JP7622506B2 - Copolymeric polycarbonate resin composition, molded article, and method for producing copolymeric polycarbonate resin - Google Patents

Description

The present invention relates to a copolymeric polycarbonate resin, and more particularly to a polycarbonate resin having excellent chemical resistance and weather resistance.

Polycarbonate resins generally use bisphenols as monomer components, and are widely used as so-called engineering plastics in the fields of electrical and electronic parts, automotive parts, medical parts, building materials, films, sheets, bottles, optical recording media, lenses, etc., taking advantage of their advantages such as transparency, heat resistance, and mechanical strength. In recent years, further improvement in the performance of molded products has been required in these application fields. However, conventional general polycarbonate resins made from bisphenol A as a raw material have insufficient chemical resistance and weather resistance for these required properties. Therefore, there has been a demand for the development of polycarbonate resins with improved chemical resistance and weather resistance, and several proposals have been made.

For example, a method of copolymerizing a specific amount of a specific polyorganosiloxane has been disclosed as a means for improving the chemical resistance of polycarbonates using bisphenols as raw material monomers (Patent Document 1).
The bisphenol compounds used in conventional polycarbonate resins have a benzene ring structure and therefore have high ultraviolet absorption, which is a factor in causing a deterioration in the light resistance of the polycarbonate resin.

In view of this, polycarbonate resins have been developed using raw material monomers such as aliphatic dihydroxy compounds and alicyclic dihydroxy compounds that do not have a benzene ring structure in the molecular skeleton, and cyclic dihydroxy compounds that have an ether bond in the molecule, such as isosorbide (Patent Documents 2 to 5). For example, it has been disclosed that a polycarbonate resin using isosorbide obtained from biomass resources as a raw material monomer has high weather resistance (Patent Document 6).

International Publication No. 2015/029841 International Publication No. 2004/111106 International Publication No. 2007/063823 International Publication No. 2008/108492 JP 2011-241277 A JP 2013-209585 A

However, conventional methods have not been able to produce polycarbonate resins that are excellent in both chemical resistance and weather resistance.
The aromatic-polyorganosiloxane copolymerized polycarbonate resin as described in Patent Document 1 is silent about its weather resistance, and the present inventors have conducted research and found that it has poor weather resistance.

In addition, there is no description of chemical resistance in the polycarbonate resin modified with a terminal polyorganosiloxane using isosorbide having no benzene ring structure in the molecular skeleton as a raw material monomer described in Patent Document 4, and the polycarbonate resin copolymerized with polyorganosiloxane using isosorbide as a raw material monomer described in Patent Document 5, and the inventors have investigated and found that they have poor chemical resistance. In addition, all of the polycarbonate resins have low transparency.

Under such circumstances, an object of the present invention is to provide a polycarbonate resin having both excellent chemical resistance and weather resistance.

The present inventors conducted extensive research to solve the above problems and discovered that a copolymeric polycarbonate having a structural unit derived from a dihydroxy compound having a specific structure and a structural unit derived from a polyorganosiloxane has high chemical resistance and weather resistance, and surprisingly, may also have excellent transparency and moisture absorption resistance, thereby arriving at the present invention.
That is, the gist of the present invention resides in the following [1] to [9].
[1] A copolymer polycarbonate resin containing a structural unit (A) represented by the following formula (1) and a structural unit (B) derived from a polyorganosiloxane having two or more reactive functional groups:

(In formula (1), W is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms; R ¹ and R ² are a branched or linear alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent; and m is an integer of 0 to 10.)
[2] The copolymeric polycarbonate resin according to [1], in which the content of the structural unit (A) is 40% by weight or more and 90% by weight or less, and the content of the structural unit (B) is 1.0% by weight or more and 20% by weight or less, when the total weight of all structural units and linking groups constituting the resin is taken as 100% by weight.
[3] The ratio of the content of the structural unit (A) to the content of the structural unit (B) is 96/4 to 70/30;
The copolymer polycarbonate resin according to [1] or [2].
[4] The copolymeric polycarbonate resin according to any one of [1] to [3], wherein the reactive functional groups are each independently one or more selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an alkenyl group, an ester group, a methacryloyl group, an acryloyl group, and a cyclic ether group.
[5] The copolymeric polycarbonate resin according to any one of [1] to [4], wherein the structural unit (B) is represented by the following formula (2):

(In formula (2), n represents 5 to 30. ^{R 3} to R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. X and X' each independently represent an oxygen atom, or an organic residue having -C(═O)-, an ether structure, an amine structure, an aromatic structure, or an aliphatic structure. n represents the average repeating number of the polyorganosiloxane portion.)
[6] The copolymeric polycarbonate resin according to any one of [1] to [5], which contains 5% by weight or more and 30% by weight or less of structural units (C) derived from one or more compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, oxyalkylene glycols, and dihydroxy compounds containing an acetal ring, when the total weight of all structural units and linking groups constituting the resin is taken as 100% by weight.
[7] The copolymer polycarbonate resin according to any one of [1] to [6], characterized in that the water absorption rate of the polycarbonate resin is 1.1% or less.
[8] The copolymer polycarbonate resin according to any one of [1] to [7], wherein the copolymer polycarbonate resin has a glass transition temperature of 50° C. or higher and 160° C. or lower.
[9] A molded article comprising the copolymer polycarbonate resin according to any one of [1] to [8].
[10] A method for producing a copolymeric polycarbonate resin, comprising the steps of: mixing a dihydroxy compound containing a dihydroxy compound represented by the following formula (3) with a polyorganosiloxane having two or more reactive functional groups to obtain a raw material solution; and subjecting the raw material solution to a polycondensation reaction with a carbonic acid diester and a polymerization catalyst.

(In formula (3), W is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms; R ¹ and R ² are a branched or linear alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent; and m is an integer of 0 to 10.)

[Reasons why the present invention is effective]
The reason why the present invention is effective is not yet clear, but is presumed to be as follows.
Polyorganosiloxane has low compatibility with various dihydroxy compounds due to the low polarity of its siloxane structure. Therefore, when polyorganosiloxane and various dihydroxy compounds are melted during polycarbonate resin polymerization by melt polymerization, the reaction solution is separated into two layers, resulting in a heterogeneous reaction. If the reaction solution is heterogeneous, the reaction of polyorganosiloxane alone increases, the dispersion of the structural unit domain derived from polyorganosiloxane in the polymer deteriorates, and the domain becomes large. As a result, it is thought that the chemical resistance of the obtained polymer deteriorates and the transparency decreases.

As a result of investigations conducted by the present inventors, it was surprisingly found that dihydroxy compounds having a cyclic acetal spiro ring structure have a high affinity with polyorganosiloxanes.
That is, the polyorganosiloxane and the dihydroxy compound having a spiro ring structure form a homogeneous reaction solution during melt polymerization, so that the reaction of the polyorganosiloxane alone is reduced, and the dispersion of the structural unit domain derived from the polyorganosiloxane in the polymer is improved, and at the same time, the domain is made smaller. As a result, the obtained polymer exhibits high chemical resistance, and in some embodiments, it is considered that the transparency is improved. On the other hand, in the case of a combination of only isosorbide, which is a dihydroxy compound having a heterocyclic structure, and polyorganosiloxane, since isosorbide does not have a spiro ring structure of a cyclic acetal, the affinity between isosorbide and polyorganosiloxane is relatively poor, and the dispersion of the structural unit domain derived from the polyorganosiloxane in the polymer is poor, and the chemical resistance of the resulting polymer is poor.

The polycarbonate copolymer of the present invention has high chemical resistance and weather resistance. Some of the embodiments of the present invention are excellent in transparency and moisture absorption resistance in addition to high chemical resistance and weather resistance. Since the polycarbonate copolymer of the present invention has such excellent properties, it can be used in a wide range of fields such as automobile interior and exterior parts, electrical parts, electronic and electrical materials, outdoor building parts, and cosmetic container applications.

FIG. 2 is a cross-sectional view of a quarter elliptical jig used in a chemical resistance test.

The present invention will be described in detail below, but the present invention is not limited to the following description, and can be modified in any manner without departing from the gist of the present invention.
In this specification, when "~" is used to express a numerical value or a physical property value,
It will be used including the values before and after it.
In this specification, the term "repeated structural unit" refers to a structural unit in which the same structure appears repeatedly in a resin, and each of the structural units is linked to form the resin. For example, in the case of a polycarbonate resin, the carbonyl group is also referred to as the repeating structural unit. In addition, the term "structural unit" refers to a partial structure that constitutes a resin, and a specific partial structure contained in the repeating structural unit. For example, it refers to a partial structure sandwiched between adjacent linking groups in a resin, or a partial structure sandwiched between a polymerizable reactive group present at the end of a polymer and a linking group adjacent to the polymerizable reactive group. More specifically, in the case of a polycarbonate resin, a carbonyl group is the linking group, and a partial structure sandwiched between adjacent carbonyl groups is referred to as a structural unit. In this specification, the weight ratio of each structural unit in a polycarbonate resin is calculated by assuming the total weight of all structural units and linking groups to be 100% by weight.

[Structure and raw materials of copolymer polycarbonate resin]
The copolymeric polycarbonate resin according to the first embodiment of the present invention comprises a structural unit (A) represented by the following formula (1) and a structural unit (B) derived from a polyorganosiloxane having two or more reactive functional groups:
) is a copolymer polycarbonate resin containing.

(In formula (1), W is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms; R ¹ and R ² are a branched or linear alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent; and m is an integer of 0 to 10.)
Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a 1-methylethylene group, and a 1-ethylethylene group.
Examples include an n-pentylene group and an n-hexalene group.

Examples of the cycloalkylene group having 6 to 20 carbon atoms include a cyclohexalene group and a cycloheptalene group.
Examples of the branched or linear alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.

Examples of the cycloalkyl group having 6 to 20 carbon atoms which may have a substituent include a cyclohexane group and a cycloheptane group.
Of these, W is preferably an alkylene group having 1 to 20 carbon atoms,
^{R 1} and R ² are each independently preferably a branched or linear alkyl group having 1 to 20 carbon atoms, more preferably a branched or linear alkyl group having 1 to 10 carbon atoms, particularly preferably a branched or linear alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group. m represents an integer of 0 to 10, preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.

The structural unit (A) represented by the above formula (1) is particularly preferably a structure represented by the following formula (Y), which is excellent in reactivity during polymerization and in ease of availability.

The structural unit (A) represented by the above formula (1) is derived from a diol having a spiro ring structure. As a diol compound having such a spiro ring structure, 3,9-bis(2
-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane,
Alicyclic diol compounds such as 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1,1-diethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, and 3,9-bis(2-hydroxy-1,1-dipropylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane are particularly preferred.
4,8,10-tetraoxaspiro(5.5)undecane (sometimes called spiroglycol) is used.

The copolymeric polycarbonate resin of the present invention contains 4 structural units (A) represented by the above formula (1) when the total weight of all structural units and linking groups constituting the resin is taken as 100% by weight.
It is preferable that the content is 0% by weight or more, more preferably 45% by weight or more, and more preferably 50% by weight or more.
More preferably, it contains 55% by weight or more, even more preferably 60% by weight or more, and most preferably 70% by weight or more. Also, it contains 90% by weight or less, more preferably 85% by weight or less, and even more preferably 80% by weight or less. When the structural unit (A) is at or above the lower limit, the heat resistance of the polycarbonate resin can be improved. Also, when the structural unit (A) is at or below the lower limit, the polycarbonate resin does not crystallize during polymerization, and polymerization is easy, which is preferable.

The copolymeric polycarbonate resin of the present invention preferably contains 1.0% by weight or more of structural units (B) derived from a polyorganosiloxane having two or more reactive functional groups, when the total weight of all structural units and linking groups constituting the resin is taken as 100% by weight;
It is more preferable that the content is 0% by weight or more, even more preferable that the content is 3.0% by weight or more, and particularly preferable that the content is 4.0% by weight or more. It is also preferable that the content is 20% by weight or less, more preferably 15% by weight or less, and even more preferable that the content is 10% by weight or less. In the copolymer polycarbonate resin of the present invention, the structural unit (B) mainly plays a role in improving chemical resistance, so that when the content of the structural unit (B) is equal to or more than the above lower limit, sufficient chemical resistance can be obtained. In addition, when the structural unit (B) is equal to or less than the above upper limit, the transparency of the polycarbonate resin is improved. In addition, the reactivity during polymerization of the polycarbonate resin is improved, and the polymerization reaction is easily allowed to proceed to a sufficient molecular weight.

In addition, the copolymer polycarbonate resin of the present invention preferably has a ratio of the content of the structural unit (A) to the structural unit (B) of 96/4 to 70/30 by weight. When the content ratio is within the above range, sufficient chemical resistance can be obtained. In addition, the transparency of the polycarbonate resin is improved. Furthermore, the reactivity of the polycarbonate resin during polymerization is improved, making it easier to proceed with the polymerization reaction to a sufficient molecular weight. From the same viewpoint, the content ratio of the structural unit (A) to the structural unit (B) is more preferably 96/4 to 80/20, and even more preferably 95/5 to 85/15.

(Polyorganosiloxane)
Organopolysiloxane is a polymer having a siloxane bond as the main chain, and an organic group is bonded to the siloxane bond. Specifically, it is a polymer having a polysiloxane skeleton and a substituent (that is, an organic group) bonded to the siloxane bond of the polysiloxane skeleton. The organopolysiloxane used in the present invention has two or more reactive functional groups when contained as a structural unit of a copolymerized polycarbonate resin by polymerization reaction. When the polyorganosiloxane has two or more reactive functional groups, a structural unit derived from the polyorganosiloxane can be introduced into the polymer chain of the copolymerized polycarbonate resin. On the other hand, when the polyorganosiloxane has only one reactive functional group, the structural unit derived from the polyorganosiloxane is introduced only to the end of the polymer chain, and the resulting polycarbonate resin does not exhibit sufficient chemical resistance.

The reactive functional group is a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom,
The reactive functional group is a group that is composed of one or more atoms selected from silicon atoms and halogens, and that can change in its chemical structure upon contact with another functional group or upon heating in the atmosphere or in a solvent within a temperature range that is normally used (e.g., 100 to 300° C.). Specifically, the reactive functional group is, for example, a functional group having an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a halogen, or a carbon-carbon multiple bond (i.e., an unsaturated bond such as a double bond or a triple bond).

The reactive functional group is not particularly limited, but from the viewpoint of high reactivity, it is preferably a functional group having a carbon-carbon multiple bond and/or a functional group containing an oxygen atom, and more preferably at least one functional group selected from the group consisting of an alkenyl group, an ester group, a methacryloyl group, an acryloyl group, a cyclic ether group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a silanol group, and a carboxyl group. From the viewpoint of higher reactivity, the reactive functional group is further preferably an alcoholic hydroxyl group or a silanol group, and particularly preferably an alcoholic hydroxyl group.

The structural unit (B) derived from a polyorganosiloxane having two or more reactive functional groups is preferably represented by the following formula (2).

(In formula (2), n is 5 to 30. ^{R 3} to R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyclic group having 6 to 12 carbon atoms.)
X and X' are residues of reactive functional groups contained in polyorganosiloxane, and specifically, each independently represents an oxygen atom, or an organic residue having -C(=O)-, an ether structure, an amine structure, an aromatic structure, or an aliphatic structure. n represents the average number of repetitions of the polyorganosiloxane portion.

n is as described above, and indicates the average repeat number of polyorganosiloxane. The average repeat number is preferably 5 or more, more preferably 6 or more, and even more preferably 7 or more. Also, it is preferably 30 or less, more preferably 25 or less, even more preferably 20 or less, and particularly preferably 15 or less. When the average repeat number is equal to or more than the above lower limit, sufficient chemical resistance is obtained. Also, when the average repeat number is equal to or less than the above upper limit, transparency is significantly improved. This is presumably because, when the average repeat number of polyorganosiloxane is relatively small, the structural units derived from polyorganosiloxane are appropriately dispersed in the polymer chain, thereby suppressing cloudiness due to local non-uniformity in the refractive index.

R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms;
It is an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an n-butyl group, and an isobutyl group.

Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group and an ethoxy group.
Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group and a naphthyl group.
R ³ to R ⁶ are each independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and more preferably a methyl group or a phenyl group. ^{R 3} to R ⁶ may be different from one another or the same, but from the viewpoint of excellent effect of improving chemical resistance, it is preferable that R ³ to R ⁶ are all the same, more preferably that R ³ to R ⁶ are all methyl groups or all phenyl groups, and most preferably that R ³ to R ⁶ are all methyl groups.

X and X' are each independently preferably a silanol residue or an alcoholic hydroxyl group residue, more preferably an alcoholic hydroxyl group residue from the viewpoint of the reactivity of the polyorganosiloxane, and particularly preferably a carbinol residue.
It is particularly preferable that X and X' are each independently a structure represented by the following formula (W), which is more excellent in terms of reactivity and transparency.

(In formula (W), * represents a bonding site between X or X′ and the adjacent silicon atom in formula (2).
* represents the bonding site on the opposite side to the silicon atom in formula (2).
The structure represented by the above formula (2) is particularly preferably a structure represented by the following formula (Z), which is more excellent in terms of reactivity and transparency.

(Other structural units)
The copolymerized polymer carboxylate resin of the present invention may contain, in addition to the structural unit (A) represented by the above formula (1) and the structural unit (B) derived from polyorganosiloxane having two or more reactive functional groups, a structural unit derived from one or more compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, oxyalkylene glycols, and dihydroxy compounds having a heterocyclic structure (hereinafter, sometimes referred to as structural unit (C)). Among these, from the viewpoint of superior mechanical properties, it is preferable to have a structural unit derived from one or more compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and dihydroxy compounds having a heterocyclic structure.

Examples of the aliphatic dihydroxy compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol,
1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1
,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,
6-Hexanediol, 1,7-Heptanediol, 1,8-Octanediol, 1,9
-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,1
Linear aliphatic dihydroxy compounds such as 2-dodecanediol, neopentyl glycol, 2
Examples of branched chain aliphatic dihydroxy compounds include 1,3-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, hydrogenated dilinoleyl glycol, and hydrogenated dioleyl glycol.
From the viewpoints of availability and ease of handling, linear aliphatic dihydroxy compounds such as 1,4-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol are preferred.

Examples of the alicyclic dihydroxy compound include the following dihydroxy compounds: 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4
-Cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2
dihydroxy compounds which are primary alcohols of alicyclic hydrocarbons, exemplified by dihydroxy compounds derived from terpene compounds such as 1,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantanedimethanol, and limonene; dihydroxy compounds which are secondary or tertiary alcohols of alicyclic hydrocarbons, exemplified by 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

As the oxyalkylene glycol, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. can be used.
Examples of dihydroxy compounds having a heterocyclic structure include dihydroxy compounds represented by the following formula (4) and dihydroxy compounds containing an acetal ring other than the structure represented by the above formula (1).

The dihydroxy compound represented by the above formula (4) includes isosorbide, isomannide, and isoidite, which are stereoisomers.
Among these dihydroxy compounds (4), isosorbide, which is available in abundance as a resource and is easily available, and is obtained by dehydration condensation of sorbitol produced from various starches, is the most preferred in terms of availability, ease of production, and moldability. These dihydroxy compounds (4) may be used alone or in combination of two or more.

As a dihydroxy compound containing an acetal ring other than the structure represented by the above formula (1), for example, dioxane glycol represented by the following formula (5) can be used.

In addition to the above, examples of the dihydroxy compound having a heterocyclic structure include polycarbonate diols obtained by polycondensation reaction of a dihydroxy compound including a dihydroxy compound represented by the following formula (4) with a carbonate diester.
As the one or more compounds selected from the group consisting of the aliphatic dihydroxy compounds, the alicyclic dihydroxy compounds, the oxyalkylene glycols, and the dihydroxy compounds having a heterocyclic structure, there may be mentioned 1,6-hexanediol, 2,2,4,4-tetramethyl-1,3
It is particularly preferable to use polycarbonate diols containing structural units derived from isosorbide, 1,4-cyclobutanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, dioxane glycol, isosorbide, etc. Polycarbonate resins containing structural units derived from these monomers have a better balance of optical properties, heat resistance, mechanical properties, etc.

When the copolymer polycarbonate resin of the present invention contains a structural unit (C) derived from one or more compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, oxyalkylene glycols, and dihydroxy compounds containing an acetal ring, the structural unit (C) is preferably contained in an amount of 5% by weight or more, more preferably 6% by weight or more, and even more preferably 7% by weight or more, when the total weight of all structural units and linking groups constituting the resin is taken as 100% by weight. Also, it is preferably contained in an amount of 30% by weight or less, more preferably 25% by weight or less, and even more preferably 20% by weight or less. When the structural unit (C) is within the above range, the balance of other physical properties such as heat resistance and melt processability can be adjusted without significantly impairing the excellent properties of the copolymer polycarbonate resin.

The copolymerized polymer carbonate resin of the present invention may contain structural units derived from an aromatic dihydroxy compound in addition to the structural units derived from the aliphatic dihydroxy compound, alicyclic dihydroxy compound, oxyalkylene glycol, and diol having a heterocyclic structure described above.
Examples of aromatic dihydroxy compounds include 2,2-bis(4-hydroxyphenyl)propane [=bisphenol A], 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, and 2,2-bis(4-hydroxy-3,5-diethylphenyl).
Propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane,
Bis(4-hydroxyphenyl)methane, Bis(4-hydroxy-5-nitrophenyl)
methane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone,
Examples of aromatic dihydroxy compounds include bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 9,9-bis(4-(2-hydroxyethoxy-2-methyl)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-2-methylphenyl)fluorene.

When the copolymeric polycarbonate resin of the present invention contains a structural unit derived from an aromatic dihydroxy compound, the structural unit is preferably 15% by weight or less, more preferably 10% by weight or less, even more preferably 5% by weight or less, and particularly preferably 0% by weight, when the total weight of all structural units and linking groups constituting the resin is taken as 100% by weight. When the structural unit derived from an aromatic bisphenol is within the above range, deterioration of weather resistance caused by ultraviolet light absorption of the benzene ring structure can be suppressed.

(carbonic acid diester)
The linking group of the structural unit contained in the polycarbonate resin of the present invention is represented by the following formula (6):
It is introduced by polymerizing a carbonate diester represented by the following formula:

In formula (6), R ⁷ and R ⁸ each represent an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or an aromatic hydrocarbon group which may have ^a substituent ^;
may be the same or different.)
^R7 and ^R8 are preferably a substituted or unsubstituted aromatic hydrocarbon group, more preferably an unsubstituted aromatic hydrocarbon group. Examples of the substituent of the aliphatic hydrocarbon group include an ester group, an ether group, an amide group, and a halogen atom, and examples of the substituent of the aromatic hydrocarbon group include an alkyl group such as a methyl group or an ethyl group.

The carbonic acid diester represented by the formula (6) is, for example, diphenyl carbonate (
Hereinafter, this may be abbreviated as DPC. Examples include substituted diphenyl carbonates such as ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate, with diphenyl carbonate and substituted diphenyl carbonate being preferred, and diphenyl carbonate being particularly preferred.
The carbonate diester may contain impurities such as chloride ions, and these impurities may inhibit the polymerization reaction or deteriorate the hue of the resulting resin. Therefore, it is preferable to use a diester that has been purified, as necessary, by distillation or the like.

[Physical properties of copolymer polycarbonate resin]
The copolymeric polycarbonate resin of the present invention preferably has the physical properties described below.

(Total light transmittance)
The copolymeric polycarbonate resin of the present invention preferably has a total light transmittance of 88% or more, more preferably 89% or more, even more preferably 90% or more, and particularly preferably 91% or more. If the total light transmittance is equal to or greater than the lower limit, it can be suitably used as a transparent material. The total light transmittance of the copolymeric polycarbonate resin can be measured by the method described in the Examples.

(Water Absorption Rate)
The water absorption rate of the copolymeric polycarbonate resin of the present invention is preferably 1.1% or less, more preferably 1.05% or less, and even more preferably 1.0% or less. If the water absorption rate is below the upper limit, it is preferable in terms of moisture absorption resistance and low dimensional change rate. The water absorption rate of the copolymeric polycarbonate resin can be measured by the method described below. The water absorption rate of the copolymeric polycarbonate resin can be appropriately adjusted, for example, by changing the type and ratio of the structural unit constituting the resin.

(Glass Transition Temperature)
The glass transition temperature of the copolymeric polycarbonate resin of the present invention is preferably 40° C. or higher,
5°C or higher is more preferable, and 50°C or higher is even more preferable. When the glass transition temperature is above the lower limit, the risk of adhesion and deformation of the copolymer polycarbonate resin or its molded article at room temperature is reduced. In addition, the glass transition temperature of the copolymer polycarbonate resin is preferably 145°C or lower, more preferably 135°C or lower, and even more preferably 125°C or lower. When the glass transition temperature is below the upper limit, the flowability during molding is increased, and even if the molded article has a complex shape, the polycarbonate resin is easily delivered to the end of the mold during molding, and the desired molded article can be obtained. In addition, the decrease in strength at the weld portion can be suppressed. The glass transition temperature of the copolymer polycarbonate resin can be measured by the method described in the examples. The glass transition temperature of the copolymer polycarbonate resin can be appropriately adjusted, for example, by changing the type and ratio of the structural units constituting the resin.

(Chemical resistance)
The copolymeric polycarbonate resin of the present invention preferably has a critical strain of 0.5 or more in a chemical resistance test using a 1/4 elliptical jig in a nonionic surfactant, and more preferably has a critical strain of 0.6 or more.
More preferably, it is 0.7 or more. If the critical strain of the copolymer polycarbonate resin is the lower limit or more, it can be suitably used for automobile interior and exterior parts, electrical parts, electronic and electrical materials, outdoor building parts, and cosmetic containers. The glass transition temperature of the copolymer polycarbonate resin can be measured by the method described in the Examples.

(Weather resistance)
In a weather resistance test in which the copolymeric polycarbonate resin of the present invention is subjected to treatment for 100 hours under a condition of an irradiation intensity of 60 W/ ^m2 , the ΔYI value before and after the test is preferably 1.0 or less,
It is more preferably 0.6 or less, and even more preferably 0.2 or less. When the ΔYI of the copolymeric polycarbonate resin is the above upper limit or less, it can be suitably used for outdoor applications such as automobile interior and exterior parts, building parts, etc. The weather resistance of the copolymeric polycarbonate resin can be measured by the method described in the Examples.

[Method for producing polycarbonate resin of the present invention]
The polycarbonate resin of the present invention can be produced by a commonly used polymerization method. For example, it can be produced by a solution polymerization method or an interfacial polymerization method using phosgene or a carboxylic acid halide, or a melt polymerization method in which a reaction is carried out without using a solvent. Among these production methods, it is preferable to produce the polycarbonate resin by the melt polymerization method, which is excellent in productivity and can reduce the environmental load because it does not use a solvent or a highly toxic compound.

In addition, when a solvent is used in polymerization, the solvent may remain in the resin, and the plasticizing effect of the solvent may lower the glass transition temperature of the resin, which may cause quality fluctuations in processing steps such as molding and stretching, which will be described later. In addition, halogen-based organic solvents such as methylene chloride are often used as solvents, but if the halogen-based solvent remains in the resin, it may cause corrosion of metal parts when a molded product using this resin is incorporated into an electronic device, etc. The resin obtained by the melt polymerization method does not contain a solvent, which is also advantageous for stabilizing processing steps and product quality.

When producing polycarbonate resin by melt polymerization, a monomer having the structural unit described above, a carbonic acid diester, and a polymerization catalyst are mixed and subjected to an ester exchange reaction (also called a polycondensation reaction) under molten conditions, and the reaction rate is increased while removing the elimination components from the system. At the end of the polymerization, the reaction is allowed to proceed under high temperature and high vacuum conditions until the desired molecular weight is reached. When the reaction is complete,
The molten resin is discharged from the reactor to obtain the polycarbonate resin of the present invention.

In the polycondensation reaction, the reaction rate and the molecular weight of the resulting resin can be controlled by strictly adjusting the molar ratio of all dihydroxy compounds and all diester compounds used in the reaction. In the case of polycarbonate resin, the molar ratio of carbonic acid diester to all dihydroxy compounds is 0.90 to 1.50.
It is preferably adjusted to 1.10, more preferably from 0.96 to 1.05, and particularly preferably from 0.98 to 1.03.

If the molar ratio is too far above or below the range, it is not possible to produce a resin with the desired molecular weight. If the molar ratio is too small, the number of hydroxyl group terminals in the produced resin increases, which may deteriorate the thermal stability of the resin. Furthermore, a large amount of unreacted dihydroxy compound remains in the resin, which may cause dirt on the molding machine and poor appearance of the molded product in the subsequent molding process. On the other hand, if the molar ratio is too large, the rate of transesterification reaction may decrease under the same conditions, or the amount of remaining carbonic acid diester in the produced resin may increase, and these remaining low molecular weight components may also cause problems in the molding process.

The melt polymerization method is usually carried out in a multi-stage process of two or more stages. The polycondensation reaction may be carried out in two or more stages by sequentially changing the conditions using one polymerization reactor, or may be carried out in two or more stages by changing the conditions for each stage using two or more reactors, but from the viewpoint of production efficiency, it is carried out using two or more, preferably three or more reactors. The polycondensation reaction may be carried out in a batch system, a continuous system, or a combination of a batch system and a continuous system, but from the viewpoint of production efficiency and stability of quality, a continuous system is preferred.

In polycondensation reactions, it is important to properly control the balance between temperature and pressure in the reaction system. If either the temperature or pressure is changed too quickly, unreacted monomers may be distilled out of the reaction system. As a result, the molar ratio of the dihydroxy compound and the carbonic acid diester compound may change, and a resin with the desired molecular weight may not be obtained.
In addition, the polymerization rate of the polycondensation reaction is controlled by the balance between the hydroxyl group terminal and the carbonate group terminal. Therefore, particularly when polymerization is performed in a continuous manner, if the balance of the terminal groups fluctuates due to the distillation of unreacted monomers, it becomes difficult to control the polymerization rate at a constant rate, and the molecular weight of the resulting resin may fluctuate greatly. Since the molecular weight of the resin is correlated with the melt viscosity, when the resulting resin is molded, the melt viscosity may fluctuate, leading to problems such as failure to obtain molded products of uniform dimensions.

Furthermore, when unreacted monomers are distilled off, not only the balance of the terminal groups but also the copolymerization composition of the resin deviates from the desired composition, which may affect the mechanical properties and optical properties. In the retardation film obtained from the polycarbonate resin of the present invention, the wavelength dispersion of the retardation is controlled by the ratio of the fluorene monomer and other copolymerization components in the resin, so if the ratio is disturbed during polymerization, the desired properties may not be obtained.

Hereinafter, the melt polycondensation reaction process will be referred to as the step of consuming monomers to produce oligomers (
This process will be described in two parts: the first reaction stage, where the polymerization is continued until the desired molecular weight is reached to produce a polymer (the second reaction stage).
Specifically, the following conditions can be adopted as the reaction conditions in the first stage reaction. That is, the internal temperature of the polymerization reactor is set in the range of usually 130° C. or higher, preferably 150° C. or higher, more preferably 170° C. or higher, and usually 250° C. or lower, preferably 240° C. or lower, more preferably 230° C. or lower. The pressure of the polymerization reactor (hereinafter, pressure refers to absolute pressure) is usually 70 kPa or lower, preferably 50 kPa or lower, more preferably 30 kPa or lower.
Pa or less, and usually 1 kPa or more, preferably 3 kPa or more, more preferably 5 kPa or more
The reaction time is set within the range of usually 0.1 hours or more, preferably 0.5 hours or more, and usually 10 hours or less, preferably 5 hours or less, more preferably 3 hours or less.

The first-stage reaction is carried out while the monohydroxy compound derived from the diester compound generated is distilled out of the reaction system. For example, when diphenyl carbonate is used as the carbonic acid diester, the monohydroxy compound distilled out of the reaction system in the first-stage reaction is phenol.
In the first stage reaction, the lower the reaction pressure, the more the polymerization reaction can be accelerated, but on the other hand, the more unreacted monomer is distilled off.
In order to achieve both the promotion of the reaction by reducing the pressure and the reaction temperature, it is effective to use a reactor equipped with a reflux condenser. The use of a reflux condenser is particularly effective in the early stages of the reaction when there is a large amount of unreacted monomer.

In the second stage reaction, the pressure of the reaction system is gradually lowered from the pressure of the first stage, and the monohydroxy compound generated is subsequently removed from the reaction system, and the pressure of the reaction system is finally lowered to 5 kPa or less, preferably 3 kPa or less, and more preferably 1 kPa or less.
The reaction temperature is set within a range of 10° C. or higher, preferably 220° C. or higher, and usually 260° C. or lower, preferably 255° C. or lower. The reaction time is set within a range of usually 0.1 hours or higher, preferably 0.5 hours or higher, more preferably 1 hour or higher, and usually 10 hours or lower, preferably 5 hours or lower, more preferably 3 hours or lower. In order to suppress side reactions such as coloring, thermal deterioration, and crosslinking and to obtain a resin with good hue, weather resistance, and thermal stability, the maximum internal temperature in all reaction stages should be set within a range of 2.
The temperature is preferably 60° C. or lower, more preferably 255° C. or lower, and even more preferably 250° C. or lower. In particular, if the dihydroxy compound used as the raw material of the structural unit (A) used in the present invention is subjected to a polymerization reaction at an excessively high temperature, it may decompose to generate branched components, and the resulting polymer may crosslink and gel. If gel is generated, the mechanical properties of the resulting resin may be deteriorated.

The transesterification catalyst (hereinafter, sometimes simply referred to as "catalyst" or "polymerization catalyst") that can be used during polymerization can have a very large effect on the reaction rate and the color tone and thermal stability of the resin obtained by polycondensation. The catalyst is not limited as long as it satisfies the transparency, hue, heat resistance, thermal stability, and mechanical strength of the produced resin, and includes basic compounds such as metal compounds of Group 1 or Group 2 (hereinafter, simply referred to as "Group 1" and "Group 2") in the long-form periodic table, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine-based compounds. Preferably, at least one metal compound selected from the group consisting of metals of Group 2 of the long-form periodic table and lithium is used.

As the Group 1 metal compound, for example, the following compounds can be used, but it is also possible to use other Group 1 metal compounds.
Sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium tetraphenylborate, potassium tetraphenylborate, lithium tetraphenylborate, cesium tetraphenylborate,
Sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, alcoholates and phenolates of sodium, potassium, lithium and cesium, and disodium, dipotassium, dilithium and dicesium salts of bisphenol A. Of these, from the viewpoints of polymerization activity and the hue of the obtained resin, it is preferable to use lithium compounds.

As the Group 2 metal compound, for example, the following compounds can be used, but it is also possible to use Group 2 metal compounds other than these.
Calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate.

Of these, it is preferable to use magnesium compounds, calcium compounds, and barium compounds, and from the viewpoints of polymerization activity and the hue of the resulting resin, it is more preferable to use magnesium compounds and/or calcium compounds, and it is most preferable to use calcium compounds.
It is also possible to use, in combination with the Group 1 metal compound and/or Group 2 metal compound, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound as an auxiliary, but it is particularly preferable to use at least one metal compound selected from the group consisting of metals in Group 2 of the long form periodic table and lithium.

The amount of the polymerization catalyst used is usually 0.1 μmol to 300 μmol, preferably 0.5 μmol to 100 μmol, in terms of the amount of metal, per mol of the total dihydroxy compounds used in the polymerization.
mol.
If the amount of catalyst is too small, the polymerization rate will be slow, and the polymerization temperature will have to be increased accordingly to obtain a resin with a desired molecular weight. This will increase the thermal history during the polymerization reaction, and the color and weather resistance of the resulting resin will likely deteriorate. In addition, unreacted raw materials may volatilize during the polymerization, causing the molar ratio of the dihydroxy compound and the carbonic acid diester compound to be disrupted, and the desired molecular weight may not be achieved. On the other hand, if the amount of polymerization catalyst used is too large, undesirable side reactions may occur, causing the color of the resulting resin to deteriorate, and causing coloring or decomposition of the resin during molding.

Among the group 1 metals, sodium, potassium, and cesium may adversely affect the color of the resin if contained in large amounts in the resin. These metals may be mixed not only from the catalyst used, but also from the raw materials and reaction equipment. Regardless of the source, the total amount of compounds of these metals in the resin is, in terms of metal amount, 2 μm or more per 1 mol of the total dihydroxy compounds.
It is preferable that the amount of the amine is 1 μmol or less, more preferably 1 μmol or less, and even more preferably 0.5 μmol or less.

The polycarbonate resin of the present invention is usually cooled and solidified after polymerization as described above.
The polycarbonate resin can be pelletized with a rotary cutter, etc. The pelletization method is not limited, but examples thereof include a method in which the polycarbonate resin is withdrawn in a molten state from the polymerization reactor at the final stage, cooled and solidified in the form of strands, and pelletized, a method in which the polycarbonate resin is supplied in a molten state from the polymerization reactor at the final stage to a single-screw or twin-screw extruder, melt-extruded, cooled and solidified, and pelletized, or a method in which the polycarbonate resin is withdrawn in a molten state from the polymerization reactor at the final stage, cooled and solidified in the form of strands, pelletized once, and then supplied to the single-screw or twin-screw extruder again, melt-extruded, cooled and solidified, and pelletized.

A second aspect of the present invention relates to a method for producing a polycarbonate resin, comprising the steps of: mixing a dihydroxy compound containing a dihydroxy compound represented by the following formula (3) with a polyorganosiloxane having two or more reactive functional groups to obtain a raw material solution; and subjecting the raw material solution, a carbonic acid diester, and a polymerization catalyst to a polycondensation reaction in a reactor.

(In formula (3), W is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms; R ¹ and R ² are a branched or linear alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent; and m is an integer of 0 to 10.)
In the above formula (3), the details of W, R ¹ , R ² and m are the same as those in the above formula (1).

In the method of the present invention, it is particularly preferable that the dihydroxy compound containing the dihydroxy compound represented by the above formula (3) is a spiro glycol represented by the following formula (X). In this case, it is possible to produce a copolymer polycarbonate resin with excellent chemical resistance because it has particularly excellent compatibility with polyorganosiloxanes having two or more reactive functional groups.

The polyorganosiloxane having two or more reactive functional groups used in the method of the present invention may be the same as the polyorganosiloxane having two or more reactive functional groups for introducing the structural unit (B) contained in the copolymeric polycarbonate resin of the first aspect of the present invention.
As described above, the method for producing a polycarbonate resin according to the second aspect of the present invention comprises reacting a carboxylic acid ester represented by the above formula (3)
The method includes a step of mixing a dihydroxy compound containing a dihydroxy compound represented by the formula (I) and a polyorganosiloxane having two or more reactive functional groups to obtain a raw material solution (hereinafter, sometimes referred to as a raw material dissolving step).

Raw material dissolving step In the method of the present invention, the method of mixing the dihydroxy compound containing the dihydroxy compound represented by the above formula (3) with the polyorganosiloxane having two or more reactive functional groups to obtain the raw material solution is not particularly limited.For example, the method of melting the dihydroxy compound represented by the above formula (3) in advance, and supplying the liquid polyorganosiloxane having two or more reactive functional groups to the raw material dissolving tank having the melt to dissolve it, or the method of simultaneously dissolving the dihydroxy compound represented by the above formula (3) and the liquid polyorganosiloxane having two or more reactive functional groups can be preferably used.

The temperature at which the raw material solution is prepared is not particularly limited, but is preferably 160° C. or lower, and more preferably 15
The internal temperature of the dissolution tank is preferably 0° C. or lower, more preferably 80° C. or higher, and even more preferably 90° C. or higher. By controlling the internal temperature of the dissolution tank within the above range, it is possible to suppress the decomposition reaction and coloration of the dihydroxy compound including the dihydroxy compound represented by the above formula (3), and also to avoid the risk of crystallization during transfer, which may cause blockage of piping or the like.

A raw material dissolving tank can also be used when preparing the raw material solution. When using a raw material dissolving tank, the raw material dissolving tank may be one tank, or two or more tanks may be connected in series. The dihydroxy compound (A) supplied to the first dissolving tank is usually supplied at a temperature of about room temperature, so the temperature required for dissolving is required to be higher than the temperature at which the liquid state is maintained. In that case, the part where the dissolution is completed continues to be exposed to a high temperature, so that thermal degradation is likely to occur. By transferring the liquid dissolved in the first layer to the second tank, the second layer can be maintained at a lower temperature than the first tank.
The method for producing a polycarbonate resin according to the second aspect of the present invention includes the steps (hereinafter,
This may be referred to as a polymerization reaction process.

In the method of the present invention, the method of polycondensation reaction of the raw material solution, the carbonic acid diester, and the polymerization catalyst in a reactor is not particularly limited. For example, the melt polycondensation reaction method described above as the method for producing the copolymeric polycarbonate resin of the first aspect of the present invention can be suitably adopted.

The dihydroxy compound containing the dihydroxy compound represented by the above formula (3) and the polyorganosiloxane polyorganosiloxane having two or more reactive functional groups are highly compatible, so that the raw material solution used as the reaction solution for polymerization reaction becomes uniform.Therefore, in the polymerization reaction process, the reaction of polyorganosiloxane alone is reduced, and the dispersion of the structural unit domain derived from polyorganosiloxane in the polymer is improved, and at the same time, the domain becomes smaller.
As a result, the resulting polymer is believed to exhibit high chemical resistance and, in some embodiments, improved transparency.

(Molded product (molded product))
The copolymeric polycarbonate of the present invention can be molded into a molded product by a commonly known method such as injection molding, extrusion molding, or compression molding.
Furthermore, before carrying out various moldings, the copolymeric polycarbonate of the present invention may be optionally treated with an antioxidant, a heat stabilizer, a light stabilizer, a neutralizing agent, an ultraviolet absorber, a mold release agent, a colorant, Antistatic agents,
Additives such as lubricants, lubricants, plasticizers, compatibilizers, flame retardants, and fillers can also be mixed using a tumbler, super mixer, floater, V-type blender, Nauta mixer, Banbury mixer, extruder, etc. .

(Heat stabilizer)
If necessary, a heat stabilizer can be blended into the polycarbonate resin of the present invention in order to prevent a decrease in molecular weight or deterioration in color during melt processing, etc. Examples of such heat stabilizers include commonly known hindered phenol-based heat stabilizers and/or phosphorus-based heat stabilizers.

As the hindered phenol compound, for example, the following compounds can be used.
2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4-methoxyphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,5-di-tert-butylhydroquinone, n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'
-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,2'-
Methylene-bis-(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis-(6-cyclohexyl-4-methylphenol), 2,2'-ethylidene-bis-(2,4-di-tert-butylphenol), tetrakis-[methylene-3-(3
',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]-methane, 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-
4-hydroxybenzyl)benzene, etc. Among them, tetrakis-[methylene-3-(3',
5'-di-tert-butyl-4'-hydroxyphenyl)propionate]-methane,
n-Octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris-(3,5-di-t
It is preferred to use tert-butyl-4-hydroxybenzyl)benzene.

As the phosphorus-based compound, for example, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof shown below can be used, but phosphorus-based compounds other than these compounds can also be used.
Triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4
-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite,
Dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite Rhythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4'-biphenylenediphosphinate tetrakis(2,4-di-tert-butylphenyl), dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate.

These heat stabilizers may be used alone or in combination of two or more.
Such a heat stabilizer may be added to the reaction liquid during melt polymerization, or may be added to the resin using an extruder and kneaded. When forming a film by melt extrusion, the heat stabilizer may be added to the extruder to form a film, or the heat stabilizer may be added in advance to the resin using an extruder and formed into pellets or the like.

The amount of these heat stabilizers is preferably 0.0001 parts by weight or more, more preferably 0.0005 parts by weight or more, and even more preferably 0.001 parts by weight or more, and is preferably 1 part by weight or less, more preferably 0.5 parts by weight or less, and even more preferably 0.2 parts by weight or less, based on 100 parts by weight of the resin.

(Catalyst Deactivator)
The color tone and thermal stability can be improved by adding an acidic compound to the polycarbonate resin of the present invention in order to neutralize and deactivate the catalyst used in the polymerization reaction. As the acidic compound used as a catalyst deactivator, a compound having a carboxylic acid group, a phosphoric acid group, or a sulfonic acid group, or an ester thereof, can be used. In particular, a compound represented by the following formula (7) or (8) can be used.
It is preferable to use a phosphorus-based compound containing a partial structure represented by the following formula:

Examples of the phosphorus-based compound represented by the formula (7) or (8) include phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, phosphonate esters, acidic phosphate esters, etc. Among the above, phosphorous acid, phosphonic acid, and phosphonate esters are more effective in deactivating the catalyst and inhibiting coloration, and phosphorous acid is particularly preferred.
Examples of phosphonic acids include phosphonic acid (phosphorous acid), methylphosphonic acid, ethylphosphonic acid, vinylphosphonic acid, decylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, aminomethylphosphonic acid, methylene diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 4-methoxyphenylphosphonic acid, nitrilotris(methylenephosphonic acid), and propylphosphonic anhydride.

Examples of phosphonate esters include dimethyl phosphonate, diethyl phosphonate, bis(2-ethylhexyl) phosphonate, dilauryl phosphonate, dioleyl phosphonate, diphenyl phosphonate, dibenzyl phosphonate, dimethyl methylphosphonate, diphenyl methylphosphonate, diethyl ethylphosphonate, diethyl benzylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, diethyl (methoxymethyl)phosphonate, diethyl vinylphosphonate, and hydroxymethyl Examples of the diethyl phosphonate include diethyl phosphonate, dimethyl (2-hydroxyethyl)phosphonate, diethyl p-methylbenzylphosphonate, diethyl phosphonoacetic acid, ethyl diethyl phosphonoacetate, tert-butyl diethyl phosphonoacetate, diethyl (4-chlorobenzyl)phosphonate, diethyl cyanophosphonate, diethyl cyanomethylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl phosphonoacetaldehyde diethyl acetal, and diethyl (methylthiomethyl)phosphonate.

Examples of acidic phosphate esters include phosphate diesters such as dimethyl phosphate, diethyl phosphate, divinyl phosphate, dipropyl phosphate, dibutyl phosphate, bis(butoxyethyl phosphate), bis(2-ethylhexyl) phosphate, diisotridecyl phosphate, dioleyl phosphate, distearyl phosphate, diphenyl phosphate, and dibenzyl phosphate, or mixtures of diesters and monoesters, diethyl chlorophosphate, and zinc stearyl phosphate.

These may be used alone or in any combination and ratio of two or more.
If the amount of the phosphorus-based compound added to the resin is too small, the effect of catalyst deactivation and coloring inhibition is insufficient, while if the amount is too large, the resin may be colored, and the resin may be easily colored, particularly in a durability test under high temperature and high humidity. The amount of the phosphorus-based compound added is an amount corresponding to the amount of catalyst used in the polymerization reaction. The amount of phosphorus-based compound is preferably 0.5 times or more by mole and 5 times or less by mole, more preferably 0.7 times or more by mole and 4 times or less by mole, and particularly preferably 0.8 times or more by mole and 3 times or less by mole, based on the amount of phosphorus atoms per 1 mol of the metal catalyst used in the polymerization reaction.
1 or less is preferred.

(Polymer alloy)
Furthermore, for the purpose of further improving or adjusting the molding processability and various physical properties, resins other than the copolymeric polycarbonate of the present invention (hereinafter, sometimes simply referred to as "other resins") can be added to the copolymeric polycarbonate of the present invention.
Other resins include, for example, thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-styrene-acrylic rubber copolymer (ASA resin).
styrene-based resins such as acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin); polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyurethane resin; polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; and polymethacrylate resin.

Incidentally, one type of the other resin may be contained, or two or more types may be contained in any combination and ratio.
Molded articles obtained by molding the copolymeric polycarbonate of the present invention are particularly excellent in weather resistance, chemical resistance, etc., and can therefore be used in a wide range of fields, such as automobile interior and exterior parts, electrical parts, electronic and electrical materials, outdoor building parts, and cosmetic containers.

Examples of the polycarbonate copolymer are shown below, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded. The methods for measuring the various properties are as follows.

(1) Glass transition temperature The glass transition temperature of the resin was measured using a differential scanning calorimeter (DSC) manufactured by SII NanoTechnology Co., Ltd.
Approximately 10 mg of a resin sample was placed in an aluminum pan manufactured by the same company and sealed.
The temperature was increased from 30° C. to 200° C. at a rate of 20° C./min under a nitrogen flow of 50 mL/min.
After holding the temperature for 10 minutes, the sample was cooled to 30° C. at a rate of 20° C./min. The sample was held at 30° C. for 3 minutes,
The temperature was again raised to 200° C. at a rate of 20° C./min. From the DSC data obtained in the second heating run, the extrapolated glass transition onset temperature, which was the temperature at the intersection of a straight line extending the low-temperature side baseline to the high-temperature side and a tangent drawn at the point where the gradient of the curve of the stepwise change in the glass transition was maximum, was determined, and this was taken as the glass transition temperature.

(2) Weather resistance test Pellets of the polycarbonate resin composition were subjected to a reduced pressure of 200 Pa or less and subjected to a test at a glass transition temperature of
Drying was performed for 12 hours or more at a temperature of -10°C. Next, about 4 g of the dried pellets were put into a small heat press (Azwan Corporation, AH-2003C AH-1TC) and cut into pieces of 7 cm length x 7 cm width.
A spacer with a thickness of 0.5 mm was used, and polyimide films were placed on the top and bottom of the sample.
The molded product was preheated at 00 to 230° C. for 3 minutes, pressurized at 7 MPa for 5 minutes, removed together with the spacer, and cooled to prepare a sheet molded product.

The obtained sheet molded product was used for a 300-kilometer-long Xenon SCX4 manufactured by Iwasaki Electric Co., Ltd.
The sheet was treated for 100 hours using UV-ray irradiation at an irradiation intensity of 60 W/m2. The color tone of the sheet before and after irradiation was measured in accordance with ASTM D1925 using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc. The plate was placed in a measurement chamber, and the YI (yellowness index) value of the transmitted light was measured. The smaller the difference (ΔYI) between the YI after irradiation and the YI before treatment, the less coloring due to UV irradiation and the more excellent the weather resistance.
<Evaluation>
When ΔYI is less than 1.0:
When ΔYI is 1.0 or more: ×

(3) Transparency The sheet molded products obtained in (2) above before the weather resistance test were visually inspected in the thickness direction and width direction. Those having the same level of transparency as Comparative Example 1 were marked with an ◯, and those having a transparency inferior to Comparative Example 1 or that were cloudy were marked with an X.

(4) Measurement of total light transmittance The sheet molded product before the weather resistance test obtained in (2) above was measured using a color/turbidity simultaneous measuring device (Nippon Denshoku Industries Co., Ltd., model: COH-400) in accordance with JIS K7105.

(5) Measurement of Water Absorption A pellet of a polycarbonate resin composition was heated under a reduced pressure of 200 Pa or less until it reached the glass transition temperature
Drying was performed for 12 hours or more at a temperature of -10°C. Next, about 4 g of the dried pellets were put into a small heat press (Azwan Corporation, AH-2003C AH-1TC) and pressed into a mold 14 cm long and 14 cm wide.
A spacer having a length of 0.1 m and a thickness of 0.1 mm was used, and polyimide films were placed on the top and bottom of the sample. The sample was preheated at a temperature of 200 to 230° C. for 3 minutes and pressurized at a pressure of 7 MPa for 5 minutes. The sample was then removed together with the spacer and cooled to prepare a sheet.

The obtained film was cut into a square measuring 100 mm in length and 100 mm in width to prepare a sample. This sample was dried for 24 hours or more at a temperature of the glass transition temperature -10°C under a reduced pressure of 200 Pa or less. The weight of the dried sample was measured to the nearest 0.1 mg, and this value was taken as the dry weight. Next, the dried sample was immersed in desalted water adjusted to 23°C for 72 hours or more. After immersion, the sample was taken out of the water, and all surface moisture was wiped off with a clean, dry cloth or filter paper, and then the sample was placed in a 0.1-mL container.
The weight was measured within 1 mg and this value was taken as the water absorption weight. The water absorption weight was measured within 1 minute after removing from the water. The water absorption rate was calculated using Equation 1.
(Water absorption weight - dry weight)/dry weight x 100 = water absorption rate (%)...Formula 1

(6) Chemical Resistance Test The pellets of the polycarbonate resin composition were subjected to a test under a reduced pressure of 200 Pa or less until the glass transition temperature
Drying was performed for 12 hours or more at a temperature of -20°C. Next, about 4 g of the dried pellets were pressed into a compact heat press (Azwan Corporation, AH-2003C AH-1TC) to make a 14 cm long, 2 cm wide mold.
A spacer with a thickness of 1 mm was used, polyimide films were placed on the top and bottom of the sample, and the temperature was kept at 20
Preheat at 0 to 230°C for 3 minutes, pressurize at 7 MPa for 5 minutes, then remove with the spacer.
The sheet was cooled to prepare a sheet, which was then cut into a rectangular shape measuring 10 cm in length and 2 cm in width to prepare a test piece.

A surfactant IGEPAL CA630 (MP Bio Japan Co., Ltd.) was applied to the surface of the test piece, which was then attached to a 1/4 elliptical jig with a major axis of 100 mm and a minor axis of 40 mm as shown in Fig. 1 and left to stand for 72 hours in an environment of 25°C x 60% RH, and the position X at which a crack that reached from the front surface to the back surface of the test piece occurred was measured, and the critical strain value was calculated using Equation 1. Based on the critical strain value, the chemical resistance was evaluated as follows.
ε: Critical strain (%)
a: Long axis of the jig (= 120 mm)
b: Short axis of the jig (= 40 mm)
t: thickness of test piece (= 1.0 mm)
X: Distance from crack occurrence position (mm)

<Evaluation>
When the critical strain value (ε) is 0.7% or more: ○
When the critical strain value (ε) is less than 0.7%,

(7) Average repeat number n of dimethylsiloxane units
The average repeat number n of dimethylsiloxane units was calculated by ¹ H-NMR measurement.
The apparatus and conditions used are as follows:
Equipment: JNM-ECZ400S (manufactured by JEOL Ltd.)
Measurement temperature: 30°C
Relaxation time: 6 seconds; Accumulation times: 64; Sample amount: 5-15 mg
Solvent: deuterated chloroform Using the polyorganosiloxanes used in the Examples and Comparative Examples described later as examples, a method for calculating the average repeat number n of dimethylsiloxane units will be described.

<In the case of polydimethylsiloxane represented by the following formula (V-1)>
Range for calculating integral value (a): 0.04 to 0.1 ppm: derived from methyl groups in dimethylsiloxane part (number of protons:
6)
(b): 0.5 to 0.6 ppm: derived from methylene groups of both terminal carbinol modified parts (number of protons: 4)
{(a)/((b)/4))/6}-1 = average number of repeating dimethylsiloxane units, n

<In the case of polydimethylsiloxane represented by the following formula (V-2)>
Range for calculating integral value (a): 0.04 to 0.1 ppm: derived from methyl groups in dimethylsiloxane part (number of protons:
6)
(b): 3.8 to 3.9 ppm: derived from methyl groups at both ends of eugenol-modified moieties (number of protons: 6)
{(a)/((b)/6))/6}-1 = average number of repeating dimethylsiloxane units, n

<In the case of polydimethylsiloxane represented by the following formula (V-3)>
(a): 0.04 to 0.1 ppm: derived from methyl groups in the dimethylsiloxane portion (number of protons:
6)
(b): 0.5 to 0.6 ppm: derived from the methylene group of the terminal carbinol modified portion and the terminal butylene portion (number of protons: 4)
{(a)/((b)/4))/6}-1 = average number of repeating dimethylsiloxane units, n

[Compound abbreviations]
The abbreviations for the compounds used in the following Synthesis Examples, Examples and Comparative Examples are as follows.
ISB: Isosorbide (manufactured by Rocket Fleuret, product name: POLYSORB)
SPG: Spiroglycol (manufactured by Mitsubishi Gas Chemical Company, Inc.)
CHDM: 1,4-cyclohexanedimethanol (cis, trans mixture, manufactured by SK Chemicals)
・1,6-HD: 1,6-hexanediol (manufactured by BASF)
DPC: Diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation)
PCD: Benebiol (manufactured by Mitsubishi Chemical Corporation, grade name: HS0840H)
Polyorganosiloxane-1: X-22-160AS, a dimethylsiloxane modified with carbinol at both ends represented by formula (V-1), number average molecular weight: 970, average repeat number n of dimethylsiloxane units: 10 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Polyorganosiloxane-2: BY16-201, a dimethylsiloxane modified with carbinol at both ends represented by formula (V-1), number average molecular weight 1860, average repeat number n of dimethylsiloxane units: 22 (manufactured by Dow Corning Toray Co., Ltd.)
Polyorganosiloxane-3: EXL1414T (Sabic)-containing polyorganosiloxane, polydimethylsiloxane modified with eugenol at both ends represented by formula (V-2), number average molecular weight 3900, average repeat number n of dimethylsiloxane units: 48
Polyorganosiloxane-4: FM-0411, number average molecular weight: 1140, formula (V-3)
One-terminal carbinol-modified dimethylsiloxane represented by the formula: Average repeat number n of dimethylsiloxane units: 13 (manufactured by JNC Corporation)
Polyorganosiloxane-5: XP1459, a dimethylsiloxane modified with carbinol at both ends represented by formula (V-1), number average molecular weight 600, average repeat number n of dimethylsiloxane units: 5 (manufactured by JNC Corporation)

[Example 1]
ISB 8.49g (0.058mol), SPG 73.70g (0.242mol)
), Polyorganosiloxane-1 9.74g (0.010mol), DPC 66.4
7g (0.310mol), and calcium acetate monohydrate 1.09×10 ^-
2 g (6.21×10 ⁻⁵ mol) was placed in a reactor, and the inside of the reactor was purged with nitrogen under reduced pressure.
The raw materials were dissolved in a reactor at 150° C. for 30 minutes under a nitrogen atmosphere while stirring. Reaction 1
In the first step, the temperature was raised to 220°C over 30 minutes, and the reaction was carried out at normal pressure for 30 minutes. The pressure was then reduced from normal pressure to 13.3 kPa over 90 minutes, and the pressure was maintained at 13.3 kPa for 30 minutes, and the generated phenol was extracted from the reaction system. In the second step, the heat transfer medium temperature was raised to 240°C over 15 minutes, while the pressure was reduced to 133 Pa or less over 20 minutes, and the generated phenol was extracted from the reaction system. When the predetermined stirring power was reached, the pressure was restored with nitrogen, and the contents were extracted in the form of strands and pelletized with a rotary cutter. The obtained polycarbonate resin pellets were used to carry out the various evaluations described above. The evaluation results are shown in Table 1.

[Example 2]
ISB 16.98g (0.116mol), SPG 64.49g (0.212mol)
l), Polyorganosiloxane-1 9.74g (0.010mol), DPC 73.
15 g (0.341 mol), and calcium acetate monohydrate 1.49 × 10
The polymerization reaction was carried out in the same manner as in Example 1, except that ² g (8.45 × 10 ^-5 mol) of 1,2-dichlorophenyl ether was used.
Polycarbonate resin pellets were obtained. The above-mentioned various evaluations were carried out using the obtained polycarbonate resin pellets. The evaluation results are shown in Table 1.

[Example 3]
ISB 8.49g (0.058mol), SPG 78.31g (0.257mol)
), Polyorganosiloxane-1 4.87g (0.005mol), DPC 68.6
4g (0.320mol), and calcium acetate monohydrate 1.41×10 ^-
A polymerization reaction was carried out in the same manner as in Example 1, except that ² g (8.01×10 ⁻⁵ mol) of the polycarbonate resin was used, to obtain polycarbonate resin pellets. The obtained polycarbonate resin pellets were used to carry out the various evaluations described above. The evaluation results are shown in Table 1.

[Example 4]
ISB 12.74g (0.087mol), SPG 73.70g (0.242mol)
l), Polyorganosiloxane-1 4.87g (0.005mol), DPC 71.
62 g (0.334 mol), and calcium acetate monohydrate 1.47 × 10
The polymerization reaction was carried out in the same manner as in Example 1, except that ² g (8.36 × 10 ^-5 mol) of dimethylformamide was used.
Polycarbonate resin pellets were obtained. The above-mentioned various evaluations were carried out using the obtained polycarbonate resin pellets. The evaluation results are shown in Table 1.

[Example 5]
CHDM 16.95g (0.118mol), SPG 64.49g (0.212m
ol), Polyorganosiloxane-1 9.74g (0.010mol), DPC 72
71 g (0.339 mol), and 1.50 x 100 g of calcium acetate monohydrate as a catalyst.
A polymerization reaction was carried out in the same manner as in Example 1, except that 0 ⁻² g (8.49×10 ⁻⁵ mol) of the polycarbonate resin was used, to obtain polycarbonate resin pellets. The obtained polycarbonate resin pellets were used to carry out the various evaluations described above. The evaluation results are shown in Table 1.

[Example 6]
1,6-HD 16.39g (0.139mol), SPG 64.50g (0.21
2 mol), Polyorganosiloxane-1 9.73 g (0.010 mol), DPC
72.80 g (0.363 mol), and calcium acetate monohydrate 1.27 as a catalyst
A polymerization reaction was carried out in the same manner as in Example 1, except that 1.5×10 ⁻² g (7.21×10 ⁻⁵ mol) of polycarbonate resin was used to obtain polycarbonate resin pellets. The obtained polycarbonate resin pellets were used to perform the various evaluations described above. The evaluation results are shown in Table 1.

[Example 7]
ISB 9.41g (0.064mol) 1,6-HD 11.41g (0.097m
ol), SPG 59.89g (0.197mol), Polyorganosiloxane-1 9
A polymerization reaction was carried out in the same manner as in Example 1, except that 74 g (0.010 mol) of dimethylformamide, 78.77 g (0.368 mol) of DPC, and 0.97×10 ^-2 g (5.52×10 ^-5 mol) of calcium acetate monohydrate were used as a catalyst, to obtain polycarbonate resin pellets. The obtained polycarbonate resin pellets were used to carry out the various evaluations described above. The evaluation results are shown in Table 1.

[Example 8]
PCD 24.09g (0.035mol), SPG 59.88g (0.197mol)
l), Polyorganosiloxane-1 9.74g (0.010mol), DPC 51.
82 g (0.242 mol), and calcium acetate monohydrate 1.07 × 10
The polymerization reaction was carried out in the same manner as in Example 1, except that ² g (6.05×10 ⁻⁵ mol) of dimethylformamide was used.
Polycarbonate resin pellets were obtained. The above-mentioned various evaluations were carried out using the obtained polycarbonate resin pellets. The evaluation results are shown in Table 1.

[Example 9]
ISB 12.74g (0.087mol), SPG 73.71g (0.242mol)
l), Polyorganosiloxane-2 4.93g (0.002mol), DPC 71.
43 g (0.333 mol), and calcium acetate monohydrate 1.46 × 10
The polymerization reaction was carried out in the same manner as in Example 1, except that ² g (8.29 × 10 ^-5 mol) of dimethylformamide was used.
Polycarbonate resin pellets were obtained. The above-mentioned various evaluations were carried out using the obtained polycarbonate resin pellets. The evaluation results are shown in Table 1.

[Example 10]
ISB 16.98g (0.116mol), SPG 64.49g (0.212mol)
l), Polyorganosiloxane-2 9.87g (0.005mol), DPC 71.
70 g (0.335 mol), and calcium acetate monohydrate 1.47 × 10
The polymerization reaction was carried out in the same manner as in Example 1, except that ² g (8.33 × 10 ^-5 mol) of dimethylformamide was used.
Polycarbonate resin pellets were obtained. The above-mentioned various evaluations were carried out using the obtained polycarbonate resin pellets. The evaluation results are shown in Table 1.

[Comparative Example 1]
ISB 16.98g (0.116mol), SPG 73.71g (0.242mol)
A polymerization reaction was carried out in the same manner as in Example 1, except that 76.76 g (0.358 mol) of DPC, and 0.95×10 ^-2 g (5.37×10 ^-5 mol) of calcium acetate monohydrate were used as a catalyst, to obtain polycarbonate resin pellets. The obtained polycarbonate resin pellets were used to carry out the various evaluations described above. The evaluation results are shown in Table 1.

[Comparative Example 2]
Siloxane copolymer polycarbonate EXL1414T (manufactured by Sabic) was used.
The above-mentioned various evaluations were carried out. The evaluation results are shown in Table 1.
[Comparative Example 3]
ISB 67.92g (0.465mol), FM-0411 0.48g (0.00
A polymerization reaction was carried out in the same manner as in Example 1, except that 99.56 g (0.465 mol) of DPC, and 6.55×10 ^-4 g (3.72×10 ^-6 mol) of calcium acetate monohydrate were used as a catalyst, to obtain polycarbonate resin pellets. The obtained polycarbonate resin pellets were used to carry out the various evaluations described above. The evaluation results are shown in Table 1.

[Comparative Example 4]
ISB 63.23g (0.433mol), XP1459 5.30g (0.009m
ol), 94.57 g (0.441 mol) of DPC, and 1 g of calcium acetate as a catalyst.
A polymerization reaction was carried out in the same manner as in Example 1, except that 6.22×10 ⁻⁴ g (3.53×10 ⁻⁶ mol) of the hydrate was used, to obtain polycarbonate resin pellets. The obtained polycarbonate resin pellets were used to carry out the various evaluations described above. The evaluation results are shown in Table 1.

[evaluation]
As is clear from Table 1, according to Examples 1 to 10 of the present invention, the polycarbonate resin having the structural unit (A) and the structural unit (B) is excellent in both chemical resistance and weather resistance. In addition, Examples 1 to 8 are also excellent in transparency.
It can be seen that Comparative Examples 3 and 4, which do not contain structural unit (A), have poor chemical resistance. It can also be seen that Comparative Example 2, which does not contain structural unit (A) or structural unit (B), has poor weather resistance and chemical resistance.

Claims (10)

A copolymeric polycarbonate resin containing a structural unit (A) represented by the following formula (1) and a structural unit (B) derived from a polyorganosiloxane having two or more reactive functional groups:

(In formula (1), W is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms; R ¹ and R ² are a branched or linear alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent; and m is an integer of 0 to 10.) The copolymerized polycarbonate resin according to claim 1, in which the content of structural unit (A) is 40% by weight or more and 90% by weight or less, and the content of structural unit (B) is 1.0% by weight or more and 20% by weight or less, when the total weight of all structural units and linking groups constituting the resin is taken as 100% by weight. The copolymer polycarbonate resin according to claim 1 or 2, in which the ratio of the content of structural unit (A) to the content of structural unit (B) is 96/4 to 70/30. The copolymeric polycarbonate resin according to any one of claims 1 to 3, wherein the reactive functional groups are each independently one or more selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, an alkenyl group, an ester group, a methacryloyl group, an acryloyl group, and a cyclic ether group. 5. The copolymeric polycarbonate resin according to claim 1, wherein the structural unit (B) is represented by the following formula (2):

(In formula (2), n represents 5 to 30. ^{R 3} to R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. X and X' each independently represent an oxygen atom, or an organic residue having -C(═O)-, an ether structure, an amine structure, an aromatic structure, or an aliphatic structure. n represents the average repeating number of the polyorganosiloxane portion.) A copolymeric polycarbonate resin according to any one of claims 1 to 5, which contains a total of 5% by weight or more and 30% by weight or less of structural units (C) derived from one or more compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, oxyalkylene glycols, and dihydroxy compounds having a heterocyclic structure, when the total weight of all structural units and linking groups constituting the resin is taken as 100% by weight. A copolymer polycarbonate resin according to any one of claims 1 to 6, characterized in that the water absorption rate of the polycarbonate resin is 1.1% or less. The copolymer polycarbonate resin according to any one of claims 1 to 7, characterized in that the glass transition temperature of the copolymer polycarbonate resin is 50°C or higher and 160°C or lower. A molded article comprising the copolymer polycarbonate resin according to any one of claims 1 to 8. A step of mixing a dihydroxy compound including a dihydroxy compound represented by the following formula (3) with a polyorganosiloxane having two or more reactive functional groups to obtain a raw material solution;
The method for producing a copolymeric polycarbonate resin comprises a step of subjecting the raw material solution, a carbonic acid diester, and a polymerization catalyst to a polycondensation reaction.

(In formula (3), W is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms; R ¹ and R ² are a branched or linear alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent; and m is an integer of 0 to 10.)

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