JP2021031499A - Polycarbonate-polydiorganosiloxane copolymer - Google Patents

Abstract

To provide a polycarbonate-polydiorganosiloxane copolymer which maintains extremely high fire resistance.SOLUTION: Provided is a polycarbonate-polydiorganosiloxane copolymer comprising a polycarbonate block represented by the following general formula (1), a polydiorganosiloxane block which contains an alkenyl group, and a polydiorganosiloxane block which does not contain an alkenyl group. (In the general formula [1], R1 and R2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1-18 carbon atoms, or the like; e and f are each an integer of 1 to 4; and W is a single bond, an oxygen atom, a sulfur atom, and the like).SELECTED DRAWING: None

Description

The present invention relates to a polycarbonate-polydiorganosiloxane copolymer having extremely high flame retardancy.

Polycarbonate has excellent impact resistance and a high thermal deformation temperature, and is therefore used in many applications that require strength and heat resistance (for example, the fields of electrical and electronic equipment, the field of automobiles, etc.). The most widely produced polycarbonate is a homopolymer formed by polymerizing bisphenol A (BPA), but with the expansion of application fields, it is desired to develop a polycarbonate having even better performance.

Therefore, in order to adapt to expanding applications, studies on copolymers by introducing various copolymer monomer units into general monomer raw materials such as BPA have been conducted. In the study of these copolymers, in particular, in Patent Documents 1 to 3, a polycarbonate-polydiorganosiloxane copolymer composed of BPA and polydiorganosiloxane comonomer has a flame retardancy as compared with a homopolycarbonate obtained by polymerizing BPA. 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 the polycarbonate-polydiorganosiloxane copolymer.

In recent years, the performance required for polycarbonate has been increasing year by year, and the performance required for polycarbonate-polydiorganosiloxane copolymers is no exception, and the performance is excellent even when used outdoors or in more harsh environments such as high temperature and high humidity conditions. It is very important to be stable.

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

Japanese Unexamined Patent Publication No. 5-186675 Japanese Unexamined Patent Publication No. 5-247195 WO 1991/00885 Japanese Unexamined Patent Publication No. 2013-209546

A first 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.

As a result of diligent research to achieve this purpose, the present inventors have found that a polycarbonate-polydiorganosiloxane copolymer using an alkenyl group-containing polydiorganosiloxane block and an alkenyl group-free polydiorganosiloxane block is extremely difficult. We have found that it is excellent in flammability, and have reached the present invention.

That is, the present invention
1. 1. A polycarbonate-polyorganosiloxane including 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 above general formula [1], R ¹ and R ² are independent hydrogen atoms, halogen atoms, alkyl groups having 1 to 18 carbon atoms, alkoxy groups having 1 to 18 carbon atoms, and 6 carbon atoms, respectively. ~ 20 cycloalkyl groups, 6-20 carbon atoms cycloalkoxy groups, 2-10 carbon atoms alkenyl groups, 6-14 carbon atoms aryl groups, 6-14 carbon atoms aryloxy groups, carbon Represents a group selected from the group consisting of an arylyl group having 7 to 20 atoms, an arylyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. It may be different, 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 the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and carbon. Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an alkoxy group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ are independent hydrogen atoms, halogen atoms, and carbon atoms 1 to 18 respectively. Alkyl group, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkoxy group with 2 to 10 carbon atoms, 6 carbon atoms From an aryl group of ~ 14, an aryloxy group having 6 to 10 carbon atoms, an alkoxy group having 7 to 20 carbon atoms, an alkoxy 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 the group, and if there are a plurality of groups, they may be the same or different, and g is an integer of 1 to 10 and h is an integer of 4 to 7.)]]

(In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. 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 independent of each other. Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, 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. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

(In the above general formula [4], R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are independently substituted or unsubstituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or 6 to 12 carbon atoms. It is an aryl group, and R ²¹ and R ²² are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms, and p'is 1 to 150. It is a natural number. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

2. The polycarbonate-polydiorganosiloxane copolymer according to 1 above, wherein the content of the alkenyl group 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 the alkenyl group of the general formula [3] is 1 to 50.
4. The polycarbonate-polydiorganosiloxane copolymer according to any one of 1 to 3 above, wherein the alkenylsiloxane component content in the copolymer is 0.1 to 6% by weight.
5. The polycarbonate-polydiorganosiloxane copolymer according to any one of 1 to 4 above, wherein the alkenyl group is a vinyl group.

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

Hereinafter, the present invention will be described in more detail.

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

In the above formula [1], R ¹ and R ² each independently have 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 to 20 carbon atoms. Cycloalkyl group, cycloalkoxy group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, aryl group with 6 to 14 carbon atoms, aryloxy group with 6 to 14 carbon atoms, 7 carbon atoms Represents a group selected from the group consisting of an arylyl group of ~ 20, an alkylyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group. When ^{there are a plurality of R 1} and R ² respectively, they may be the same or different.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group and a tetradecyl group. .. It is preferably an alkyl group having 1 to 6 carbon atoms.

Examples of the alkoxy group having 1 to 18 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, an octoxy group, and the like. Alkoxy groups having 1 to 6 carbon atoms are preferable.

Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group and a cyclooctyl group. A cycloalkyl group having 6 to 12 carbon atoms is preferable.

Examples of the cycloalkoxy group having 6 to 20 carbon atoms include a cyclohexyloxy group and a cyclooctyloxy group. A cycloalkyl group having 6 to 12 carbon atoms is preferable.

Examples of the alkenyl group having 2 to 10 carbon atoms include a metenyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group and the like. An alkenyl group having 1 to 6 carbon atoms is preferable.

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 a phenyloxy group and a naphthyloxy group.

Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.

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

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

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

Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and a dodecyl group. It is preferably an alkyl group having 1 to 6 carbon atoms.

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

Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.

R ¹⁹ and R ²⁰ are 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, and carbon atom. Cycloalkoxy group with 6 to 20, alkenyl group with 2 to 10 carbon atoms, aryl group with 6 to 14 carbon atoms, aryloxy group with 6 to 10 carbon atoms, aralkyl group with 7 to 20 carbon atoms, It represents a group selected from the group consisting of an aryloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group. If there are more than one, they may be the same or different.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group and a tetradecyl group. .. It is preferably an alkyl group having 1 to 6 carbon atoms.

Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group. Alkoxy groups having 1 to 6 carbon atoms are preferable.

Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group and a cyclooctyl group. A cycloalkyl group having 6 to 12 carbon atoms is preferable.

Examples of the cycloalkoxy group having 6 to 20 carbon atoms include a cyclohexyloxy group and a cyclooctyl group. A cycloalkoxy group having 6 to 12 carbon atoms is preferable.

Examples of the alkenyl group having 2 to 10 carbon atoms include a metenyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group and the like. An alkenyl group having 1 to 6 carbon atoms is preferable.

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 a phenyloxy group and a naphthyloxy group.

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

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

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

The polycarbonate block represented by the formula [1] includes 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxyphenyl). 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 preferable, 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 a block derived from 2,2-bis (4-hydroxyphenyl) propane.

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

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

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

In the above formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or 6 to 12 carbon atoms. Alternatively, it is 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 the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and a dodecyl group. It is preferably an alkyl group having 1 to 6 carbon atoms.

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

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

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

R ⁹ and R ¹⁰ are independent hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and a dodecyl group. It is preferably an alkyl group having 1 to 6 carbon atoms.

Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, and an octoxy group. It is preferably an alkoxy group having 1 to 6 carbon atoms.

It is particularly preferable that R ⁹ and R ¹⁰ are hydrogen atoms and methoxy groups.

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

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 to 120, more preferably 5 to 100, and particularly preferably 10 to 90.

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

The repeating unit of ^p, R 3, R ⁴ may also include a number of different units. For example, there may be repeating units of p1 and p2 as shown in the following equation [8]. In that case, the total 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 units of ^q, R 5, R ⁶ may also include a number of different units. For example, there may be repeating units of q1 and q2 as shown in the following equation [9]. In that case, the total of the repeating units of q1 and q2 is q, and the repeating units of q1 and q2 at this time may be blocks and random. Good.

In order to satisfy such a specific chain length range, hydroxyaryl-terminated polydiorganosiloxane raw materials having two or more 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 appropriate polydiorganosiloxane raw materials having hydroxyaryl-modified ends can also be used, or polydiorganosiloxane having an appropriate average chain length before hydroxyaryl-modifying the ends. Either method may be used in which the precursors are mixed in advance and then the terminals are hydroxyaryl-modified.

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

If the content of the alkenyl group is less than the lower limit, the drip prevention effect due to the cross-linking thickening of the alkenyl group is weakened and sufficient flame retardancy is not exhibited, and if it is more than the upper limit, siloxane aggregation due to cross-linking proceeds. It is presumed that the flame retardancy deteriorates too much.

The number of siloxane repeating units p containing an alkenyl group in the above formula [3] is 1 to 80, preferably 1 to 60, more preferably 1 to 50, and even more preferably 5 to 50. , Most preferably 8 to 50.

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

In the above 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 having 6 to 12 carbon atoms. It is synonymous with ^{R 5} , R ⁶ , R ⁷ and R ^{8 of the} above formula [3], respectively, except that it is a group and does not contain an alkenyl group. It is particularly preferable that R ²³ , R ²⁴ , R ²⁵ , and R ^{26 are methyl groups.}

R ²¹ and R ²² are independent hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms, respectively, and R ⁹ and R ^{10 of the above formula [3], respectively.} Is synonymous with. It is particularly preferable that R ²¹ and R ²² are hydrogen atoms and methoxy groups.

X is a divalent aliphatic group having 2 to 8 carbon atoms and is synonymous with the above formula [3].

p'is a natural number from 1 to 150, preferably 10 to 120, more preferably 20 to 100, and particularly preferably 30 to 90.

The repeating unit of p'may include a number of units having different ^{R 23} and R ^24. For example, there may be repeating units of p'1 and p'2 as in the following formula [10], and in that case, the total of the repeating units of p'1 and p'2 is p'.

In order to satisfy such a specific chain length range, hydroxyaryl-terminated polydiorganosiloxane raw materials having two or more different average chain lengths p'may be mixed and prepared. As a method for mixing and preparing polydiorganosiloxane raw materials, a method of mixing appropriate polydiorganosiloxane raw materials having hydroxyaryl-modified ends can also be used, or polydiorganosiloxane having an appropriate average chain length before hydroxyaryl-modifying the ends. Either method may be used in which the precursors are mixed in advance and then the terminals are hydroxyaryl-modified.

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

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

The content of the polydiorganosiloxane block in the copolymer (hereinafter, may be abbreviated as the content of the polydiorganosiloxane component) is preferably 1 to 15% by weight, more preferably 1 to 15% by weight, based on the total weight of the copolymer. It is 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 the siloxane repeating structure containing an alkenyl group in the copolymer (hereinafter, may be abbreviated as the 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, and most preferably 0.15 to 4.5% by weight. When the content of the alkenylsiloxane component is lower than the lower limit, the drip prevention effect due to the cross-linking thickening of the alkenyl group is weakened, so that the flame retardancy is particularly inferior after high-temperature and high-humidity treatment. It is presumed that the aggregation of siloxane progresses too much and the thermal stability is inferior as well as flame retardancy.

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 having a viscosity average molecular weight in this range are widely used because they provide practical mechanical strength in many fields.

In the UL94 vertical combustion test of the copolymer, the total combustion seconds of 3.2 mm are preferably 100 seconds or less, more preferably 90 seconds or less, still 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 a polycarbonate-polydiorganosiloxane copolymer)
The polycarbonate-polydiorganosiloxane copolymer of the present invention can be used as a resin composition by blending a functional agent or another resin, and examples of the other resin include thermoplastic resins, specifically, polyurethane. It may contain at least one polypropylene, polyethylene, polyamide, polyacetal, polysulfone, polyarylate, ABS resin, phenol resin, polyphenylene sulfide, polyether, polyimide, polyester, polyester carbonate, polycarbonate and the like. Of these, polycarbonate is preferable, and the copolymer (A) described later can be mentioned.

The polycarbonate is composed of a divalent phenol that induces the above formula [1], and specific divalent phenols include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, and 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'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide , 2,2'-Dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 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-hydroxy) Phenyl) propyl} benzene and the like can be mentioned.

Among them, 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. Of these, 2,2-bis (4-hydroxyphenyl) propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used individually or in combination of 2 or more types.

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

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, and even more preferably 25 to 100% by weight.

The content of the polydiorganosiloxane component 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, the appearance (color unevenness, deterioration of peeling failure, rigidity decrease, glass transition temperature decrease, thermal bending resistance decrease, etc.) Inferior in terms of surface).

The content of the alkenylsiloxane component 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. It is ~ 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. When the content of the alkenylsiloxane component is lower than the lower limit, the flame retardancy is particularly poor after high-temperature and high-humidity treatment, and when the content 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. Resin compositions containing a polycarbonate-polydiorganosiloxane copolymer having a viscosity average molecular weight in this range are widely used because they provide practical mechanical strength in many fields.

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

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

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

(In the formula, R ¹ , R ² , e, f and W are the same as described above.)
As the divalent phenol represented by the formula [5], the divalent phenol that induces the above-mentioned polycarbonate (B) is preferably used.

<Step (ii)>
An intercondensation polycondensation reaction was carried out between the carbonate oligomer of the dihydric phenol prepared in the step (i) and the hydroxyaryl-terminated polydiorganosiloxane represented by the following formula [6] and the following formula [7] to carry out the polycarbonate-polydiorganosiloxane of the present invention. This is a 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 described above.)

In the present invention, after obtaining a mixed solution containing a divalent phenol oligomer having a terminal chloroformate group in this way, the mixed solution was mixed with the general formulas [6] and [7] while stirring. The hydroxyaryl-terminated polydiorganosiloxane is added at a rate of 0.004 molar equivalent / min or less with respect to the amount of the divalent phenol charged, and the hydroxyaryl-terminated polydiorganosiloxane and the oligomer are subjected to interfacial polycondensation to cause polycarbonate-polydi. Obtain an organosiloxane copolymer.

In the production of the present invention, as the solvent, a solvent inert to various reactions such as those used in the production of known polycarbonate may be used alone or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used. The concentration of divalent phenol is preferably 500 g / L or less, more preferably 450 g / L or less, still more preferably 300 g / L or less. The lower limit of the concentration of divalent phenol is preferably 150 g / L or more from the viewpoint of production efficiency.

In carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate in consideration of the stoichiometric ratio (equivalent) of the reaction. As the acid binder, for example, 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 are used. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane to be used or a part of the dihydric phenol as described above is added as an addition monomer in this reaction step, the post-added dihydric phenol (I) and hydroxy It is preferable to use 2 equivalents or an excess amount of alkali with respect to the total number of moles with the aryl-terminated polydiorganosiloxane (1 mol usually corresponds to 2 equivalents).

Polycondensation by an interfacial polycondensation reaction between a divalent phenol oligomer and a hydroxyaryl-terminated polydiorganosiloxane is carried out by vigorously stirring the above mixture.

In such a polymerization reaction, a terminal terminator or a molecular weight modifier is usually used. Examples of the terminal terminator include compounds having a monovalent phenolic hydroxyl group, and in addition to ordinary phenols, p-tert-butylphenols, p-cumylphenols, tribromophenols, etc., long-chain alkylphenols and aliphatic carboxylic acids Examples thereof include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenyl alkyl acid ester, and alkyl ether phenol. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, with respect to 100 mol of all the divalent phenolic compounds used, and it is naturally possible to use two or more kinds of compounds in combination. is there.

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

The reaction time of such a polymerization reaction needs to 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 an antioxidant such as sodium sulfite or hydrosulfide may be added.

In addition, the polycarbonate-polydiorganosiloxane copolymer of the present invention and the resin composition containing the copolymer contain various flame retardants, reinforcing fillers, and additives that are usually blended in the polycarbonate resin as long as 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 the copolymer are pelletized by melt-kneading using an extruder such as a single-screw extruder or a twin-screw extruder. be able to. In producing such pellets, the above-mentioned various flame retardants, strengthening fillers and additives can also be blended.

As the flame retardant, various compounds conventionally known as flame retardants of thermoplastic resins, particularly aromatic polycarbonate resins, can be applied, but more preferably, organic metal salt-based flame retardants (for example, organic sulfonic acid alkali (soil)). (Category) Metal salts, metal borate flame retardants, and metal tinic acid flame retardants, etc.), organic phosphorus flame retardants (eg, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphones) Acid amide compounds and phosphazene, etc.), silicone flame retardants made of silicone compounds, fibrillated PTFE and the like. Among them, organometallic salt flame retardants and organophosphorus flame retardants are particularly preferable. The compounding of such a compound brings about an improvement in flame retardancy, but in addition to that, an improvement in antistatic property, fluidity, rigidity, thermal stability and the like is brought about based on the properties of each compound.

In the present invention, the polycarbonate-polydiorganosiloxane copolymer of the present invention and the resin composition containing the copolymer can be produced by injection molding pellets produced as described above. Further, it is also possible to directly convert the resin melt-kneaded by the extruder into a sheet, a film, a modified extrusion molded product, a direct blow molded product, and an injection molded product without passing 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, and insert molding, depending on the intended purpose. Molded products can be obtained using injection molding methods such as in-mold coating molding, heat insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known. Further, either a cold runner method or a hot runner method can be selected for molding.

Further, in the present invention, the polycarbonate-polydiorganosiloxane copolymer of the present invention can also be used in the form of various deformed extruded products, sheets, films and the like by extrusion molding. Inflation method, calendar method, casting method, etc. can also be used for forming sheets and films. Further, it can be molded as a heat-shrinkable tube by applying a specific stretching operation.

Further, in the present invention, various surface treatments can be applied to the molded product made of the polycarbonate-polydiorganosiloxane copolymer of the present invention. Surface treatment here means a new layer on the surface layer of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, printing, etc. It is formed, and the method used for ordinary polycarbonate resins can be applied. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metallizing (evaporation, etc.).

Hereinafter, the present invention will be described in more detail 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% is% by weight. The evaluation was performed according to the following method.

(1) Viscosity average molecular weight (Mv)
The specific viscosity (ηSP) calculated by the following formula was determined from a solution of 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C. using an Ostwald viscometer.
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight Mv is calculated by the following formula.
η _SP / c = [η] + 0.45 × ^{[η] 2} c (however, [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 Mv ^0.83
c = 0.7

(2) Polydiorganosiloxane component content, alkenylsiloxane component content and polydiorganosiloxane repetition number Using JNM-AL400 manufactured by Nippon Denshi Co., Ltd., a polycarbonate-polydiorganosiloxane copolymer obtained and a resin composition containing the same ¹ H-NMR spectrum was measured, and the integration curve of the peak derived from divalent phenol (bisphenol A) (1.4 to 1.8 ppm) and the peak derived from polydiorganosiloxane (-0.2 to 0.3 ppm) The content of each component was calculated from the integral ratio calculated from the integral curve and the integral curve of the peak derived from alkenylsiloxane (5.6 to 6.1 ppm in the case of vinyl group). Similarly, by comparing the integral curves of the peaks derived from the hydroxyaryl ends (0.4-0.6 ppm and 2.5-2.7 ppm) with the integral curves of the peaks derived from polydiorganosiloxane, the polydi The number of repetitions of organosiloxane was calculated.

(3) Flame retardant Vertical combustion test (UL94V) was conducted by the method (UL94) specified by Underwriter Laboratory in the United States.
A vertical combustion test was carried out at (a) 3.2 mm total combustion seconds and (b) 3.2 mm flame retardant class test piece thickness 3.2 mm and evaluated. At that time, the five samples were exposed to flames a total of 10 times, and the total number of burning seconds was indicated. Those that do not fit into any of the determinations of V-0, V-1, and V-2 are described as not-V.
(C) 1.6 mm (with flame retardant prescription) Flame retardant class A vertical combustion test was carried out with a test piece thickness of 1.6 mm and evaluated. Separately, after storing in warm water at 80 ° C. for 1 week, humidity was adjusted for 2 weeks in an environment of 25 ° C. and 50% RH, and the same evaluation was carried out. Those that do not fit into any of the determinations of V-0, V-1, and V-2 are described as not-V.

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

[Manufacturing 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 thermometer, a stirrer, and a reactor with a reflux condenser, and 2,2 as the dihydric phenol (I) represented by the above general formula [1]. After dissolving 3748 parts (16.41 mol) of −bis (4-hydroxyphenyl) propane (bisphenol A) and 7.5 parts of hydrosulfite, 14060 parts of methylene chloride (10 to divalent phenol (I)). (Molar equivalent) was added, and 1900 parts of phosgen was blown in at 16 to 24 ° C. under stirring for 70 minutes. A solution prepared by dissolving 1324 parts of a 25% sodium hydroxide aqueous solution and 107 parts of p-tert-butylphenol in 8000 parts of methylene chloride was added, and PMVS-1 222 parts (0.071 mol) and PDMS 208 parts (0.071 mol) were added with stirring. ) Was dissolved in 800 parts of methylene chloride, the solution was added to bring the product into an emulsified state, and the mixture was 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 at a temperature of 26 to 31 ° C. for 1 hour to complete the reaction. After completion of the reaction, the organic phase was separated, diluted with methylene chloride and washed with water repeatedly, and when the washing liquid became neutral, it was washed with aqueous hydrochloric acid. After that, it was repeatedly washed with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was put into a kneader filled with warm water to evaporate methylene chloride while stirring, and both polycarbonate and polydiorganosiloxane were used. Polymer powder was obtained. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation type dryer. The obtained polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-1) has a viscosity average molecular weight of 19,500, a polydiorganosiloxane component content of 8.4% by weight, and an alkenylsiloxane component content of 1.5% by weight. %Met.

(Example 2)
The method was the same as that for PMVS-PC-1, except that PMVS-1 was changed to 240 parts (0.071 mol) of PMVS-2. The obtained polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-2) has 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)
The method was the same as that for PMVS-PC-1, except that PMVS-1 was changed to 217 parts (0.071 mol) of PMVS-3. The obtained polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-3) has a viscosity average molecular weight of 19,500, a polydiorganosiloxane component content of 8.3% by weight, and an alkenylsiloxane component content of 0.7% by weight. %Met.

(Example 4)
The procedure was the same as that for PMVS-PC-1, except that PMVS-1 was changed to 213 parts (0.071 mol) of PMVS-4. The obtained polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-4) has a viscosity average molecular weight of 19,400, a polydiorganosiloxane component content of 8.3% by weight, and an alkenylsiloxane component content of 0.12% by weight. %Met.

(Example 5)
The method was the same as that for PMVS-PC-1, except that PMVS-1 was changed to 270 parts (0.071 mol) of PMVS-5. The obtained polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-5) has a viscosity average molecular weight of 19,300, a polydiorganosiloxane component content of 9.0% by weight, and an alkenylsiloxane component 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 same method was used for producing PMVS-PC-1 except that PDMS was not used. The obtained polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-6) has a viscosity average molecular weight of 19,500, a polydiorganosiloxane component content of 8.4% by weight, and an alkenylsiloxane component content of 1.5% by weight. %Met.

(Comparative Example 2)
PMVS-1 was changed to 444 parts (0.142 mol), and the same method was used for producing PMVS-PC-1 except that PDMS was not used. The obtained polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-7) has a viscosity average molecular weight of 19,600, a polydiorganosiloxane component content of 8.4% by weight, and an alkenylsiloxane component content of 3.0% by weight. %Met.

(Comparative Example 3)
PMVS-2 was changed to 480 parts (0.142 mol), and the same method was used for producing PMVS-PC-1 except that PDMS was not used. The obtained polycarbonate-polydiorganosiloxane copolymer (PMVS-PC-8) has a viscosity average molecular weight of 19,600, a polydiorganosiloxane component content of 9.1% by weight, and an alkenylsiloxane component content of 8.6% by weight. %Met.

(Comparative Example 4)
The method was the same as that for PMVS-PC-1, except that PMVS-1 was not used and was changed to 415 parts (0.142 mol) of PDMS. The obtained 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)
A linear aromatic polycarbonate resin powder having a solution viscosity molecular weight of 19,700 having 2,2-bis (4-hydroxyphenyl) propane as a repeating skeleton (Panlite L-1225WX manufactured by Teijin Limited).

The above results are shown in Table 1.

(Examples 1-1 to 4, 2-1 and 3-1 to 2, 4-1 and 5-1 and Comparative Examples 1-1 to 3 and 2-1 to 2, 3-1 and 4-1)
With reference to the blending ratio of PMVS-PC, PDMS-PC, and PC obtained by the above production method in Table 2, tris (2,4-di-tert-butylphenyl) phosphite (manufactured by BASF Corporation: Irgaphos) 168) 300 ppm was mixed. 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 Ltd.) ): 1000 ppm of Irganox 1076), 500 ppm of Megafuck F-114P (manufactured by DIC Corporation), and 2000 ppm of SN3310 (Guangzhou Shine Polymer Technology Co., Ltd .: PTFE powder) were also mixed separately. Then, it was melt-kneaded at 280 ° C. by a vent type twin-screw extruder (KZW15-25MG manufactured by Technobel Co., Ltd.) to obtain pellets composed 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 portion. Two types of UL test pieces (3.2 mm and 1.6 mm (with flame retardant prescription)) were prepared from the obtained pellets using an injection molding machine (JSW J-75EIII, manufactured by Japan Steel Works, Ltd.) to make them flame retardant. Was evaluated. In addition, the total number of burning seconds of the 3.2 mm test piece was measured. The evaluation results are shown in Table 2.

It can be seen that in Examples 1-1 to 5-1, high flame retardancy was obtained even in the flame retardancy test in UL-94 and the total combustion seconds of 3.2 mm.

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

It is recognized that the polycarbonate-polydiorganosiloxane copolymer of the present invention and the composition using the copolymer 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, electrical / electronic equipment, and automobiles. Above all, 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)

A polycarbonate-polyorganosiloxane including 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 above general formula [1], R ¹ and R ² are independent hydrogen atoms, halogen atoms, alkyl groups having 1 to 18 carbon atoms, alkoxy groups having 1 to 18 carbon atoms, and 6 carbon atoms, respectively. ~ 20 cycloalkyl groups, 6-20 carbon atoms cycloalkoxy groups, 2-10 carbon atoms alkenyl groups, 6-14 carbon atoms aryl groups, 6-14 carbon atoms aryloxy groups, carbon Represents a group selected from the group consisting of an arylyl group having 7 to 20 atoms, an arylyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. It may be different, 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 the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and carbon. Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an alkoxy group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ are independent hydrogen atoms, halogen atoms, and carbon atoms 1 to 18 respectively. Alkyl group, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkoxy group with 2 to 10 carbon atoms, 6 carbon atoms From an aryl group of ~ 14, an aryloxy group having 6 to 10 carbon atoms, an alkoxy group having 7 to 20 carbon atoms, an alkoxy 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 the group, and if there are a plurality of groups, they may be the same or different, and g is an integer of 1 to 10 and h is an integer of 4 to 7.)]]

(In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. 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 independent of each other. Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, 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. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

(In the above general formula [4], R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are independently substituted or unsubstituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or 6 to 12 carbon atoms. It is an aryl group, and R ²¹ and R ²² are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms, and p'is 1 to 150. It is a natural number. X is a divalent aliphatic group having 2 to 8 carbon atoms.) The polycarbonate-polydiorganosiloxane copolymer according to claim 1, wherein the content of the alkenyl group in ^{all R 3 to} R ⁸ in the general formula [3] is 1 to 60 mol%. The polycarbonate-polydiorganosiloxane copolymer according to claim 1 or 2, wherein the number of siloxane repeating units containing the 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 alkenylsiloxane component content in the copolymer is 0.1 to 6% by weight. The polycarbonate-polydiorganosiloxane copolymer according to any one of claims 1 to 4, wherein the alkenyl group is a vinyl group.