These glass fibers may be used alone or in combination of two or more kinds.
Further, these glass materials are surface-treated with a silane coupling agent such as aminosilane-based, epoxysilane-based, vinylsilane-based, methacrylsilane-based, a chromium complex compound, a boron compound or the like in order to enhance the affinity with the resin. It may be

This PC-PDMS copolymer composition is blended with the above-mentioned components and various additive components used as necessary and kneaded. The compounding and kneading are carried out by a commonly used method, for example, a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single-screw extruder, a twin-screw extruder, a co-kneader or a multi-screw extruder. It can be carried out. The heating temperature during kneading is usually 250 to
It is selected in the range of 300 ° C. PC-P thus obtained
The DMS copolymer composition is a molded article in the field of automobiles such as glass for automobiles, sunroof, etc. by applying various known molding methods such as injection molding, blow molding, extrusion molding, compression molding, calender molding, rotational molding and the like. It is possible to manufacture molded products in the field of home appliances. In addition, various additives, other synthetic resins, elastomers, and the like can be added to this composition, if necessary. Moreover, you may use it, mixing with an inorganic filler. For example, various additives include antioxidants such as hindered phenol-based, phosphite-based, phosphate-based, and amine-based antioxidants, ultraviolet absorbers such as benzotriazole-based and benzophenone-based antioxidants, and hindered amine-based light-absorbing agents. Examples thereof include stabilizers, aliphatic carboxylic acid ester-based and paraffin-based external lubricants, flame retardants, flame retardant aids, release agents, antistatic agents, and colorants.

The PC-PDMS copolymer I of the present invention is
Sufficient flame retardancy with trahalogenobisphenols
It is possible to obtain molded articles having
Further, the flame retardancy can be imparted.
As the flame retardant used to impart further flame retardancy,
Alkali metal salts or alkanes of suitable organic or inorganic acids
Potassium earth metal salts, and halogen-containing compounds
It Here, as a preferable inorganic alkali metal salt,
Thorium salt, potassium salt, lithium salt, etc.
It In addition, calcium is used as the inorganic alkaline earth metal salt.
Examples include salts and magnesium salts. In addition, inorganic
For obtaining potassium metal salt or inorganic alkaline earth metal salt
The inorganic acid that can be used is H₃AlF₆, H₃BF₆，
H₃SbF₆, H₂TiF₆, H₂SiF₆, H₃PO
_Four, H₂ZrF ₆, H₂WF₆, HBF_FourEtc.
It Preferred inorganic alkali metal salt or inorganic alkaline earth
As the metal salt, Na₃AlF₆, Ca₃(AlF₆)₂
Is mentioned. In addition, organic alkali metal salt or organic acid
Preferred organic acids used in obtaining the Lucari earth metal salts
As, aliphatic sulfonic acid, aromatic sulfonic acid, aromatic
Group carboxylic acids and aliphatic carboxylic acids. With specific examples
And trifluoromethane-sulfonic acid; perfluor
Robutane sulfonic acid; Perfluorooctane sulfone
Acid; Dodecanesulfonic acid; Benzenesulfonic acid; 2,
4,6-Trichlorobenzenesulfonic acid; benzenedis
Rufonic acid; Naphtholsulfonic acid; Caprylic acid; Laurie
Acid; benzoic acid; naphtholcarboxylic acid; 2,4,6-
Examples include tribromobenzoic acid and the like. Preferred organic al
Potassium metal salts or organic alkaline earth metal salts include
-Potassium fluorobutane sulfonate, perfluorobute
Calcium tansulfonate may be mentioned. Also, the halogen
Various compounds can be used as the phosphorus-containing compound.
It A typical example is tetrahalogenobis.
Low molecular weight polycarbonate containing phenols,
Epoxy resin containing tetrahalogenobisphenols
You can list oils and other halogen-based flame retardants.
Wear. Of these, flame retardants belonging to the above are particularly preferred.
Good

The low molecular weight polycarbonate containing the above tetrahalogenobisphenols has the general formula

[0058]

[Chemical 28]

[Wherein, X ^{6 to} X ⁹ represent a halogen atom, R ¹⁴ represents an alkylene group having 2 to 8 carbon atoms, and 1 to 9 carbon atoms.
Represents an alkylidene group, a carbonyl group, a sulfone group, a sulfur atom or an oxygen atom. ] The repeating unit X represented by
And r is the general formula

[0060]

[Chemical 29]

[In the formula, R ¹⁴ is the same as defined above. ] The repeating unit Y represented by these is s [however, r is an integer of 1-30, s is an integer of 0-30, and is an integer of r + s = 1-50 (especially 3-20). ], And is represented by a low molecular weight polycarbonate (polycarbonate oligomer) having a halogen content of 30% by weight or more. Here, as the halogen-containing bisphenol compound constituting the repeating unit X, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-
Bis (3,5-dichloro-4-hydroxyphenyl) propane; Bis (3,5-dibromo-4-hydroxyphenyl) methane; Bis (3,5-dibromo-4-hydroxyphenyl) ether; Bis (3,5 -Dibromo-4-
Hydroxyphenyl) sulfone or the like is used, and in particular,
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane [commonly known as tetrabromobisphenol A]
Is effective. The bisphenol compound constituting the repeating unit Y is 2,2-bis (4-hydroxyphenyl) propane; bis (4-hydroxyphenyl)
Methane; bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) ether, etc. are used,
Particularly, 2,2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A] is effective.

Next, an epoxy resin containing a tetrahalogenobisphenol is represented by the general formula

[0063]

[Chemical 30]

[Wherein R ¹⁴ is the same as defined above, R ¹⁵ represents a hydrogen atom, a methyl group, an epoxypropyl group, a phenyl group, a 2-hydroxypropyl group or an oxygen atom, and X ^{10 to} X ¹³ are halogens. Represents an atom, and t represents an integer of 1 to 30. ] And a halogen content of 30% by weight or more.

Further, other halogen-based flame retardants include, for example, tetrabromobenzene; tetrachlorobenzene; hexabromobenzene; hexachlorobenzene; hexabromobiphenyl; octabromobiphenyl;
2,4'-Dibromobiphenyl;2,4'-Dichlorobiphenyl;Hexabromobiphenyl; Triphenyl chloride; Tetrachlorophthalic acid; Tetrachlorophthalic anhydride; Tetrabromophthalic acid; Tetrabromophthalic acid Anhydrous; tribromophenol and other known halogenated aromatic compounds, and 2,2-bis (3,5-dichlorophenyl) propane; bis (2-chlorophenyl) methane; bis (2,6-dibromophenyl) Methane; 1,2-bis (2,6-dichlorophenyl) ethane; 1,1-bis (2-chloro-4-methylphenyl) ethane; 1,1-
Bis (3,5-dichlorophenyl) ethane; 2,2-bis (3-phenyl-4-bromophenyl) ethane; 2,
3-bis (4,6-dichloronaphthyl) propane; 2,
2-bis (2,6-dichlorophenyl) pentane; 2,
2-bis (2,6-dichlorophenyl) hexane; bis (4-chlorophenyl) methane; bis (3,5-dichlorophenyl) cyclohexylmethane; bis (3-nitro-4-bromophenyl) ethane; bis (4-hydroxy-) 2,6-dichloro-3-methoxyphenyl) methane;
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dibromo-4)
-Hydroxyphenyl) propane; 2,2-bis (3-
Bromo-4-hydroxyphenyl) propane; 2,2-
There are diaromatics such as bis (3,5-dibromo-4-hydroxyphenyl) propane diglycidyl ether. Further, halogenated diphenyl ethers, especially those containing 2 to 10 halogen atoms are preferable, and examples thereof include decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, pentabromodiphenyl ether, tetrabromodiphenyl ether,
Examples include tribromodiphenyl ether, dibromodiphenyl ether, hexachlorodiphenyl ether, pentachlorodiphenyl ether, tetrachlorodiphenyl ether, trichlorodiphenyl ether and dichlorodiphenyl ether.

The pigment as the component (B) constituting the resin composition of the present invention is not particularly limited. Usually, to hide in white, for example, titanium dioxide, zinc oxide,
Examples include zinc sulfide, barium sulfate, lithopone, and lead white. Of these, titanium oxide, which has excellent coloring power, is preferable. The titanium oxide may be either rutile type or anatase type, but it is preferable to use rutile type which is excellent in thermal stability and weather resistance. Then, it is effective to treat the titanium oxide with various surface treating agents and coat the surface thereof. As the treating agent, hydrated aluminum,
Silica, zinc, etc. are usually used. In addition, in order to improve the dispersibility of titanium oxide in the resin, silicone oil, polyol or the like can be used. Then, carbon black is preferably used to obtain a black color.

The resin composition of the present invention comprises the above-mentioned component (A).
And the component (B), and the mixing ratio of each component is PC-PDMS copolymer II which is the component (A).
85-99.99% by weight, preferably 90-99.9% by weight
And 15 to 0.01% by weight, preferably 10 to 0.1% by weight of the pigment as the component (B). here,
If the amount of the component (B) pigment is less than 0.01% by weight, the concealing effect cannot be obtained. On the other hand, if it exceeds 15% by weight, impact resistance is lowered, which is not preferable.

If necessary, the resin composition of the present invention may be used as a component (C) in combination with a commercially available polycarbonate resin, other synthetic resin, or an elastomer, as long as it does not impair the object of the present invention. May be. Further, an inorganic filler, various additives and the like can be blended. Examples of the synthetic resin include polyethylene, polypropylene, polystyrene, acrylonitrile-styrene resin (AS resin), acrylonitrile-butadiene-styrene resin (ABS resin), and polymethylmethacrylate. Examples of the elastomer include isobutylene-isopropylene rubber, styrene-butadiene rubber, ethylene-propylene rubber, acrylic elastomer and the like.

Various inorganic fillers can be used. Specifically, glass, carbon fiber, and other inorganic fillers are used. First, as the glass material, for example, glass fiber, glass beads, glass flakes, glass powder or the like can be used. Here, the glass fiber used may be any of alkali-containing glass, low-alkali glass and non-alkali glass. Its fiber length is 0.1 to 8 mm, preferably 0.1.
3 to 6 mm, and the fiber diameter is 0.1 to 30 μm,
It is preferably 0.5 to 25 μm. And the form of this glass fiber is not particularly limited, for example, roving,
There are various types such as milled fiber and chopped strand. These glass fibers may be used alone or in combination of two or more. These glass materials are surface-treated with a silane coupling agent such as aminosilane, epoxysilane, vinylsilane or methacrylsilane, a chromium complex compound or a boron compound in order to enhance the affinity with the resin. It may be one. As such a glass material, for example, commercially available MA-4 manufactured by Asahi Fiber Glass Co., Ltd.
09C (average fiber diameter 13 μm) or TA-409C
(Average fiber diameter 23 μm) and the like can be preferably used.

Next, the carbon fiber to be used is generally produced by calcining cellulose fiber, acrylic fiber, lignin, petroleum or coal-based pitch as a raw material, which is flame resistant, carbonaceous or There are various types such as graphite. The fiber length of the carbon fiber is usually 0.01 to 10 mm, preferably 0.02 to 8 m.
The fiber diameter is in the range of m, and the fiber diameter is 1 to 15 μm, preferably 5 to 13 μm. 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. These glass fibers may be used alone or in combination of two or more. The surface of these carbon fibers, in order to increase the affinity with the resin,
It may be one that has been surface-treated with an epoxy resin or a urethane resin. As such a carbon fiber, for example, a commercially available product such as Vesphite (average fiber diameter 7 μm) manufactured by Toho Rayon Co., Ltd. can be preferably used.

Other inorganic fillers include, for example, aluminum fibers, calcium carbonate, magnesium carbonate,
Dolomite, silica, diatomaceous earth, alumina, iron oxide, zinc oxide, magnesium oxide, calcium sulfate, magnesium sulfate, calcium sulfite, talc, clay, mica,
Asbestos, calcium silicate, montmorillonite, bentonite, graphite, iron powder, lead powder, aluminum powder, etc. can also be used.

Further, various additives include antioxidants such as hindered phenol-based, phosphite ester-based, and phosphoric ester-based antioxidants, ultraviolet absorbers such as benzotriazole-based and benzophenone-based antioxidants, and hindered amine-based light absorbers. Examples thereof include stabilizers, internal lubricants such as aliphatic carboxylic acid esters, paraffin, silicone oil and polyethylene wax, flame retardants, flame retardant aids, antistatic agents and colorants.

The resin composition of the present invention comprises the above-mentioned component (A).
And the component (B) and, if necessary, the component (C),
It can be obtained by 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 polycarbonate resin composition thus obtained can be applied to various known molding methods such as injection molding, blow molding, extrusion molding, compression molding, calender molding, rotational molding, etc. to produce various molded articles. Can be used for

Since the resin composition of the present invention contains PC-PDMS copolymer II having flame retardancy such as tetrahalogenobisphenols or polyhalogenophenol, a molded article having sufficient flame retardancy is obtained. Obtainable. Further, by adding a flame retardant, it is possible to impart further flame retardancy. Examples of the flame retardant used for imparting further flame retardancy include the same ones as described above.

[0075]

The present invention will be further described in detail with reference to production examples, examples and comparative examples. Production Example 1-1 [Production of PC oligomer A] 5% by weight of 400 liters
60 kg of bisphenol A in sodium hydroxide 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 passed through the orifice plate at a flow rate of 138 liters / hour and methylene chloride at a flow rate of 69 liters / hour through a tubular reactor having an inner diameter of 10 mm and a 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 still to separate and remove the aqueous phase, and a methylene chloride phase (220 liters) was collected. To this, 170 liters of methylene chloride was further added and sufficiently stirred. This was designated as PC oligomer A (concentration: 317 g / liter). The degree of polymerization of the PC oligomer A obtained here is 2 to 4
And the concentration of the chloroformate group was 0.7N.

Production Example 1-2 [Production of PC Oligomer B] Bisphenol A 2,275
g (9.96 mol) of 2.0 N sodium hydroxide aqueous solution 14
Dissolve in liter, put in a vessel with an internal volume of 50 liter with a stirrer, add 8.25 liter of methylene chloride and stir (50 rpm), and while cooling, blow phosgene at a flow rate of 0.2 mol / min for 70 minutes to carry out the reaction. went. After stopping the blowing of phosgene, stirring was continued for another 30 minutes.
Then, 312 g of tetrabromobisphenol A (0.5
74 mol), 68 g of p-tert-butylphenol (0.4
53 mol of sodium hydroxide (NaOH: 78.6 g,
What was dissolved in water: 1.35 liters) was added while continuing stirring, and 1.8 cc of triethylamine was added, and 450
The reaction was carried out at rpm for 60 minutes. After the reaction, the mixture was allowed to stand for about 30 minutes and the aqueous phase was separated to obtain an organic phase. This was designated as PC oligomer B (concentration: 496 g / liter, chloroformate group concentration: 0.48 mol / liter).

Production Example 2-1 [Synthesis of Reactive PDMS-A] 1,483 g of octamethylcyclotetrasiloxane, 18.1 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% sulfuric acid were added. Mix and stir at room temperature for 17 hours. Then the oil phase is separated and
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 to obtain oil. 60 g of 2-allylphenol and 0.00
In a mixture with 14 g of platinum chloride-platinum as an alcoholate complex, 294 g of the oil obtained above was added at 90 ° C.
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,
The procedure of Production Example 2-1 was repeated, except that the amount of 1,1,3,3-tetramethyldisiloxane was changed to 7.72 g. In the obtained terminal phenol PDMS, the number of repeating dimethylsilanooxy units was 350 as determined by NMR.

Production Example 2-3 [Synthesis of Reactive PDMS-C] In Production Example 2-1
The procedure of Production Example 2-1 was repeated, except that the amount of 1,1,3,3-tetramethyldisiloxane was changed to 96 g. In the obtained terminal phenol PDMS, the number of repeating dimethylsilanooxy units was 30 as measured by NMR.

Example 1 [Production of PC-PDMS Copolymer A] In a vessel equipped with a stirrer having an internal volume of 50 liters, 10 liters of PC oligomer A (bisphenol A unit: 11.6 mol) was reacted with PDMS.
-Dissolved A8g, tetrabromobisphenol A 195g (0.358mol) and tribromophenol 169g (0.51mol) dissolved in sodium hydroxide aqueous solution (NaOH: 110g, water: 1.35L) Were mixed, triethylamine 2.9 cc was added,
The mixture was stirred and reacted at 300 rpm for 60 minutes. After completion of the reaction, 500 g of bisphenol A dissolved in an aqueous sodium hydroxide solution (NaOH: 290 g, water: 3.42 liter) was mixed with the above reaction system, 6.1 liter of methylene chloride was added, and the mixture was stirred at 450 rpm for 60 minutes. , Reacted. After the reaction, the organic phase and the aqueous phase were separated, and the organic phase was washed and separated in the order of alkali (0.01 N NaOH), acid (0.1 N HCl) and water. A flake-shaped polymer was obtained by removing methylene chloride.

Example 2 [Production of PC-PDMS Copolymer B] In Example 1, instead of reactive PDMS-A, reactive PDMS-B was used.
A flake polymer was obtained in the same manner as in Example 1 except that was used.

Example 3 [Production of PC-PDMS Copolymer C] In Example 1, except that 8 g of reactive PDMS-A was changed to 40 g and 195 g of tetrabromobisphenol was changed to 330 g (0.61 mol). A flake polymer was obtained in the same manner as in Example 1.

Example 4 [Production of PC-PDMS Copolymer D] The PC oligomer B obtained in Production Example 1-2 and the reactive PDMS obtained in Production Example 2-1 were subjected to the flow shown in FIG. -A was reacted. PC oligomer B, reactive PDMS-A
5% by weight methylene chloride solution, 1% by weight triethylamine (TEA) aqueous solution and 25% by weight sodium hydroxide (NaOH) aqueous solution were used, respectively. Each flow rate is PC oligomer B: 13 liters / hour, reactive P
DMS-A: 2 liter / hour, TEA: 0.3 liter / hour, and NaOH: 0.23 liter / hour. Pipeline homomixer [made by Tokushu Kika Kogyo Co., Ltd., 2SL type: internal volume 0.3 liter, diameter of first turbine blade 42.5 mm, diameter of second turbine blade 48] for both mixer and reactor
mm], the mixer is 500 rpm, and the reactor is 3,000
It was rotated at 0 rpm. The main pipe (PC oligomer line) used had an inner diameter of 16 mm. TE
A was charged 60 cm from the mixer, and NaOH was charged 80 cm from the mixer. Reactor temperature is 25 ~
It was 30 ° C. The obtained reaction product (containing a PC-PDMS copolymer oligomer) was left standing and separated to obtain an organic phase 330c.
c was transferred to a 1-liter batch type reactor, 120 cc of methylene chloride and 2.2 g of p-tert-butylphenol were added, and the mixture was stirred to make it uniform. An alkaline aqueous solution of bisphenol A (bisphenol A: 19 g, sodium hydroxide: 11 g, water: 130 cc) was added to this, and 500 rpm
And reacted for 1 hour. After the reaction, the mixture was transferred to a 7-liter washing tank, 400 cc of methylene chloride and 400 cc of water were added, and the organic phase and the aqueous phase were separated. After separation, the organic phase is alkali (0.
It was washed with 01 N NaOH), acid (0.1 N HCl), and water, and then methylene chloride was removed to obtain PC-PDMS copolymer flakes.

Example 5 [Production of PC-PDMS Copolymer E] In a vessel equipped with a stirrer having an internal volume of 50 liters, 10 liters of PC oligomer A (11.6 mol of bisphenol A unit) was reacted with PDMS.
-A8g and p-tert-butylphenol 77g (0.5
1 mol) and tetrabromobisphenol A 413 g (0.76 mol) dissolved in an aqueous sodium hydroxide solution (NaOH: 110 g, water: 1.35 liters) were mixed to obtain triethylamine 2.9 cc. Was added, and the mixture was stirred and reacted at 300 rpm for 60 minutes. After completion of the reaction, 500 g of bisphenol A dissolved in an aqueous sodium hydroxide solution (NaOH: 290 g, water: 3.42 liter) was mixed with the above reaction system, and methylene chloride 6.1 was added.
1 liter was added, and the mixture was stirred and reacted at 450 rpm for 60 minutes. After the reaction, the organic phase and the aqueous phase were separated, and the organic phase was washed and separated in the order of alkali (0.01 N NaOH), acid (0.1 N HCl) and water. A flake-shaped polymer was obtained by removing methylene chloride.

Example 6 [Production of PC-PDMS Copolymer F] In Example 5, 578 g of tetrabromobisphenol A 413 g was used.
(Example 6) except that the amount was changed to (1.06 mol).
A flake-like polymer was obtained.

Comparative Example 1 [Production of PC-PDMS Copolymer G] A flake polymer was prepared in the same manner as in Example 1 except that the reactive PDMS-A 8 g was changed to 0.2 g. Obtained. Comparative Example 2 [Production of PC-PDMS Copolymer H] In Example 1, instead of reactive PDMS-A, reactive PDMS- was used.
A flake polymer was obtained in the same manner as in Example 1 except that C was used. Comparative Example 3 [Production of PC-PDMS Copolymer I] In Example 5, 38 g of tetrabromobisphenol A 413 g was used.
The same procedure as in Example 1 except that the amount was changed to (0.07 mol),
A flake-like polymer was obtained.

With respect to the PC-PDMS copolymers A to I obtained in Examples 1 to 6 and Comparative Examples 1 to 3, the viscosity average molecular weight and the glass transition temperature (Tg) were evaluated as the physical properties.
Etc. were measured. The results are shown in Table 1.

[0088]

[Table 1]

[0089]

[Table 2]

Each measurement was performed as follows. * 1: Determined from the intensity ratio of the aromatic H of the bisphenol A residue found at 7.1 to 7.3 ppm by TBA ¹ HNMR and the aromatic H of the TBA residue found at 7.43 ppm. * 2: Aromatic H of bisphenol A residue found at 7.1 to 7.3 ppm by PDMS ¹ HNMR, aromatic H of TBA residue found at 7.43 ppm, and methyl H of PTBP found at 0.11 ppm. It was calculated from the intensity ratio. * 3: Br content (total Br content in the copolymer) The sample was alkali decomposed and analyzed by the Horhard method. * 4: 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 * 5: Measured by Tg DSC (Differential scanning calorimeter).

The PC-PDMS copolymers A to I obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were each 1
After drying overnight at 20 ° C., the mixture was pelletized with an extruder at 280 ° C. and molded at 280 ° C. When preparing the pellets, 800 ppm of trisnonylphenyl phosphite was added as an antioxidant to PC-PDMS copolymers A, C, F and H. The flame retardancy and Izod impact strength of the obtained molded product were measured as a quality evaluation. The results are shown in Table 2.

[0092]

[Table 3]

Each measurement was performed as follows. * 1: Flame retardancy Flame retardance test UL-94 1/32 inch (thickness) A vertical flammability test was performed according to Underwriters Laboratory Subject 94. * 2: Izod impact strength (with notch) Using a 1/8 inch thick test piece, JIS-K-711
It measured based on 0. The measurement at -10 ° C was performed by air cooling.

Production Example 1-3 [Production of PC Oligomer C] Bisphenol A 2,275
g (9.96 mol) of 2.0 N sodium hydroxide aqueous solution 14
Dissolve in liter, put in a vessel with an internal volume of 50 liter with a stirrer, add 8.25 liter of methylene chloride and stir (50 rpm), and while cooling, blow phosgene at a flow rate of 0.2 mol / min for 70 minutes to carry out the reaction. went. After stopping the blowing of phosgene, stirring was continued for another 30 minutes.
After that, 250 g of tetrabromobisphenol A (0.4
6 mol) and 150 g (0.453 mol) of tribromophenol, sodium hydroxide (NaOH: 78.6 g, water: 1.
(35 liters) was added while continuing stirring, 1.8 cc of triethylamine was added, and 450 rpm
And reacted for 60 minutes. After the reaction, let it stand for about 30 minutes,
The aqueous phase was separated to obtain an organic phase. This was designated as Polycarbonate Oligomer B (concentration: 500 g / liter, chloroformate group concentration: 0.5 mol / liter).

Production Example 3-1 [Production of PC-PDMS Copolymer A ₁ ] In a vessel with an internal volume of 50 liters equipped with a stirrer, 10 liters of PC oligomer A (bisphenol A unit: 11.6 mol) was reacted with PDM.
S-C 40 g mixed and dissolved, tetrabromobisphenol A 330 g (0.61 mol) and tribromophenol 169 g (0.51 mol) sodium hydroxide aqueous solution (NaOH: 110 g, water: 1.35 liters) )
What was dissolved in was mixed and triethylamine 2.9cc
Was added, and the mixture was stirred and reacted at 300 rpm for 60 minutes. After completion of the reaction, 500 g of bisphenol A was added to the above reaction system, and an aqueous sodium hydroxide solution (NaOH: 290 g, water: 3.4) was added.
2 liters) dissolved in it and mixed with methylene chloride
6.1 liter was added, and the mixture was stirred and reacted at 450 rpm for 60 minutes. After the reaction, the organic phase and the aqueous phase are separated, and the organic phase is treated with alkali (0.01N-NaOH) and acid (0.1N-HC).
l) and water were sequentially washed and separated. A flake-shaped polymer was obtained by removing methylene chloride.

Production Example 3-2 [Production of PC-PDMS Copolymer A ₂ ] In Production Example 3-1 except that 160 g of reactive PDMS-C was used,
A flake polymer was obtained in the same manner as in Production Example 3-1.

Production Example 3-3 [Production of PC-PDMS Copolymer A ₃ ] The PC oligomer C obtained in Production Example 1-3 and the production example 2-3 in a flow as shown in FIG. Reactive PDMS-C was reacted. That is, PC oligomer C, reactive PDMS-C
5% by weight methylene chloride solution, 1% by weight triethylamine (TEA) aqueous solution and 25% by weight sodium hydroxide (NaOH) aqueous solution were used, respectively. Each flow rate is PC oligomer C: 13 liters / hour, reactive P
DMS-C was 4 liters / hour, TEA was 0.3 liters / hour, and NaOH was 0.23 liters / hour. Pipeline homomixer [made by Tokushu Kika Kogyo Co., Ltd., 2SL type: inner volume 0.3 liter, diameter of first turbine blade 42.5 mm, diameter of second turbine blade 48]
mm], the mixer is 500 rpm, and the reactor is 3,000
It was rotated at 0 rpm. The main pipe (PC oligomer line) used had an inner diameter of 16 mm. TE
A was charged 60 cm from the mixer, and NaOH was charged 80 cm from the mixer. Reactor temperature is 25 ~
It was 30 ° C. The obtained reaction product (containing a PC-PDMS copolymer oligomer) was left standing and separated to obtain an organic phase 330c.
c was transferred to a 1-liter batch type reactor, 120 cc of methylene chloride and 2.2 g of p-tert-butylphenol were added, and the mixture was stirred to make it uniform. An alkaline aqueous solution of bisphenol A (bisphenol A: 19 g, sodium hydroxide: 11 g, water: 130 cc) was added to this, and 500 rpm
And reacted for 1 hour. After the reaction, the mixture was transferred to a 7-liter washing tank, 400 cc of methylene chloride and 400 cc of water were added, and the organic phase and the aqueous phase were separated. After separation, the organic phase is alkali (0.
01N-NaOH) washing, acid (0.1N-HCl) washing,
Wash with water, then remove methylene chloride, then PC-PDMS
Flake of copolymer was obtained.

Production Example 3-4 [Production of PC-PDMS Copolymer A ₄ ] In the same manner as in Production Example 3-1, except that 40 g of reactive PDMS-C was changed to 20 g in Production Example 3-1. A flake-like polymer was obtained.

Production Example 3-5 [Production of PC-PDMS Copolymer A ₅ ] In Production Example 3-1, 40 g of reactive PDMS-C was changed to 8 g, and 330 g of tetrabromobisphenol A was changed to 195 g. A flake polymer was obtained in the same manner as in Production Example 3-1.

Production Example 3-6 [Production of PC-PDMS Copolymer A ₆ ] Production Example 3-1 except that reactive PDMS-C was changed to reactive PDMS-A in Production Example 3-1. Similarly, a flake polymer was obtained.

Production Example 3-7 [Production of PC-PDMS Copolymer A ₇ ] Production Example 3-1 except that reactive PDMS-C was changed to reactive PDMS-B in Production Example 3-1. Similarly, a flake polymer was obtained.

Production Example 4-1 [Production of Polycarbonate C ₁ ] Production Example 3 except that reactive PDMS-C was not used in Production Example 3-1.
A flake polymer was obtained in the same manner as in -1.

Production Example 4-2 [Production of Polycarbonate C ₂ ] In Production Example 4-1, p-tert was used instead of 169 g of tribromophenol.
-Production Example 3-1 except that 77 g of butylphenol was used
A flake-shaped polymer was obtained in the same manner as in.

PC-PDM obtained in Production Examples 3-1 to 7
The S copolymers A _{1 to} A ₇ and the polycarbonates C _{1 to} C ₂ obtained in Production Examples 4-1 and ₂ are each 1
After drying at 20 ° C for 24 hours, it was pelletized at 280 ° C with an extruder. Then, for each of the physical property evaluations, P
The DMS content, Br content and viscosity average molecular weight were measured.
The results are shown in Table 3. The PDMS content, Br content and viscosity average molecular weight were measured as described above.

[0105]

[Table 4]

Examples 17 to 28 and Comparative Examples 4 to 8 PC-PDMS copolymer A obtained in Production Examples 3-1 to 7
_{1 to} A ₇ and the polycarbonates C _{1 to} C ₂ obtained in Production Examples 4-1 and ₂ are dried at 120 ° C. for a whole day and night, and then the non-halogen-containing polycarbonate C ₃ and the pigments B _{1 to} B ₄ are used. Dry blend at the compounding ratio shown in the table, and
The mixture was kneaded at 0 ° C. and pelletized. The obtained pellets are
After drying at 120 ° C. for 12 hours, injection molding was performed to obtain test pieces. For the obtained test pieces, flame retardancy and Izod impact strength were measured as a quality evaluation. The results are shown in Table 5. The flame retardance and the Izod impact strength were measured as described above. Then, in the production of pellets, trisnonylphenyl phosphite as an antioxidant was added in an amount of 800 ppm to Examples 7, 8, 19, 20 and Comparative Example 4. Also, Examples 11 and 23
In addition, as a flame retardant, potassium perfluorobutyl sulfonate [Megafax F11 manufactured by Dainippon Ink and Chemicals, Inc.
4: C ₄ F ₉ SO ₃ K] was added at 1,000 ppm. Then, in Examples 10 and 22, 5,000 ppm of stearic acid monoglyceride was added as a lubricant. The non-halogen-containing polycarbonate is as follows. C _3: Tarflon A2200 [Idemitsu Petrochemical Co., Ltd., M
v: 21,500] Then, the pigment is as follows. B ₁ : Titanium dioxide B ₂ : Zinc sulfide B ₃ : Carbon black B ₄ : Barium sulfate

[0107]

[Table 5]

[0108]

[Table 6]

[0109]

[Table 7]

[0110]

[Table 8]

[0111]

As described above, the PC-PDMS copolymer of the present invention has excellent flame retardancy, mechanical properties, transparency and releasability. A resin composition containing a PC-PDMS copolymer is also excellent in flame retardancy, impact resistance and releasability. Therefore, the resin composition containing the PC-PDMS copolymer and the PC-PDMS copolymer of the present invention is
It is widely and effectively used for various molded products, for example, building materials, household appliances, flame-retardant parts such as office automation equipment.

[Brief description of drawings]

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

FIG. 2 is a diagram showing a flow of production of a polycarbonate-polyorganosiloxane copolymer oligomer in Example 4.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08L 83/10 LRX

Claims (4)

[Claims] 1. The main chain comprises (a) the general formula (I): [In the formula, R ¹ and R ² each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may be the same or different, m and n
Are integers of 0 to 4, respectively. Z is a single bond, an alkylene group having 1 to 6 carbon atoms or an alkylden group, and 5 carbon atoms.
~ 20 cycloalkylene groups, cycloalkylidene groups,
Fluorenylidene group, or -O-, -S-, -SO-,
Indicates a —SO ₂ — or —CO— bond. ] The repeating unit I represented by the formula (b), the general formula (II): [In the formula, X ^{1 to} X ⁴ each represent a halogen atom.
Y is a single bond, an alkylene group having 1 to 6 carbon atoms or an alkylden group, a cycloalkylene group having 5 to 20 carbon atoms, a cycloalkylidene group, a fluorenylidene group, or -O-,
-S -, - SO -, - shows or -CO- bond - SO _2. ] The repeating unit II and (c) the general formula (III) [In the formula, R ^{3 to} R ⁶ are each a hydrogen atom and a carbon number of 1 to
6 are alkyl groups or phenyl groups, which may be the same or different. Also, R ⁷ and R
⁸ represents an organic residue containing aliphatic or aromatic, respectively, and A represents -O-, -NH- or a single bond. j is 1
It is an integer of 01 to 500. ] Structural unit III represented by
And a repeating unit II in the main chain
Is 1 to 10 mol% with respect to the total amount of repeating unit I and repeating unit II, and structural unit III
Content of repeating unit I, repeating unit II and structural unit
0.01 to 10% by weight, based on the total amount of III,
Polycarbonate-polyorganosiloxane copolymer I characterized in that its viscosity average molecular weight is from 10,000 to 50,000. 2. The terminal terminating group IV is represented by the general formula (IV): [In the formula, X ⁵ represents a halogen atom, and k is an integer of 1 to 5. When k is plural, plural X ⁵ may be the same or different. ] The polycarbonate-polyorganosiloxane copolymer I according to claim 1, which is a polyhalogenophenoxy group represented by the following formula. 3. The main chain (A) is (a) the general formula (I): [In the formula, R ¹ and R ² each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may be the same or different, m and n
Are integers of 0 to 4, respectively. Z is a single bond, an alkylene group having 1 to 6 carbon atoms or an alkylden group, and 5 carbon atoms.
~ 20 cycloalkylene groups, cycloalkylidene groups,
Fluorenylidene group, or -O-, -S-, -SO-,
Indicates a —SO ₂ — or —CO— bond. ] Repeating unit I, (b) General formula (II) [In the formula, X ^{1 to} X ⁴ each represent a halogen atom.
Y is a single bond, an alkylene group having 1 to 6 carbon atoms or an alkylden group, a cycloalkylene group having 5 to 20 carbon atoms, a cycloalkylidene group, a fluorenylidene group, or -O-,
-S -, - SO -, - shows or -CO- bond - SO _2. ] The repeating unit II represented by the following formula (c) and the general formula (III '): [In the formula, R ^{3 to} R ⁶ are each a hydrogen atom and a carbon number of 1 to
6 are alkyl groups or phenyl groups, which may be the same or different. Also, R ⁷ and R
⁸ represents an organic residue containing aliphatic or aromatic, respectively, and A represents -O-, -NH- or a single bond. p is 1
Is an integer of ~ 500. ] Having a structural unit III ′ represented by the following general formula (IV) [In the formula, X ⁵ represents a halogen atom, and k is an integer of 1 to 5. When k is plural, plural X ⁵ may be the same or different. ] Polycarbonate-polyorganosiloxane copolymer II85-containing terminal group IV of polyhalogenophenoxy group represented by
A resin composition comprising 99.99% by weight and (B) a pigment of 15 to 0.01% by weight. 4. The repeating unit I of the polycarbonate-polyorganosiloxane copolymer II has the general formula (V): [In the formula, R ⁹ and R ¹⁰ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different. ] And the repeating unit II is represented by the general formula (VI): [In the formula, R ¹¹ and R ¹² each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different. Further, X ^{1 to} X ⁴ each represent a halogen atom. ] It is represented by these, The resin composition of Claim 3 characterized by the above-mentioned.