JP7096030B2 - Polycarbonate resin and method for manufacturing polycarbonate resin - Google Patents

Description

The present invention relates to a polycarbonate resin having excellent heat resistance, high transparency, good initial hue, and suppressing yellowing during long-term use, and a method for producing the polycarbonate resin.

Polycarbonate resin (hereinafter referred to as PC) has excellent transparency, impact resistance, heat resistance, and dimensional stability, so it can be used as an engineering plastic for electrical and electronic applications, automobile applications, building materials, furniture, musical instruments, and miscellaneous goods. It is used in a wide range of fields such as. In addition, compared to inorganic glass, the degree of freedom in the processed shape is high, and since it is possible to integrate a plurality of parts, it is expected that the weight of the vehicle body will be reduced and the productivity will be improved.

However, when a conventional PC is exposed to the outdoors for a long period of time, the hue, transparency, and mechanical strength are deteriorated by the sun's rays, so that there is a limitation in the use outdoors.

In order to solve such a problem, a method of adding an ultraviolet absorber to a PC is known. When an ultraviolet absorber is added, although improvement in hue during ultraviolet irradiation is observed, the hue, heat resistance, and transparency of the resin itself are deteriorated, and the ultraviolet absorber volatilizes during molding to contaminate the mold. However, there are problems such as poor appearance of the molded product.

Therefore, a polycarbonate resin made from an alicyclic dihydroxy compound typified by 2,2,4,4-tetramethyl-1,3-cyclobutanediol, which does not have a benzene ring structure in its molecular skeleton, has been studied ( For example, Patent Documents 1 to 4). Since these polycarbonate resins are usually produced by a method called a transesterification method or a melt polymerization method, the above dihydroxy compound and a carbonic acid diester such as diphenyl carbonate are transesterified at a high temperature of 200 ° C. or higher in the presence of a catalyst. Polymerization is promoted by removing by-produced phenol and the like to the outside of the system to obtain a polycarbonate resin. Although it is described that a metal compound is useful as a polymerization catalyst, since coloring after polymerization and yellowing in a weather resistance test occur, further improvement is required in consideration of practical application and application development.

Therefore, there is still no polycarbonate resin capable of excellent heat resistance, high transparency, good initial hue, and suppression of yellowing during weather resistance tests.

Japanese Unexamined Patent Publication No. 2-86618 Special Publication No. 38-26798 Special Publication No. 39-1546 Japanese Unexamined Patent Publication No. 2015-78257

An object of the present invention is to provide a polycarbonate resin having excellent heat resistance, high transparency, good initial hue, and a method for producing a polycarbonate resin and a polycarbonate resin capable of suppressing yellowing during a weather resistance test.

As a result of diligent studies to solve the above problems, the present inventor has a cyclobutane ring typified by 2,2,4,4-tetramethyl-1,3-cyclobutanediol (hereinafter referred to as TMCB). We have found that a polycarbonate resin obtained by using a dihydroxy compound and using a specific metal compound and a nitrogen-containing compound as a polymerization catalyst is excellent in heat resistance, transparency, initial hue, and suppression of yellowing during a weather resistance test. It was completed.

That is, according to the present invention, the subject of the invention is achieved by the following (Structure 1) to (Structure 18).
(Structure 1)
An anion represented by the following formula (2) using a dihydroxy compound component containing 10 mol% or more of the dihydroxy compound represented by the following formula (1) and a carbonic acid diester represented by the following formula (3) as a polymerization catalyst. A method for producing a polycarbonate resin that reacts in the presence of a metal compound composed of a cation composed of a metal and a nitrogen-containing compound, and the metal compound is 1 × 10 with respect to all the dihydroxy compounds used for polymerization. A method for producing a polycarbonate resin, which comprises using ^-7 to 3 × 10 ^-4 mol equivalents and 1 × 10 ^-6 to 1 × 10 ^-3 mol equivalents of a nitrogen-containing compound.

（式（１）中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４は夫々独立に、水素原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数３～２０のシクロアルキル基、炭素原子数６～２０のシクロアルコキシ基、炭素原子数６～１０のアリール基、炭素原子数７～２０のアラルキル基、炭素原子数６～１０のアリールオキシ基、炭素原子数７～２０のアラルキルオキシ基またはハロゲン原子を示す。シクロブタン環はシス・トランス異性体混合物、シス異性体単独またはトランス異性体単独を示す。）

(In the formula (1), R ₁ , R ₂ , R ₃ , and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and 3 carbon atoms. ~ 20 cycloalkyl groups, 6-20 carbon atoms cycloalkoxy groups, 6-10 carbon atoms aryl groups, 7-20 carbon atoms aralkyl groups, 6-10 carbon atoms aryloxy groups, carbon It represents an aralkyloxy group or a halogen atom having 7 to 20 atoms. The cyclobutane ring indicates a cis-trans isomer mixture, cis isomer alone or trans isomer alone.)

（式（２）中、Ｒ_５は炭素原子数１～２２の直鎖状でも分岐状でも良いアルキル基、シクロアルキル基、アリールアルキル基である。）

(In the formula ( ₂ ), R5 is an alkyl group, a cycloalkyl group, or an arylalkyl group having 1 to 22 carbon atoms which may be linear or branched.)

（式（３）中、Ｒ_６、Ｒ_７は夫々独立に、置換若しくは無置換の芳香族基である。）

(In formula (3), R ₆ and R ₇ are independently substituted or unsubstituted aromatic groups, respectively.)

(Structure 2)
The method for producing a polycarbonate resin according to Configuration 1, wherein R5 in the formula ( ₂ ) is a linear alkyl group having 1 to 22 carbon atoms.
(Structure 3)
2. The polycarbonate according to any one of configurations 1 to 2, wherein the cation composed of a metal is at least one cation selected from the group consisting of groups 1 and 2 of the long-periodic table. Resin manufacturing method.
(Structure 4)
Item 2. The polycarbonate resin according to any one of the constituents 1 to 3, wherein the cation composed of a metal is at least one cation selected from the group consisting of lithium and Group 2 of the long-periodic table. Manufacturing method.
(Structure 5)
The method for producing a polycarbonate resin according to any one of configurations 1 to 4, wherein the nitrogen-containing compound is a quaternary ammonium salt.
(Structure 6)
The method for producing a polycarbonate resin according to any one of configurations 1 to 5, wherein the dihydroxy compound represented by the formula (1) is contained in an amount of 30 mol% or more.
(Structure 7)
The polycarbonate according to any one of the constituents 1 to 6, wherein the dihydroxy compound represented by the formula (1) is composed of a cis-trans isomer mixture and has a cis isomer ratio of 30 to 90%. Resin manufacturing method.
(Structure 8)
Further, the configurations 1 to 1 to include the dihydroxy compound represented by the following formula (4), and the total of the above formula (1) and the following formula (4) is 40 mol% or more in the total dihydroxy compound components. 7. The method for producing a polycarbonate resin according to any one of 7.

（式（４）中、ｍは２～１２の整数を示す）

(In equation (4), m indicates an integer of 2 to 12)

(Structure 9)
The method for producing a polycarbonate resin according to any one of configurations 1 to 8, wherein the polycarbonate resin has a viscosity average molecular weight of 10,000 to 50,000.
(Structure 10)
The method for producing a polycarbonate resin according to any one of configurations 1 to 9, wherein the glass transition temperature of the polycarbonate resin is 100 to 200 ° C.
(Structure 11)
The method for producing a polycarbonate resin according to any one of configurations 1 to 10, wherein the polycarbonate resin contains 1000 ppm or less of an aromatic monohydroxy compound.
(Structure 12)
Item 1 of Configuration 1 to 11, wherein the polycarbonate resin has a terminal phenyl group derived from a carbonic acid diester represented by the above formula (3), and the terminal phenyl group concentration is 30 μeq / g or more. The method for producing a polycarbonate resin according to.
(Structure 13)
The repeating unit contains 10 mol% or more of a carbonate unit derived from a dihydroxy compound represented by the following formula (1), and the total amount of lithium and the metal of Group 2 of the long periodic table is 0.1 to 100 ppm as the metal amount. A polycarbonate resin having a total nitrogen content in the range of 0.1 to 7 ppm.

（式（１）中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４は夫々独立に、水素原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数３～２０のシクロアルキル基、炭素原子数６～２０のシクロアルコキシ基、炭素原子数６～１０のアリール基、炭素原子数７～２０のアラルキル基、炭素原子数６～１０のアリールオキシ基、炭素原子数７～２０のアラルキルオキシ基またはハロゲン原子を示す。シクロブタン環はシス・トランス異性体混合物、シス異性体単独またはトランス異性体単独を示す。）

(In the formula (1), R ₁ , R ₂ , R ₃ , and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and 3 carbon atoms. ~ 20 cycloalkyl groups, 6-20 carbon atoms cycloalkoxy groups, 6-10 carbon atoms aryl groups, 7-20 carbon atoms aralkyl groups, 6-10 carbon atoms aryloxy groups, carbon It represents an aralkyloxy group or a halogen atom having 7 to 20 atoms. The cyclobutane ring indicates a cis-trans isomer mixture, cis isomer alone or trans isomer alone.)

(Structure 14)
The polycarbonate resin according to composition 13, wherein the total amount of lithium, calcium, magnesium and barium is 0.1 to 100 ppm as a metal amount.
(Structure 15)
The polycarbonate resin according to any one of configurations 13 to 14, wherein the polycarbonate resin has a viscosity average molecular weight of 10,000 to 50,000.
(Structure 16)
The polycarbonate resin according to any one of configurations 13 to 15, wherein the polycarbonate resin has a glass transition temperature of 100 to 200 ° C.
(Structure 17)
The polycarbonate resin according to any one of configurations 13 to 16, wherein the polycarbonate resin contains 1000 ppm or less of an aromatic monohydroxy compound.
(Structure 18)
Item 1 of the configuration 13 to 17, wherein the polycarbonate resin has a terminal phenyl group derived from a carbonic acid diester represented by the following formula (3), and the terminal phenyl group concentration is 30 μeq / g or more. The method for producing a polycarbonate resin according to.

（式（３）中、Ｒ_６、Ｒ_７は夫々独立に、置換若しくは無置換の芳香族基である。）

(In formula (3), R ₆ and R ₇ are independently substituted or unsubstituted aromatic groups, respectively.)

The polycarbonate resin of the present invention has excellent heat resistance, high transparency, and initial hue, and is excellent in suppressing yellowing during a weather resistance test, and its industrial effect is exceptional.

Hereinafter, the details of the present invention will be described, but the description of the constituent elements described below is a representative example of the embodiment of the present invention, and the present invention is not limited to the following contents as long as the gist thereof is not exceeded.

<Dihydroxy compound>
In the present invention, a dihydroxy compound represented by the following formula (1) is used as a raw material. The dihydroxy compound represented by the following formula (1) is 10 mol% or more, preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and even more preferably 60 mol% of the total dihydroxy compound component. The above is particularly preferable, and 70 mol% or more is most preferable.

（式（１）中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４は夫々独立に、水素原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数３～２０のシクロアルキル基、炭素原子数６～２０のシクロアルコキシ基、炭素原子数６～１０のアリール基、炭素原子数７～２０のアラルキル基、炭素原子数６～１０のアリールオキシ基、炭素原子数７～２０のアラルキルオキシ基またはハロゲン原子を示す。シクロブタン環はシス・トランス異性体混合物、シス異性体単独またはトランス異性体単独を示す。）
Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４は夫々独立して、水素原子、炭素原子数１～６のアルキル基、炭素原子数３～６のシクロアルキル基、炭素原子数６～１０のアリール基であることが好ましく、メチル基がより好ましい。

(In the formula (1), R ₁ , R ₂ , R ₃ , and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and 3 carbon atoms. ~ 20 cycloalkyl groups, 6-20 carbon atoms cycloalkoxy groups, 6-10 carbon atoms aryl groups, 7-20 carbon atoms aralkyl groups, 6-10 carbon atoms aryloxy groups, carbon It represents an aralkyloxy group or a halogen atom having 7 to 20 atoms. The cyclobutane ring indicates a cis-trans isomer mixture, cis isomer alone or trans isomer alone.)
R ₁ , R ₂ , R ₃ , and R ₄ are independent hydrogen atoms, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. Is preferable, and a methyl group is more preferable.

Specific examples of the dihydroxy compound represented by the formula (1) include 2-methyl-1,3-cyclobutanediol, 2,4-dimethyl-1,3-cyclobutanediol, and 2,2,4,4-. Tetramethyl-1,3-cyclobutanediol, 2-ethyl-1,3-cyclobutanediol, 2,4-diethyl-1,3-cyclobutanediol, 2,2,4,4-tetraethyl-1,3-cyclobutanediol , 2-butyl-1,3-cyclobutanediol, 2,4-dibutyl-1,3-cyclobutanediol, 2,2,4,4-tetrabutyl-1,3-cyclobutanediol and the like. The most suitable dihydroxy compound is 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Two or more of these dihydroxy compounds may be used in combination.

The dihydroxy compound represented by the formula (1) is usually a cis-trans isomer mixture. The ratio is not limited, but the cis isomer ratio is preferably 30% or more, more preferably 45% or more, still more preferably 50% or more. The cis isomer ratio is preferably 90% or less, more preferably 80% or less, still more preferably 70% or less. According to Japanese Patent Application Laid-Open No. 39-1546, when the cis isomer is less than 30%, the melting point of the polymerized polymer becomes high, so that it is necessary to raise the molding processing temperature, which causes resin decomposition and the machine of the molded product. It is stated that the target strength is reduced. The cis-trans isomer ratio can be calculated by measuring the ¹ H-NMR spectrum using JNM-AL400 manufactured by JEOL Ltd.

<Other dihydroxy compounds>
The polycarbonate resin of the present invention can be a copolymer made from a dihydroxy compound component containing a structural unit other than the dihydroxy compound represented by the above formula (1). The dihydroxy compound component that induces other copolymerization constituent units may be any of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and an aromatic dihydroxy compound, and International Publication No. 2004/111106, International Publication No. 2011/021720. Examples thereof include dihydroxy compounds described in the pamphlet and dihydroxy compounds having oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycol.

When at least one dihydroxy compound of the above-mentioned aliphatic dihydroxy compound, alicyclic dihydroxy compound and aromatic dihydroxy compound is contained, the dihydroxy compound represented by the above formula (1) and the aliphatic dihydroxy compound are contained in all the dihydroxy compound components. , The total of the alicyclic dihydroxy compound and the aromatic dihydroxy compound at least one dihydroxy compound is preferably 40 mol% or more, more preferably 50 mol% or more, further preferably 60 mol% or more, and even more preferably 70 mol. % Or more is particularly preferable, and 80 mol% or more is most preferable.

As the aliphatic dihydroxy compound, a dihydroxy compound represented by the following formula (4) can be preferably used.

（式（４）中、ｍは２～１２の整数を示す）

(In equation (4), m indicates an integer of 2 to 12)

Specific examples of the aliphatic dihydroxy compound include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and 1.9-nonane. Diol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-n-butyl-2- Ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexaneglycol, 1,2-octylglycol, 2 -Ethyl-1,3-hexanediol, 2,3-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol And so on. Two or more of these dihydroxy compounds may be used in combination.

Examples of the alicyclic dihydroxy compound include cyclohexanedimethanol, tricyclodecanedimethanol, adamantandiol, pentacyclopentadecanedimethanol, and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4. Examples thereof include 8,10-tetraoxaspiro [5.5] undecane and isosorbide, and cyclohexanedimethanol, tricyclodecanedimethanol, adamantandiol, and pentacyclopentadecanedimethanol are preferable. Two or more of these dihydroxy compounds may be used in combination.

Examples of the oxyalkylene glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol and the like. One of these compounds may be used alone, or two or more thereof may be used in combination.

As the aromatic dihydroxy compound, a dihydroxy compound represented by the following formula (5) can be used.

（式（５）中、Ｗは下記式（６）～（９）からなる群より選択される少なくとも１種の二価の有機残基、単結合、または下記式（１０）のいずれかの結合を表し、ＸおよびＹはそれぞれ独立して０または１～４の整数であり、Ｒ_８およびＲ_９はそれぞれ独立して、ハロゲン原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数６～２０のシクロアルキル基、炭素原子数６～２０のシクロアルコキシ基、炭素原子数６～１０のアリール基、炭素原子数７～２０のアラルキル基、炭素原子数６～１０のアリールオキシ基、および炭素原子数７～２０のアラルキルオキシ基からなる群より選択される有機残基を表す。）

(In the formula (5), W is at least one divalent organic residue selected from the group consisting of the following formulas (6) to (9), a single bond, or a bond of any of the following formulas (10). X and Y are independently integers of 0 or 1 to 4, and R ₈ and R ₉ are independently halogen atoms, alkyl groups having 1 to 10 carbon atoms, and 1 to 1 carbon atoms. 10 alkoxy groups, cycloalkyl groups with 6 to 20 carbon atoms, cycloalkoxy groups with 6 to 20 carbon atoms, aryl groups with 6 to 10 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, carbon atoms Represents an organic residue selected from the group consisting of 6 to 10 aryloxy groups and 7 to 20 carbon atoms of aralkyloxy groups.)

（式（６）中、Ｒ_１０、Ｒ_１１、Ｒ_１２およびＲ_１３はそれぞれ独立して、水素原子、ハロゲン原子または炭素数１～３のアルキル基を表す。）

(In formula (6), R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.)

（式（７）中、Ｒ_１４およびＲ_１５はそれぞれ独立して、水素原子、ハロゲン原子または炭素数１～３のアルキル基を表す。）

(In formula (7), R ₁₄ and R ₁₅ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms.)

（式（８）中、Ｕは４～１１の整数を表し、かかる複数のＲ_１６およびＲ_１７はそれぞれ独立して水素原子、ハロゲン原子、および炭素数１～３のアルキル基から選択される基を表す。）

(In formula (8), U represents an integer of 4 to 11, and the plurality of R ₁₆ and R ₁₇ are independently selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 3 carbon atoms. Represents.)

（式（９）中、Ｒ_１８およびＲ_１９はそれぞれ独立して、水素原子、ハロゲン原子、および炭素数１～１０の炭化水素基から選択される基を表す。）

(In formula (9), R ₁₈ and R ₁₉ each independently represent a group selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 10 carbon atoms.)

前記式（５）におけるＷが単結合である構成単位を誘導するジヒドロキシ化合物の具体例としては、４，４’－ビフェノールおよび４，４’－ビス（２，６－ジメチル）ジフェノール等が挙げられる。

Specific examples of the dihydroxy compound for deriving a structural unit in which W is a single bond in the formula (5) include 4,4'-biphenol and 4,4'-bis (2,6-dimethyl) diphenol. Be done.

Specific examples of the dihydroxy compound in which W is the structural unit of the formula (6) are α, α'-bis (4-hydroxyphenyl) -o-diisopropylbenzene and α, α'-bis (4-hydroxyphenyl). ) -M-Diisopropylbenzene (usually referred to as "bisphenol M"), α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene and the like.

Specific examples of the dihydroxy compound in which W is the structural unit of the formula (7) are 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl). Fluorene and the like can be mentioned.

Specific examples of the dihydroxy compound in which W is the structural unit of the formula (8) are 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3. 5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3methylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, and 1,1-bis (3-cyclohexyl-4) -Hydroxyphenyl) cyclohexane 1,1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the like can be mentioned.

Specific examples of the dihydroxy compound in which W is the structural unit of the formula (9) are 1,1-bis (4-hydroxyphenyl) methane, 2,4'-dihydroxydiphenylmethane, and bis (2-hydroxyphenyl) methane. , Bis (4-hydroxyphenyl) methane, Bis (4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane, Bis (4-hydroxyphenyl) cyclohexylmethane, Bis (4-hydroxyphenyl) diphenylmethane, 1, 1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-2-phenyl) -1-phenyl ethane, 1,1-bis (4-hydroxy-2-chlorophenyl) ethane, 2,2 -Bis (4-hydroxyphenyl) propane (usually referred to as "bisphenol A"), 2,2-bis (4-hydroxy-3-methylphenyl) propane (usually referred to as "bisphenol C"), 2 , 2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-Bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-) Hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-hydroxyphenyl) -1-phenylpropane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) Octane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (3-methyl-4-hydroxyphenyl) decane, and 1,1-bis (2,3-dimethyl-4-hydroxyphenyl) decane Etc. are exemplified.

Among the above dihydroxy compounds, the formula (6) is bisphenol M, the formula (7) is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and the formula (8) is 1,1-bis (4-hydroxy). Phenyl) cyclohexane, 1,1-bis (4-hydroxy-3 methylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, formula (9) 3,3' -Dimethyl-4,4'-dihydroxydiphenylsulfide, and bisphenol A and bisphenol C in the formula (10) are preferable.

Specific examples of the dihydroxy compound in which W is one of the formulas (10) for deriving a structural unit are 4,4'-dihydroxydiphenylether and 4,4'-dihydroxy-3,3'-dimethyldiphenyle. -Tell, 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenylsulfide, 3,3'-dimethyl-4,4' -Dihydroxydiphenyl sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone and the like can be mentioned.

Further, as the dihydroxy compound for inducing a structural unit other than the formula (5), preferably 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, resorcinol substituted with an alkyl group having 1 to 3 carbon atoms, 3- (4-hydroxy). Phenyl) -1,1,3-trimethylindan-5-ol, 1- (4-hydroxyphenyl) -1,3,3-trimethylindan-5-ol, 6,6'-dihydroxy-3,3,3 ', 3'-Tetramethylspirindan, 1-methyl-1,3-bis (4-hydroxyphenyl) -3-isopropylcyclohexane, 1-methyl-2- (4-hydroxyphenyl) -3- [1-( 4-Hydroxyphenyl) isopropyl] cyclohexane, 1,6-bis (4-hydroxyphenyl) -1,6-hexanedione, and ethylene glycol bis (4-hydroxyphenyl) ether, 6,6'-dihydroxy-3,3 , 3', 3'-tetramethyl-1,1'-spirobiindan, spirobichroman and the like are exemplified.

Other details of such polycarbonate are described in, for example, WO03 / 080728 pamphlet, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, JP-A-2002-117580 and the like. Has been done.

The exemplified compound is an example of a dihydroxy compound that can be used as a constituent unit of the polycarbonate copolymer in the present invention, and is not limited thereto.

<Manufacturing method>
In the present invention, carbonic acid is used in the presence of a metal compound composed of a specific anion which is an ester exchange catalyst and a cation composed of a metal, and a nitrogen-containing compound, using a dihydroxy compound component containing the compound of the formula (1). A polycarbonate resin is produced by reacting with a diester.
Next, the basic means for these manufacturing methods will be described.

In the present invention, it is preferable that the dihydroxy compound component as a raw material and the carbonic acid diester are uniformly mixed before the transesterification reaction. The mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and the upper limit thereof is usually 250 ° C. or lower, preferably 200 ° C. or lower, and more preferably 150 ° C. or lower. Above all, 100 ° C. or higher and 120 ° C. or lower are preferable. If the mixing temperature is too low, the dissolution rate may slow down or the solubility may be insufficient, which often leads to problems such as solidification, and if the mixing temperature is too high, thermal deterioration of the dihydroxy compound component may occur. The hue of the resulting resin may deteriorate.

In the present invention, the operation of mixing the dihydroxy compound as a raw material and the carbonic acid diester has an oxygen concentration of 10 vol% or less, further 0.0001 vol% to 10 vol%, particularly 0.0001 vol% to 5 vol%, particularly 0.0001 vol% or more. It is preferable to perform the operation in an atmosphere of 1 vol% from the viewpoint of preventing deterioration of hue.

In the present invention, the carbonic acid diester is a compound represented by the above formula (3), and examples thereof include esters such as an aryl group having 6 to 12 carbon atoms and an aralkyl group which may be substituted. Specific examples thereof include diphenyl carbonate, ditriel carbonate, bis (chlorophenyl) carbonate and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferable. The amount of the diphenyl carbonate used is preferably 0.90 to 1.10 mol, more preferably 0.95 to 1.05 mol, based on 1 mol of the total dihydroxy compound component. If the molar ratio is less than 0.90 or larger than 1.10, the rate of transesterification reaction may decrease or it may be difficult to obtain a polycarbonate resin having a desired molecular weight. In addition, the decrease in speed in the transesterification reaction increases the thermal history during the polymerization reaction, which may worsen the hue of the resulting polycarbonate resin.

In the present invention, the method of polycondensing a dihydroxy compound component and a carbonic acid diester is usually carried out in a multi-step manner using a plurality of reactors in the presence of a catalyst. The form of the reaction may be batch type, continuous type, or a combination of batch type and continuous type.

In the early stage of polymerization, it is preferable to obtain a prepolymer at a relatively low temperature, low vacuum or normal pressure, and in the late stage of polymerization, it is preferable to raise the molecular weight to a predetermined value at a relatively high temperature and high vacuum. From the viewpoint of color, it is important to properly select the jacket temperature, internal temperature, and pressure in the reaction system. For example, if either the temperature or the pressure is changed too quickly before the polymerization reaction reaches a predetermined value, the unreacted monomer is distilled out, the molar ratio of the dihydroxy compound component and the carbonic acid diester is disturbed, and the polymerization rate is increased. There is a possibility that the color tone of the resulting polycarbonate resin may be deteriorated due to a decrease or failure to obtain a polycarbonate resin having a desired molecular weight.

Furthermore, it is effective to use a reflux condenser as the polymerization reactor in order to suppress the amount of the dihydroxy compound component distilled off, and the effect is particularly effective in the reactor at the initial stage of polymerization in which a large amount of unreacted dihydroxy compound components are present. big. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected depending on the dihydroxy compound component used, but usually the temperature of the refrigerant introduced into the reflux condenser is 45 to 180 at the inlet of the reflux condenser. ° C., preferably 80 to 150 ° C., particularly preferably 100 to 130 ° C. If the temperature of the refrigerant is too high, the amount of recirculation decreases and its effect decreases, and conversely, if the temperature is too low, the distillation efficiency of the monohydroxy compound that should be distilled off tends to decrease. As the refrigerant, hot water, steam, heat medium oil and the like are used, and steam and heat medium oil are preferable.

It is important to select the type and amount of the catalyst described above in order to maintain the polymerization rate appropriately, suppress the distillation of the dihydroxy compound component, and not impair the hue and thermal stability of the final resin. Is.

The polycarbonate resin of the present invention is preferably produced by polymerizing in multiple stages using a plurality of reactors using a catalyst, but the reason why the polymerization is carried out in a plurality of reactors is that the reaction is carried out at the initial stage of the polymerization reaction. Since there are many monomers contained in the liquid, it is important to suppress the volatilization of the monomers while maintaining the required polymerization rate. In the latter stage of the polymerization reaction, by-products are used to shift the equilibrium to the polymerization side. This is because it is important to sufficiently distill off the monohydroxy compound. As described above, in order to set different polymerization reaction conditions, it is preferable to use a plurality of polymerization reactors arranged in series from the viewpoint of production efficiency.

As described above, the number of reactors used in the method of the present invention may be at least two or more, but from the viewpoint of production efficiency and the like, three or more, preferably three to five, particularly preferably four. It is one.

In the present invention, if there are two or more reactors, a plurality of reaction stages having different conditions may be provided in the reactor, or the temperature and pressure may be continuously changed.

In the present invention, the polymerization catalyst can be added to the raw material preparation tank and the raw material storage tank, or can be added directly to the polymerization tank, but is supplied to the polymerization tank from the viewpoint of supply stability and polymerization control. A catalyst supply line is installed in the middle of the raw material line before the polymerization, and the catalyst supply line is preferably supplied as an aqueous solution.

If the temperature of the polymerization reaction is too low, it causes a decrease in productivity and an increase in the thermal history of the product, and if it is too high, it not only causes the monomer to volatilize, but also may promote the decomposition and coloring of the resin.

Specifically, in the first-stage reaction, the maximum internal temperature of the polymerization reactor is 140 to 270 ° C, preferably 180 to 240 ° C, and more preferably 200 to 230 ° C. The internal pressure is 110 to 90 kPa, preferably 105 to 95 kPa, more preferably 101 to 98 kPa (absolute pressure), and the reaction time of the initial polymerization is 0.1 to 10 hours, preferably 0.5 to 3 hours. be.

From the second stage onward, the pressure of the reaction system is gradually lowered from the pressure of the first stage, and the continuously generated monohydroxy compound is removed from the reaction system, and finally the pressure of the reaction system (absolute pressure) is reduced. The internal temperature is set to 200 Pa or less, and the maximum internal temperature is 210 to 280 ° C., preferably 220 to 260 ° C., usually 0.1 to 10 hours, preferably 1 to 6 hours, and particularly preferably 0.5 to 3 hours.

In particular, in order to suppress coloration and thermal deterioration of the resin and obtain a resin having a good hue, the maximum internal temperature in all reaction stages is preferably less than 280 ° C, particularly preferably 220 to 260 ° C. Further, in order to suppress a decrease in the polymerization rate in the latter half of the polymerization reaction and minimize deterioration due to thermal history, it is preferable to use a horizontal reactor having excellent interfacial renewal property at the final stage of polymerization.

If the polymerization temperature is high and the polymerization time is too long in order to obtain a resin having a predetermined molecular weight, the initial hue tends to deteriorate.

As described above, the resin of the present invention is preferably polycondensed, usually cooled and solidified, and pelletized with a rotary cutter or the like.

The method of pelletization is not limited, but is a method of extracting from the final polymerization reactor in a molten state and cooling and solidifying in the form of strands to pelletize, and uniaxial or biaxial extrusion in the molten state from the final polymerization reactor. The resin is supplied to the machine, melt-extruded, then cooled and solidified to be pelletized, or extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of strands, once pelletized, and then uniaxial again. Alternatively, a method of supplying a resin to a twin-screw extruder, melt-extruding the resin, and then cooling and solidifying the resin into pellets can be mentioned. At that time, in the extruder, the residual monomer is volatilized under reduced pressure, and commonly known heat stabilizers, neutralizers, ultraviolet absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, etc. It is also possible to add and knead a plasticizer, a compatibilizer, a flame retardant and the like.

The melt-kneading temperature in the extruder depends on the glass transition temperature and the molecular weight of the resin, but is usually 150 to 300 ° C, preferably 200 to 270 ° C, and more preferably 230 to 260 ° C. When the melt-kneading temperature is lower than 150 ° C., the melt viscosity of the resin is high, the load on the extruder is large, and the productivity is lowered. If the temperature is higher than 300 ° C., the heat deterioration of the resin becomes severe, which causes a decrease in mechanical strength due to a decrease in molecular weight, coloring, and generation of gas.

When manufacturing the resin of the present invention, it is desirable to install a filter in order to prevent foreign matter from entering. The installation position of the filter is preferably on the downstream side of the extruder, and the size (opening) of removing foreign matter on the filter is preferably 100 μm or less as the filtration accuracy of 99% removal. In particular, when it is disliked to mix a minute foreign substance in a film application or the like, it is preferably 40 μm or less, more preferably 10 μm or less.

Extrusion of the resin of the present invention is preferably carried out in a clean room having a higher cleanliness than Class 7, preferably Class 6, as defined in JISB 9920 (2002), in order to prevent foreign matter from being mixed after extrusion. Is desirable.

Further, when cooling the extruded resin, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a HEPA filter or the like to prevent reattachment of foreign substances in the air. When using water cooling, it is desirable to use water from which metal components in the water have been removed with an ion exchange resin or the like and then foreign substances in the water have been removed with a filter. The opening of the filter used is preferably 10 to 0.45 μm as the filtration accuracy for 99% removal.

<Polymerization catalyst>
In the production method of the present invention, a polymerization catalyst is used in order to increase the polymerization rate during polymerization. One of the polymerization catalysts is a metal compound composed of an anion represented by the following formula (2) and a cation composed of a metal.

（式（２）中、Ｒ_５は炭素数１～２２の直鎖状でも分岐状でも良いアルキル基、シクロアルキル基、アリールアルキル基である。）

(In the formula ( ₂ ), R5 is an alkyl group, a cycloalkyl group, or an arylalkyl group having 1 to 22 carbon atoms which may be linear or branched.)

In the formula ( ₂ ), R5 is preferably a linear alkyl group having 1 to 22 carbon atoms. Specifically, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, capric acid, undesic acid, lauric acid, tridecyl acid, myristic acid, pentadecic acid, palmitic acid, margaric acid. , Stearic acid, nonadesyl acid, arachidic acid, henicosyl acid, tricosyl bechenic acid, lignoseric acid and the like are preferable, and acetic acid and stealic acid are particularly preferable. These can be used alone or in combination. If the number of carbon atoms exceeds 22, it becomes difficult to obtain.

Further, the cation consisting of a metal in the above metal compound is preferably at least one cation selected from the group consisting of the metals of Group 1 and Group 2 of the Periodic Table of the Long Periodic Table, preferably lithium and a long periodic table. It is more preferable that the cation is at least one selected from the group consisting of the metals of Group 2 in Table 2. Specifically, lithium, sodium, potassium, cesium, magnesium, calcium, barium, manganese, zinc and the like are preferable, lithium, calcium, magnesium and barium are more preferable, and lithium, calcium and barium are particularly preferable. These can be used alone or in combination.

The amount of these metal compounds used is in the range of 1 × 10 ^-7 to 3 × 10 ^-4 molar equivalents relative to the total dihydroxy compound. It is preferably used in the range of 1 × 10 ^-6 to 2 × 10 ^-4 molar equivalents, more preferably 1 × 10 ^-5 to 1 × 10 ^-4 molar equivalents. If the amount of the polymerization catalyst used is less than the above lower limit, the reaction time is long and the degree of polymerization is low, which is not preferable. If the amount exceeds the upper limit, the polymer is significantly colored during polymerization, which is not preferable.

In the present invention, the reaction rate is improved at the time of polymerization by combining a nitrogen-containing compound with a metal compound composed of an anion represented by the above formula (3) and a cation composed of a metal, and the amount of the metal compound is reduced. By significantly reducing the amount, it is possible to obtain a polycarbonate resin having a good initial hue of the polymer after polymerization and less yellowing after the weather resistance test.

Examples of the nitrogen-containing compound used as one of the polymerization catalysts in the present invention include basic ammonium compounds and amine-based compounds.

Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, and trimethylphenylammonium hydroxide. Triethylmethylammonium hydride, triethylbenzylammonium hydride, triethylphenylammonium hydride, tributylbenzylammonium hydride, tributylphenylammonium hydride, tetraphenylammonium hydride, benzyltriphenylammonium hydride, methyltriphenylammonium hydride, Examples thereof include butyltriphenylammonium hydroxide.

Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Includes dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

These can be used alone or in combination. As the nitrogen-containing compound, a quaternary ammonium salt is preferable, and tetramethylammonium hydroxide is particularly preferable.

The amount of these nitrogen-containing compounds used is in the range of 1 × 10 ^-6 to 1 × 10 ^-3 molar equivalents with respect to all dihydroxy compounds. Preferably 3 × 10 ^-6 to 5 × 10 ^-4 molar equivalents, more preferably 5 × 10 ^-6 to 3 × 10 ^-4 molar equivalents, still more preferably 1 × 10 ^-5 to 1 × 10 ^-4 molar equivalents. Used in range. If the amount of the polymerization catalyst used is less than the above lower limit, the reaction time may become long and the desired degree of polymerization may not be obtained, and if it exceeds the above upper limit, the coloration of the polymer after polymerization becomes remarkable, which is not preferable.

It is also possible to add a catalytic deactivating agent in the latter stage of the reaction. As the catalyst deactivating agent to be used, known catalyst deactivating agents are effectively used, and among these, ammonium salts and phosphonium salts of sulfonic acids are preferable. Further, salts of dodecylbenzenesulfonic acid such as dodecylbenzenesulfonic acid tetrabutylphosphonium salt and salts of paratoluenesulfonic acid such as paratoluenesulfonic acid tetrabutylammonium salt are preferable.

As esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenylbenzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, Octyl paratoluenesulfonate, phenyl paratoluenesulfonate and the like are preferably used. Of these, the dodecylbenzene sulfonic acid tetrabutylphosphonium salt is most preferably used.

The amount of these catalyst deactivating agents used is preferably 0.5 to 50 mol, more preferably 0.5 to 10 mol, and even more preferably 0.8 to 5 mol, per mol of the polymerization catalyst. Can be used at the rate of.

<Polycarbonate resin>
In the present invention, the repeating unit contains 10 mol% or more of the carbonate unit derived from the dihydroxy compound represented by the following formula (1), and the total amount of lithium and the metal of Group 2 of the long periodic table is used as the metal amount. Provided are polycarbonate resins characterized by a range of 0.1 to 100 ppm and a total nitrogen content in the range of 0.1 to 7 ppm.

（式（１）中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４は夫々独立に、水素原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数３～２０のシクロアルキル基、炭素原子数６～２０のシクロアルコキシ基、炭素原子数６～１０のアリール基、炭素原子数７～２０のアラルキル基、炭素原子数６～１０のアリールオキシ基、炭素原子数７～２０のアラルキルオキシ基またはハロゲン原子を示す。シクロブタン環はシス・トランス異性体混合物、シス異性体単独またはトランス異性体単独を示す。）

(In the formula (1), R ₁ , R ₂ , R ₃ , and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and 3 carbon atoms. ~ 20 cycloalkyl groups, 6-20 carbon atoms cycloalkoxy groups, 6-10 carbon atoms aryl groups, 7-20 carbon atoms aralkyl groups, 6-10 carbon atoms aryloxy groups, carbon It represents an aralkyloxy group or a halogen atom having 7 to 20 atoms. The cyclobutane ring indicates a cis-trans isomer mixture, cis isomer alone or trans isomer alone.)

It is preferable to obtain such a polycarbonate resin by the polymerization method as described above. That is, by using a polymerization catalyst in which a nitrogen-containing compound is combined with a metal compound composed of an anion represented by the above formula (3) and a cation composed of a metal, the reaction rate is improved at the time of polymerization and the catalyst is used. Since the amount of the metal compound used as a catalyst can be significantly reduced, it is possible to obtain a polycarbonate resin having a good initial hue after polymerization and less yellowing after a weather resistance test.

The compounds containing lithium and the metals of Group 2 of the Long Periodic Table, preferably lithium, calcium, magnesium and barium in the polycarbonate resin of the present invention are derived from the catalyst used for the polymerization of the polycarbonate resin, and are polycarbonate. The total amount of these in the resin is 0.1 to 100 ppm, preferably 0.2 to 70 ppm or less, and more preferably 0.3 to 50 ppm or less as the total amount of metal. If the amount of metal exceeds the upper limit, the hue after polymerization deteriorates, which is not preferable. The amount of metal in the polycarbonate resin can be measured by ICP emission spectrometry.

The total amount of nitrogen in the polycarbonate resin of the present invention is 0.1 to 7 ppm, preferably 0.2 to 5 ppm. If the total amount of nitrogen in the polycarbonate resin exceeds the upper limit, the hue after polymerization deteriorates, which is not preferable.

The molecular weight of the polycarbonate resin of the present invention can be expressed by a viscosity average molecular weight (hereinafter, abbreviated as Mv). The Mv is preferably 10,000 to 50,000, more preferably 12,000 to 45,000, and even more preferably 15,000 to 40,000. If Mv is less than the above lower limit, practically sufficient toughness and impact resistance may not be obtained. On the other hand, when Mv exceeds the above upper limit, it is inferior in versatility because it requires a high molding temperature or a special molding method, and further, it depends on the injection speed due to the increase in melt viscosity. It tends to be high, and the yield may decrease due to poor appearance or the like.

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

The polycarbonate resin of the present invention preferably exhibits a single glass transition temperature (hereinafter abbreviated as Tg) when differential scanning calorimetry (DSC) is performed. The lower limit of Tg is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 120 ° C. or higher, and the upper limit of Tg is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, still more preferably 160 ° C. or higher. It is as follows. When Tg is at least the above lower limit value, the heat resistance is sufficient, and when it is at least the above upper limit value, the molding processability is good, which is preferable.
Tg can be measured at a heating rate of 20 ° C./min using a 2910 type DSC manufactured by TA Instruments Japan Co., Ltd.

The polycarbonate resin of the present invention has a light transmittance (hereinafter abbreviated as% T1) of a molded plate (thickness 3 mm) at a wavelength of 320 nm, preferably 30% or more, more preferably 40% or more, still more preferably. It is 45% or more, and most preferably 50% or more. If% T1 is below the above lower limit, yellowing may become noticeable during the weather resistance test.

The polycarbonate resin of the present invention preferably has a light transmittance (hereinafter abbreviated as% T2) of a molded plate (thickness 3 mm) at a wavelength of 350 nm of 55% or more, more preferably 60% or more, still more preferably. It is 65% or more, and particularly preferably 70% or more. If% T2 is below the above lower limit, yellowing may become noticeable during the weather resistance test.

In the polycarbonate resin of the present invention, a molded product (thickness 3 mm) is irradiated with a xenon lamp at 63 ° C. and a relative humidity of 50% at a wavelength of 300 nm to 400 nm at an irradiance of 180 W / m ² for 1000 hours. The yellow index (YI) value according to JIS K7373 measured with transmitted light is preferably 10 or less, more preferably 9 or less, and most preferably 8 or less.

The content of the aromatic monohydroxy compound in the polycarbonate resin of the present invention is preferably 1000 ppm or less, more preferably 800 ppm or less, still more preferably 700 ppm or less. When it is within the above range, the color tone and fluidity of the polycarbonate copolymer are good, which is preferable.

The polycarbonate resin of the present invention has a terminal phenyl group derived from the carbonic acid diester represented by the above formula (3), and the concentration of the terminal phenyl group is preferably 30 μeq / g or more, more preferably 40 μeq / g or more. It is particularly preferably 50 μeq / g or more, the upper limit is preferably 160 μeq / g or less, more preferably 140 μeq / g or less, and further preferably 100 μeq / g or less. If the concentration of the terminal phenyl group is too high, even if the hue immediately after polymerization or at the time of molding is good, the hue may deteriorate after the weather resistance test. Also, if it is too low, the thermal stability will decrease. In order to control the concentration of the terminal phenyl group, in addition to controlling the molar ratio of the dihydroxy component that is the raw material and the carbonic acid diester, the type and amount of the catalyst during the transesterification reaction, the pressure and temperature during the polymerization, etc. Can be mentioned.

<Ingredients other than polycarbonate resin>
The polycarbonate resin of the present invention can contain a functional agent known per se, such as a mold release agent, a heat stabilizer, an ultraviolet absorber, a flow modifier and an antistatic agent, as long as the effects of the present invention are not impaired.

(I) Release agent The polycarbonate resin of the present invention may be used in combination with a release agent as long as the effects of the present invention are not impaired. Examples of the release agent include fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymer, etc., which are modified with a functional group-containing compound such as acid modification), fluorine compounds (poly). Fluorine oil typified by fluoroalkyl ether), paraffin wax, beeswax and the like can be mentioned. Among these, fatty acid esters are preferable from the viewpoint of easy availability, releasability and transparency. The ratio of the release agent to 100 parts by weight is preferably 0.001 to 2 parts by weight, more preferably 0.005 to 1 part by weight, and further preferably 0.007 to 0.5 part by weight with respect to 100 parts by weight of the polycarbonate resin. Parts, particularly preferably 0.01 to 0.3 parts by weight. When the content is at least the above lower limit, the effect of improving the mold releasability is clearly exhibited, and when it exceeds the above upper limit, adverse effects such as mold contamination during molding are reduced, which is preferable.

Among the above, the fatty acid ester used as a preferable mold release agent will be described in more detail. Such fatty acid esters are esters of fatty alcohols and aliphatic carboxylic acids. The aliphatic alcohol may be a monohydric alcohol or a divalent or higher polyhydric alcohol. The carbon number of the alcohol is preferably in the range of 3 to 32, and more preferably in the range of 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, triacanthanol and the like. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), trimethylolpropane, xylitol, sorbitol, and mannitol. In fatty acid esters, polyhydric alcohols are more preferred.

On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid and icosanoic acid. And saturated aliphatic carboxylic acids such as docosanoic acid (bechenic acid), and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and sethalic acid. can. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferable. Since such aliphatic carboxylic acids are usually produced from natural fats and oils such as animal fats and oils (such as beef tallow and pork fat) and vegetable fats and oils (such as palm oil), these aliphatic carboxylic acids usually have carbon atoms. It is a mixture containing other carboxylic acid components different from each other. Therefore, it is also produced from such natural fats and oils in the production of aliphatic carboxylic acids, and is in the form of a mixture containing other carboxylic acid components. The acid value of the fatty acid ester is preferably 20 or less (substantially 0 can be taken). However, in the case of the total ester (full ester), it is preferable to contain not a little free fatty acid in order to improve the releasability, and in this respect, the acid value of the full ester is preferably in the range of 3 to 15. The iodine value of the fatty acid ester is preferably 10 or less (substantially 0 can be taken). These characteristics can be obtained by the method specified in JIS K 0070.

The fatty acid ester described above may be either a partial ester or a full ester, but a partial ester is preferable in terms of better releasability and durability, and a glycerin monoester is particularly preferable. The glycerin monoester is mainly composed of a monoester of glycerin and a fatty acid, and suitable fatty acids include saturated fatty acids such as stearic acid, partiminic acid, bechenic acid, araquinic acid, montanic acid, and lauric acid, and oleic acid and linoleic acid. , And unsaturated fatty acids such as sorbic acid, and those containing glycerin monoesters of stearic acid, behenic acid, and partiminic acid as main components are particularly preferable. The fatty acid is synthesized from a natural fatty acid and is a mixture as described above. Even in such a case, the ratio of the glycerin monoester in the fatty acid ester is preferably 60% by weight or more.

The partial ester is often inferior to the full ester in terms of thermal stability. In order to improve the thermal stability of the partial ester, the partial ester preferably has a sodium metal content of less than 20 ppm, more preferably less than 5 ppm, still more preferably less than 1 ppm. The fatty acid partial ester having a sodium metal content of less than 1 ppm can be produced by producing the fatty acid partial ester by a usual method and then purifying it by molecular distillation or the like.

Specifically, after removing gas and low boiling point substances with a spray nozzle type degassing device, glycerin is used under the conditions of a distillation temperature of 120 to 150 ° C. and a vacuum degree of 0.01 to 0.03 kPa using a downflow membrane type distillation device. Distillation of high-purity fatty acid partial ester under the conditions of distillation temperature 160-230 ° C. and vacuum degree 0.01-0.2 Torr after removing polyhydric alcohols such as The sodium metal can be removed as a distillation residue. By repeatedly performing molecular distillation on the obtained distillate, it is possible to further increase the purity and obtain a fatty acid partial ester having a lower sodium metal content. It is also important to thoroughly clean the inside of the molecular distillation apparatus by an appropriate method in advance and to prevent the mixing of sodium metal components from the external environment by improving the airtightness. Such fatty acid esters can be obtained from specialists (for example, Riken Vitamin Co., Ltd.).

(Ii) Phosphorus-based Stabilizer It is preferable that various phosphorus-based stabilizers are further blended in the polycarbonate resin of the present invention mainly for the purpose of improving the thermal stability during the molding process. Examples of such phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, and esters thereof. Further such phosphorus-based stabilizers include tertiary phosphine.

Specifically, examples of the phosphite compound include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, and dioctylmonophenyl. Phenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2, 6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) -4-Methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis (nonylphenyl) penta Examples thereof include erythritol diphosphite and dicyclohexylpentaerythritol diphosphite.

Further, as another phosphite compound, a compound that reacts with divalent phenols and has a cyclic structure can also be used. For example, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert-). Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite , 2,2'-Etilidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and the like.

Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, and dioctyl phosphate. Examples thereof include diisopropyl phosphate, preferably triphenyl phosphate and trimethyl phosphate.

Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenedi. Phenylphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite , Tetrax (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, Tetrakiss (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di) -N-Phenylphenyl) -3-Phenyl-Phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Examples thereof include -3-phenyl-phenylphosphonite, tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite, and tetrakis (2, 4-Di-tert-butylphenyl) -biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group in which the above alkyl group is substituted by 2 or more, and is preferable.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like.

Examples of the tertiary phosphine include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, and tri-p-tolyl. Examples thereof include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

The phosphorus-based stabilizer can be used not only by one type but also by mixing two or more types. Among the above phosphorus-based stabilizers, a phosphite compound or a phosphonite compound is preferable. In particular, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and bis (2,4-di-). tert-Butylphenyl) -Phenyl-Phenylphosphonite is preferred. Further, the combined use of these with a phosphate compound is also a preferable embodiment.

(Iii) Hindered phenolic stabilizer (antioxidant)
The polycarbonate resin of the present invention can be blended with a hindered phenolic stabilizer mainly for the purpose of improving the thermal stability and heat aging resistance during the molding process. Examples of such hindered phenol-based stabilizers include α-tocopherol, butyl hydroxytoluene, cinapyl alcohol, vitamin E, n-octadecyl-β- (4'-hydroxy-3', 5'-di-tert-butyl. Phenyl) propionate, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-Dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis ( 4-Methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethyleneglycol-N-bis-3- (3-tert-butyl-4-hydroxy-) 5-Methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-Butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,-Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4' -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide , 4,4'-di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butyl) Luphenol), 2,2-thiodiethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-) Hydroxy-3', 5'-di-tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide) , N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert- Butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl- 4-Hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethylisocyanurate, and tetrakis [methylene-3- (3', 3',) 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like are exemplified. All of these are easily available. The above-mentioned hindered phenolic antioxidant can be used alone or in combination of two or more.

The amount of the (ii) phosphorus-based stabilizer and / or (iii) hindered phenol-based antioxidant is preferably 0.0001 to 1 part by weight, more preferably 0.001 with respect to 100 parts by weight of the polycarbonate resin. It is about 0.5 part by weight, more preferably 0.005 to 0.1 part by weight. When the stabilizer is more than the above range, a good stabilizing effect can be obtained, and when it is less than the above range, it is preferable that the physical properties of the material are not deteriorated and the mold is not contaminated during molding.

As the polycarbonate resin of the present invention, an antioxidant other than the above-mentioned hindered phenolic antioxidant may be used as appropriate. Other such antioxidants include, for example, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate and the like. The amount of these other antioxidants used is preferably 0.001 to 0.05 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

(Iv) Ultraviolet absorber The polycarbonate resin of the present invention can contain an ultraviolet absorber. Specific examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzyloxy. Benzophenone, 2-Hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxitrihydride benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2', 4,4'-Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis (5-) Benzophenone-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like are exemplified.

Specific examples of the ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole system. -(2-Hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [ 4- (1,1,3,3-Tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzo Triazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-Hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2, 2'-Methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4-one), and 2- [2-hydroxy-3- (3) , 4, 5, 6-Tetrahydrophthalimidemethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and vinyl copolymerizable with the monomer. 2-Hydroxyphenyl such as a copolymer with a system monomer or a copolymer of 2- (2'-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a vinyl-based monomer copolymerizable with the monomer. Examples thereof include polymers having a -2H-benzotriazole skeleton.

Specific examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-hexyloxyphenol and 2- (4) in the hydroxyphenyltriazine system. , 6-Diphenyl-1,3,5-triazine-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2-yl) Il) -5-butyloxyphenol and the like are exemplified. Further, the phenyl group of the above-exemplified compound such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. A compound that has become a phenyl group is exemplified.

Specific examples of the ultraviolet absorber include 2,2'-p-phenylenebis (3,1-benzoxazine-4-one) and 2,2'-(4,4'-diphenylene) in the cyclic iminoester system. ) Bis (3,1-benzoxazine-4-one), 2,2'-(2,6-naphthalene) bis (3,1-benzoxazine-4-one) and the like are exemplified.

As the ultraviolet absorber, specifically, in the case of a cyanoacrylate-based agent, for example, 1,3-bis-[(2'-cyano-3', 3'-diphenylacryloyl) oxy] -2,2-bis [(2-2-bis]. Examples thereof include cyano-3,3-diphenylacryloyl) oxy] methyl) propane, and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

Further, the above-mentioned ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that it has a photostable monomer having such an ultraviolet-absorbing monomer and / or a hindered amine structure, and an alkyl (meth) acrylate. It may be a polymer type ultraviolet absorber which is copolymerized with a monomer such as. As the ultraviolet-absorbing monomer, a compound containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth) acrylic acid ester is preferably exemplified. The skeleton.

Among the above, benzotriazole-based and hydroxyphenyltriazine-based are preferable in terms of ultraviolet absorption ability, and cyclic iminoester-based and cyanoacrylate-based are preferable in terms of heat resistance and hue. The above-mentioned ultraviolet absorber may be used alone or in a mixture of two or more kinds.

The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 2 parts by weight, still more preferably 0.04 to 1 part by weight, and particularly preferably 0.04 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin. Is 0.05 to 0.5 parts by weight.

(V) Flow modifier The polycarbonate resin of the present invention may contain a fluid modifier as long as the effects of the present invention are not impaired. Examples of such flow modifiers include styrene-based oligomers, polycarbonate oligomers (including highly branched, hyperbranched and cyclic oligomer types), and polyalkylene terephthalate oligomers (including highly branched, hyperbranched and cyclic oligomer types). Branched and hyperbranched aliphatic polyester oligomers, terpene resins, polycaprolactone and the like are preferably exemplified. The flow modifier is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, still more preferably 2 to 15 parts by weight, per 100 parts by weight of the polycarbonate resin. Polycaprolactone is particularly preferable, and the composition ratio is particularly preferably 2 to 7 parts by weight per 100 parts by weight of the polycarbonate resin. The molecular weight of polycaprolactone is 1,000 to 70,000 in terms of number average molecular weight, preferably 1,500 to 40,000, more preferably 2,000 to 30,000, and 2,500 to 15,000. More preferred.

(Vi) Antistatic Agent The polycarbonate resin of the present invention may contain an antistatic agent mainly for the purpose of improving antistatic properties. As the antistatic agent, a sulfonic acid phosphonium salt, a phosphite ester, a caprolactone-based polymer and the like can be used, and the sulfonic acid phosphonium salt is preferably used. Specific examples of such sulfonic acid phosphonium salts include tetrabutylphosphonium dodecylsulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tributyloctylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, tetraethylphosphonium octadecylbenzenesulfonate, and dibutyl. Examples thereof include tributylmethylphosphonium benzenesulfonate, triphenylphosphonium dibutylnaphthylsulfonate, trioctylmethylphosphonium diisopropylnaphthylsulfonate and the like. Of these, tetrabutylphosphonium dodecylbenzenesulfonate is preferable because of its compatibility with polycarbonate and easy availability. The amount of the antistatic agent is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 3.0 parts by weight, still more preferably 0.3 to 2.0 parts by weight with respect to 100 parts by weight of the polycarbonate resin. It is blended by weight, particularly preferably 0.5 to 1.8 parts by weight. When it is 0.1 part by weight or more, the effect of antistatic is obtained, and when it is 5.0 parts by weight or less, the transparency and mechanical strength are excellent, and silver or peeling does not occur on the surface of the molded product, and it is difficult to cause an appearance defect.

The polycarbonate resin of the present invention can also contain various additives such as brewing agents, fluorescent dyes, flame retardants, and dyes and pigments. These can be appropriately selected and contained as long as the effects of the present invention are not impaired.

The brewing agent is preferably contained in the polycarbonate resin at 0.05 to 3.0 ppm (weight ratio). Typical examples of the brewing agent include Bayer's Macrolex Violet B and Macrolex Blue RR, and Clariant's Polysynthslen Blue RLS.

Examples of fluorescent dyes (including fluorescent whitening agents) include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthracinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, and xantone-based fluorescent dyes. , Thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, diaminostilben-based fluorescent dyes, and the like. The blending amount of the fluorescent dye (including the fluorescent whitening agent) is preferably 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

Examples of the flame retardant include a sulfonic acid metal salt-based flame retardant, a halogen-containing compound-based flame retardant, a phosphorus-containing compound-based flame retardant, and a silicon-containing compound-based flame retardant. Among these, sulfonic acid metal salt-based flame retardants are preferable. The blending amount of the flame retardant is usually preferably 0.01 to 1 part by weight, more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin.

The polycarbonate resin of the present invention may contain other components in addition to those described above, as long as the effects of the present invention are not significantly impaired. Examples of other components include resins other than polycarbonate resin. In addition, 1 type may be contained in other components, and 2 or more types may be contained in arbitrary combinations and ratios. Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin); polystyrene resin (PS resin) and high impact polystyrene. Resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene propylene rubber- Styrene resin such as styrene copolymer (AES resin); polyolefin such as polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), cyclic cycloolefin copolymer (COP) resin Resin; Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin); Polysulfone resin (PSU resin); polymethacrylate resin (PMMA resin); and the like.

The method for blending the polycarbonate resin of the present invention with an additive or the like is not particularly limited, and a known method can be used. The most commonly used method is to premix the polycarbonate resin and additives, then put them in an extruder for melt kneading, cool the extruded threads, and cut them with a pelletizer to produce pellet-shaped molding materials. There is a way to do it.

As the extruder in the above method, either a single-screw extruder or a twin-screw extruder can be used, but a twin-screw extruder is preferable from the viewpoint of productivity and kneadability. As a typical example of such a twin-screw extruder, ZSK (manufactured by Werner & Pfreederer, trade name) can be mentioned. Specific examples of the same type include TEX (manufactured by Japan Steel Works, Ltd., product name), TEM (manufactured by Toshiba Machine Co., Ltd., product name), KTX (manufactured by Kobe Steel, Ltd., product name), etc. Can be mentioned. As the extruder, one having a vent capable of degassing the moisture in the raw material and the volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed from the vent to efficiently discharge the generated water and volatile gas to the outside of the extruder. It is also possible to install a screen for removing foreign matter and the like mixed in the extruded raw material in the zone in front of the die portion of the extruder to remove the foreign matter from the resin composition. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (disc filter, etc.) and the like.

Further, although the additive can be independently supplied to the extruder, it is preferable to premix it with the resin raw material as described above. Examples of such premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. A more preferred method is, for example, to prepare a master agent by mixing a part of the raw material resin and the additive with a high-speed stirrer such as a Henchel mixer, and then leaving the remaining amount of the master agent as a total amount of the resin raw material and a Nauter mixer. It is a method of mixing with a non-high speed stirrer.

The polycarbonate resin composition extruded from the extruder is directly cut and pelletized, or after forming the strands, the strands are cut with a pelletizer and pelletized. When it is necessary to reduce the influence of external dust and the like, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resins for optical discs are used to narrow the shape distribution of pellets, further reduce miscuts, and generate fine powder during transportation or transportation. It is preferable to further reduce the amount of bubbles (vacuum bubbles) generated inside the strands and pellets. To reduce miscuts, measures such as controlling the temperature of threads during cutting with a pelletizer, blowing ion air during cutting, optimizing the rake angle of the pelletizer, and properly formulating a release agent, as well as cutting were performed. Examples thereof include a method of filtering a mixture of pellets and water to separate the pellets from water and miscut. An example of the measuring method is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-200421. With these formulations, it is possible to increase the cycle of molding and reduce the rate of defects such as silver.

The amount of miscut in the molding material (pellet) is preferably 10 ppm or less, more preferably 5 ppm or less. Here, the miscut means a powder or granular material finer than a pellet of a desired size that passes through a JIS standard sieve having an opening of 1.0 mm. The shape of the pellet can be a general shape such as a cylinder, a prism, and a sphere, but more preferably a cylinder (including an elliptical pillar), and the diameter of the cylinder is preferably 1.5 to 4 mm, more preferably. Is 2 to 3.5 mm. In the elliptical column, the ratio of the minor axis to the major axis is preferably 60% or more, more preferably 65% or more. On the other hand, the length of the cylinder is preferably 2 to 4 mm, more preferably 2.5 to 3.5 mm.

<Polycarbonate resin molded product>
The method for producing a molded product made of the polycarbonate resin of the present invention is not particularly limited, and any molding method generally used for the polycarbonate resin can be arbitrarily adopted. For example, an injection molding method, an ultra-high speed injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method such as gas assist, a molding method using a heat insulating mold, and a rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermal molding method, rotary molding method, laminated molding method, press molding method, etc. Can be mentioned. Further, a molding method using a hot runner method can also be used.

Further, the polycarbonate resin of the present invention can also be obtained as a sheet-shaped or film-shaped molded product by a method such as a melt extrusion method or a solution casting method (conversion method). As a specific method of the melt extrusion method, for example, a polycarbonate resin is quantitatively supplied to an extruder, melted by heating, and the molten resin is extruded from the tip of a T-die into a sheet on a mirror surface roll, and the melt extrusion method is performed by a plurality of rolls. A method is used in which the material is taken up while being cooled, and when it is solidified, it is cut to an appropriate size or wound up. As a specific method of the solution casting method, for example, a solution (concentration 5% to 40%) in which a polycarbonate resin is dissolved in methylene chloride is poured from a T-die onto a mirror-polished stainless steel plate, and the temperature is controlled stepwise. A method is used in which the sheet is peeled off while passing through the plasticized oven, the solvent is removed, and then the solution is cooled and wound up.

Further, the polycarbonate resin of the present invention can also be molded into a laminated body. Any method may be used for producing the laminated body, and it is particularly preferable to use a thermocompression bonding method or a coextrusion method. Any method is adopted as the thermocompression bonding method, but for example, a method of thermocompression bonding a sheet of a polycarbonate resin or a resin composition with a laminating machine or a pressing machine, a method of thermocompression bonding immediately after extrusion, and particularly a sheet immediately after extrusion are preferable. The method of continuously thermocompression bonding is industrially advantageous.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the measurement method of each characteristic is as follows.
(1) Sys-trans ratio A ¹ H-NMR spectrum at room temperature was measured using JNM-AL400 manufactured by JEOL Ltd., and the cis-trans isomer ratio was calculated from the signal intensity ratio.
Sample 50 mg
Solvent weight DMSO 0.6mL
Number of integrations: 512 times (2) Polymer composition ratio and terminal phenyl group concentration JEM-AL400 (resonance frequency 400 MHz) manufactured by JEOL Ltd. was used to measure ¹ H-NMR spectrum at room temperature, and the structure derived from each dihydroxy compound. The composition ratio of each structural unit in the polymer was calculated from the signal intensity ratio based on the unit. The terminal phenyl group concentration was determined by ¹ H-NMR with 1,1,2,2-tetrabromoethane as the internal standard and the signal intensity ratio based on the internal standard and the terminal phenyl group.
Polymer amount 40 mg
Solvent Deuterated chloroform 0.6mL
Number of integrations: 256 times (3) Viscosity average molecular weight (Mv)
The Mv of the polycarbonate resin was measured by the following method. From a solution of 0.7 g of polycarbonate resin in 100 ml of methylene chloride, the specific viscosity (η _sp ) of the solution at 20 ° C. was measured. Then, Mv calculated by the following formula was used as the viscosity average molecular weight.
η _sp / c = [η] +0.45 × [η] ² c
[Η] = 1.23 × 10 ^-4 Mv ^0.83
η _sp : Specific viscosity η: Extreme viscosity c: Constant (= 0.7)
Mv: Viscosity average molecular weight (4) Glass transition temperature (Tg)
Using the thermal analysis system DSC-2910 manufactured by TA Instruments Co., Ltd. using 8 mg of polycarbonate resin, in a nitrogen atmosphere (nitrogen flow rate: 40 ml / min), heating rate: 20 ° C. according to JIS K7121. Tg was measured under the condition of / min.
(5) Initial hue (YI ₀ )
Polycarbonate resin pellets are dried at 100 ° C. for 12 hours, supplied to an injection molding machine (EC100NII-2Y manufactured by Toshiba Machine Co., Ltd.), and molded at a resin temperature of 260 ° C. and a mold temperature of 80 ° C. (width 100 mm × width 100 mm ×). 3 mm thick) was molded. The initial hue of the molded plate was measured by NDH-2000 (C light source, viewing angle 2 °) manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS K6735.
(6) Spectral ray transmittance (320 nm, 350 nm)
The light transmittance of the molded plate (thickness 3 mm) was measured using an ultraviolet-visible spectrophotometer (U4100 manufactured by Hitachi High-Technologies Corporation).
(7) Weather resistance test Using a Super Xenon Weather Meter manufactured by Suga Test Instruments Co., Ltd., the molded plate was allowed to stand for 1000 hours under the conditions of 63 ° C. and a relative humidity of 50%, and the hue (YI ₁ ) of the molded plate was adjusted. The color difference (ΔYI = YI ₁ − YI ₀ ) was calculated by measuring with SE-2000 (C light source, viewing angle 2 °) manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS K7373.
(8) Monohydroxy compound content After dissolving 1.25 g of the resin composition in 7 mL of methylene chloride, acetone was added so that the total amount became 25 ml, and the reprecipitation treatment was performed. Then, the treated liquid was filtered through a 0.2 μm disposable filter and quantified by liquid chromatography.
(9) Total amount of nitrogen The total amount of nitrogen in the polycarbonate resin was measured using a TN-10 type trace nitrogen analyzer (chemiluminescence method) manufactured by Mitsubishi Chemical Corporation. In addition, N. D indicates less than 0.1 ppm.
(10) Total Metallicity Concentrated sulfuric acid and potassium hydrogensulfate were added to the polycarbonate resin, and the mixture was incinerated at 650 ° C. and then heat-melted. This was dissolved in dilute nitric acid to make it pure and constant, and then quantitative analysis of the metal component was performed by the ICP (high frequency plasma emission spectrometry) method. The measuring device used was Shimadzu ICPS-8000. The total amount of each metal amount was taken as the total metal amount. In addition, N. D indicates less than 0.1 ppm.

The abbreviations of the compounds used in the examples are as follows.
TMCB-1: 2,2,4,4-tetramethyl-1,3-cyclobutanediol, cis isomer ratio is 60% (manufactured by Wako Pure Chemical Industries, Ltd.)
TMCB-2: 2,2,4,4-tetramethyl-1,3-cyclobutanediol, cis isomer ratio is 45% (manufactured by Tokyo Chemical Industry)
DPC: Diphenyl carbonate TMC: 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylsichexane (manufactured by Honshu Chemical Industry Co., Ltd., trade name BP-TMC)
SBI: 6,6'-dihydroxy-3,3,3', 3'-tetramethylspirobiindane BPA: 2,2-bis (4-hydroxyphenyl) propane (manufactured by Mitsui Chemicals, trade name bisphenol A)
CHDM: 1,4-Cyclohexanedimethanol (manufactured by Tokyo Chemical Industry)
TCDDM: Tricyclodecanedimethanol (manufactured by Tokyo Chemical Industry)
HD: 1,6-Hexanediol (manufactured by Tokyo Chemical Industry)
ND: 1,9-nonanediol (manufactured by Tokyo Chemical Industry)
DDD: 1,12-dodecanediol (manufactured by Tokyo Chemical Industry)
TMAH: Tetramethylammonium hydroxide (manufactured by Tokyo Chemical Industry)

[Example 1]
TMCB-1 / TMC / DPC / CH ₃ COOLi (manufactured by Wako Pure Chemical Industries, Ltd.) / TMAH = 0.80 / 0.20 as a raw material in a polymerization reaction device equipped with a stirring blade and a reflux condenser controlled at 100 ° C. It was charged to have a ratio of /1.01 / 5.0 × 10 ^-6 / 5.0 × 10 ^-4 (molar ratio), and was sufficiently replaced with nitrogen so that the oxygen concentration was 0.001 vol% or less. Subsequently, heating was performed with a heat medium, stirring was started when the internal temperature reached 100 ° C., and the contents were uniformly melted while controlling the internal temperature to be 150 ° C. After that, the temperature was further raised and the internal temperature was adjusted to 240 ° C. in 120 minutes. During that time, the internal pressure of the reactor was controlled to be normal pressure (absolute pressure = 101 kPa, the same applies hereinafter). Then, the pressure was reduced to 13.3 kPa over 60 minutes, and then the internal pressure was maintained for 30 minutes. The phenol vapor produced as a by-product with the polymerization reaction is guided to a reflux condenser using steam controlled at 100 ° C. as the inlet temperature to the reflux condenser as a refrigerant, and a small amount of the monomer component contained in the phenol vapor is added to the polymerization reactor. Then, the non-condensed phenol vapor was recovered by guiding it to a condenser using hot water at 45 ° C. as a refrigerant.

The reactants thus oligomerized are once repressurized to atmospheric pressure and then transferred to another polymerization reactor equipped with a stirring blade and a similarly controlled reflux condenser to raise the temperature and reduce the pressure. The internal temperature was 240 ° C. and the pressure was 200 Pa in 60 minutes. After that, the internal temperature was adjusted to 260 ° C. and the pressure to 133 Pa or less over 30 minutes, and the pressure was restored when the predetermined stirring power was reached. Obtained. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.80 / 0.20 (molar ratio).

[Example 2]
As a raw material, TMCB-1 / TMC / DPC / CH ₃ COOLi / TMAH = 0.80 / 0.20 / 1.01 / 7.5 × ^10-5 / 1.5 × 10 ^-4 (molar ratio) The operation was carried out in the same manner as in Example 1 except that the preparation was changed to, and various evaluations were performed. The results are shown in Table 1. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.80 / 0.20 (molar ratio).

[Example 3]
As a raw material, TMCB-1 / TMC / DPC / CH ₃ COOLi / TMAH = 0.80 / 0.20 / 1.01 / 1.0 × 10 ^-4 / 3.0 × 10 ^-4 (molar ratio) The operation was carried out in the same manner as in Example 1 except that the preparation was changed to, and various evaluations were performed. The results are shown in Table 1. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.80 / 0.20 (molar ratio).

[Example 4]
Various evaluations were performed by operating in the same manner as in Example 2 except that CH ₃ COOLi was changed to CH ₃ COONa (manufactured by Wako Pure Chemical Industries, Ltd.). The results are shown in Table 1. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.80 / 0.20 (molar ratio).

[Example 5]
Various evaluations were performed by operating in the same manner as in Example 2 except that CH ₃ COOLi was changed to Ca [CH ₃ COO] ₂ (manufactured by Wako Pure Chemical Industries, Ltd.). The results are shown in Table 1. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.80 / 0.20 (molar ratio).

[Example 6]
Various evaluations were performed by operating in the same manner as in Example 2 except that CH ₃ COOLi was changed to Ba [CH ₃ COO] ₂ (manufactured by Wako Pure Chemical Industries, Ltd.). The results are shown in Table 1. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.80 / 0.20 (molar ratio).

[Example 7]
Various evaluations were performed by operating in the same manner as in Example 2 except that CH ₃ COOLi was changed to Mg [CH ₃ COO] ₂ (manufactured by Wako Pure Chemical Industries, Ltd.). The results are shown in Table 1. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.80 / 0.20 (molar ratio).

[Example 8]
Various evaluations were performed by operating in the same manner as in Example 2 except that CH ₃ COOLi was changed to Ca [CH ₃ (CH ₂ ) ₁₆ COO] ₂ (manufactured by Wako Pure Chemical Industries, Ltd.). The results are shown in Table 1. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.80 / 0.20 (molar ratio).

[Example 9]
Various evaluations were performed by operating in the same manner as in Example 2 except that CH ₃ COOLi was changed to Ba [CH ₃ (CH ₂ ) ₁₆ COO] ₂ (manufactured by Wako Pure Chemical Industries, Ltd.). The results are shown in Table 1. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.80 / 0.20 (molar ratio).

[Example 10]
Various evaluations were carried out in the same manner as in Example 3 except that the preparation was changed so that TMCB-2 / BPA / CHDM = 0.70 / 0.20 / 0.10 (molar ratio) as a raw material. The results are shown in Table 2. The composition ratio of the obtained polycarbonate resin was TMCB-2 / BPA / CHDM = 0.70 / 0.20 / 0.10 (molar ratio).

[Example 11]
Various evaluations were carried out by operating in the same manner as in Example 3 except that the preparation was changed so that TMCB-2 / TCDDM / = 0.90 / 0.10 (molar ratio) was used as the raw material. The results are shown in Table 2. The composition ratio of the obtained polycarbonate resin was TMCB-2 / TCDDM / = 0.90 / 0.10 (molar ratio).

[Example 12]
Various evaluations were carried out by operating in the same manner as in Example 3 except that the preparation was changed so that TMCB-2 / SBI / HD = 0.50 / 0.40 / 0.10 (molar ratio) as a raw material. The results are shown in Table 2. The composition ratio of the obtained polycarbonate resin was TMCB-2 / SBI / HD = 0.50 / 0.40 / 0.10 (molar ratio).

[Example 13]
Various evaluations were carried out by operating in the same manner as in Example 3 except that the preparation was changed so that TMCB-2 / SBI / ND = 0.42 / 0.50 / 0.08 (molar ratio) as a raw material. The results are shown in Table 2. The composition ratio of the obtained polycarbonate resin was TMCB-2 / SBI / ND = 0.42 / 0.50 / 0.08 (molar ratio).

[Example 14]
Various evaluations were performed by operating in the same manner as in Example 3 except that the preparation was changed so that TMCB-1 / SBI / CHDM = 0.30 / 0.50 / 0.20 (molar ratio) as a raw material. The results are shown in Table 2. The composition ratio of the obtained polycarbonate resin was TMCB-1 / SBI / CHDM = 0.30 / 0.50 / 0.20 (molar ratio).

[Example 15]
Various evaluations were carried out by operating in the same manner as in Example 3 except that the preparation was changed so that TMCB-1 / TMC / DDD = 0.50 / 0.43 / 0.07 (molar ratio) as a raw material. The results are shown in Table 2. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC / DDD = 0.50 / 0.43 / 0.07 (molar ratio).

[Example 16]
Various evaluations were carried out by operating in the same manner as in Example 3 except that the preparation was changed so that TMCB-1 = 1.00 (molar ratio) as a raw material. The results are shown in Table 2. The composition ratio of the obtained polycarbonate resin was TMCB-1 = 1.00 (molar ratio).

[Comparative Example 1]
The operation was carried out in the same manner as in Example 3 except that the preparation was changed so that TMCB-1 / TMC = 0.05 / 0.95 (molar ratio) as a raw material, but molding was not possible. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.05 / 0.95 (molar ratio).

[Comparative Example 2]
The operation was carried out in the same manner as in Example 1 except that the preparation was changed so that CH ₃ COOLi = 5.0 × 10 ^-4 (molar ratio) without using TMAH as a raw material, but the coloring of the polymer after polymerization was remarkable. there were. The results are shown in Table 3. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.80 / 0.20 (molar ratio).

[Comparative Example 3]
A moldable polymer could be obtained by the same operation as in Example 1 except that the preparation was changed so that CH ₃ COOLi = 1.0 × 10 ^-4 (molar ratio) was used without using TMAH as a raw material. There wasn't. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.80 / 0.20 (molar ratio).

[Comparative Example 4]
Same as Example 1 except that the preparation was changed so that the raw material was TMCB-1 / TMC / DPC / NaOH = 0.80 / 0.20 / 1.01 / 1.0 × 10 ^-4 (molar ratio). Various evaluations were carried out, but the coloring of the polymer after polymerization was remarkable. The results are shown in Table 3. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.80 / 0.20 (molar ratio).

[Comparative Example 5]
As a raw material, ^TMCB -1 / TMC / DPC / NaHCO ₃ / TMAH = 0.80 / 0.20 / 1.01 / 1.0 × 10 -4 / 3.0 × 10 ^-4 (molar ratio) The operation was carried out in the same manner as in Example 1 except that the preparation was changed, but a moldable polymer could not be obtained. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.80 / 0.20 (molar ratio).

[Comparative Example 6]
As a raw material, TMCB-1 / TMC / DPC / CH ₃ COOLi / TMAH = 0.80 / 0.20 / 1.01 / 1.0 × 10 ^-4 / 2.0 × 10 ^-3 (molar ratio) The operation was carried out in the same manner as in Example 1 except that the preparation was changed to, but the coloring of the polymer after the polymerization was remarkable. The results are shown in Table 3. The composition ratio of the obtained polycarbonate resin was TMCB-1 / TMC = 0.80 / 0.20 (molar ratio).

The polycarbonate resin of the present invention has excellent heat resistance, high transparency, and initial hue, suppresses yellowing during a weather resistance test, and is useful as a material for various molded products.

Claims (12)

An anion represented by the following formula (2) using a dihydroxy compound component containing 10 mol% or more of the dihydroxy compound represented by the following formula (1) and a carbonic acid diester represented by the following formula (3) as a polymerization catalyst. A method for producing a polycarbonate resin that reacts in the presence of a metal compound composed of a cation composed of a metal and a nitrogen-containing compound, and the metal compound is 1 × 10 with respect to all the dihydroxy compounds used for polymerization. A method for producing a polycarbonate resin, which comprises using ^-7 to 3 × 10 ^-4 mol equivalents and 1 × 10 ^-6 to 1 × 10 ^-3 mol equivalents of a nitrogen-containing compound.

(In the formula (1), R ₁ , R ₂ , R ₃ , and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and 3 carbon atoms. ~ 20 cycloalkyl groups, 6-20 carbon atoms cycloalkoxy groups, 6-10 carbon atoms aryl groups, 7-20 carbon atoms aralkyl groups, 6-10 carbon atoms aryloxy groups, carbon It represents an aralkyloxy group or a halogen atom having 7 to 20 atoms. The cyclobutane ring indicates a cis-trans isomer mixture, cis isomer alone or trans isomer alone.)

(In the formula ( ₂ ), R5 is an alkyl group, a cycloalkyl group, or an arylalkyl group having 1 to 22 carbon atoms which may be linear or branched.)

(In formula (3), R ₆ and R ₇ are independently substituted or unsubstituted aromatic groups, respectively.) The method for producing a polycarbonate resin according to claim 1, wherein R5 in the formula ( ₂ ) is a linear alkyl group having 1 to 22 carbon atoms. The invention according to any one of claims 1 to 2, wherein the cation made of a metal is at least one cation selected from the group consisting of the groups 1 and 2 of the long-periodic table. Method for manufacturing polycarbonate resin. The polycarbonate according to any one of claims 1 to 3, wherein the cation composed of a metal is at least one cation selected from the group consisting of lithium and Group 2 of the long-periodic table. Resin manufacturing method. The method for producing a polycarbonate resin according to any one of claims 1 to 4, wherein the nitrogen-containing compound is a quaternary ammonium salt. The method for producing a polycarbonate resin according to any one of claims 1 to 5, wherein the dihydroxy compound represented by the formula (1) is contained in an amount of 30 mol% or more. The invention according to any one of claims 1 to 6, wherein the dihydroxy compound represented by the formula (1) comprises a cis-trans isomer mixture and has a cis isomer ratio of 30 to 90%. Manufacturing method of polycarbonate resin. Claim 1 further comprises a dihydroxy compound represented by the following formula (4), and the total of the above formula (1) and the following formula (4) is 40 mol% or more in the total dihydroxy compound components. The method for producing a polycarbonate resin according to any one of 7 to 7.

(In equation (4), m indicates an integer of 2 to 12) The method for producing a polycarbonate resin according to any one of claims 1 to 8, wherein the polycarbonate resin has a viscosity average molecular weight of 10,000 to 50,000. The method for producing a polycarbonate resin according to any one of claims 1 to 9, wherein the glass transition temperature of the polycarbonate resin is 100 to 200 ° C. The method for producing a polycarbonate resin according to any one of claims 1 to 10, wherein the polycarbonate resin contains 1000 ppm or less of an aromatic monohydroxy compound. One of claims 1 to 11, wherein the polycarbonate resin has a terminal phenyl group derived from a carbonic acid diester represented by the above formula (3), and the terminal phenyl group concentration is 30 μeq / g or more. The method for producing a polycarbonate resin according to the above item.