JP7332389B2 - Polycarbonate-polydiorganosiloxane copolymer - Google Patents

Description

The present invention relates to polycarbonate-polydiorganosiloxane copolymers with extremely high flame retardancy.

Polycarbonate is excellent in impact resistance and has a high heat distortion temperature, so that it is used in many applications (for example, electric/electronic equipment field, automobile field, etc.) that require strength and heat resistance. The most widely produced polycarbonate is a homopolymer formed by polymerizing bisphenol A (BPA), but with the expansion of the application field, the development of polycarbonate with even better performance is desired.

Therefore, in order to adapt to expanding applications, studies have been conducted on copolymers by introducing various copolymerization monomer units into general monomer raw materials such as BPA. In the study of these copolymers, in particular, in Patent Documents 1 to 3, polycarbonate-polydiorganosiloxane copolymers composed of BPA and polydiorganosiloxane comonomers are compared to homopolycarbonate polymerized with BPA, and have flame retardancy and It is known to have excellent low-temperature impact resistance.

Patent Document 4 describes the use of a vinyl group-containing phenol-modified siloxane as a method for further improving the flame retardancy of a polycarbonate-polydiorganosiloxane copolymer.

In recent years, the performance required of polycarbonate has been increasing year by year, and the performance required of polycarbonate-polydiorganosiloxane copolymer is no exception. Being stable is very important.

Even if the polycarbonate-polydiorganosiloxane resin composition described in Patent Document 4 was employed for the purpose of improving flame retardancy, the flame retardancy was insufficient under severe usage environments such as those mentioned above.

JP-A-5-186675 JP-A-5-247195 WO1991/00885 JP 2013-209546 A

A primary object of the present invention is to provide a polycarbonate-polydiorganosiloxane copolymer that maintains extremely high flame retardancy.
A second object of the present invention is to provide a polycarbonate-polydiorganosiloxane copolymer that maintains extremely high flame retardancy even after hot water treatment.

The present inventors have made intensive studies to achieve this object, and as a result, it is extremely difficult to produce a polycarbonate-polydiorganosiloxane copolymer using an alkenyl group-containing polydiorganosiloxane block and an alkenyl group-free polydiorganosiloxane block. The inventors have found that the combustibility is excellent, and arrived at the present invention.

That is, the present invention
1. Polycarbonate-polydiorganosiloxane copolymer containing a polycarbonate block represented by the following general formula [1], a polydiorganosiloxane block represented by the following general formula [3] and a polydiorganosiloxane block represented by the following general formula [4] polymer.

[(In the general formula [1] above, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and 6 carbon atoms. -20 cycloalkyl group, 6-20 carbon cycloalkoxy group, 2-10 carbon alkenyl group, 6-14 carbon aryl group, 6-14 carbon aryloxy group, carbon represents a group selected from the group consisting of an aralkyl group having 7 to 20 atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group; e and f may be different, and e and f are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula [2].)

(In general formula [2] above, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a carbon represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms; R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, a halogen atom, or a an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 carbon atoms. an aryl group of up to 14, an aryloxy group of 6 to 10 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an aralkyloxy group of 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group represents a group selected from the group consisting of, when there are more than one, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7.)]

(In general formula [3] above, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 6 to 12 carbon atoms. is a substituted or unsubstituted aryl group, at least one of R ³ , R ⁴ , R ⁷ and R ⁸ is an alkenyl group having 2 to 10 carbon atoms, and R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and the average chain length p+q is 1 to 150 is a natural number of X is a divalent aliphatic group having 2 to 8 carbon atoms.)

(In general formula [4] above, R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted an aryl group, R ²¹ and R ²² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and p′ is 1 to 150; is a natural number, and X is a divalent aliphatic group having 2 to 8 carbon atoms.)

2. 2. The polycarbonate-polydiorganosiloxane copolymer according to 1 above, wherein the alkenyl group content in all R ³ to R ⁸ in the general formula [3] is 1 to 60 mol %.
3. 3. The polycarbonate-polydiorganosiloxane copolymer according to 1 or 2 above, wherein the number of siloxane repeating units containing an alkenyl group of the general formula [3] is 1 to 50.
4. 4. The polycarbonate-polydiorganosiloxane copolymer as described in any one of 1 to 3 above, wherein the content of the alkenylsiloxane component in the copolymer is 0.1 to 6% by weight.
5. 5. The polycarbonate-polydiorganosiloxane copolymer according to any one of 1 to 4 above, wherein the alkenyl group is a vinyl group.

The polycarbonate-polydiorganosiloxane copolymer of the present invention has extremely high flame retardancy, and even after hot water treatment, a polycarbonate-polydiorganosiloxane copolymer that maintains extremely high flame retardancy can be obtained. The industrial effect it produces is exceptional.

The present invention will be described in more detail below.

(Polycarbonate-polydiorganosiloxane copolymer)
The polycarbonate-polydiorganosiloxane copolymer of the present invention contains a polycarbonate block of formula [1], a polydiorganosiloxane block of formula [3] and a polydiorganosiloxane block of formula [4].
<Polycarbonate Block of Formula [1]>
A polycarbonate block is represented by the following formula [1].

In the above formula [1], R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a cycloalkyl group, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, aryloxy group having 6 to 14 carbon atoms, 7 carbon atoms represents a group selected from the group consisting of an aralkyl group having up to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group; When there are multiple R ¹ and R ² , they may be the same or different.

A fluorine atom, a chlorine atom, a bromine atom etc. are mentioned as a halogen atom.

Examples of alkyl groups having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and tetradecyl group. . An alkyl group having 1 to 6 carbon atoms is preferred.

The alkoxy group having 1 to 18 carbon atoms includes methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, octoxy and the like. Alkoxy groups having 1 to 6 carbon atoms are preferred.

Examples of the cycloalkyl group having 6 to 20 carbon atoms include cyclohexyl group and cyclooctyl group. Cycloalkyl groups having 6 to 12 carbon atoms are preferred.

Cycloalkoxy groups having 6 to 20 carbon atoms are preferably cyclohexyloxy groups, cyclooctyloxy groups and the like. Cycloalkyl groups having 6 to 12 carbon atoms are preferred.

Examples of alkenyl groups having 2 to 10 carbon atoms include methenyl, ethenyl, propenyl, butenyl and pentenyl groups. Alkenyl groups having 1 to 6 carbon atoms are preferred.

Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

Examples of the aryloxy group having 6 to 14 carbon atoms include phenyloxy group and naphthyloxy group.

The aralkyl group having 7 to 20 carbon atoms includes benzyl group, phenylethyl group and the like.

Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group and phenylethyloxy group.

Among these, hydrogen, methyl group and phenyl group are particularly preferred.

e and f are each independently an integer of 1-4.

W is at least one group selected from the group consisting of a single bond or a group represented by the following formula [2].

In formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, It represents a group selected from the group consisting of aryl groups of 6 to 14 carbon atoms and aralkyl groups of 7 to 20 carbon atoms.

Examples of alkyl groups having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group. These may be substituted. Substituents include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl and butyl groups.

The aralkyl group having 7 to 20 carbon atoms includes benzyl group, phenylethyl group and the like.

R ¹⁹ and R ²⁰ are each independently hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 10 carbon atoms, cycloalkyl group having 6 to 20 carbon atoms, carbon atom a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, represents a group selected from the group consisting of an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group; When there are more than one, they may be the same or different.

A fluorine atom, a chlorine atom, a bromine atom etc. are mentioned as a halogen atom.

Examples of alkyl groups having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and tetradecyl group. . An alkyl group having 1 to 6 carbon atoms is preferred.

Examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, butoxy and pentoxy groups. Alkoxy groups having 1 to 6 carbon atoms are preferred.

Examples of the cycloalkyl group having 6 to 20 carbon atoms include cyclohexyl group and cyclooctyl group. Cycloalkyl groups having 6 to 12 carbon atoms are preferred.

Cycloalkoxy groups having 6 to 20 carbon atoms include cyclohexyloxy groups and cyclooctyl groups. Cycloalkoxy groups having 6 to 12 carbon atoms are preferred.

Examples of alkenyl groups having 2 to 10 carbon atoms include methenyl, ethenyl, propenyl, butenyl and pentenyl groups. Alkenyl groups having 1 to 6 carbon atoms are preferred.

Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

Examples of the aryloxy group having 6 to 14 carbon atoms include phenyloxy group and naphthyloxy group.

The aralkyl group having 7 to 20 carbon atoms includes benzyl group, phenylethyl group and the like. Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group and phenylethyloxy group.

g is an integer of 1-10, preferably an integer of 1-6, more preferably an integer of 1-3.

h is an integer of 4-7, preferably an integer of 4-5.

The polycarbonate block represented by formula [1] includes 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4- Hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4-biphenol, 4 ,4′-sulfonyldiphenol, 2,2′-dimethyl-4,4′-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-( 4-Hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene and the like are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 2,2- Bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4-biphenol, 4,4'-sulfonyldiphenol, 9,9-bis( 4-hydroxy-3-methylphenyl)fluorene, particularly preferably blocks derived from 2,2-bis(4-hydroxyphenyl)propane.

The length of the polycarbonate block is preferably 10 to 100, more preferably 30 to 100, still more preferably 50 to 70, as the average number of repeating units of formula [1].

The content of the polycarbonate block represented by formula [1] is preferably 50 to 99.9% by weight, more preferably 70 to 99.5% by weight, more preferably 70 to 99.5% by weight, based on the total weight of the copolymer 80 to 99.0% by weight.

<Polydiorganosiloxane block of formula [3]>
It is represented by the following formula [3] derived from a hydroxyaryl-terminated polydiorganosiloxane.

In the above formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted group having 6 to 12 carbon atoms. or an unsubstituted aryl group, and at least one of R ³ , R ⁴ , R ⁷ and R ⁸ is an alkenyl group having 2 to 10 carbon atoms.

Examples of alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

Examples of substituted or unsubstituted aryl groups having 6 to 12 carbon atoms include phenyl group and naphthyl group. Examples of substituents include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group.

As the alkenyl group having 2 to 10 carbon atoms, a methenyl group, ethenyl group, propenyl group, butenyl group, pentenyl group and the like are preferable, and an alkenyl group having 1 to 6 carbon atoms is more preferable.

It is particularly preferred that R ³ , R ⁴ , R ⁷ and R ⁸ are a methyl group or an ethenyl group (common name: vinyl group).

R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

A fluorine atom, a chlorine atom, a bromine atom etc. are mentioned as a halogen atom.

Examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

Examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy and octoxy groups. An alkoxy group having 1 to 6 carbon atoms is preferred.

It is particularly preferred that R ⁹ and R ¹⁰ are a hydrogen atom or a methoxy group.

X is a divalent aliphatic group having 2 to 8 carbon atoms. Divalent aliphatic groups include alkylene groups having 2 to 8 carbon atoms. Preferred examples of the alkylene group include ethylene, trimethylene and tetramethylene groups.

p is a natural number, q is 0 or a natural number, and p+q is a natural number from 1 to 150. p+q is preferably 3-120, more preferably 5-100, particularly preferably 10-90.

The repeating units of p and q may be block or random.

The repeating unit of p may contain any number of units in which R ³ and R ⁴ are different. For example, there may be repeating units of p1 and p2 as in the following formula [8], in which case the sum of the repeating units of p1 and p2 is p, and the repeating units of p1 and p2 at this time may be blocks and random. good.

The repeating unit of q may contain any number of units in which R ⁵ and R ⁶ are different. For example, there may be repeating units of q1 and q2 as in the following formula [9], in which case the sum of the repeating units of q1 and q2 is q, and the repeating units of q1 and q2 at this time may be block and random. good.

To satisfy such a specific chain length range, two or more different hydroxyaryl-terminated polydiorganosiloxane raw materials having different average chain lengths p+q may be mixed and prepared. As a method for mixing and preparing polydiorganosiloxane raw materials, a method of mixing suitable polydiorganosiloxane raw materials whose terminals are modified with hydroxyaryl may be used. Either of the methods of premixing the precursors and then modifying the terminals with hydroxyaryl may be used.

The alkenyl group content in all R ³ to R ⁸ in the above formula [3] is 1 to 70 mol%, preferably 1 to 60 mol%, more preferably 4 to 60 mol%. , more preferably 4 to 50 mol %, most preferably 10 to 50 mol %. For example, when R ³ is an alkenyl group, R ⁴ to R ⁸ are methyl groups, p = 12 and q = 23, the result is 16.7 mol%, and R ³ and R ⁴ are alkenyl groups and R ⁵ to R ⁸ are In the case of a methyl group, p=12 and q=23, it is 33.3 mol %.

If the alkenyl group content is less than the lower limit, the anti-drip effect due to cross-linking and thickening of the alkenyl group will be weak, resulting in insufficient flame retardancy. It is presumed that the flame retardancy is deteriorated due to the excessive amount.

The alkenyl group-containing siloxane repeating unit number p in the formula [3] is 1 to 80, preferably 1 to 60, more preferably 1 to 50, and still more preferably 5 to 50. , most preferably 8-50.

<Polydiorganosiloxane block of formula [4]>
It is represented by the following formula [4] derived from hydroxyaryl-terminated polydiorganosiloxane.

In the general formula [4], R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. is a group and has the same meaning as R ⁵ , R ⁶ , R ⁷ and R ⁸ in formula [3] above, except that it does not contain an alkenyl group. It is particularly preferred that R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are methyl groups.

R ²¹ and R ²² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ in the above formula [3], respectively; is synonymous with It is particularly preferred that R ²¹ and R ²² are a hydrogen atom or a methoxy group.

X is a divalent aliphatic group having 2 to 8 carbon atoms and has the same definition as in formula [3] above.

p' is a natural number of 1-150, preferably 10-120, more preferably 20-100, particularly preferably 30-90.

The repeating unit of p' may contain any number of units in which R ²³ and R ²⁴ are different. For example, there may be repeating units p'1 and p'2 as in the following formula [10], in which case the sum of the repeating units p'1 and p'2 is p'.

To satisfy such a specific chain length range, two or more different hydroxyaryl-terminated polydiorganosiloxane raw materials having different average chain lengths p' may be mixed and prepared. As a method for mixing and preparing polydiorganosiloxane raw materials, a method of mixing suitable polydiorganosiloxane raw materials whose terminals are modified with hydroxyaryl may be used. Either of the methods of premixing the precursors and then modifying the terminals with hydroxyaryl may be used.

The polycarbonate-polydiorganosiloxane copolymer consists of 99 to 1 mol % of polydiorganosiloxane blocks of formula [3] and 1 to 99 mol % of polydiorganosiloxane blocks of formula [4]. Preferably formula [3] / formula [4] = 70 to 1/30 to 99 (mol% / mol%), more preferably formula [3] / formula [4] = 50 to 1/50 to 99 (mol% / mol %). The copolymer consisting of formula [3] and formula [4] is expressed by copolymerizing formula [4] to moderately control the siloxane aggregation ability due to cross-linking, and by copolymerizing formula [3]. It is presumed that higher flame retardancy can be obtained because the anti-drip effect can be maximized by cross-linking and thickening.

As a polycarbonate-polydiorganosiloxane copolymer, the polydiorganosiloxane average chain length is 30-150, preferably 30-100, more preferably 35-90. Within the above range, both low-temperature impact resistance and productivity are sufficiently achieved.

The content of polydiorganosiloxane blocks in the copolymer (hereinafter sometimes abbreviated as polydiorganosiloxane component content) is preferably 1 to 15% by weight, more preferably 1 to 15% by weight, based on the total weight of the copolymer. 2 to 14% by weight, more preferably 3 to 13% by weight, particularly preferably 4 to 13% by weight, and most preferably 5 to 13% by weight.

The content of siloxane repeating structures containing alkenyl groups in the copolymer (hereinafter sometimes abbreviated as alkenylsiloxane component content) is preferably 0.05 to 8% by weight, based on the total weight of the copolymer. , more preferably 0.05 to 6% by weight, still more preferably 0.1 to 6% by weight, particularly preferably 0.12 to 5% by weight, most preferably 0.15 to 4.5% by weight. If the alkenylsiloxane component content is lower than the lower limit, the anti-drip effect due to cross-linking and thickening of the alkenyl group will be weak, resulting in poor flame retardancy, especially after high-temperature and high-humidity treatment. It is presumed that the aggregation proceeds too much, resulting in poor flame retardancy and poor thermal stability.

The viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer is preferably 13,000 to 25,000, more preferably 14,000 to 23,000. Copolymers with a viscosity-average molecular weight within this range are widely used in many fields because of their practical mechanical strength.

In the UL94 vertical burning test of the copolymer, the total burning time of 3.2 mm is preferably 100 seconds or less, more preferably 90 seconds or less, even more preferably 80 seconds or less, and particularly preferably 60 seconds or less. Within the above range, extremely high flame retardancy can be maintained even after hot water treatment.

(Resin composition containing polycarbonate-polydiorganosiloxane copolymer)
The polycarbonate-polydiorganosiloxane copolymer of the present invention can be used as a resin composition by blending a functional agent and other resins, and other resins include thermoplastic resins, specifically polyurethane, At least one of polypropylene, polyethylene, polyamide, polyacetal, polysulfone, polyarylate, ABS resin, phenol resin, polyphenylene sulfide, polyether, polyimide, polyester, polyester carbonate, polycarbonate and the like may be included. Of these, polycarbonate is preferred, and examples thereof include the copolymer (A) described below.

The polycarbonate is composed of a dihydric phenol that induces the above formula [1], and specific dihydric phenols include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1 -bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy- 3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3′-biphenyl)propane, 2,2 -bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2- Bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis (3-Cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene , 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4′- Dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide , 2,2′-dimethyl-4,4′-sulfonyldiphenol, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 2 ,2′-diphenyl-4,4′-sulfonyldiphenol, 4,4′-dihydroxy-3,3′-diphenyldiphenylsulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenylsulfide, 1,3 -bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene and the like.

Among others, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4-biphenol, 4,4'-sulfonyldiphenol, 2 , 2′-dimethyl-4,4′-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene is preferred, especially 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ) , 4,4-biphenol, 4,4′-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferred. Among them, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used alone or in combination of two or more.

The aforementioned copolymer (A) has a structure that contains the polycarbonate block of the above formula [1] and the polydiorganosiloxane block of the above formula [4] and does not contain the polycarbonate block of the above formula [3]. It is preferable to use a combination of different polycarbonate-polyorganosiloxanes.

The content of the polycarbonate-polydiorganosiloxane copolymer in the resin composition containing the polycarbonate-polydiorganosiloxane copolymer is 10 to 100% by weight, preferably 15 to 100% by weight, based on the total weight of the resin composition. It is 100% by weight, more preferably 20 to 100% by weight, even more preferably 25 to 100% by weight.

The polydiorganosiloxane component content of the resin composition containing the polycarbonate-polydiorganosiloxane copolymer is preferably 1 to 15% by weight, more preferably 2 to 14% by weight, based on the total weight of the resin composition. More preferably, it is 3 to 13% by weight. If it is lower than the lower limit, sufficient cryogenic impact resistance will not be exhibited, and if it is higher than the upper limit, physical properties such as color unevenness, deterioration of peeling failure, rigidity decrease, glass transition temperature decrease, heat bending resistance decrease surface).

The alkenylsiloxane component content in the resin composition containing the polycarbonate-polydiorganosiloxane copolymer is preferably 0.01 to 6% by weight, more preferably 0.01, based on the total weight of the resin composition. to 5% by weight, more preferably 0.05 to 5% by weight, particularly preferably 0.1 to 3% by weight, and most preferably 0.1 to 2.5% by weight. If the content of the alkenylsiloxane component is lower than the lower limit, the flame retardancy after high-temperature and high-humidity treatment is particularly poor, and if it is higher than the upper limit, the flame retardancy and thermal stability are poor.

The viscosity average molecular weight of the resin composition containing the polycarbonate-polydiorganosiloxane copolymer is preferably 13,000 to 25,000, more preferably 14,000 to 23,000. A resin composition containing a polycarbonate-polydiorganosiloxane copolymer having a viscosity-average molecular weight within this range is widely used in many fields because of its practical mechanical strength.

In the UL94 vertical burning test of a resin composition containing a polycarbonate-polydiorganosiloxane copolymer, the total burning time for a thickness of 3.2 mm is preferably 100 seconds or less, more preferably 90 seconds or less, and even more preferably 80 seconds or less. , particularly preferably 60 seconds or less. Within the above range, extremely high flame retardancy can be maintained even after hot water treatment.

(Method for producing polycarbonate-polydiorganosiloxane copolymer)
The polycarbonate-polydiorganosiloxane copolymer of the present invention can be produced by steps (i) and (ii).

<Step (i)>
In step (i), a dihydric phenol represented by the following formula [5] and a carbonate-forming compound are reacted in a mixture of a water-insoluble organic solvent and an alkaline aqueous solution to form a terminal chloroformate group. It is a step of preparing a solution containing a carbonate oligomer having

(Wherein, R ¹ , R ² , e, f and W are the same as above.)
As the dihydric phenol represented by formula [5], a dihydric phenol from which the polycarbonate (B) is derived is preferably used.

<Step (ii)>
The polycarbonate-polydiorganosiloxane of the present invention is subjected to an interfacial polycondensation reaction between the carbonate oligomer of dihydric phenol prepared in step (i) and the hydroxyaryl-terminated polydiorganosiloxane represented by the following formulas [6] and [7]. This is the step of obtaining a copolymer.

（式中Ｒ^３～Ｒ^１０、Ｒ^２１～Ｒ^２６、Ｘ、ｐ、ｑおよびｐ’は、前記と同じである。）

(In the formula, R ³ to R ¹⁰ , R ²¹ to R ²⁶ , X, p, q and p' are the same as above.)

In the present invention, after thus obtaining a mixed solution containing a dihydric phenol oligomer having a terminal chloroformate group, A hydroxyaryl-terminated polydiorganosiloxane is added at a rate of 0.004 molar equivalent/min or less with respect to the charged amount of the dihydric phenol, and the interfacial polycondensation of the hydroxyaryl-terminated polydiorganosiloxane and the oligomer results in polycarbonate-polydiorganosiloxane. An organosiloxane copolymer is obtained.

In the production of the present invention, as the solvent, solvents inert to various reactions, such as those used in the production of known polycarbonates, may be used singly or as a mixed solvent. Representative examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred. The dihydric phenol concentration is preferably 500 g/L or less, more preferably 450 g/L or less, and even more preferably 300 g/L or less. From the viewpoint of production efficiency, the lower limit of the dihydric phenol concentration is preferably 150 g/L or more.

In carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate in consideration of the stoichiometric ratio (equivalents) of the reaction. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, if the hydroxyaryl-terminated polydiorganosiloxane used or, as noted above, a portion of the dihydric phenol is added to this reaction step as an added monomer, the post-addition of the dihydric phenol (I) and the hydroxy It is preferable to use 2 equivalents or more of the alkali with respect to the total number of moles (usually 1 mol corresponds to 2 equivalents) with the aryl-terminated polydiorganosiloxane.

The interfacial polycondensation reaction between the dihydric phenol oligomer and the hydroxyaryl-terminated polydiorganosiloxane is carried out by vigorously stirring the mixture.

Terminal terminator or molecular weight modifier is usually used in such polymerization reaction. Examples of terminal terminating agents include compounds having a monovalent phenolic hydroxyl group, such as usual phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, long-chain alkylphenols and aliphatic carboxylic acids. Examples include chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of all dihydric phenol compounds used, and it is of course possible to use two or more kinds of compounds together. be.

A catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added to facilitate the polycondensation reaction.

The reaction time of such polymerization reaction should be relatively long in order to improve transparency. It is preferably 30 minutes or longer, more preferably 50 minutes or longer.

If desired, a small amount of antioxidant such as sodium sulfite, hydrosulfide, etc. may be added.

In addition, the polycarbonate-polydiorganosiloxane copolymer of the present invention and the resin composition containing it contain various flame retardants, reinforcing fillers and additives that are usually blended in polycarbonate resins to the extent that the effects of the present invention are not impaired. can do.

In the present invention, the polycarbonate-polydiorganosiloxane copolymer of the present invention and the resin composition containing it are pelletized by melt-kneading using an extruder such as a single-screw extruder or a twin-screw extruder. be able to. In preparing such pellets, the various flame retardants, reinforcing fillers, and additives described above may be blended.

As the flame retardant, various compounds conventionally known as flame retardants for thermoplastic resins, particularly aromatic polycarbonate resins, can be applied. class) metal salts, metal borate flame retardants, metal stannate flame retardants, etc.), organophosphorus flame retardants (e.g. monophosphate compounds, phosphate oligomeric compounds, phosphonate oligomeric compounds, phosphonitrile oligomeric compounds, phosphonic acid amide compounds and phosphazenes), silicone-based flame retardants made of silicone compounds, fibrillated PTFE, and the like. Among them, organic metal salt flame retardants and organic phosphorus flame retardants are particularly preferred. It should be noted that the addition of such compounds brings about improvement in flame retardancy, but also brings about improvements in, for example, antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.

In the present invention, the polycarbonate-polydiorganosiloxane copolymer of the present invention and the resin composition containing it can be produced into various products by injection molding the pellets produced as described above. Further, it is also possible to directly form sheets, films, profile extrusion moldings, direct blow moldings, and injection moldings from resins melted and kneaded in an extruder without going through pellets.

In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluid), insert molding, Molded articles can be obtained using injection molding methods such as in-mold coating molding, adiabatic molding, rapid heat and cool molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known. For molding, either cold runner method or hot runner method can be selected.

In the present invention, the polycarbonate-polydiorganosiloxane copolymer of the present invention can also be used in the form of various profile extrudates, sheets, films, etc. by extrusion molding. In addition, the inflation method, calender method, casting method, and the like can be used for forming sheets and films. Furthermore, it is also possible to mold it as a heat-shrinkable tube by subjecting it to a specific stretching operation.

Furthermore, in the present invention, various surface treatments can be applied to the molded article made of the polycarbonate-polydiorganosiloxane copolymer of the present invention. Surface treatment here refers to deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. It is formed, and a method used for ordinary polycarbonate resins can be applied. Specific examples of the surface treatment include hard coating, water-repellent/oil-repellent coating, ultraviolet-absorbing coating, infrared-absorbing coating, and various surface treatments such as metallizing (vapor deposition, etc.).

EXAMPLES The present invention will be described in more detail below with reference to Examples, but these are not intended to limit the present invention. Unless otherwise specified, the parts in the examples are parts by weight and the percentages are percentages by weight. In addition, evaluation followed the following method.

(1) Viscosity average molecular weight (Mv)
The specific viscosity (ηSP) calculated by the following formula is obtained from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C. using an Ostwald viscometer,
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
The viscosity-average molecular weight Mv is calculated from the obtained specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[η]=1.23×10 ⁻⁴ Mv ^0.83
c=0.7

(2) Polydiorganosiloxane component content, alkenylsiloxane component content and polydiorganosiloxane repetition number Polycarbonate-polydiorganosiloxane copolymer obtained using JNM-AL400 manufactured by JEOL Ltd. and a resin composition containing the same The ¹ H-NMR spectrum of was measured, and the integration curve of the peak (1.4 to 1.8 ppm) derived from dihydric phenol (bisphenol A) and the peak (-0.2 to 0.3 ppm) derived from polydiorganosiloxane. The content of each component was calculated from the integration curve and the integration ratio calculated from the integration curve of the alkenylsiloxane-derived peak (5.6 to 6.1 ppm for vinyl groups). Similarly, by comparing the integral ratio calculated from the integral curve of the peaks (0.4 to 0.6 ppm and 2.5 to 2.7 ppm) derived from hydroxyaryl terminals and the peak derived from polydiorganosiloxane, The number of repetitions of the organosiloxane was calculated.

(3) Flame Retardancy A vertical combustion test (UL94V) was conducted according to the method (UL94) specified by Underwriter Laboratories, Inc., USA.
(a) 3.2 mm Total Burn Seconds and (b) 3.2 mm Flame Retardant Class A vertical burn test at a specimen thickness of 3.2 mm was performed and evaluated. At that time, 5 samples were exposed to the flame 10 times in total, and the total number of burning seconds was indicated. In addition, not-V was written for those that did not correspond to any of the judgments of V-0, V-1, and V-2.
(c) 1.6 mm (with flame retardant formulation) flame retardant class Evaluation was performed by performing a vertical burning test on a test piece with a thickness of 1.6 mm. Separately, after storing in hot water at 80° C. for one week, it was subjected to humidity conditioning for two weeks in an environment of 25° C. and 50% RH, and then evaluated in the same manner. In addition, not-V was written for those that did not correspond to any of the judgments of V-0, V-1, and V-2.

[Hydroxyaryl-Terminated Polydiorganosiloxane]
In Examples and Comparative Examples, a polydiorganosiloxane compound having the following structure was used.

[Production of polycarbonate-polydiorganosiloxane copolymer]
(Example 1)
17590 parts of ion-exchanged water and 6883 parts of a 25% sodium hydroxide aqueous solution are placed in a reactor equipped with a thermometer, a stirrer and a reflux condenser, and 2,2 as the dihydric phenol (I) represented by the general formula [1] - 3748 parts (16.41 mol) of bis(4-hydroxyphenyl)propane (bisphenol A) and 7.5 parts of hydrosulfite are dissolved, followed by 14060 parts of methylene chloride (10 parts per dihydric phenol (I)). molar equivalent) was added, and 1900 parts of phosgene was blown in at 16 to 24° C. with stirring over 70 minutes. A solution obtained by dissolving 1324 parts of a 25% aqueous sodium hydroxide solution and 107 parts of p-tert-butylphenol in 8000 parts of methylene chloride was added, and while stirring, 222 parts of PMVS-1 (0.071 mol) and 208 parts of PDMS (0.071 mol) were added. ) was dissolved in 800 parts of methylene chloride to prepare a solution, the solution was added to emulsify, and then vigorously stirred again. Under such stirring, 4.2 parts of triethylamine was added while the reaction solution was at 26° C., and stirring was continued for 1 hour at a temperature of 26 to 31° C. to complete the reaction. After completion of the reaction, the organic phase was separated, diluted with methylene chloride, and washed with water repeatedly. When the washing liquid became neutral, it was washed with acidified hydrochloric acid. After that, it is repeatedly washed with ion-exchanged water, and when the conductivity of the water phase becomes almost the same as that of the ion-exchanged water, it is put into a kneader filled with warm water, and the methylene chloride is evaporated while stirring. A polymer powder was obtained. After dehydration, it was dried at 120° C. for 12 hours with a hot air circulating dryer. The resulting polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-1) had a viscosity-average molecular weight of 19,500, a polydiorganosiloxane content of 8.4% by weight, and an alkenylsiloxane content of 1.5% by weight. %Met.

(Example 2)
PMVS-PC-1 was produced in the same manner, except that PMVS-1 was changed to 240 parts (0.071 mol) of PMVS-2. The resulting polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-2) had a viscosity-average molecular weight of 19,700, a polydiorganosiloxane component content of 8.8% by weight, and an alkenylsiloxane component content of 4.4% by weight. %Met.

(Example 3)
Except for changing PMVS-1 to 217 parts (0.071 mol) of PMVS-3, the process was the same as for PMVS-PC-1. The resulting polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-3) had a viscosity-average molecular weight of 19,500, a polydiorganosiloxane content of 8.3% by weight, and an alkenylsiloxane content of 0.7% by weight. %Met.

(Example 4)
Except for changing PMVS-1 to 213 parts (0.071 mol) of PMVS-4, the process was the same as for PMVS-PC-1. The resulting polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-4) had a viscosity-average molecular weight of 19,400, a polydiorganosiloxane content of 8.3% by weight, and an alkenylsiloxane content of 0.12% by weight. %Met.

(Example 5)
Except for changing PMVS-1 to 270 parts (0.071 mol) of PMVS-5, the procedure was the same as for PMVS-PC-1. The resulting polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-5) had a viscosity-average molecular weight of 19,300, a polydiorganosiloxane content of 9.0% by weight, and an alkenylsiloxane content of 1.6% by weight. %Met.

(Comparative example 1)
PMVS-1 was changed to 434 parts (0.142 mol) of PMVS-3, and the process was the same as for PMVS-PC-1 except that no PDMS was used. The resulting polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-6) had a viscosity-average molecular weight of 19,500, a polydiorganosiloxane content of 8.4% by weight, and an alkenylsiloxane content of 1.5% by weight. %Met.

(Comparative example 2)
PMVS-PC-1 was prepared in the same manner except that PMVS-1 was changed to 444 parts (0.142 mol) and no PDMS was used. The resulting polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-7) had a viscosity-average molecular weight of 19,600, a polydiorganosiloxane content of 8.4% by weight, and an alkenylsiloxane content of 3.0% by weight. %Met.

(Comparative Example 3)
PMVS-2 was changed to 480 parts (0.142 mol), and the process was the same as for PMVS-PC-1 except that no PDMS was used. The obtained polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-8) had a viscosity-average molecular weight of 19,600, a polydiorganosiloxane content of 9.1% by weight, and an alkenylsiloxane content of 8.6% by weight. %Met.

(Comparative Example 4)
PMVS-PC-1 was produced in the same manner as PMVS-PC-1 except that 415 parts (0.142 mol) of PDMS was used instead of PMVS-1. The resulting polycarbonate-polydiorganosiloxane copolymer (PDMS-PC) had a viscosity average molecular weight of 19,500 and a polydiorganosiloxane component content of 8.3% by weight.

(PC)
Linear aromatic polycarbonate resin powder having a solution viscosity of 2,2-bis(4-hydroxyphenyl)propane as a repeating skeleton and a molecular weight of 19,700 (PANLITE L-1225WX manufactured by Teijin Limited).

Table 1 shows the above results.

(Examples 1-1 to 4, 2-1, 3-1 to 2, 4-1, 5-1, Comparative Examples 1-1 to 3, 2-1 to 2, 3-1, 4-1)
PMVS-PC, PDMS-PC, and PC obtained by the above production method are mixed with tris (2,4-di-tert-butylphenyl) phosphite (manufactured by BASF Corporation: Irgafos 168) was blended with 300 ppm. In addition, as a flame retardant formulation, tris (2,4-di-tert-butylphenyl) phosphite 1000 ppm, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid (BASF Japan Co., Ltd. ): Irganox 1076) 1000 ppm, Megafac F-114P (manufactured by DIC Corporation) 500 ppm, and SN3310 (manufactured by Guangzhou Shine Polymer Technology Co., Ltd.: PTFE powder) 2000 ppm were also mixed separately. Thereafter, the mixture was melt-kneaded at 280° C. using a vented twin-screw extruder (manufactured by Technovel Co., Ltd., KZW15-25MG) to obtain pellets of each mixture. The extrusion conditions were a discharge rate of 2.5 kg/h, a screw rotation speed of 200 rpm, and an extrusion temperature of 280° C. from the first supply port to the die. Two types of UL test pieces (3.2 mm, 1.6 mm (with flame retardant prescription)) were prepared from the obtained pellets using an injection molding machine (manufactured by Japan Steel Works, Ltd., JSW J-75EIII). evaluated. Also, the total burning seconds of the 3.2 mm test piece was measured. Table 2 shows the evaluation results.

It can be seen that Examples 1-1 to 5-1 are highly flame retardant in the UL-94 flame retardant test and 3.2 mm total burning seconds.

In addition, it can be seen that extremely high flame retardancy is maintained even in a vertical combustion test with a thickness of 1.6 mm after being stored in hot water at 80°C for one week.

It is recognized that the polycarbonate-polydiorganosiloxane copolymer of the present invention and compositions using it have extremely high flame retardancy.

Since the polycarbonate-polydiorganosiloxane copolymer of the present invention has high flame retardancy, it can be widely used in the fields of optical parts, electric/electronic equipment, and automobiles. In particular, it is highly practical for various housing molded products that are expected to be exposed to harsh environments such as cold regions and high-temperature heat treatment.

Claims (5)

Polycarbonate-polydiorganosiloxane copolymer containing a polycarbonate block represented by the following general formula [1], a polydiorganosiloxane block represented by the following general formula [3] and a polydiorganosiloxane block represented by the following general formula [4] A polymer in which the ratio of the polydiorganosiloxane block represented by the formula [3] and the polydiorganosiloxane block represented by the following general formula [4] is: formula [3]/formula [4] = 70 to 1 / 30 to 99 (mol%/mol%), a polycarbonate-polydiorganosiloxane copolymer .
[(In the general formula [1] above, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and 6 carbon atoms. -20 cycloalkyl group, 6-20 carbon cycloalkoxy group, 2-10 carbon alkenyl group, 6-14 carbon aryl group, 6-14 carbon aryloxy group, carbon represents a group selected from the group consisting of an aralkyl group having 7 to 20 atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group; e and f may be different, and e and f are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula [2].)
(In general formula [2] above, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a carbon represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R19 and R20 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms; alkoxy group having 1 to 10 carbon atoms, cycloalkyl group having 6 to 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, and 6 to 14 carbon atoms. A group consisting of an aryl group, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group represents a group selected from, and when there are more than one, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7.)]
(In general formula [3] above, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 6 to 12 carbon atoms. is a substituted or unsubstituted aryl group, at least one of R ³ , R ⁴ , R ⁷ and R ⁸ is an alkenyl group having 2 to 10 carbon atoms, and R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and the average chain length p+q is 1 to 150 is a natural number of X is a divalent aliphatic group having 2 to 8 carbon atoms.)
(In general formula [4] above, R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted an aryl group, R21 and R22 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and p' is a natural number of 1 to 150; X is a divalent aliphatic group having 2 to 8 carbon atoms.) 2. The polycarbonate-polydiorganosiloxane copolymer according to claim 1, wherein the content of alkenyl groups in all R ³ to R ⁸ in the general formula [3] is 1 to 60 mol %. 3. The polycarbonate-polydiorganosiloxane copolymer according to claim 1, wherein the number of siloxane repeating units containing an alkenyl group of the general formula [3] is 1 to 50. The polycarbonate-polydiorganosiloxane copolymer according to any one of claims 1 to 3, wherein the content of alkenylsiloxane component in said copolymer is 0.1 to 6% by weight. 5. The polycarbonate-polydiorganosiloxane copolymer according to any one of claims 1 to 4, wherein said alkenyl group is a vinyl group.