JP7348798B2 - Polycarbonate-polydiorganosiloxane copolymer and its resin composition - Google Patents

Description

The present invention relates to a polycarbonate-polydiorganosiloxane copolymer (hereinafter sometimes abbreviated as "PC-POS copolymer") or a resin composition. More specifically, the present invention relates to a PC-POS copolymer or polycarbonate resin composition that has excellent impact resistance, particularly impact resistance at extremely low temperatures and chemical resistance, and is also flame retardant.

Polycarbonate has excellent impact resistance and high heat resistance, so it is widely used in the fields of optical components, electrical and electronic equipment, and automobiles. Furthermore, in order to respond to the recent expansion of application fields, development of copolymerized polycarbonates in which various copolymerized monomer units are introduced into common monomer raw materials such as bisphenol A (hereinafter abbreviated as BPA) is underway. Among them, PC-POS copolymers made of BPA and polydiorganosiloxane comonomers are known to have excellent flame retardancy and impact resistance, and many documents have been disclosed (Patent Documents 1 to 3).

As a method of improving the impact resistance of PC-POS copolymers, especially the impact resistance at low temperatures, a method is disclosed that focuses on the chain length in the polydiorganosiloxane structure used and uses polydiorganosiloxane with a long chain length. (Patent Documents 4 to 5).

In addition, Patent Document 6 focuses on the size of siloxane domains formed in molded products, and by appropriately blending two types of PC-POS copolymers with different light transmittances, a certain level of transparency and durability can be achieved. A method of achieving both impact resistance is disclosed.

Patent Document 7 discloses a method for producing a polycarbonate resin composition containing a PC-POS copolymer made from a polydiorganosiloxane with a long chain length and a polydiorganosiloxane with a short chain length, and also has a certain degree of transparency. An example is shown that achieves both impact resistance and impact resistance.

Patent Document 8 describes the use of a vinyl group-containing phenol-modified siloxane as a method for further improving the flame retardancy of polycarbonate-polydiorganosiloxane copolymers.

However, conventional PC-POS copolymers or polycarbonate resin compositions containing PC-POS copolymers have poor impact resistance, especially at extremely low temperatures, even in high latitudes and mountainous areas. However, it is difficult to obtain a PC-POS copolymer or a polycarbonate resin composition containing a PC-POS copolymer that has even higher chemical resistance, paint durability, and flame retardancy. I haven't been able to do that.

Japanese Patent Application Publication No. 5-186675 Japanese Patent Application Publication No. 5-247195 Patent No. 2662310 WO1991/00885 publication Japanese Patent Application Publication No. 2012-246430 Special Publication No. 2006-523243 Japanese Patent Application Publication No. 2015-163722 JP2013-209546A

An object of the present invention is to provide a PC-POS copolymer or polycarbonate resin composition that has excellent impact resistance, especially impact resistance at extremely low temperatures and chemical resistance, and is also flame retardant. be.

The inventors of the present invention have conducted intensive research to achieve this objective, and as a result, they have discovered that the above-mentioned problems can be solved by the following configuration, and have arrived at the present invention.

(Configuration 1)
A polycarbonate-polydiorganosiloxane co-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] The above-mentioned copolymer or resin composition thereof, comprising a polymer and an optional polycarbonate resin.

[(In the above general formula [1], 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, or a 6 carbon atom -20 cycloalkyl group, C6-20 cycloalkoxy group, C2-10 alkenyl group, C6-14 aryl group, C6-14 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, and if there are multiple of each, they may be the same. may be different, e and f are each integers of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups 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 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 R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a C 1 to 18 atom. Alkyl group having 1 to 10 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, 6 carbon atoms ~14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group, and carboxyl group (If there are multiple groups, they may be the same or different, g is an integer from 1 to 10, and h is an integer from 4 to 7.)

(In the above general 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 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 50. is a natural number.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 each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted group having 6 to 12 carbon atoms) It is 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, or an alkoxy group having 1 to 10 carbon atoms, and p' is 50 to 150. is a natural number. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

(Configuration 2)
The copolymer or resin thereof according to configuration 1, wherein the polydiorganosiloxane component content is 2.5 to 14.0% by weight based on the total weight of the copolymer or resin composition. Composition.
(Configuration 3)
The copolymer or resin composition thereof according to configuration 1 or 2, wherein the average polydiorganosiloxane repeating number is 30 to 100.
(Configuration 4)
The copolymer or resin composition thereof according to any one of Structures 1 to 3, having a viscosity average molecular weight of 11,000 to 30,000.
(Configuration 5)
The resin composition according to any one of configurations 1 to 4, comprising 99 to 1% by weight of the polycarbonate-polydiorganosiloxane copolymer and 1 to 99% by weight of the polycarbonate resin.

(Configuration 6)
The resin composition according to configuration 5, wherein the polycarbonate resin is composed of a polycarbonate block represented by the following general formula [1]:

[(In the above general formula [1], 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, or a 6 carbon atom -20 cycloalkyl group, C6-20 cycloalkoxy group, C2-10 alkenyl group, C6-14 aryl group, C6-14 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, and if there are multiple of each, they may be the same. may be different, e and f are each integers of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups 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 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 R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a C 1 to 18 atom. Alkyl group having 1 to 10 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, 6 carbon atoms ~14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group, and carboxyl group (If there are multiple groups, they may be the same or different, g is an integer from 1 to 10, and h is an integer from 4 to 7.)

(Configuration 7)
The copolymer or copolymer according to any one of configurations 1 to 6, wherein the alkenylsiloxane component content is 0.01 to 2.0% by weight based on the total weight of the copolymer or the resin composition. Resin composition.
(Configuration 8)
The copolymer or resin composition thereof according to configurations 1 to 7, which has a notched Charpy impact strength of 30 kJ/m ² or more at a thickness of 4 mm measured at -50° C. in accordance with ISO 179.
(Configuration 9)
The copolymer or resin composition thereof according to structures 1 to 8, which has a notched Charpy impact strength of 20 kJ/m ² or more at a thickness of 4 mm measured at -60° C. in accordance with ISO 179.
(Configuration 10)
The copolymer or its resin composition according to configurations 1 to 9, which has a notched Charpy impact strength of 15 kJ/m ² or more after being coated with a paint spray measured at -50°C in accordance with ISO 179. .
(Configuration 11)
A molded article formed from the copolymer or resin composition thereof according to any one of Structures 1 to 10.

The PC-POS copolymer or polycarbonate resin composition of the present invention has excellent impact resistance, especially impact resistance at extremely low temperatures and chemical resistance, and also has high coating durability and is highly durable against difficult coatings. Since it is also flammable, its industrial effects are exceptional.

FIG. 3 is a diagram of a three-point bending chemical resistance evaluation jig.

The present invention will be explained in more detail below.
[Polycarbonate copolymer or resin composition]
The polycarbonate copolymer of the present invention contains a polycarbonate block represented by formula [1], a polydiorganosiloxane block represented by formula [3], and a polydiorganosiloxane block represented by formula [4]. Moreover, the resin composition of the present invention is a resin composition containing the above-mentioned copolymer.

(Polycarbonate-polydiorganosiloxane (PC-POS) copolymer)
The polycarbonate copolymer of the present invention contains a polycarbonate block represented by formula [1], a polydiorganosiloxane block represented by formula [3], and a polydiorganosiloxane block represented by 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 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 a 6 to 20 carbon atom Cycloalkyl group having 6 to 20 carbon atoms, 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, number of carbon atoms Represents a group selected from the group consisting of 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.If there is more than one of each, they may be the same or different. You can leave it there.

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

Examples of the alkyl group 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, tetradecyl group, etc. . Preferred is an alkyl group having 1 to 6 carbon atoms.

Examples of the alkoxy group having 1 to 18 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyl group, octoxy group, and the like. An alkoxy group having 1 to 6 carbon atoms is preferred.

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 preferred.

Preferred 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 preferred.

Examples of the alkenyl group having 2 to 10 carbon atoms include methenyl group, ethenyl group, propenyl group (common name: allyl group), butenyl group, and pentenyl group. Alkenyl groups having 1 to 6 carbon atoms are preferred.

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

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

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

Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group and phenylethyloxy group.
Among these, hydrogen, methyl group, propenyl group (common name: allyl group), and phenyl group are particularly preferred.
e and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups 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, or 6 carbon atoms. Represents a group selected from the group consisting of an aryl group having ~14 carbon atoms and an aralkyl group having 7 to 20 carbon atoms.

Examples of the alkyl group 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 the like. Preferred is 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 substituted. Examples of the substituent include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, and butyl groups.

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

R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or a cycloalkyl group having 6 to 20 carbon atoms. 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 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, carbon Represents a group selected from the group consisting of an aralkyloxy group, a nitro group, an aldehyde group, a cyano group, and a carboxyl group having 7 to 20 atoms. If there is more than one, they may be the same or different.

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

Examples of the alkyl group 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, tetradecyl group, etc. . Preferred is an alkyl group having 1 to 6 carbon atoms.

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

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 preferred.

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 preferred.

Examples of the alkenyl group having 2 to 10 carbon atoms include methenyl group, ethenyl group, propenyl group (common name: allyl group), butenyl group, and pentenyl group. Alkenyl groups having 1 to 6 carbon atoms are preferred.

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

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

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

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

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

The polycarbonate block represented by formula [1] is 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3- Allyl-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, etc. are preferred, and more preferably 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1 -bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4-biphenol, 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, particularly preferably It is a block derived from 2,2-bis(4-hydroxyphenyl)propane and 2,2-bis(3-allyl-4-hydroxyphenyl)propane.

The polycarbonate block represented by formula [1] may include a plurality of different repeating units, and the repeating units at this time may be blocks or random.

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

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, even more preferably It is 80 to 99.0% by weight.

<Polydiorganosiloxane block of formula [3]>
It is represented by the following formula [3] derived from 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 the alkyl group 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, dodecyl group, and the like. Preferred is an alkyl group having 1 to 6 carbon atoms.

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

As the alkenyl group having 2 to 10 carbon atoms, methenyl group, ethenyl group, propenyl group (common name: allyl group), butenyl group, pentenyl group, etc. are preferable, and 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 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.

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

Examples of the alkyl group 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, dodecyl group, and the like. Preferred is an alkyl group having 1 to 6 carbon atoms.

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

It is particularly preferable 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. Examples of divalent aliphatic groups include alkylene groups having 2 to 8 carbon atoms. Preferred examples of the alkylene group include ethylene group, trimethylene group, and tetramethylene group.

p is a natural number, q is 0 or a natural number, and p+q is a natural number from 1 to 50. p+q is preferably 1 to 45, more preferably 5 to 45, even more preferably 10 to 45, particularly preferably 10 to 40. p is preferably 1-45, more preferably 5-40, even more preferably 5-30. q is preferably 0 to 40, more preferably 0 to 35, even more preferably 1 to 30. The average chain lengths p and q are calculated by nuclear magnetic resonance (NMR) measurement.

If p+q is within the above range, it is presumed that the aggregation of siloxane due to crosslinking will not proceed too much and deterioration of flame retardancy can be suppressed.

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

The repeating unit of p may include 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 shown in the following formula [8]. In that 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 block or random. good.

The repeating unit q may include any number of units in which R ⁵ and R ⁶ are different. For example, there may be a repeating unit of q1 and q2 as in the following formula [9]. In that case, the sum of the repeating units of q1 and q2 is q, and the repeating unit of q1 and q2 at this time may be block or 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, it is also possible to mix suitable polydiorganosiloxane raw materials with hydroxyaryl-modified terminals, or to prepare a polydiorganosiloxane having an appropriate average chain length before hydroxyaryl-modifying the terminals. Either method may be used, in which the precursors are mixed in advance and then the terminals are modified with hydroxyaryl.

The content of alkenyl groups 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, R ⁴ to R ⁸ are methyl groups, and p = 12 and q = 23, it will be 16.7 mol%, R ³ and R ⁴ are alkenyl groups, and R 5 to R 8 are methyl groups. And when p=12 and q=23, it becomes 33.3 mol%.

Within the above range, the anti-drip effect due to crosslinking and thickening of alkenyl groups will be stronger, and more superior flame retardancy will be obtained, and furthermore, the aggregation of siloxane due to crosslinking will not progress too much, resulting in worsening of flame retardancy. It is estimated that this can be suppressed.

<Polydiorganosiloxane block of formula [4]>
It is represented by the following formula [4] derived from 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 group having 6 to 12 carbon atoms. group, and each has the same meaning as R ⁵ , R ⁶ , R ⁷ and R ⁸ in the above formula [3] except that it does not contain an alkenyl group. However, it may be selected independently from the above formula [3]. 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 are R ⁹ and R ¹⁰ of the above formula [3], respectively. is synonymous with However, it may be selected independently from the above formula [3]. It is particularly preferable 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 meaning as the above formula [3].

p' is a natural number of 50 to 150, preferably 50 to 120, more preferably 55 to 110, particularly preferably 60 to 100. The average chain length p' is calculated by nuclear magnetic resonance (NMR) measurement.

If p' is within the above range, it is possible to achieve both high impact resistance and chemical resistance at low temperatures.

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 of p'1 and p'2 as in the following formula [10]. In that case, the sum of the repeating units of p'1 and p'2 becomes p', and in this case p' The repeat unit of 1 and p'2 may be block or random.

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

The PC-POS copolymer has a polydiorganosiloxane block of formula [3] and a polydiorganosiloxane block of formula [4] in a weight ratio of formula [3]/formula [4] = 1 to 99/99 to 1 (weight %/wt%), preferably formula [3]/formula [4] = 10~90/90~10 (wt%/wt%), more preferably formula [3]/formula [4] = 10~ 70/90 to 30 (wt%/wt%), most preferably formula [3]/formula [4] = 15 to 50/85 to 50 (wt%/wt%). The copolymer consisting of formula [3] and formula [4] can maximize the anti-drip effect due to crosslinking and thickening developed by copolymerizing formula [3], and It is presumed that copolymerization provides impact resistance and chemical resistance at low temperatures, as well as moderate control of siloxane aggregation ability due to crosslinking, resulting in higher flame retardancy.

As a PC-POS copolymer, the average polydiorganosiloxane repeating number is 30 to 150, preferably 30 to 100, more preferably 35 to 90. Within the above range, both impact resistance and productivity at low temperatures can be sufficiently achieved.

The content of the polydiorganosiloxane component in the PC-POS copolymer is 2.5 to 30.0% by weight, preferably 2.5 to 20.0% by weight based on the total weight of the PC-POS copolymer. % by weight, more preferably 2.5 to 14.0% by weight, even more preferably 2.5 to 8.0, particularly preferably 3.0 to 8.0. Note that the polydiorganosiloxane component content is the content of siloxane repeating structures. For example, when the polydiorganosiloxane block is composed of the above formula [3] and the above formula [4], the repeating units p, q and This is the content of the structure corresponding to p'. If it is within the above range, superior cryogenic impact resistance and chemical resistance will be obtained, as well as deterioration of appearance (color unevenness, poor peeling), decrease in rigidity, decrease in glass transition temperature, decrease in heat bending resistance, etc. Deterioration in physical properties can be suppressed, and powdering becomes easier, improving productivity.

In addition, the content of siloxane repeating structures containing alkenyl groups in the PC-POS copolymer (hereinafter sometimes abbreviated as alkenylsiloxane component content) is 0 based on the total weight of the PC-POS copolymer. .01 to 3.0% by weight, preferably 0.01 to 2.0% by weight, more preferably 0.01 to 1.6% by weight, even more preferably 0.01 to 1.0% by weight, especially Preferably it is 0.05-0.6% by weight, most preferably 0.1-0.5% by weight. In addition, the alkenylsiloxane component content is the content of a siloxane repeating structure containing an alkenyl group. For example, when the polydiorganosiloxane block is composed of the above formula [3] and the above formula [4], the alkenyl group is This is the content of the structure corresponding to the repeating unit p. Within the above range, the anti-drip effect due to crosslinking and thickening of alkenyl groups will be stronger, and more superior flame retardancy will be obtained, and furthermore, the aggregation of siloxane due to crosslinking will not progress too much, resulting in worsening of flame retardancy. It is estimated that this can be suppressed.

The viscosity average molecular weight of the copolymer is preferably 11,000 to 30,000, more preferably 12,000 to 25,000, even more preferably 14,000 to 24,000. Within the above range, it is easy to obtain practical mechanical strength in many fields, and since it has an appropriate melt viscosity during molding, problems such as thermal deterioration are suppressed, and it can be used with polycarbonate resin that is mixed at any time. The difference in melt viscosity is small, resulting in good kneading properties. Furthermore, the efficiency of the water washing process during resin production is good, and productivity is excellent.

(Polycarbonate resin)
The type of polycarbonate resin optionally contained in the resin composition of the present invention is not particularly limited as long as it can provide the advantageous effects of the present invention.

The polycarbonate resin is composed of a dihydric phenol that induces the above formula [1], and specific dihydric 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(3-allyl- 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'-diphenyldiphenyl sulfoxide, 4, 4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane , 4,4'-(1,3-adamantanediyl)diphenol, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, and the like.

Among them, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-allyl-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'-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 are preferred, particularly 2,2-bis(4-hydroxyphenyl)propane, 1,1- Bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 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 suitable. Further, these may be used alone or in combination of two or more.

<Composition of copolymer and resin composition>
The copolymer and resin composition of the present invention comprises 100 to 1% by weight of a PC-POS copolymer and 0 to 99% by weight of a polycarbonate resin, preferably 99 to 1% by weight of a PC-POS copolymer and a polycarbonate resin. It consists of 1 to 99% by weight, more preferably 90 to 1% by weight of PC-POS copolymer and 1 to 90% by weight of polycarbonate resin.

The polydiorganosiloxane component content in the present invention is 2.5 to 20.0% by weight, preferably 2.5 to 14.0% by weight based on the resin composition (particularly, only the resin weight of the resin composition). %, more preferably 2.5 to 10.0% by weight, still more preferably 2.5 to 8.0, particularly preferably 2.5 to 7.0% by weight. If it is within the above range, superior cryogenic impact resistance and chemical resistance will be obtained, as well as deterioration of appearance (color unevenness, poor peeling), decrease in rigidity, decrease in glass transition temperature, decrease in heat bending resistance, etc. Deterioration in physical properties can be suppressed.

The alkenylsiloxane component content in the resin composition in the present invention is 0.01 to 3.0% by weight, preferably 0.01% by weight, based on the resin composition (particularly, only the resin weight of the resin composition). -2.0% by weight, more preferably 0.01-1.4% by weight, even more preferably 0.01-1.0% by weight, particularly preferably 0.05-1.0% by weight, most preferably 0 .1 to 1.0% by weight.

The viscosity average molecular weight of the resin composition is preferably 11,000 to 30,000, more preferably 12,000 to 25,000, even more preferably 14,000 to 24,000. Within the above range, more superior cryogenic impact resistance can be achieved.Within the above range, more superior cryogenic impact resistance can be obtained, while reducing productivity and molding fluidity due to increased solution viscosity. In addition, it is possible to suppress deterioration in physical properties such as deterioration of appearance (color unevenness, poor peeling), decrease in rigidity, decrease in glass transition temperature, and decrease in heat bending resistance. can.

The average polydiorganosiloxane repeating number in the resin composition is 30 to 150, preferably 30 to 100, and more preferably 35 to 90. Note that the polydiorganosiloxane component content means the total content of siloxane repeating structures. Within the above range, sufficient impact resistance and chemical resistance at low temperatures can be obtained, and deterioration in appearance (color unevenness, poor peeling) can be suppressed.

<Method for producing PC-POS copolymer>
The PC-POS copolymer in the present invention can be produced by step (a) and step (b).

Step (a) is to react a dihydric phenol (I) represented by the following formula [5] with phosgene in a mixture of a water-insoluble organic solvent and an aqueous alkaline solution to produce a compound having a terminal chloroformate group. This is a step of preparing a solution containing carbonate oligomers.

(In the formula, R ¹ , R ² , e, f and W are the same as above.)
Examples of the dihydric phenol (I) represented by formula [5] include 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2 , 2-bis(3-allyl-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'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxybiphenyl, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl) propyl}benzene is preferred.

In particular, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4, Preferred are 4'-sulfonyldiphenol, 4,4'-dihydroxybiphenyl, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Among them, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is most suitable. Further, these may be used alone or in combination of two or more.

Step (b) consists of hydroxyaryl-terminated polyorganosiloxane (II) (X-1) represented by the following formula [6] and hydroxyaryl-terminated polydiorganosiloxane (II) (X-1) represented by the following formula [7]. -2) and the carbonate oligomer prepared in step (a) are interfacially polymerized to obtain the PC-POS copolymer of the present invention.

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

(In the formula, R ²¹ to R ²⁶ , X, and p' are the same as above.)
As the hydroxyaryl-terminated polydiorganosiloxane (II) (X-2) represented by the above general formula [7], for example, the following compounds are preferably used.

(X-1) and (X-2) may be used by blending them in advance as a mixed raw material, or they may be used by pre-mixing polydiorganosiloxane precursors with an appropriate average chain length before hydroxyaryl modification at the terminals. After mixing, the terminals may be modified with hydroxyaryl and the obtained raw material may be used.

Furthermore, before reacting with the carbonate precursor and dihydric phenol, (X-1) and (X-2) may be blended in advance, or may be added to the reaction solution in parallel without being blended in advance, or ( X-1) and (X-2) may be divided and sequentially added to the reaction solution to react with the carbonate precursor and dihydric phenol.

When mixing (X-1) and (X-2), the weight ratio of (X-1) and (X-2) is (X-1)/(X-2) = 1 ~ 99/99 ~ 1 (wt%/wt%), preferably the weight ratio (X-1)/(X-2)=10-90/90-10 (wt%/wt%), more preferably (X -1)/(X-2)=10-70/90-30 (wt%/wt%), more preferably (X-1)/(X-2)=15-50/85-50 (wt%) /wt%).

As the polydiorganosiloxane raw material, it is more preferable to use polydiorganosiloxane (X) obtained by blending (X-1) and (X-2) in advance, and this blending ratio is as described above for (X-1). Similar to the weight ratio of X-1)/(X-2)=10-90/90-10 (wt%/wt%), more preferably (X-1)/(X-2)=10-70/90-30 (wt. %/wt%), more preferably (X-1)/(X-2)=15-50/85-50 (wt%/wt%).

In the interfacial polycondensation method for obtaining the PC-POS copolymer of the present invention, the water-insoluble organic solvent is The amount is preferably 8 mol or more and less than 12 mol, more preferably 8 to 9.5 mol.

Here, the total amount of dihydric phenol means the total amount ([(I)+(II)]) of dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II).

In addition, the amount of the insoluble organic solvent is the total amount used up to the time when the catalyst is added and the polycondensation reaction is started, including the amount used during the production of the polycarbonate oligomer, the polydiorganosiloxane monomer, and the terminal capping agent. This is the total amount of the amount used for dissolution and the amount added to adjust the emulsification state during the interfacial polycondensation reaction.

Furthermore, a water-insoluble organic solvent may be added immediately after the reaction of the carbonate precursor and dihydric phenol with the polydiorganosiloxane proceeds. Specifically, when the proportion of unreacted polydiorganosiloxane in the reaction solution becomes 10% or less among the polydiorganosiloxanes used, a water-insoluble organic solvent is mixed with dihydric phenol (I) and a hydroxyaryl terminal. It is desirable to add 2 mol or more per 1 mol of the total amount of dihydric phenol in polydiorganosiloxane (II). This makes it possible to ensure a sufficient degree of reaction progress while also suppressing the risk of precipitation of polymer components due to high concentration.

In addition, other comonomers other than the above-mentioned dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be contained in an amount of 10% by weight or less based on the total weight of the copolymer, within a range that does not interfere with the production method of the present invention. They can also be used together within the range. In this case, the comonomer is added to the calculation of the total amount of dihydric phenol.

In the production method of the present invention, a mixture containing an oligomer having a terminal chloroformate group is prepared by reacting dihydric phenol (I) with a carbonate-forming compound in a mixture of a water-insoluble organic solvent and an aqueous alkaline solution. Prepare the solution.

In producing an oligomer of dihydric phenol (I), the entire amount of dihydric phenol (I) used in the method of the present invention may be made into an oligomer at once, or a part thereof may be used as a post-added monomer to form an oligomer at the subsequent interface. It may be added as a reaction raw material to the polycondensation reaction. The post-addition monomer is added to speed up the subsequent polycondensation reaction, and there is no need to intentionally add it if it is not necessary.

The method of this oligomer production reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

The proportion of the carbonate ester-forming compound to be used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Furthermore, when using a gaseous carbonate ester-forming compound such as phosgene, a method of blowing it into the reaction system can be suitably employed.

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, or mixtures thereof are used.

Similarly to the above, the proportion of the acid binder to be used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, it is preferable to use the acid binder in an amount of 2 equivalents or slightly in excess of the number of moles of dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents). .

As the solvent, solvents inert to various reactions, such as those used in the production of known polycarbonates, may be used alone or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride, and chlorobenzene. In particular, halogenated hydrocarbon solvents such as methylene chloride are preferably used.

The reaction pressure for oligomer production is not particularly limited and may be at normal pressure, increased pressure, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50°C, and since heat is generated during polymerization in many cases, it is desirable to cool with water or ice. Although the reaction time depends on other conditions and cannot be absolutely defined, it is usually carried out for 0.2 to 10 hours.

The pH range of the oligomer production reaction is similar to known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

In this way, the present invention obtains a mixed solution containing an oligomer of dihydric phenol (I) having a terminal chloroformate group, and then adds the hydroxyaryl-terminated polydiorganosiloxane (II) while stirring the mixed solution. In addition, a polycarbonate-polydiorganosiloxane copolymer is obtained by interfacial polycondensation of the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer.

When 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, or mixtures thereof are used. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) used or a part of the dihydric phenol (I) as described above is added to this reaction step as a post-addition monomer, the post-addition amount is It is preferable to use the alkali in an amount of 2 equivalents or in excess of the total number of moles of the hydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

Polycondensation by interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixture.

In such polymerization reactions, terminal terminators or molecular weight regulators are usually used. Examples of the terminal capping agent include compounds having a monovalent phenolic hydroxyl group, including ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols and aliphatic carboxylic acids. Examples include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl ester, and alkyl ether phenol. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of all the dihydric phenol compounds used, and it is naturally possible to use two or more types of compounds together. be.

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

The reaction time of such a polymerization reaction needs to be relatively long in order to reduce unreacted polydiorganosiloxane components. Preferably it is 30 minutes or more, more preferably 50 minutes or more. On the other hand, since polymer precipitation may occur due to stirring of the reaction solution for a long time, the stirring time is preferably 180 minutes or less, more preferably 90 minutes or less.

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

Moreover, the polycarbonate resin composition of the present invention can be made into a branched polycarbonate by using a branching agent in combination with the above-mentioned dihydric phenol compound. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2,2. , 4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl) Ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[ Trisphenol such as 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, Examples include 4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and their acid chlorides, among which 1,1,1-tris(4-hydroxy Phenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure, but usually, the reaction can be suitably carried out at normal pressure or about the own pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and since heat is generated during polymerization in many cases, it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as reaction temperature, it cannot be absolutely specified, but it is usually carried out for 0.5 to 10 hours.

In some cases, the obtained polycarbonate copolymer is subjected to appropriate physical treatment (mixing, fractionation, etc.) and/or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain the desired reduced viscosity [η _SP /c] can also be obtained as a polycarbonate copolymer.

The obtained reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods and recovered as a PC-POS copolymer of desired purity (purification degree).

Furthermore, the PC-POS copolymer of the present invention can be blended with various flame retardants, reinforcing fillers, and additives that are usually blended into polycarbonate resins within a range that does not impair the effects of the present invention.

The PC-POS copolymer in the present invention can be pelletized by melt-kneading using an extruder such as a single-screw extruder or a twin-screw extruder. When producing such pellets, the above-mentioned various flame retardants, reinforcing fillers, and additives can also be blended.

The PC-POS copolymer of the present invention can be produced into various products by injection molding the pellets produced as described above. Furthermore, it is also possible to directly make a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product from the resin melt-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 molding of supercritical fluid), insert molding, Molded articles can be obtained using injection molding methods such as in-mold coating molding, adiabatic mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. Further, for molding, either a cold runner method or a hot runner method can be selected.

The PC-POS copolymer of the present invention can also be used in the form of various extrusion molded products, sheets, films, etc. by extrusion molding. In addition, an inflation method, a calendar method, a casting method, etc. can also be used for forming sheets and films. Furthermore, by applying a specific stretching operation, it is also possible to form a heat-shrinkable tube. The polycarbonate-polydiorganosiloxane copolymer of the present invention can also be made into a molded article by rotational molding, blow molding, or the like.

Furthermore, in the present invention, the molded article made of the PC-POS copolymer can be subjected to various surface treatments. Surface treatment here refers to adding a new layer to the surface of a resin molded product, such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, printing, etc. 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 absorbing coat, infrared absorbing coat, and metallizing (vapor deposition, etc.).

<<Characteristic values of PC-POS copolymer or its resin composition>>
(Cryogenic impact strength)
The PC-POS copolymer or its resin composition of the present invention preferably has a notched Charpy impact strength of 40 kJ/m ² or more when measured on a 4 mm thick test piece cooled to -30°C in accordance with ISO179. , more preferably 50 kJ/m ² or more, still more preferably 55 kJ/m ² or more.

Further, the measured value of the notched Charpy impact strength of a 4 mm thick test piece cooled to -50°C is preferably 30 kJ/m ² or more, more preferably 34 kJ/m ² or more, and even more preferably 36 kJ/m 2 or more. m ² or more, particularly preferably 38 kJ/m ² or more, and most preferably 40 kJ/m ² or more.
Further, the measured value of the notched Charpy impact strength of a 4 mm thick test piece cooled to -60°C is preferably 20 kJ/m ² or more, more preferably 25 kJ/m ² or more, and even more preferably 28 kJ/m 2 or more. ^m2 or more. Further, the measured value of the notched Charpy impact strength of the test piece cooled to -75°C is preferably 18 kJ/m ² or more, more preferably 22 kJ/m ² or more.

If the measured value of the notched Charpy impact strength is within the above-mentioned range, it is more suitable for outdoor structural members for extremely cold regions, various housing members, and automobile-related parts.

(Paint chemical impact strength)
The PC-POS copolymer or its resin composition of the present invention preferably has a notched Charpy impact strength of 30 kJ after being coated and cooled to -30°C in accordance with ISO179. /m ² or more, more preferably 35 kJ/m ² or more, still more preferably 40 kJ/m ² or more. Further, the value measured for the notched Charpy impact strength of a 4 mm thick test piece cooled to -50°C in accordance with ISO 179 after prescribed coating is preferably 10 kJ/m ² or more, more preferably 15 kJ/m ² More preferably, it is 20 kJ/m ² or more.

Within the above range, it is more suitable for outdoor structural members, various housing members, and automobile-related parts for extremely cold regions.

(Transparency and appearance)
The PC-POS copolymer of the present invention or its resin composition has a total light transmittance and a haze of a 2.0 mm thick portion of the obtained three-tier plate using Haze Meter NDH 2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. The total light transmittance value measured according to ASTM D1003 is preferably 80% or less, more preferably 55% or less. In addition, the appearance of the obtained three-tiered plate is characterized by no noticeable defects such as streaky appearance defects, marble-like appearance defects, yellowing/blackening appearance defects, surface peeling, uneven coloring, and uneven transmission. Preferably, the above-mentioned appearance defects are observed, but they are slight or the defect incidence is less than 50%, and more preferably, no particularly noticeable appearance defects are observed. In particular, when the transparency and appearance are above the above ranges, the appearance defect rate is high, productivity decreases, and the material cannot be used as an exterior material.

(chemical resistance)
The PC-POS copolymer of the present invention or its resin composition preferably shows only minute cracks of about 1 to 3 mm in the test piece in the chemical resistance test below, and more preferably shows no change in visual appearance. There is no. Using the resin composition containing the polycarbonate-polydiorganosiloxane copolymer of the present invention, an ISO dumbbell-shaped tensile test piece with a width of 10 mm, a length of 80 mm, a total length of 150 mm, and a thickness of 4 mm obtained by injection molding was heat-treated at 120°C for 90 minutes. Thereafter, the molded piece was fixed to a three-point bending jig shown in FIG. 1, and a strain of 0.4% was applied to the center of the molded piece. A small exposed piece was placed over the application area, and 0.5 mL of a stock solution of alkaline detergent Phosphate-Free Forward (C-Bas Co., Ltd.) was applied thereto, and then kept in a constant temperature bath kept at 40° C. for 24 hours. The appearance of the exposed part of the molded piece taken out from the chemical solution was evaluated.

In particular, if the chemical resistance does not meet the above range, it is difficult to apply it to applications where exposure to alkalis or detergents or cleaning is expected.

(Flame retardance)
The PC-POS copolymer of the present invention or its resin composition can achieve V-0 at a thickness of 1.6 mm in the vertical combustion test (UL94V) specified by Underwriter Laboratories, Inc. of the United States. By achieving this class, it can be widely used in the electrical/electronic equipment field and the automobile field, which require high flame retardancy.

(shear viscosity)
The PC-POS copolymer of the present invention or its resin composition is prepared in accordance with ISO11443 (JIS K 7199) using a capillary type rheometer (Capillograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd.). Using capillary type EF (diameter: 1.0 mm, length: 10.01 mm, L/D: 10) manufactured by Co., Ltd., at a furnace temperature of 300°C and a shear rate of 1.22 × 10 ³ sec-1. The shear viscosity value is 50 to 400 Pa·s, more preferably 150 to 350 Pa·s, particularly preferably 200 to 300 Pa·s. If it is above the lower limit of this preferred range, practical mechanical strength can be obtained in many fields, and if it is below this upper limit, sufficient resin fluidity can be ensured in injection molding, thus supporting a wide range of product design specifications. It becomes possible to do so.

EXAMPLES The present invention will be explained in more detail with reference to examples below, but these are not intended to limit the invention. Unless otherwise specified, parts in the examples are parts by weight and percentages are percentages by weight. Note that the evaluation was conducted according to the following method.

(1) Viscosity average molecular weight (Mv)
The specific viscosity (ηSP) calculated by the following formula was determined using an Ostwald viscometer from a solution of 0.7 g of polycarbonate pellet resin dissolved in 100 ml of methylene chloride at 20 ° C.
Specific viscosity (ηSP) = (t-t ₀ )/t ₀
[ _t0 is the number of seconds that methylene chloride falls, t is the number of seconds that the sample solution falls]
The viscosity average molecular weight Mv is calculated from the determined specific viscosity (ηSP) using the following formula.
ηSP/c=[η]+0.45×[η] ² c (however, [η] is the limiting viscosity)
[η]=1.23×10 ⁻⁴ Mv ^0.83
c=0.7

(2) Content of siloxane repeating structures (polydiorganosiloxane component content), content of siloxane repeating structures containing alkenyl groups (alkenylsiloxane component content), and average polydiorganosiloxane repeating number JNM-AL400 manufactured by JEOL Ltd. The ¹ H-NMR spectrum of the obtained PC-POS copolymer and the resin composition containing it was measured using From the integral curve calculated from the curve, the integral curve of the peak derived from polydiorganosiloxane (-0.2 to 0.3 ppm), and the integral curve of the peak derived from alkenylsiloxane (5.6 to 6.1 ppm in the case of vinyl group) The polydiorganosiloxane component content and the alkenylsiloxane component content were calculated. Similarly, by comparing the integral ratio calculated from the integral curve of the peak derived from the hydroxyaryl end (0.4 to 0.6 ppm and 2.5 to 2.7 ppm) and the integral curve of the peak derived from polydiorganosiloxane, the average The number of polydiorganosiloxane repeats was calculated.

(3) Visual appearance of one molded pellet After drying the pellet with hot air at 120°C for 5 hours, molding temperature was 290°C and mold temperature was 80°C using an injection molding machine (manufactured by Japan Steel Works, Ltd., JSW J-75EIII). , the width is 50 mm, the length is 90 mm, and the thickness is 3.0 mm (length 20 mm), 2.0 mm (length 45 mm), and 1.0 mm (length 25 mm) from the gate side at a molding cycle of 50 seconds, and the arithmetic mean is A three-stage plate with a roughness (Ra) of 0.03 μm was molded.
Visual appearance evaluation is performed on the obtained three-tiered plate. Appearance abnormalities include streaky appearance defects, marble-like appearance defects, yellowing/blackening appearance defects, surface peeling, color unevenness/transmission unevenness, etc., and evaluations were made based on the presence/absence and degree of each.
◎: No particularly noticeable defect in appearance is observed. ○: The above defect in appearance is observed, but it is slight or the defect incidence is less than 50%.
×: The above appearance defects are clearly visible, making it difficult to use.

(4) Low-temperature impact evaluation (Charpy impact strength with notch)
The obtained pellets were dried with hot air at 120°C for 5 hours, and then injection molded (manufactured by Japan Steel Works, Ltd., JSW J-75EIII) at a molding temperature of 290°C, a mold temperature of 80°C, and a molding cycle of 40. A molded piece with a width of 10 mm, a length of 80 mm, and a thickness of 4.0 mm was produced in seconds. In accordance with ISO179, the notched Charpy impact strength of a test piece cooled to -30°C, -50°C, and -60°C was measured with a test piece thickness of 4 mm.

(5) Paint chemical impact resistance evaluation (Charpy impact strength with notch)
A notch was made in the molded piece obtained in (4) above in accordance with ISO 179, and the notch surface was spray-painted with Aspen Lacquer Spray (Clear) (manufactured by Asahipen Co., Ltd.). In order to apply the coating evenly, the molded piece was sprayed for 1 second with the spray nozzle separated from the spray nozzle by 20 cm, waited for 1 minute, and this process was repeated three times in total for overcoating. The painted piece was dried at room temperature for 24 hours. The test piece was cooled to -30°C and -50°C, and the notched Charpy impact strength was measured in accordance with ISO179.

(6) Chemical resistance evaluation (3-point bending test)
The obtained pellets were dried with hot air at 120°C for 5 hours, and then molded at a molding temperature of 290°C, a mold temperature of 80°C, and a molding cycle of 50 using an injection molding machine (manufactured by Japan Steel Works, Ltd., JSW J-75EIII). An ISO dumbbell-shaped tensile test piece (type A) having a width of 10 mm at the center, a length of 80 mm, a total length of 150 mm, and a thickness of 4 mm was molded in seconds. After heat-treating the obtained molded piece at 120° C. for 90 minutes, it was fixed in a three-point bending jig shown in FIG. 1, and a strain of 0.4% was applied to the center of the molded piece. A small exposed piece was placed over the application area, and 0.5 mL of an alkaline detergent undiluted solution of Phosphate-Free Forward (C.B.S. Co., Ltd.) was applied thereto, and then kept in a constant temperature bath kept at 40° C. for 24 hours. The appearance of the exposed part of the molded piece taken out from the chemical solution was evaluated.
◎: No change in visual appearance ○: Only minute cracks (length 1 or more and less than 3 mm) △: Cracks (length 3 or more and less than 7 mm) ×: Multiple large cracks (length 7 mm or more) is present or has reached the point of rupture.

(7) Flame retardancy evaluation After drying the obtained pellets with hot air at 120°C for 5 hours, injection molding was performed using a molding temperature of 300°C (JSW J-75EIII manufactured by Japan Steel Works, Ltd.). A UL test piece (width 13 mm, length 125 mm, thickness 1.6 mm) was produced at a temperature of 80° C. and a molding cycle of 40 seconds. Using the obtained UL test piece, a vertical combustion test (UL94V) was conducted according to the method (UL94) specified by Underwriter Laboratory, Inc. of the United States.
1.6 mm (with flame retardant prescription) Flame retardant class A vertical combustion test was performed on a test piece with a thickness of 1.6 mm for evaluation. Note that those that did not meet any of the criteria of V-0, V-1, and V-2 were expressed as not-V.

＜＜Raw materials＞＞
[Polydiorganosiloxane modified with phenol at both ends]
In the Examples and Comparative Examples, a polydiorganosiloxane compound having the following structure was used as the dihydric phenol (II) having a polydiorganosiloxane structure.
(II)-1:p'=35 (KF-2201 manufactured by Shin-Etsu Chemical Co., Ltd.)
(II)-2: p'=87 (KF-2102 manufactured by Shin-Etsu Chemical Co., Ltd.)
(II)-3: Polydiorganosiloxane compound having the following structure

(II)-4: Polydiorganosiloxane compound having the following structure

(II)-5: Polydiorganosiloxane compound having the following structure

The above average repeating number p' of polydiorganosiloxane units was evaluated by 1H-NMR measurement.

<<Manufacture>>
[Production of PC-POS copolymer]
(Production method of PC-POS-1)
17,590 parts of ion-exchanged water and 6,883 parts of a 25% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, stirrer, and reflux condenser, and 2,2- After dissolving 3764 parts (16.49 mol) of bis(4-hydroxyphenyl)propane (bisphenol A) and 7.5 parts of hydrosulfite, 11246 parts of methylene chloride (8 molar equivalents based on the total amount of dihydric phenol) was added, and 1900 parts of phosgene was bubbled in at 16 to 24° C. over a period of 70 minutes while stirring. A solution of 1324 parts of a 25% aqueous sodium hydroxide solution and 102 parts of p-tert-butylphenol dissolved in 918 parts of methylene chloride (0.65 molar equivalent to the total amount of dihydric phenol) was added, and while stirring, the general formula [5] Add a solution of 40 parts (0.030 mol) of the above formula [11] as dihydric phenol (II) represented by 22 parts of methylene chloride (0.015 molar equivalent based on the total amount of dihydric phenol), Next, a solution of 179 parts (0.025 mol) of KF-2102 dissolved in 96 parts of methylene chloride (0.07 molar equivalent based on the total amount of dihydric phenol) was added to form an emulsified state, and the mixture was vigorously stirred again. Under such stirring, 4.2 parts of triethylamine was added to the reaction solution at 26°C, and 15 minutes later, 2812 parts of methylene chloride (2 molar equivalents based on the total amount of dihydric phenol) was added, and triethylamine was added at a temperature of 26 to 31°C. After the addition, stirring was continued for 1 hour to complete the reaction. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and washed with water repeatedly. When the washing liquid became neutral, it was washed with water acidified with hydrochloric acid. After that, it was washed repeatedly with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, it was poured into a kneader filled with warm water, and the methylene chloride was evaporated while stirring, and the PC-POS copolymer was of powder was obtained. After dehydration, it was dried at 120° C. for 12 hours using a hot air circulation dryer. The obtained PC-POS copolymer had a viscosity average molecular weight of 21,000, a polydiorganosiloxane component content of 4.6% by weight, and an alkenylsiloxane component content of 0.2% by weight.

(Manufacturing method of PC-POS-2)
As dihydric phenol (II) represented by general formula [5], 198 parts (0.060 mol) of the above formula [12] were added to 107 parts of methylene chloride (0.076 molar equivalent based on the total amount of dihydric phenol). Adding the dissolved solution, and then adding a solution of 463 parts (0.064 mol) of the above KF-2102 dissolved in 249 parts of methylene chloride (0.177 molar equivalent to the total amount of dihydric phenol), The method for producing PC-POS-1 was repeated, except that -tert-butylphenol was changed to 149 parts and dissolved in 1341 parts of methylene chloride (0.95 molar equivalent to the total amount of dihydric phenol). The obtained PC-POS copolymer had a viscosity average molecular weight of 16,000, a polydiorganosiloxane component content of 13.0% by weight, and an alkenylsiloxane component content of 1.4% by weight.

(Manufacturing method of PC-POS-3)
As the dihydric phenol (I) represented by the general formula [4], 3661 parts (16.03 mol) of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) and 2,2-bis(3-allyl) The method for producing PC-POS-2 was repeated except that 119 parts (0.386 mol) of -4-hydroxyphenyl)propane was used. The obtained PC-POS copolymer had a viscosity average molecular weight of 15,800, a polydiorganosiloxane component content of 12.9% by weight, and an alkenylsiloxane component content of 1.6% by weight.

(Production method of PC-POS-4)
As dihydric phenol (II) represented by general formula [5], 666 parts (0.122 mol) of the above formula [13] was dissolved in 359 parts of methylene chloride (0.255 molar equivalent based on the total amount of dihydric phenol). PC-POS- The same manufacturing method as No. 1 was followed. The resulting PC-POS copolymer had a viscosity average molecular weight of 17,000, a polydiorganosiloxane component content of 11.9% by weight, and an alkenylsiloxane component content of 4.3% by weight.

(Manufacturing method of PC-POS-5)
The above KF-2201 was changed to 21,090 parts of methylene chloride (15 molar equivalent to the total amount of dihydric phenol), and the above KF-2201 was changed to 208 parts (0.067 mol) as the dihydric phenol (II) represented by the general formula [5]. ) in 386 parts of methylene chloride (0.275 molar equivalent to the total amount of dihydric phenol) was added, and then 208 parts (0.063 mol) of the above formula [12] was dissolved in 386 parts of methylene chloride (dihydric phenol). The above p-tert-butylphenol was changed to 107 parts and dissolved in 963 parts of methylene chloride (0.69 molar equivalent to the total amount of dihydric phenol). The manufacturing method for PC-POS-1 was the same as that for PC-POS-1 except for the addition. The obtained PC-POS copolymer had a viscosity average molecular weight of 19,600, a polydiorganosiloxane component content of 8.4% by weight, and an alkenylsiloxane component content of 1.5% by weight.

(Manufacturing method of PC-POS-6)
As dihydric phenol (II) represented by general formula [5], 198 parts (0.064 mol) of KF-2201 was dissolved in 100 parts of methylene chloride (0.07 molar equivalent based on the total amount of dihydric phenol). The above p- The method for producing PC-POS-1 was repeated, except that tert-butylphenol was changed to 149 parts and dissolved in 1341 parts of methylene chloride (0.95 molar equivalent to the total amount of dihydric phenol). The resulting PC-POS copolymer had a viscosity average molecular weight of 16,100 and a polydiorganosiloxane component content of 12.5% by weight.

(PC-POS-7)
The physical properties of a commercially available siloxane-containing polycarbonate (Lexan EXL1414 manufactured by Sabic, polydiorganosiloxane component content: 3.5% by weight) were measured and are listed in Table 1 below.

(PC-POS-8)
The physical properties of a commercially available siloxane-containing polycarbonate (Taflon Neo AG1950 manufactured by Idemitsu Co., Ltd., polydiorganosiloxane component content: 5.0% by weight) were measured and are listed in Table 1 below.

(PC-1)
A linear aromatic polycarbonate resin powder having a repeating skeleton of 2,2-bis(4-hydroxyphenyl)propane and a solution viscosity and molecular weight of 23,900 (Panlite L-1250WP manufactured by Teijin Ltd.).

[Manufacture of polycarbonate resin composition containing PC-POS copolymer]
[Example 1]
300 ppm of tris(2,4-di-tert-butylphenyl) phosphite (manufactured by BASF Corporation: Irgafos 168) was added to 100 parts by weight of the PC-POS-1 100% by weight polycarbonate resin obtained in the production example. After mixing so that The mixture was melted and kneaded at 270° C. from the mouth to the die portion to form pellets. After drying the obtained pellets with hot air at 120°C for 5 hours, they were molded using an injection molding machine (JSW J-75EIII manufactured by Japan Steel Works, Ltd.) at a molding temperature of 290°C and a mold temperature of 80°C. A molded piece having a width of 10 mm, a length of 80 mm, and a thickness of 4.0 mm was molded at a cycle of 40 seconds. Further, under the same conditions, an ISO dumbbell-shaped tensile test piece (type A) having a width of 10 mm at the center, a length of 80 mm, a total length of 150 mm, and a thickness of 4 mm was molded using a molding cycle of 50 seconds. The polydiorganosiloxane component content of the test piece was 4.6% by weight, the alkenylsiloxane component content was 0.2% by weight, the average polydiorganosiloxane repeating number was 46, and the viscosity average molecular weight Mv was 21,000. . Furthermore, using the obtained test pieces, the notched Charpy impact value at -30°C, -50°C, and -60°C, impact resistance after painting, visual appearance, and chemical resistance by three-point bending test were evaluated. . Furthermore, 500 ppm of tris(2,4-di-tert-butylphenyl) phosphite and octadecyl-3 were added as flame retardant formulations to 100 parts by weight of the 100% by weight polycarbonate resin of PC-POS-1 obtained in the above production example. -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid (manufactured by BASF Japan Co., Ltd.: Irganox 1076) 500 ppm, Megafac F-114P (manufactured by DIC Corporation) 500 ppm, Metablane A3750 (manufactured by DIC Corporation) A separate mixture of 2000 ppm of PTFE powder (manufactured by Mitsubishi Rayon Co., Ltd.) was extruded in the same manner as above, and the resulting pellets were placed in the above molding machine at a molding temperature of 300°C, a mold temperature of 80°C, and a molding cycle of 40 seconds. A UL test piece (width 13 mm, length 125 mm, thickness 1.6 mm) was prepared and flame retardance was evaluated. The evaluation results are shown in Table 2.

[Examples 2-3 and Comparative Examples 1-4, 7]
The resin compositions of Examples 2 to 3 and Comparative Examples 1 to 4 and 7 were produced in the same manner as in Example 1, except that the type of PC-POS copolymer used and/or the blend weight ratio was changed, and The same evaluation as in Example 1 was performed. The results are listed in Table 2.

[Comparative example 5]
After PC-POS-7 was dried with hot air at 120° C. for 5 hours, a molded piece was produced in the same manner as in Example 1 and evaluated in the same manner. The results are listed in Table 2.

[Comparative example 6]
The same operations as in Comparative Example 5 were performed, except that PC-POS-7 was changed to PC-POS-8, and the same evaluation was performed. The results are listed in Table 2.

It is recognized that by using the polycarbonate resin composition of the present invention, it has high impact performance even at extremely low temperatures, and also has both impact durability and chemical resistance after coating, as well as flame retardancy.

The copolymer or resin composition obtained in the present invention has excellent cryogenic impact properties and chemical resistance, and also has high coating durability and flame retardancy, so it can be used for optical parts. It can be widely used in the electric/electronic equipment field, and the transportation/mobility field such as automobiles and aircraft. Among these, it is highly practical for various housing molded products that are expected to be exposed to harsh environments such as extremely cold environments such as high latitudes, mountain areas, and the sky, high temperature heat treatment, and chemical treatment.

1 y: Deflection amount (mm)
2 h: Test piece thickness (4mm)
3 L: Measurement width (150mm)

Claims (11)

A polycarbonate-polydiorganosiloxane co-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 resin composition comprising a polymer and an optional polycarbonate resin.
[(In the above general formula [1], 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, or a 6 carbon atom -20 cycloalkyl group, C6-20 cycloalkoxy group, C2-10 alkenyl group, C6-14 aryl group, C6-14 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, and if there are multiple of each, they may be the same. may be different, e and f are each integers of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups 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 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 R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a C 1 to 18 atom. Alkyl group having 1 to 10 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, 6 carbon atoms ~14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group, and carboxyl group (If there are multiple groups, they may be the same or different, g is an integer from 1 to 10, and h is an integer from 4 to 7.)
(In the above general 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 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 50. is a natural number.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 each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted group having 6 to 12 carbon atoms) It is 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, or an alkoxy group having 1 to 10 carbon atoms, and p' is 50 to 150. is a natural number. X is a divalent aliphatic group having 2 to 8 carbon atoms.) The resin composition according to claim 1 , wherein the content of the polydiorganosiloxane component is 2.5 to 14.0% by weight based on the total weight of the resin composition. The resin composition according to claim 1 or 2, characterized in that the average polydiorganosiloxane repeating number is 30 to 100. The resin composition according to any one of claims 1 to 3, having a viscosity average molecular weight of 11,000 to 30,000. The resin composition according to any one of claims 1 to 4, comprising 99 to 1% by weight of the polycarbonate-polydiorganosiloxane copolymer and 1 to 99% by weight of the polycarbonate resin. The resin composition according to claim 5, wherein the polycarbonate resin consists of a polycarbonate block represented by the following general formula [1]:
[(In the above general formula [1], 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, or a 6 carbon atom -20 cycloalkyl group, C6-20 cycloalkoxy group, C2-10 alkenyl group, C6-14 aryl group, C6-14 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, and if there are multiple of each, they may be the same. may be different, e and f are each integers of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups 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 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 R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a C 1 to 18 atom. Alkyl group having 1 to 10 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, 6 carbon atoms ~14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group, and carboxyl group (If there are multiple groups, they may be the same or different, g is an integer from 1 to 10, and h is an integer from 4 to 7.) The resin composition according to any one of claims 1 to 6 , wherein the alkenylsiloxane component content is 0.01 to 2.0% by weight based on the total weight of the resin composition. The resin composition according to any one of claims 1 to 7, which has a notched Charpy impact strength of 30 kJ/m ² or more at a thickness of 4 mm measured at -50°C in accordance with ISO 179. The resin composition according to any one of claims 1 to 8, which has a notched Charpy impact strength of 20 kJ/m ² or more at a thickness of 4 mm measured at -60°C in accordance with ISO 179. The resin composition according to any one of claims 1 to 9, which has a notched Charpy impact strength of 15 kJ/m ² or more at a thickness of 4 mm after being coated with a paint spray and measured at -50°C in accordance with ISO 179. A molded article formed from the resin composition according to any one of claims 1 to 10.

Images