JP2003327684A - Method for manufacturing aromatic-aliphatic copolymerized polycarbonate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transesterification-based method for continuously manufacturing an aromatic-aliphatic copolymerized polycarbonate having high transparency and an excellent color phase. <P>SOLUTION: The method comprises manufacturing an aromatic-aliphatic copolymerized polycarbonate by melt-polymerizing an aromatic carbonic diester, an aromatic polycarbonate oligomer and a dihydroxy compound having at least one alicyclic structure in the presence of one or more of alkali metal and alkaline earth metal compounds, and in the polymerization, the mixed liquid of raw materials consisting of the diester and the polycarbonate is fed separately from the dihydroxy compound to the first polymerization vessel to obtain the polycarbonate having the excellent color phase. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a continuous production method of an aromatic-aliphatic copolymerized polycarbonate resin excellent in hue and transparency by a transesterification method.

[0002]

2. Description of the Related Art Polycarbonates which are widely used in general are aromatic dihydroxy compounds such as 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as BPA) and phosgene in the presence of an acid binder. Manufactured by a method of interfacial polymerization or a method of melt polymerization of BPA and aromatic carbonic acid diester in the presence of an ester exchange catalyst,
Excellent mechanical properties such as impact resistance and excellent heat resistance,
Since it has transparency, it is used in various fields. As an optical material, it is used in various lenses, prisms, optical disk substrates, and the like. However, in a polycarbonate using only BPA as an aromatic dihydroxy compound, the photoelastic constant is large and the melt flowability is relatively poor, so that the birefringence of the molded product is large, and the refractive index is as high as 1.58. Since the Abbe number indicating the degree of dispersion is as low as 30, and the balance between the refractive index and the Abbe number is poor, there is a drawback that it does not have sufficient performance to be widely used for applications such as optical recording materials and optical lenses. is there. For the purpose of solving the above drawbacks of BPA-polycarbonate, BPA as an aromatic-aliphatic copolymerized polycarbonate obtained by copolymerizing an aliphatic compound and an aromatic compound is used.
A copolymerized polycarbonate of tricyclo (5.2.1.0 ^2,6 ) decane dimethanol (hereinafter referred to as TCDDM) has been proposed (Japanese Patent Laid-Open No. 64-66234). However, this method for producing a copolycarbonate is based on TCDD in which bischloroformate of BPA and TCDDM or TCDDM and BPA are polycondensed.
A method for polycondensing MPA bischloroformate with BPA or BPA and TCDDM, and a method for polycondensing BPA and / or TCDDM with a mixture of BPA bischloroformate and TCDDM bischloroformate is described. I'm just there. In the production of such a copolymer of an aliphatic dihydroxy compound and an aromatic dihydroxy compound, the production process is complicated by the two-step reaction of producing bischloroformate of the dihydroxy compound and then polycondensing with the dihydroxy compound. However, as a result, the manufacturing cost becomes high. on the other hand,
A transesterification method is known in which a carbonic acid diester and an aromatic dihydroxy compound are polycondensed in a molten state. In this manufacturing method, since the polymerization conditions are high temperature and long time, it is easily colored, and the catalyst remaining in the polymer causes the polymer properties to be deteriorated. Therefore, many patents have been filed to improve these properties. Has been done. However, in the polycarbonate containing an aliphatic structure, the tendency is remarkable because the heat resistance is slightly inferior to the aromatic polycarbonate, and it is particularly difficult to obtain an aromatic-aliphatic copolymerized polycarbonate having an excellent hue. there were. In addition, in the batch-type manufacturing method, when the produced polymer is withdrawn from the reaction kettle, the polymer is inevitably left in the kettle, resulting in poor yield.Furthermore, it is necessary to wash the kettle after withdrawing a large amount of waste. In order to produce by-products, it is necessary to establish a method for continuously producing a high-quality aromatic-aliphatic copolymerized polycarbonate with a good yield.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for continuously producing a transesterified aromatic-aliphatic copolymerized polycarbonate having high transparency and an excellent hue.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies in view of the above circumstances, the present inventors have found that aromatic-aliphatic compounds having an excellent hue by suppressing the formation of coloring components in a raw material storage tank. The inventors have found that a copolycarbonate can be obtained and completed the present invention.

That is, the present invention relates to an aromatic carbonic acid diester and an aromatic polycarbonate oligomer and at least one.
When an aromatic-aliphatic copolymerized polycarbonate is produced by melt-polymerizing a dihydroxy compound having a kind of alicyclic structure in the presence of an alkali metal compound and / or an alkaline earth metal compound catalyst, an aromatic carbonic acid diester is used. Provided is a method for producing an aromatic-aliphatic copolymerized polycarbonate having an excellent hue by separately supplying a mixed raw material liquid of an aromatic polycarbonate oligomer and at least one dihydroxy compound having an alicyclic structure to a first polymerization tank. To do.

In the continuous melt polymerization method as in the present invention, the first
A raw material storage tank is indispensable to stably supply the raw material to the polymerization tank. The dihydroxy compound having an alicyclic structure used in the present invention has a property that it is weakly thermally and easily colored, and an aromatic carbonic acid diester prepared by dissolving in a raw material preparation tank, an aromatic polycarbonate oligomer, and an alicyclic compound. When holding a mixture of dihydroxy compounds having a structure in a raw material storage tank, it is necessary to hold at a high temperature to prevent precipitation and the like, thereby producing a coloring component derived from a dihydroxy compound having an alicyclic structure, It was difficult to obtain an excellent aromatic-aliphatic copolymer polycarbonate.

To solve this problem, a raw material storage tank for holding a dihydroxy compound having an alicyclic structure at a temperature that can suppress the formation of coloring components while maintaining fluidity with low viscosity, and an aromatic carbonic acid diester A raw material storage tank for holding a mixed solution of an aromatic polycarbonate oligomer at a temperature at which precipitation or the like does not occur is separately supplied to the first polymerization tank to produce an aromatic-aliphatic copolymerized polycarbonate having excellent hue. It has become possible. When two or more kinds of dihydroxy compounds having an alicyclic structure are used as raw materials, it is necessary to appropriately determine the number of storage tanks in consideration of thermal stability, fluidity of each compound and compatibility when mixing. It is valid.

In the present invention, the mixed liquid of the aromatic carbonic acid diester and the aromatic polycarbonate oligomer forms a coloring component when kept at a high temperature for a long time. Therefore, the aromatic monohydroxy compound is contained in an amount of 1 to 50% by weight, preferably 5 to 40%.
By containing it in an amount of wt%, it is effective for producing an aromatic-aliphatic copolymerized polycarbonate which can be maintained at a temperature at which it is possible to suppress the formation of a coloring component without being precipitated and which has an excellent hue. When the content of the aromatic monohydroxy compound is 1% by weight or less, the content of the aromatic monohydroxy compound cannot be lowered to a temperature at which generation of the coloring component can be suppressed without precipitation, and 50
When the content is more than 10% by weight, the amount of the aromatic monohydroxy compound distilled out of the system in the first polymerization tank is large, so that the capacity of the apparatus and the like must be increased, which is not efficient. It is not preferable because it causes coloring.

The aromatic monohydroxy compound is preferably an aromatic monohydroxy compound produced as a by-product when an aromatic carbonic acid diester is reacted with an aromatic dihydroxy compound, and particularly preferably phenol. The holding temperature in the raw material storage tank is appropriately selected depending on the types of the aromatic carbonic acid diester and the aromatic polycarbonate oligomer.
The temperature is 160 ° C, preferably 50 ° C to 150 ° C.

The method for producing the aromatic polycarbonate oligomer used in the present invention is not limited, and examples thereof include an interfacial polymerization method using an aromatic dihydroxy compound and phosgene, or a melt polymerization method using an aromatic carbonic acid diester and an aromatic dihydroxy compound. To be

When the aromatic polycarbonate oligomer and the aromatic carbonic acid diester are dissolved and prepared in the raw material preparation tank, the method is not particularly limited, but each is charged in the form of powder, or charged in a liquid or molten state. Although there are methods, aromatic carbonate diester held in an inert gas atmosphere without being solidified in a molten state through a purification step such as distillation is sent to a raw material preparation tank in a molten state, and an aroma such as powder It is preferred to mix the group polycarbonate oligomer. At this time, an aromatic monohydroxy compound is preferably added at the same time, which is preferable because the dissolution time can be shortened. In addition, it is effective to prevent coloring that the raw material is prepared in an inert gas atmosphere in which oxygen substantially does not exist. The aromatic polycarbonate oligomer used in the present invention is preferably a 10-mer or less, and if it is more than 10%, the dissolution preparation temperature and the holding temperature in the storage tank are set to be high in order to decrease the dissolution rate and increase the melt viscosity. It is indispensable and is not preferable because it causes the formation of coloring substances.

When the aromatic polycarbonate oligomer is produced by the melting method, the aromatic polycarbonate oligomer produced as described above may be dissolved and prepared, but it is solidified even once in an inert gas atmosphere substantially free of oxygen. It is preferable to use it in the molten state without using it because the process can be simplified and the number of processes that may come into contact with oxygen which causes coloring is reduced. As a catalyst used for producing an aromatic polycarbonate oligomer, an alkali metal compound, and /
Alternatively, an alkaline earth metal compound is used. The amount of the catalyst is 1 × 10 ⁻⁸ to 1 with respect to 1 mol of the total amount of the constituent unit derived from the aromatic dihydroxy compound and the constituent unit derived from the dihydroxy compound having an alicyclic structure in the aromatic-aliphatic copolymerized polycarbonate. × 10 ^-4 mol and further 1 × 10
^-7 to 1 × 10 ^-5 mol is preferably used, and by leaving the catalyst contained, it is not necessary to add a catalyst in the polycondensation step with the dihydroxy compound having an alicyclic structure, Can be simplified. When the amount of the catalyst is less than the above range, the activity is low in the polycondensation step with the dihydroxy compound having an alicyclic structure and the desired molecular weight cannot be obtained. Therefore, a catalyst must be added, which is not suitable. On the other hand, if the amount is larger than the above range, the thermal stability of the polymer produced is lowered, which is not preferable.

Further, it is preferable to add an antioxidant during the production of the aromatic polycarbonate oligomer within a range not impairing the activity of the catalyst, and it is effective for preventing the coloring in the raw material storage tank and the polycondensation step during the production of the aromatic polycarbonate oligomer. Target. As the antioxidant, for example,
Pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5)
-Di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, triethylene glycol-bis [3- (3-t-butyl-)
5-Methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t-butyl-4]
-Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-
Tetraoxaspiro [5,5] undecane, 1,1,3
-Tris [2-methyl-4- (3,5-di-t-butyl-4-hydroxyphenylpropionyloxy) -5-
hindered phenolic compounds such as t-butylphenyl] butane, and 5,7-di-t-butyl-3- (3,4
-Di-methylphenyl) -3H-benzofuran-2-one. These may be used alone or in combination of two or more. Among these, especially 5,7-di-t-
Butyl-3- (3,4-di-methylphenyl) -3H-
Benzofuran-2-one is preferred. As the addition amount,
10 ppm to 1000 ppm, further 50 ppm to 5
00 ppm is preferable, and if it is less than this range, the effect cannot be obtained, and if it is more than this range, the activity of the catalyst is impaired and it is not suitable.

The amount of the aromatic carbonic acid diester used in the production of the aromatic polycarbonate oligomer is not particularly limited as long as it is an amount sufficient to produce the aromatic polycarbonate oligomer. 0.97 to 1.2, more preferably 0.99 to 1.1, based on the total amount of the structural unit derived from the group dihydroxy compound and the structural unit derived from the dihydroxy compound having an alicyclic structure.
It is preferable to use an amount that results in a molar ratio of 0, and even if it exceeds this range, an aromatic-aliphatic copolymerized polycarbonate having at least a desired molecular weight cannot be obtained. In many cases, a step of removing excess DPC must be provided, which is not suitable.

[0015] As described above, the aromatic compound is aromatic so that the molar ratio of the constitutional unit derived from the aromatic dihydroxy compound to the constitutional unit derived from the dihydroxy compound having an alicyclic structure in the desired aromatic-aliphatic copolycarbonate to be produced. The production of the group polycarbonate oligomer is preferably carried out at the optimum catalyst amount and the mixing ratio of the aromatic carbonic acid diester and the aromatic dihydroxy compound for the production of the aromatic-aliphatic copolymerized polycarbonate because the production process can be simplified. Further, in the production of the aromatic polycarbonate oligomer, since the aromatic monohydroxy compound is by-produced by reacting the aromatic carbonic acid diester and the aromatic dihydroxy compound,
There is no need to add an aromatic monohydroxy compound. The polymerization degree of the aromatic polycarbonate oligomer is preferably a trimer or less as a main component, and in order to further increase the polymerization degree, the aromatic monohydroxy compound by-produced under reduced pressure is discharged out of the system. It is necessary, and the content of the aromatic monohydroxy compound decreases, which is not preferable. Therefore, the production of the aromatic polycarbonate oligomer is carried out under an atmospheric pressure inert gas atmosphere without discharging the by-produced aromatic monohydroxy compound etc. out of the system, so that the polymerization degree of the aromatic polycarbonate oligomer is a trimer. It is suitable to control the following to be the main components, and after the reaction is complete, cool to the holding temperature of the raw material storage tank, and then send the entire amount to the raw material storage tank. At this time, a small amount of unreacted aromatic dihydroxy compound may be contained. The degree of polymerization of the aromatic polycarbonate oligomer is the number of bonds of the aromatic dihydroxy compound, and, for example, a trimer is one in which three aromatic dihydroxy compounds are carbonate-bonded.

The aromatic carbonic acid diester used in the present invention is a compound represented by the following general formula (II).

[0017]

[Chemical 2] (In the formula, Ar is a monovalent aromatic group, and Ar may be the same or different.)

The aromatic carbonic acid diester represented by the above general formula (II) is, for example, diphenyl carbonate, ditolyl carbonate, dixylyl carbonate, bispropylphenyl carbonate, bisoctylphenyl carbonate, bisnonylphenyl carbonate or bismethoxyphenyl. Carbonates, substituted diphenyl carbonates such as bisethoxyphenyl carbonate and the like are exemplified, but diphenyl carbonate is particularly preferable, and organic impurities such as different structures are preferably 1000 ppm or less, more preferably 100 ppm or less,
With respect to metal impurities such as chlorine and Fe, it is preferable to use a high-purity aromatic carbonic acid diester of 10 ppm or less, more preferably 1 ppm or less.

Examples of the dihydroxy compound having an alicyclic structure used in the reaction of the present invention include tricyclo (5.2.1.0 ^2,6 ) decane dimethanol, β, β,
β ′, β′-tetramethyl-2,4,8,10-tetraoxaspiro [5,5] undecane-3,9-diethanol (spiroglycol), pentacyclo [9.2.1.
1 ^3,9 . 0 ^2,10 . 0 ^4,8 ] Pentadecane dimethanol, pentacyclo [9.2.1.1 ^4,7 . 0 ^2,10 . 0 ^3,8 ] Pentadecane dimethanol, 2,6-decalin dimethanol or 1,4-cyclohexane dimethanol. Among these, especially tricyclo (5.2.
1.0 ^2,6 ) Decanedimethanol (hereinafter referred to as TCDDM) is preferable.

As the dihydroxy compound having an alicyclic structure, those having a carbonyl group content contained as impurities of 1.0 mg / g or less in terms of KOH, preferably 0.5 mg, more preferably 0.1 mg or less are used. To be Organic impurities such as heterogeneous structures are preferably 1000 ppm or less, and more preferably 100 ppm or less.
It is also preferable to use a dihydroxy compound having a high-purity alicyclic structure of 10 ppm or less, and further 1 ppm or less for each of the metal impurities. .

The aromatic dihydroxy compound used for producing the aromatic polycarbonate oligomer of the present invention is a compound represented by the following general formula (III).

[0022]

[Chemical 3] (In the above formula (III), X is

[0023]

[Chemical 4] Where R ₃ and R ₄ are hydrogen atoms or have 1 carbon atom.
Is an alkyl group or a phenyl group represented by R 10 and R ₃ and R ₄ may combine to form a ring. R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or halogen, and R ₁
And R ₂ may be the same or different. Also, m and n
Represents the number of substituents and is an integer of 0-4. )

Examples of the aromatic dihydroxy compound represented by the above general formula (III) include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis ( 4-hydroxy-3
-Methylphenyl) propane, 2,2-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-
Bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1 -Bisphenols such as bis (4-hydroxyphenyl) cyclohexane; 4,
4'-dihydroxydibiphenyl, 3,3 ', 5,5'
-Biphenols such as tetramethyl-4,4'-dihydroxybiphenyl; bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) Examples include ether and bis (4-hydroxyphenyl) ketone. Of these, particularly 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as BPA) 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter referred to as BPZ)
Is preferred. Further, two or more kinds of aromatic dihydroxy compounds represented by the formula (III) can be used in combination. When these are used, organic impurities such as heterogeneous structures are preferably 1000 ppm or less, more preferably 100 ppm or less, and metal impurities such as chlorine and Fe are also 10 ppm or less, further 1 ppm or less of high-purity aromatics. Preference is given to using dihydroxy compounds.

In the present invention, an alkali metal compound or an alkaline earth metal compound is used as a catalyst.

As such compounds, organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkali metals and alkaline earth metals are preferably used, and these compounds may be used alone or in combination. Can be used.

As such an alkali metal compound,
For example, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, Potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, Examples include dilithium hydrogen phosphate, disodium phenylphosphate, bisphenol A disodium salt, 2 potassium salt, 2 cesium salt, 2 lithium salt, phenol sodium salt, potassium salt, cesium salt and lithium salt. It is.

Further, as the alkaline earth metal compound,
For example, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate,
Examples thereof include barium hydrogen carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenyl phosphate and the like.

These catalysts are used in an amount of 1 × 10 5 with respect to 1 mol of the total amount of the constituent unit derived from the aromatic dihydroxy compound of the aromatic-aliphatic copolymerized polycarbonate and the constituent unit derived from the dihydroxy compound having an alicyclic structure. ^-8 to 1 x 10
^-4 mol, more preferably 1 × 10 ^-7 to 1 × 10 ^-5 mol, added during the production of the aromatic polycarbonate oligomer, in the first polymerization tank, or in both divided portions.

Aromatic having an alicyclic structure in the present invention
The aliphatic copolycarbonate has a property that it is weak in heat and easily colored as compared with generally commercially available aromatic polycarbonate, and the extrusion process from the introduction of the resin into the extruder to the pelletization It is effective to control the maximum temperature of the resin within 280 ° C or lower, preferably 270 ° C or lower, and more preferably 260 ° C or lower,
If the temperature is higher than this temperature, the molecular weight is lowered and the hue is deteriorated, which is not suitable. Further, the average residence time in the extrusion step is 10 minutes or less, preferably 8 minutes or less, more preferably 5 minutes or less. If it is longer than this, the hue is deteriorated and the mechanical properties are deteriorated due to the decrease of the molecular weight, which is not suitable.

When a polymer filter is used in the present invention, it is effective to install a gear pump between the extruder and the polymer filter. The aromatic-aliphatic copolycarbonate having an alicyclic structure controls the maximum temperature at 280 ° C or lower as described above, so that the viscosity of the resin is high and the resin pressure in the polymer filter is high, so venting up and discharging of the resin Problems such as unstable quantity occur. The installation of the gear pump stabilizes the discharge amount and solves these problems.

The temperature of the extruder and gear pump is 180 ° C to 2
50 ° C., preferably 190 ° C. to 220 ° C., and the temperature of the polymer filter is controlled to be 240 ° C. or higher and 265 ° C. or lower, preferably 245 ° C. or higher and 260 ° C. or lower.
Usually, the molten resin is introduced into the extruder at a temperature of 240 ° C to 260 ° C, and the resin temperature rises due to shearing heat generated by rotation of the extruder screw, rotation of the gear of the gear pump, passage of the filter disk of the polymer filter, etc. Therefore, it is preferable to control the extruder, the gear pump, and the polymer filter at a temperature lower than the resin temperature. If the temperature is higher than the above temperature, the resin temperature becomes higher and problems such as a decrease in molecular weight and deterioration of hue occur. As a result, the resin pressure becomes high and the filter disc is broken, or the load on the gear pump and the motor of the extruder becomes large, which is not suitable.

Also, when the temperature of the extruder, gear pump, polymer filter is raised, especially when the resin remains, or when the resin is left to cool, the so-called “burn” (insoluble foreign matter colored brown) is prevented from occurring. Therefore, it is desirable to perform it in a nitrogen atmosphere.

Regeneration and cleaning of the filter disk of the polymer filter may be carried out by a method similar to that generally used for polycarbonate, and if necessary, passivation treatment,
Alternatively, washing with an organic compound such as phenol or diphenyl carbonate is also effective.

Examples of the catalyst deactivator include phosphoric acid,
Phosphorous acid, hypophosphorous acid, phenylphosphoric acid, phenylphosphine, phenylphosphinic acid, phenylphosphonic acid,
Diphenyl phosphate, diphenyl phosphite, diphenyl phosphine, diphenyl phosphine oxide,
Diphenylphosphinic acid, monomethyl acid phosphate, monomethyl acid phosphite, dimethyl acid phosphate, dimethyl acid phosphite, monobutyl acid phosphate, monobutyl acid phosphite, dibutyl acid phosphate, dibutyl acid phosphite, monostearyl acid phosphate, distearyl acid Phosphorus-containing acidic compounds such as phosphate, p-toluenesulfonic acid, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, p
-Propyl toluenesulfonate, butyl p-toluenesulfonate, pentyl p-toluenesulfonate, hexyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate, phenethyl p-toluenesulfonate, p- Aromatic sulfonic acid compounds such as naphthyl toluene sulfonate may be mentioned. Particularly, phosphorous acid, diphenyl phosphite, and butyl p-toluenesulfonate are preferable. These deactivators may be used alone or in combination of two or more.

The amount of the phosphorus-containing acidic compound and aromatic sulfonic acid compound added is 1/5 of the neutralization equivalent to the alkali metal compound and / or alkaline earth metal compound catalyst.
The amount is up to 20 times, preferably 1/2 to 10 times, and if it is less than this, the desired effect cannot be obtained, and if it is excessive, heat resistance and mechanical properties are deteriorated, which is not suitable.

Aromatic sulfonic acid phosphonium salts can also be used preferably, for example, benzenesulfonic acid tetrabutylphosphonium salt, p-toluenesulfonic acid tetrabutylphosphonium salt, butylbenzenesulfonic acid tetrabutylphosphonium salt, octylbenzene. Examples thereof include sulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetramethylphosphonium salt, dodecylbenzenesulfonic acid tetraethylphosphonium salt and dodecylbenzenesulfonic acid tetrahexylphosphonium salt.

The amount of the phosphonium salt of aromatic sulfonic acid added is 1 to 300 ppm, preferably 10 to 100 ppm, based on the aromatic-aliphatic copolymerized polycarbonate, and if it is less than this, the desired effect cannot be obtained. If the amount is excessive, heat resistance and mechanical properties are deteriorated, which is not suitable.

In the present invention, it is desirable to add various known additives to the aromatic-aliphatic copolymerized polycarbonate together with the above-mentioned specific compound, depending on the purpose, within the range in which the physical properties thereof are not impaired.

Examples of the antioxidant include triphenyl phosphite, tris (4-methylphenyl) phosphite, tris (4-t-butylphenyl) phosphite, tris (monononylphenyl) phosphite, tris (2 -Methyl-4-ethylphenyl) phosphite,
Tris (2-methyl-4-t-butylphenyl) phosphite, Tris (2,4-di-t-butylphenyl) phosphite, Tris (2,6-di-t-butylphenyl) phosphite, Tris (2,4-di-t-butyl-
5-methylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, bis (monononylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di -Phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-
Phosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butyl-5-methylphenyl) pentaerythritol-di-phosphite 2,2-methylenebis (4,6-dimethylphenyl) octylphosphite, 2,2-methylenebis (4-t-butyl-6-)
Methylphenyl) octylphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, 2,2-methylenebis (4,6-dimethylphenyl) hexylphosphite, 2,2-methylenebis Phosphite compounds such as (4,6-di-t-butylphenyl) hexylphosphite and 2,2-methylenebis (4,6-di-t-butylphenyl) stearylphosphite, pentaerythritol-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, triethylene glycol-bis [3- (3-
t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t-
Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4
8,10-tetraoxaspiro [5,5] undecane,
1,1,3-Tris [2-methyl-4- (3,5-di-
Examples thereof include hindered phenolic compounds such as t-butyl-4-hydroxyphenylpropionyloxy) -5-t-butylphenyl] butane. These may be used alone or in combination of two or more.

The amount of these antioxidants added is aromatic
0.005-0.1 part by weight, preferably 0.01-
0.08 parts by weight, more preferably 0.01 to 0.0
The amount is 5% by weight, and if it is less than this range, the desired effect cannot be obtained, and if it is excessive, heat resistance and mechanical properties are deteriorated, which is not suitable.

As the ultraviolet absorber, for example, 2- (5
-Methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t- Butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-
5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2)
-Hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole ,
2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]], 2- (4,6-diphenyl-1) , 3,5-Triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2,4-dihydroxobenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxy −
2'-carboxybenzophenone, dimethyl succinate-
1- (2-hydroxyethyl) -4-hydroxy-2,
2,6,6-tetramethylpiperidine polycondensate, bis (1-octyloxy-2,2,6,6, -tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6)
6, -tetramethyl-4-piperidyl) sebacate and the like can be mentioned, but especially 2,2′-methylenebis [4-
(1,1,3,3-tetramethylbutyl) -6- (2H
-Benzotriazol-2-yl) phenol]] is preferably used. These may be used alone or in combination of two or more kinds, and it is preferable to use those having a small amount of organic impurities and metal impurities and high purity.

As the release agent, those which are generally used may be used, for example, natural and synthetic paraffins, silicone oils, polyethylene waxes, beeswax, stearic acid monoglyceride, palmitic acid monoglyceride, pentaerythritol tetrastearate. And fatty acid esters such as stearic acid monoglyceride,
Palmitic acid monoglyceride and pentaerythritol tetrastearate are preferred. These may be used alone or in combination of two or more.

Other flame retardants, antistatic agents, pigments, dyes, etc. can be used alone or in combination as required. Further, the addition timing, addition method, and addition form are not particularly limited, but it is preferable to add at the same time as the catalyst deactivator or after the catalyst deactivator is added.

There is no restriction on the timing of addition of these catalyst deactivators, additives, etc. to the aromatic-aliphatic copolymerized polycarbonate, for example, a method of adding them while the resin is in a molten state after the completion of the polycondensation reaction, Alternatively, a method in which the pellets are once cooled and pelletized and then remelted and mixed is used. The addition method is also not limited, and examples thereof include a method of directly charging and mixing in a polymerization vessel, and a method of kneading using a single-screw or twin-screw extruder. Examples of the form of addition include, but are not particularly limited to, a method of adding as it is without dilution, a method of diluting in a soluble solvent and adding, and a method of adding in the form of a masterbatch.

After deactivating the catalyst, a step of removing the low boiling point compound in the polymer by degassing under reduced pressure at a temperature of 200 to 280 ° C. may be provided. For this purpose, paddle blades, lattice blades, spectacle blades, etc. A horizontal stirrer equipped with a stirring blade having an excellent surface renewal property, a multi-vent type twin-screw extruder, or a thin film evaporator is preferably used, and it is usually effective to carry out at 2666 Pa or less.

Ion-exchanged water or distilled water is preferably used as the cooling water for pelletizing, and cooling is usually performed at a temperature of 20 ° C to 80 ° C.

In the optical aromatic-aliphatic copolymer polycarbonate of the present invention, the molar ratio of the structural unit (A) derived from the aromatic dihydroxy compound to the structural unit (B) derived from the alicyclic aliphatic dihydroxy compound (A) ) / (B) is 90
It is preferably / 10 to 10/90, more preferably 80/20 to 20/80. That is,
If the molar ratio (A) / (B) of this structural unit is lower than 10/90, the heat resistance becomes poor, and if it is higher than 90/10, the photoelastic constant, water absorption rate, etc. increase, and the refractive index and Abbe number are further increased. Is unfavorable as an optical material.

When the resin of the present invention is used for optical applications, it is desirable to manufacture it in an environment such as a clean room or a clean booth in order to prevent foreign matter from entering the product. Further, in that case, it is effective to install a filter for raw material, install a filter for cooling water used at the time of pelletizing, or install a polymer filter at the exit of the extruder to prevent foreign matter from entering, and have a low viscosity. A raw material filter for filtering a fluid or a filter for cooling water is preferably 1 μm or less, more preferably 0.6 μm or less, and a polymer filter for filtering a resin having high viscosity is 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less. To be In addition, two or more raw material filters are installed in parallel so that the raw materials can be stably supplied by allowing the raw material filters to be switched quickly when the processing capacity is lowered due to clogging or the like.

The amount of foreign matter contained in the optical aromatic-aliphatic copolymerized polycarbonate is 1 / kg or less for 50 μm or more and 10 / g or less for 10 μm or more, preferably 5 / g. 1 to 5 to 10 μm
00 pieces / g or less, preferably 50 pieces / g or less, more preferably 10 pieces / g or less, 1 to 5 μm is 3000
1 / g or less, preferably 1000 / g or less, more preferably 300 / g or less, 0.5 to 1 μm
It is desirable that the number is 00000 pieces / g or less, preferably 50,000 pieces / g or less, and more preferably 30,000 pieces / g or less.

The weight average molecular weight of the aromatic-aliphatic copolymer polycarbonate used in the present invention is 30,000 to 2
It is preferably 0,000, more preferably 50,000 to 120,000.

It is also possible to add other thermoplastic resins such as aromatic polycarbonate, polyethylene terephthalate and acrylic resin, if necessary. Aromatic polycarbonates are particularly effective because they can improve mechanical properties while maintaining high transparency and good hue.

The transesterification reaction relating to the present invention can be carried out by a known melt polycondensation method. That is, the melt polycondensation is carried out using the above-mentioned raw materials and catalyst while removing the by-product by transesterification under heating under normal pressure or reduced pressure. The reaction is generally carried out in two or more stages.

Specifically, the reaction in the first step is 120 to 2
The reaction is carried out at a temperature of 60 ° C., preferably 180 to 240 ° C. for 0 to 5 hours, preferably 0.5 to 3 hours. Next, the reaction temperature is raised while raising the degree of vacuum of the reaction system to cause the reaction between the aromatic polycarbonate oligomer, the aliphatic dihydroxy compound and the aromatic carbonic acid diester, and finally 133
The polycondensation reaction is performed at a temperature of 200 to 300 ° C. under a reduced pressure of Pa or less. As a reaction apparatus used for carrying out the above reaction, a tank type, an extruder type, or a horizontal stirring apparatus having stirring blades having excellent surface renewal property such as paddle blades, lattice blades, and eyeglass blades is used. The liquid contact surface of the device used and the material of the pipe are SUS-304, SUS-316, SUS-
It is preferable to use stainless steel such as 316L or SUS-310S whose surface is in contact with liquid such as buffing, electropolishing or complex electropolishing, or Hastelloy, nickel, chromium, cobalt or the like.

[0055]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

(1) Weight average molecular weight (Mw) GPC (Shodex GPC system 21)
H) was used to measure the polystyrene reduced molecular weight (weight average molecular weight: Mw). Chloroform was used as the developing solvent. (2) Solution hue (YI value) 9.0 g of the sample was dissolved in 90 ml of methylene chloride, and then 5.
The YI value (yellow index) was measured using a 0 cm quartz glass cell. As a color difference meter, a spectrocolor meter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. was used.

Example 1 In a nitrogen gas atmosphere in which oxygen is substantially absent at normal pressure, 1
Diphenyl carbonate (hereinafter referred to as DPC) 25 kept at 130 ° C. in a raw material preparation tank kept at 65 ° C.
Aromatic polycarbonate oligomer (hereinafter referred to as PC oligomer) 187 containing heptamer as a main component produced by an interface method in which 9.8 kg was sent to a raw material preparation tank and nitrogen substitution was performed in a hopper. .1 kg,
And 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one (HP-1
36; Ciba Specialty Chemicals) (46.6 g) was dissolved and mixed, and 120.5 kg of phenol (phenol content in the raw material preparation liquid: 21.2% by weight) held at 45 ° C. in a nitrogen atmosphere was fed. After stirring for 30 minutes, the temperature of the raw material preparation tank was cooled to 150 ° C., and then the solution was transferred to the first raw material storage tank kept at 150 ° C. In a nitrogen gas atmosphere in which oxygen substantially does not exist, the first vertical stirring polymerization tank (reaction conditions: 13329 Pa, 205 ° C., stirring speed 160 rp)
In m), a mixed raw material solution prepared by dissolving and preparing DPC and PC oligomer is prepared so that the molar ratio of the BPA-derived structural unit and the TCDDM-derived structural unit of the aromatic-aliphatic copolymer polycarbonate to be produced is 40:60. From the first raw material storage tank, through a SUS316L sintered filter of 0.6 μm, at a flow rate of 42.5 kg / h, at the same time TCDDM at 80 ° C.
Was continuously supplied to the first polymerization tank at a flow rate of 16.5 kg / h from the second raw material storage tank held by the above through a 0.2 μm Teflon (registered trademark) filter, and hydrogen carbonate was used as a catalyst. An aqueous solution of 2.8072 g of sodium dissolved in 18.0 kg of pure water was flowed at a flow rate of 150 g / h (a structural unit derived from BPA of an aromatic-aliphatic copolymerized polycarbonate and TCD).
2 × 10 with respect to 1 mol of the total amount of the constitutional unit derived from DM
^-6 mol) is continuously supplied to the first polymerization tank, and the valve opening degree provided in the polymer discharge line at the bottom of the tank is controlled so that the average residence time in the first polymerization tank is 60 minutes. The liquid level was kept constant. The polymerization liquid (prepolymer) discharged from the bottom of the tank is successively passed to the second, third, and fourth vertical polymerization tanks and the fifth horizontal polymerization tank (Hitachi lattice blade polymerization machine (trade name)). Supplied continuously. The liquid level was controlled so that the average residence time was 60 minutes for each of the second to fourth vertical polymerization tanks and 90 minutes for the fifth horizontal polymerization tank, and at the same time, by-produced phenol was distilled off. . The polymerization conditions of each of the second to fifth polymerization tanks are the second polymerization tank (220 ° C.,
1999 Pa, stirring speed 160 rpm), 3rd polymerization tank (2
30 degreeC, 40 Pa, stirring speed 60 rpm), 4th polymerization tank (240 degreeC, 40 Pa, stirring speed 20 rpm), and 5th horizontal type polymerization tank (245 degreeC, 40 Pa, stirring speed 5 rpm) were used. The polymer discharged from the fifth horizontal polymerization tank was continuously introduced in a molten state into a 3-vent type twin-screw extruder (46 mm twin-screw extruder manufactured by Kobe Steel), in front of the vent port closest to the resin supply port. The additives described below are supplied in the form of a masterbatch at a ratio of 2 wt% with respect to the resin by a side feed compactor (manufactured by Kobe Steel), and after devolatilization at each vent, a gear pump (manufactured by Kobe Steel), a polymer filter ( Water-cooled pellets were made through Nippon Pall: filtration accuracy 5 μm). The obtained polymer had a weight average molecular weight (Mw) of 61,000 and a solution hue (YI value) of 0.8 to 0.9.

The composition of the masterbatch is Iupilon S-
Based on flakes of 3000 (Mitsubishi Gas Chemical Co., Ltd.), butyl p-toluenesulfonate (Tokyo Kasei Kogyo; hereinafter pTSB) was added 9 times the neutralization equivalent of sodium hydrogen carbonate [18 μmol / mol (based on the total molar amount of the BPA-derived structural unit and the TCDDM-derived structural unit of the aromatic-aliphatic copolymerized polycarbonate)], and the aromatic-aliphatic copolymerized polycarbonate 1
Bis (2,6-di-t-butyl-
4-methylphenyl) pentaerythritol-di-phosphite (PEP-36 manufactured by Asahi Denka Kogyo) is 400 ppm,
5,7-Di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one (HP-13
6; 100 ppm of Ciba Specialty Chemicals),
Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Asahi Denka Kogyo A
O-50) 1000 ppm, pentaerythritol tetrastearate (NOF Corporation) 300 ppm, 2,2 '
-Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]] (LA-31 manufactured by Asahi Denka Co., Ltd.) is 1
000ppm, toning agent (Diamond Resin Blue-G manufactured by Mitsubishi Chemical)
Was adjusted to 0.3 ppm.

Example 2 In a nitrogen gas atmosphere in which oxygen is substantially absent at normal pressure, 1
In a reaction tank kept at 55 ° C, D kept at 130 ° C
After sending 401.3 kg of PC to the first reaction tank, 200.5 kg of BPZ nitrogen-substituted in the hopper, 0.313 g of sodium hydrogen carbonate as a catalyst (a structural unit derived from BPZ of aromatic-aliphatic copolymerized polycarbonate and TCD).
2 × 10 with respect to 1 mol of the total amount of the constitutional unit derived from DM
^-6 mol), and 5,7-di-t-butyl-3- (3,3
4-dimethylphenyl) -3H-benzofuran-2-one (HP-136; manufactured by Ciba Specialty Chemicals)
46.6 g was dissolved and mixed while stirring and reacted for 2 hours. After completion of the reaction, the temperature of the first reaction tank was cooled to 130 ° C., and then the entire amount was transferred to the first raw material storage tank kept at 130 ° C. The resulting oligomer has 2 units of BPZ
The main components were the monomers and the following, and the phenol content was 19.7 parts by weight. The aromatics produced in a first vertical stirring polymerization tank (hereinafter referred to as the first polymerization tank, reaction conditions of the first polymerization tank: 13329 Pa, 205 ° C., stirring speed 160 rpm) in a nitrogen gas atmosphere in which oxygen substantially does not exist. -DPC so that the molar ratio of the constitutional unit derived from BPZ and the constitutional unit derived from TCDDM of the aliphatic copolycarbonate is 40:60.
The mixed raw material liquid of oligomer and oligomer is 0.6 from the first raw material storage tank.
45 .mu.m through a SUS316L sintered filter.
It was continuously supplied to the first polymerization tank at a flow rate of 1 kg / h, and at the same time, TCDDM was fed from a second raw material storage tank held at 80 ° C through a 0.2 μm Teflon filter to
It was continuously fed at a flow rate of 6.5 kg / h. Hereinafter, the same procedure as in Example 1 was carried out except that the catalyst was not supplied to the first polymerization tank. The weight average molecular weight (Mw) of the obtained polymer was 6
3000, the solution hue (YI value) was 0.9 to 1.0.

Comparative Example 1 In a nitrogen gas atmosphere in which oxygen is substantially absent at normal pressure, 1
To the raw material preparation tank kept at 55 ° C., 401.3 kg of DPC kept at 130 ° C. was sent to the raw material preparation tank, 80
After sending 220.0 kg of TCDDM kept at ℃ to a raw material preparation tank, BPZ20 was replaced with nitrogen by a hopper.
0.5 kg, 0.313 sodium hydrogen carbonate as a catalyst
g (2 × 10 4 for 1 mol of the total amount of BPZ and TCDDM)
^-6 mol), and 5,7-di-t-butyl-3- (3,3
4-dimethylphenyl) -3H-benzofuran-2-one (HP-136; manufactured by Ciba Specialty Chemicals)
46.6 g was dissolved and mixed with stirring, and after 1 hour, the temperature of the raw material preparation tank was cooled to 130 ° C., and then the entire amount was transferred to the raw material storage tank held at 130 ° C. The first vertical stirring polymerization tank (reaction condition: 13329 Pa, 205 ° C., stirring speed 160 rpm) in a nitrogen gas atmosphere in which oxygen substantially does not exist.
Further, polymerization was carried out by continuously supplying from the raw material storage tank through a 0.6 μm SUS316-made sintering filter at a flow rate of 61.6 kg / h. Hereinafter, the same procedure as in Example 1 was performed except that the catalyst was not supplied to the first vertical stirring polymerization tank. The weight average molecular weight (Mw) of the obtained polymer was 63000, and the solution hue (YI value) was 1.4 to 1.5.

Comparative Example 2 Example 1 was repeated except that phenol was not added and the holding temperature of the raw material preparation tank and the first raw material storage tank were both set to 165 ° C. when dissolving and preparing DPC and PC oligomer. I went the same way. The obtained polymer had a weight average molecular weight (Mw) of 61,000 and a solution hue (YI value) of 1.3.
Was ~ 1.5.

Comparative Example 3 The procedure of Example 2 was repeated, except that the temperatures of the first reaction tank and the first raw material storage tank were both set to 165 ° C. The weight average molecular weight (Mw) of the obtained polymer was 6
3000, the solution hue (YI value) was 1.7 to 1.8.

[0063]

According to the present invention, when an aromatic-aliphatic copolymerized polycarbonate is produced by a transesterification method,
An ester having high transparency and excellent hue by separately supplying a mixed raw material liquid of an aromatic carbonic acid diester and an aromatic polycarbonate oligomer and at least one dihydroxy compound having an alicyclic structure to the first polymerization tank. The exchange-method aromatic-aliphatic copolymerized polycarbonate can be continuously produced, and is an industrially extremely effective method.

Continued front page    (72) Inventor Hiromitsu Nagashima             Mt. Yokkaichi, Mie Prefecture             Mitsubishi Gas Chemical Co., Ltd. Yokkaichi Plant F-term (reference) 4J029 AA09 AB04 BD10 HC05A                       HC05B JA091 JA121 JB171                       JF011 JF111 KA02 KA03                       KA04 KB13 KE07 KE15 KH05

Claims (8)

[Claims] 1. An aromatic carbonic acid diester, an aromatic polycarbonate oligomer, and at least one dihydroxy compound having an alicyclic structure are combined with an alkali metal compound and / or
Alternatively, in a method for producing an aromatic-aliphatic copolymerized polycarbonate which is continuously melt-polymerized in the presence of an alkaline earth metal compound, a mixed liquid of an aromatic carbonic acid diester and an aromatic polycarbonate oligomer, and at least one alicyclic structure A method for producing an aromatic-aliphatic copolycarbonate, which comprises separately supplying a dihydroxy compound having: to the first polymerization tank. 2. The aromatic-aliphatic copolymerized polycarbonate according to claim 1, wherein the mixed solution of the aromatic carbonic acid diester and the aromatic polycarbonate oligomer contains 1 to 50% by weight of an aromatic monohydroxy compound. Manufacturing method. 3. The aromatic-aliphatic copolymer according to claim 1, wherein the mixed solution of aromatic carbonic acid diester and aromatic polycarbonate oligomer is held in a raw material storage tank at 30 ° C. or higher and 160 ° C. or lower. Method for producing polymerized polycarbonate. 4. The aromatic polycarbonate oligomer is 1
The method for producing an aromatic-aliphatic copolymerized polycarbonate according to any one of claims 1 to 3, wherein the aromatic-aliphatic copolymerized polycarbonate has a content of 0 or less. 5. The aromatic polycarbonate oligomer is 3
The method for producing an aromatic-aliphatic copolymerized polycarbonate according to any one of claims 1 to 3, wherein the main component is a monomer or less. 6. Melt polymerization is carried out using a mixed solution of an aromatic carbonic acid diester and an aromatic polycarbonate oligomer filtered by a raw material filter and a dihydroxy compound having an alicyclic structure filtered by a raw material filter. 2. A method for producing an aromatic-aliphatic copolycarbonate according to item 1. 7. The method for producing an aromatic-aliphatic copolycarbonate having a small amount of foreign matters according to claim 1, wherein after the completion of the polymerization, the polymer is filtered through a polymer filter while it is in a molten state. . 8. A dihydroxy compound having at least one alicyclic structure is tricyclo (5.2.1.0 ^2,6 ) decane dimethanol represented by the following structural formula (I): The method for producing an aromatic-aliphatic copolymerized polycarbonate according to any one of claims 1 to 7. [Chemical 1]