JP6716652B2 - Polycarbonate resin, and sheet, film and thermoformed body formed using the same - Google Patents

Description

The present invention has good thermoformability even at low temperatures as compared with conventional polycarbonate resins,
In addition, the present invention relates to a sheet, a polycarbonate resin capable of suppressing drawdown of a film during thermoforming, a sheet using the same, a film, and a thermoformed article using the same.

Polycarbonate resin is widely used in various fields because it is not only excellent in transparency but also excellent in workability and impact resistance as compared with glass and there is no fear of toxic gas compared to other plastic materials. It is also used as a material for sheets, films and thermoformed bodies.

Thermoforming is molding of a sheet or film of a thermoplastic resin (plastic) that has been heated and softened using a mold. There are vacuum molding in which a heated sheet is fixed by covering it with a mold and a vacuum is applied between the mold and the sheet, and compressed air pressure molding in which the sheet is pressurized with compressed air.
In order to produce a thermoplastic resin sheet or film, it is necessary to heat the thermoplastic resin to a melting point or higher, and when the sheet or film is thermoformed, it must be heated to a glass transition point or a softening point or higher. I have to.
A general polycarbonate resin has a melting point of about 230 to 240° C. and a glass transition point of 140.
Since it is ~150°C, the energy consumption for heating is large.

In order to lower the glass transition point of the polycarbonate resin, a method of lowering the molecular weight of the polycarbonate resin is known.

Non-Patent Document 1 discloses that Fo is a relational expression between the glass transition point and the molecular weight of a polycarbonate resin.
The x-Flory formula, the Uberreiter-Kaning formula, and the Fedors formula are listed.
If it is attempted to lower the glass transition point to 100 to 135° C. according to these equations, the molecular weight becomes a very low value. If the molecular weight is too low, the fluidity at the time of melting will be too high, or the mechanical strength will be too low, making it impossible to produce a sheet or film.

On the other hand, in Patent Documents 1 to 3, the main skeleton is the bisphenol A type as it is, but the type of the terminal terminator is changed to keep the molecular weight within an appropriate range (13,000 to 20,000).
It is disclosed that a polycarbonate resin having a lowered glass transition point and suitable for injection molding can be produced.

Since the methods of injection molding and extrusion molding and thermoforming of sheets and films are different, the range of the melt viscosity of the appropriate resin is different.

Further, when the sheet or film is thermoformed, if the molecular weight of the polycarbonate resin is too low, the melt viscosity of the resin is also low, so when the sheet or film is heated to the glass transition point or the softening point, the sheet or film sags, that is, drawdown. Occurs and causes defective molding. For these reasons, thermoforming has different constraints than injection molding.

Japanese Patent Laid-Open No. 11-300842 Japanese Patent Laid-Open No. 2000-153535 WO2007/132874

Polycarbonate Resin Handbook Seiichi Honma 1992 (Pages 143-150)

The present inventors have conducted extensive studies to solve the conventional problems, have a specific terminal structure, the glass transition point and the melt fluidity is a specific range of the polycarbonate resin, the conventional polycarbonate resin Comparing the present invention, it is possible to provide a polycarbonate resin having good thermoformability at low temperature and high thermoformability at the time of thermoforming, and high drawdown resistance of the film, and a sheet and film using the same. Came to.
That is, the present invention relates to the following polycarbonate resin and sheets, films, and thermoformed articles using the same.

1. A polycarbonate resin obtained by reacting a monohydric phenol represented by the following general formula (1), a dihydric phenol represented by the general formula (2), and a carbonate binder, having a glass transition point of 100°C to 135°C. And the Q value showing the melt fluidity is 1×10 ⁻² cm ³
/S to 35×10 ⁻² cm ³ /s polycarbonate resin.
(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and R _{2 to} R ₅ each independently have hydrogen, halogen, or a substituent. Represents an optionally substituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have a substituent.)
(In the formula, R _{6 to} R ₉ are each hydrogen, halogen, an alkoxyl group having 1 to 5 carbon atoms which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, An alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent,
Represents an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent,
X is, -O -, - S -, - SO -, - SO 2 -, - CO-, or the following formula (3) to (6
) Is any of the structures shown. )
In formula (3), R ₁₀ and R ₁₁ are each hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkoxy group having 1 to 5 carbon atoms which may have a substituent. An aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, or an aryl group having 7 to 17 carbon atoms which may have a substituent. Represents an aralkyl group,
R ₁₀ and R ₁₁ may be bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms,
c represents an integer of 0 to 20, and in the formula (4), R ₁₂ and R ₁₃ each have hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a substituent. Represents an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, or an aralkyl group having 7 to 17 carbon atoms which may have a substituent,
R ₁₂ and R ₁₃ may be bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms,
In formula (5), R _{14 to} R ₁₇ are each hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkoxy group having 1 to 5 carbon atoms which may have a substituent. An aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, or a carbon number 7 to 17 which may have a substituent. Represents an aralkyl group of
R ₁₄ and R ₁₅ , and R ₁₆ and R ₁₇ may be bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms,
In formula (6), R _{18 to} R ₂₇ are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 2. The polycarbonate resin according to 1 above, wherein the carbon number of R _{1 in} the monohydric phenol represented by the formula (1) is 12 to 22.
3. 3. The polycarbonate resin according to 1 or 2 above, wherein the monohydric phenol represented by the formula (1) is selected from para-hydroxybenzoic acid 2-hexyldecyl ester and para-hydroxybenzoic acid hexadecyl ester.
4. The polycarbonate resin according to any one of 1 to 3 above, wherein the dihydric phenol represented by the formula (2) is a bis(4-hydroxyphenyl)alkane.
5. The polycarbonate resin according to 4 above, wherein the dihydric phenol represented by the formula (2) is 2,2-bis(4-hydroxyphenyl)propane.
4. The polycarbonate resin as described in 1 to 3 above, which is a material for sheets and films.
5. A sheet or film made from the polycarbonate resin as defined in any one of 1 to 4 above.
6. 6. The polycarbonate resin according to any one of 1 to 5 above, which has a viscosity average molecular weight of 18,000 to 35,000.
7. A sheet or film made of the polycarbonate resin as defined in any one of 1 to 6 above.
8. A thermoformed body molded using the polycarbonate resin according to any one of 1 to 6 above.
9. A thermoformed body molded using the film according to 7 above.

The polycarbonate resin having a specific terminal structure, a glass transition point in a specific range, and a melt viscosity in a specific range according to the present invention has good thermoformability at low temperatures as compared with conventional polycarbonate resins. Therefore, according to the present invention, by using the above polycarbonate resin which is particularly suitable for thermoformability, a sheet at the time of thermoforming, a sheet having good drawdown resistance of the film,
A film can be provided.

<Polycarbonate resin>
The polycarbonate resin of the present invention is obtained by reacting a monovalent phenol represented by the following general formula (1), a divalent phenol represented by the general formula (2), and a carbonate binder.

(In the formula, R _{6 to} R ₉ are each a hydrogen atom, a halogen atom, or an optionally substituted carbon atom having 1 to 20 carbon atoms.
, Preferably an alkyl group having 1 to 9 carbon atoms, 1 to 5 carbon atoms which may have a substituent, preferably an alkoxy group having 1 to 3 carbon atoms, and 6 to 12 carbon atoms which may have a substituent. , Preferably an aryl group having 6 to 8 carbon atoms, 7 to 17 carbon atoms which may have a substituent, preferably 7 to 1 carbon atoms
2 aralkyl groups, or 2 to 15 carbon atoms which may have a substituent, preferably 2 to 2 carbon atoms.
5 represents an alkenyl group. The substituent which may be present is halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. X is -O -, - S -, - SO -, - SO 2 -,
-CO- or any structure represented by the following formula (3). )

(In the formula, R ₁₀ and R ₁₁ are each a hydrogen atom, a halogen atom or a carbon atom which may have a substituent.
20, preferably an alkyl group having 1 to 9 carbon atoms, an alkyl group having 1 to 5 carbon atoms which may have a substituent, preferably an alkoxy group having 1 to 3 carbon atoms, and an alkyl group having 6 to carbon atoms which may have a substituent. 12, preferably an aryl group having 6 to 8 carbon atoms, 7 to 17 carbon atoms which may have a substituent, preferably 7 carbon atoms
It represents an aralkyl group having 12 to 12 or an alkenyl group having 2 to 15 carbon atoms, preferably 2 to 5 carbon atoms, which may have a substituent. The substituent which may be present is halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
R ₁₀ and R ₁₁ are each bonded to each other to have 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms.
12 carbocycles or heterocycles may be formed,
c represents an integer of 0 to 20, preferably an integer of 1 to 12.
R ₁₂ and R ₁₃ are each hydrogen, halogen, or 1 to 20 carbon atoms which may have a substituent,
Preferably, an alkyl group having 1 to 9 carbon atoms, 1 to 5 carbon atoms which may have a substituent, preferably an alkoxy group having 1 to 3 carbon atoms, and 6 to 12 carbon atoms which may have a substituent, An aryl group having 6 to 8 carbon atoms, 7 to 17 carbon atoms which may have a substituent, preferably 7 to 12 carbon atoms
2 to 15 carbon atoms, which may have a substituent, preferably 2 to 5 carbon atoms.
Represents an alkenyl group. The substituent which may be present is halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
R ₁₂ and R ₁₃ are each bonded to each other to have 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms.
Twelve carbocycles or heterocycles may be formed.
R _{14 to} R ₁₇ are each hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, preferably an alkyl group having 1 to 9 carbon atoms, an alkyl group having 1 to 5 carbon atoms which may have a substituent, Preferably, an alkoxy group having 1 to 3 carbon atoms, or 6 to 12 carbon atoms which may have a substituent, preferably 6 carbon atoms.
To C8 aryl group, optionally substituted C7 to C17, preferably C7 to C12 aralkyl group, or optionally substituted C2 to C15, preferably carbon It represents an alkenyl group of the numbers 2 to 5. The substituent which may have is halogen, an alkyl group having 1 to 20 carbon atoms,
It is an aryl group having 6 to 12 carbon atoms. R ₁₄ and R ₁₅ and R ₁₆ and R ₁₇ may be bonded to each other to form a carbocycle or a heterocycle having 1 to 20 carbon atoms.
R _{18 to} R ₂₇ are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
At least one, preferably three of R _{18 to} R ₂₇ is an alkyl group having 1 to 3 carbon atoms. )

Examples of the divalent phenol represented by the general formula (2) include 2,2-bis(4-hydroxyphenyl)propane [=bisphenol A], bis(4-hydroxyphenyl)-p-diisopropylbenzene, and 4,4′-. Dihydroxydiphenyl, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3) ,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-3-ethylphenyl)propane, 2,2-bis(
4-hydroxy-3,5-diphenylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2 ,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis-(4-hydroxy-3-methylphenyl) Methane, bis-(4-hydroxy-3-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxy-3-methylphenyl)ethane, 3,3- Bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane [=bisphenol Z], bis(4-hydroxyphenyl)sulfone, 2,4′-dihydroxydiphenylsulfone, bis(4-hydroxy) Phenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether, 1-phenyl-1,1- Bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1-phenyl-1,1-bis(4-hydroxy-3-methylphenyl)ethane, bis(4 -Hydroxyphenyl)diphenylmethane,
Bis(4-hydroxy-3-methylphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)
Examples thereof include fluorene and 2,2-bis(4-hydroxyphenyl)hexafluoropropane, but bis(4-hydroxyphenyl)alkanes are preferable, and 2,2-bis(4) is particularly preferable. -Hydroxyphenyl)propane [bisphenol A]
Is. These aromatic dihydroxy compounds can be used alone or in combination of two or more.

<Carbonate binder>
Examples of the carbonate binder of the present invention include phosgene, triphosgene, carbonic acid diesters, and carbonyl compounds such as carbon monoxide and carbon dioxide.

Examples of carbonic acid diesters include dimethyl carbonate, diethyl carbonate, di-
Examples thereof include dialkyl carbonate compounds such as tert-butyl carbonate, diphenyl carbonate or substituted diphenyl carbonates such as di-p-tolyl carbonate, phenyl-p-tolyl carbonate and di-p-chlorophenyl carbonate. Among them, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. These carbonic acid diester compounds may be used alone or in combination of two or more.

<Monohydric phenol>
The monohydric phenol of the present invention acts as a terminal stopper and is represented by the general formula (1).

(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms. R _{2 to} R ₅ are each hydrogen, halogen, or a carbon which may have a substituent. An alkyl group having 1 to 20 or an aryl group having 6 to 12 carbon atoms which may have a substituent is represented by R _{2 to} R _5.
Is preferably hydrogen, halogen, an alkyl group having 1 to 9 carbon atoms which may have a substituent, or an aryl group having 6 to 8 carbon atoms which may have a substituent. )

Preferably, the monohydric phenol of the general formula (1) is a compound represented by the general formula (7).

(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.)

The carbon number of R _{1 in} the general formula (1) or the general formula (7) is more preferably within a specific numerical range.
Specifically, the upper limit of the carbon number of R ₁ is preferably 36, more preferably 22 and 18
Is particularly preferable.
The lower limit of the carbon number of R ₁ is preferably 8 and more preferably 12.

Among the monohydric phenols (end terminators) represented by the general formula (1) or the general formula (7), either parahydroxybenzoic acid hexadecyl ester or parahydroxybenzoic acid 2-hexyldecyl ester, or both of them are terminated. It is particularly preferred to use it as a terminator.

When, for example, a monohydric phenol (end terminator) having an alkyl group having 16 carbon atoms is used as R ₁ , the polycarbonate resin obtained has a glass transition point, melt fluidity, moldability, drawdown resistance, and polycarbonate. The monohydric phenol is excellent in solubility in an organic solvent at the time of production, and is particularly preferable as a terminal stopper used in the polycarbonate resin of the present invention.

On the other hand, when the carbon number of R _{1 in} the general formula (1) or the general formula (7) is excessively increased, the solubility of the monohydric phenol (end terminating agent) in the organic solvent tends to decrease, which may cause a decrease in polycarbonate resin production. Productivity may decrease.
As an example, when the carbon number of R ₁ is 36 or less, the productivity is high and the economical efficiency is good in producing a polycarbonate resin. When the carbon number of R ₁ is 22 or less, the monohydric phenol is particularly excellent in solubility in an organic solvent, the productivity can be made extremely high in producing a polycarbonate resin, and the economical efficiency is also improved.
When the carbon number of R _{1 in} the general formula (1) or the general formula (7) is too small, the glass transition point of the polycarbonate resin does not become a low value, and the thermoformability may deteriorate.

Depending on the properties required of the material, it is not possible to use the main skeleton or the terminal terminating agent in combination with those having other structures, or to mix with other polycarbonate resin or further other transparent resin, within the range not departing from the gist of the present invention. Permissible. 80 mol% or more of all the terminal stoppers used is the above formula (1).
The structure represented by the formula (1) is preferable, and 90 mol% or more of all the end-capping agents used is more preferably the structure represented by the formula (1). The structure represented by is particularly preferable.
Other end-capping agents that may be used in combination include phenol, p-cresol, o-cresol, 2,4-xylenol, p-t-butylphenol, o-allylphenol, p-allylphenol, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-propylphenol, p-cumylphenol, p-phenylphenol, o-phenylphenol, p-trifluoromethylphenol, p-nonylphenol, p-dodecylphenol, eugenol, amylphenol , Hexylphenol, heptylphenol,
Alkylphenols such as octylphenol, nonylphenol, decylphenol, dodecylphenol, myristylphenol, palmitylphenol, stearylphenol, behenylphenol, and methyl esters of parahydroxybenzoic acid, ethyl esters, propyl esters, butyl esters, amyl esters, hexyl esters, heptyl. Examples thereof include alkyl esters of para-hydroxybenzoic acid such as esters. It is also possible to use two or more of the above monohydric phenols in combination.

Depending on the synthesis conditions, the terminal group may be formed as a phenolic OH group that does not react with the terminal terminator. The less the phenolic OH groups are, the more preferable. Specifically, 8 in all ends
It is preferable that 0 mol% or more is sealed with the structure represented by the above formula (1), and 90 mol% or more of all terminals is particularly preferably sealed with the structure represented by the above formula (1). ..

<Polymerization degree, amount of monohydric phenol (end terminator) used>
The molecular weight of the polycarbonate resin of the present invention is controlled by the amount of monohydric phenol (end terminator) used.
The degree of polymerization of the dihydric phenol (represented by the general formula (2) above) used for the main skeleton,
The amount of monohydric phenol (end terminator) used is shown in the following formula.

The amounts of monohydric phenol and dihydric phenol used are determined based on this formula, but the preferred amount of dihydric phenol (mol): monohydric phenol (end terminator) is 50 : 1 to 15:1, and more preferably 40:1 to 17:1.

To obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,4,6-dimethyl-2 is used.
,4,6-Tris(4-hydroxyphenyl)heptane, 2,6-dimethyl-2,4,6
A polyhydroxy compound represented by tris(4-hydroxyphenyl)heptene-3,1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, Alternatively, 3,3-bis(4-hydroxyaryl)oxindole (=isatin bisphenol), 5-chloroisatin bisphenol, 5,7
-Dichloroisatin bisphenol, 5-bromoisatin bisphenol, etc. may be used as a part of the aromatic dihydroxy compound described above, and the amount used is 0.01 to 10 mol%.
, And preferably 0.1 to 3 mol %.

<Additive>
Various additives may be blended with the polycarbonate resin of the present invention within a range not departing from the gist of the present invention. Examples of the additive include at least one additive selected from the group consisting of a heat stabilizer, an antioxidant, a flame retardant, a flame retardant aid, an ultraviolet absorber, a release agent and a colorant.
Further, an antistatic agent, an optical brightening agent, an antifogging agent, a fluidity improving agent, a plasticizer, a dispersant, an antibacterial agent, etc. may be added as long as desired physical properties are not significantly impaired.

Examples of the heat stabilizer include phenol-based, phosphorus-based, and sulfur-based heat stabilizers. Specifically, phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic sodium pyrophosphate salts such as sodium acidic pyrophosphate, potassium acidic pyrophosphate, and acidic calcium pyrophosphate; potassium phosphate , Phosphates of Group 1 or Group 10 metals such as sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, and the like. Alternatively, at least one ester in the molecule is esterified with phenol and/or phenol having at least one alkyl group having 1 to 25 carbon atoms (a), phosphorous acid (b) and At least one selected from the group of tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene-di-phosphonite (c) can be mentioned.
Specific examples of the phosphite compound (a) include trioctyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triphenyl phosphite, tris(monononylphenyl)phosphite. Fight, tris(monononyl/dinonyl phenyl)phosphite, trisnonylphenyl phosphite, tris(octylphenyl)phosphite, tris(2,4-di-ter)
t-butylphenyl)phosphite, trinonylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, bis(2,4- Di-tert-butylphenyl)pentaerythritol phosphite, bis(
2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite, monooctyl diphenyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, diphenyl pentaerythritol diphosphite, bis(2,2 6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, bis(nonylphenyl)pentaerythritol diphosphite , Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite. These may be used alone or in combination of two or more.

Specific examples of the organic phosphite compound include, for example, "ADEKA STAB 1178", "ADEKA STAB 2112", and "ADEKA STAB HP-10" manufactured by ADEKA CORPORATION (trade name, the same applies hereinafter).
, "JP-351", "JP-360", "JP-3CP" manufactured by Johoku Chemical Industry Co., Ltd., "Irgafos 168" manufactured by Ciba Specialty Chemicals Co., Ltd., and the like.

Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl)phosphate, 2-ethylphenyldiphenylphosphate and the like.

When compounded, the heat stabilizer is added in an amount of, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, and more preferably 0, based on 100 parts by mass of the aromatic polycarbonate resin.
． It is at least 03 parts by mass, and at most 1 part by mass, preferably at most 0.7 parts by mass, more preferably at most 0.5 parts by mass. If the amount of the heat stabilizer is too small, the heat stabilizing effect may be insufficient, and if the amount of the heat stabilizer is too large, the effect may reach the ceiling and may be uneconomical.

Examples of antioxidants include phenolic antioxidants, hindered phenolic antioxidants, bisphenolic antioxidants, and polyphenolic antioxidants. Specifically, 2,6-di-tert-butyl-4-methylphenol, tris(3,5-di-
tert-Butyl-4-hydroxybenzyl)isocyanurate, n-octadecyl-3
-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate,
Tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 4,4'-butylidenebis-(3-methyl-6-tert-)
Butylphenol), triethyleneglycol-bis[3-(3-tert-butyl-4)
-Hydroxy-5-methylphenyl)propionate], 3,9-bis{2-[3-(3
-Tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1
,1-Dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], Thiodiethylenebis[3-(3,5-di-tert-
Butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide),2,4-dimethyl- 6-(1-methylpentadecyl)phenol, diethyl[
[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a'. , A
"-(Mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-
tert-Butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]
, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1
,3,5-Triazine-2,4,6(1H,3H,5H)-trione,2,6-di-te
Examples include rt-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol. Specific examples of the phenol-based antioxidant include “Irganox 1010” (Ciba Specialty Chemicals Co., Ltd.)
(Registered trademark, same below), "Irganox 1076", "ADEKA STAB AO-" manufactured by ADEKA CORPORATION
50", "ADEKA STAB AO-60" and the like.

When added, the antioxidant is added in an amount of, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, and 1 part by mass with respect to 100 parts by mass of the aromatic polycarbonate resin.
It is not more than 0.5 parts by mass, preferably not more than 0.5 parts by mass. If the addition ratio of the antioxidant is less than the lower limit value, the effect as the antioxidant may be insufficient, and if the addition ratio of the antioxidant exceeds the upper limit value, the effect will reach the ceiling and it is economical. It may disappear.

Examples of flame retardants include metal salts of organic sulfonic acids. Examples of the organic sulfonic acid metal salt include an aliphatic sulfonic acid metal salt and an aromatic sulfonic acid metal salt. These may be used alone or in combination of two or more. Moreover, as the metal salt, an alkali metal salt and an alkaline earth metal salt are preferable. As alkali metals, sodium, lithium,
Mention may be made of potassium, rubidium and cesium. Examples of alkaline earth metals include calcium and strontium. The preferred metal of the organic sulfonic acid metal salt used in the present invention is an alkali metal such as sodium, potassium, rubidium and cesium, and more preferably sodium and potassium. By adopting such a metal, it is possible to effectively promote formation of a carbonized layer during combustion and maintain high transparency.

As the aliphatic sulfonate, a fluoroalkane-sulfonic acid metal salt is preferable, and a perfluoroalkane-sulfonic acid metal salt is more preferable.
Examples of the fluoroalkane-sulfonic acid metal salt include alkali metal salts and alkaline earth metal salts, and alkali metal salts are preferable. The carbon number of the fluoroalkanesulfonic acid metal salt is preferably 1-8, more preferably 2-4. With such a range, the effect of maintaining high transparency can be obtained. As a specific example of a preferable fluoroalkane-sulfonic acid metal salt, perfluorobutane-sodium sulfonate,
Examples include perfluorobutane-potassium sulfonate, sodium perfluoroethane-sulfonate, potassium perfluoroethane-sulfonate, and the like.

Examples of the aromatic sulfonic acid metal salt include an alkali metal salt and an alkaline earth metal salt, and an alkali metal salt is preferable. Specific examples of the alkali metal salt of aromatic sulfone sulfonic acid include 3,4-dichlorobenzenesulfonic acid sodium salt, 2,4,5-trichlorobenzenesulfonic acid sodium salt, benzenesulfonic acid sodium salt, and diphenylsulfone-3-sulfone. Acid sodium salt, diphenylsulfone-3-sulfonic acid potassium salt, 4,4'-dibromodiphenyl-sulfone-3-sulfonic acid sodium salt, 4,4'
-Dibromophenyl-sulfone-3-sulfonic acid potassium salt, diphenylsulfone-3
,3'-Disulfonic acid disodium salt, diphenylsulfone-3,3'-disulfonic acid dipotassium salt, dodecylbenzenesulfonic acid sodium salt, dodecylbenzenesulfonic acid potassium salt, p-toluenesulfonic acid potassium salt, p-styrene Examples thereof include potassium sulfonic acid salt.

The organic sulfonic acid metal salt used in the present invention is, particularly from the viewpoint of improving transparency, a potassium salt of diphenylsulfone-3-sulfonic acid, a potassium salt of p-toluenesulfonic acid, a p-toluenesulfonic acid.
Styrene sulfonic acid potassium salt and dodecylbenzene sulfonic acid potassium salt are preferable, and diphenyl sulfone-3-sulfonic acid potassium salt is more preferable. The addition mass of the organic sulfonic acid metal salt to the aromatic polycarbonate resin of 100 mass parts is 0.005 mass part to 0.1 mass part, but preferably 0.01 mass part to, as described above. 0.1 parts by mass, more preferably 0.03 parts by mass to 0.09 parts by mass.
Further, in the present invention, a flame retardant other than the organic sulfonic acid metal salt may be blended.

As a flame retardant aid, for example, a silicone compound can be added. The silicone compound preferably has a phenyl group in the molecule. By having a phenyl group, the dispersibility of the silicone compound in the polycarbonate is improved, and the transparency and flame retardancy are excellent. The weight average molecular weight of the silicone compound is preferably 450 to 5000, and more preferably 750 to 4
000, more preferably 1000 to 3000, and particularly preferably 1500 to 2500. When the mass average molecular weight is 450 or more, the production is facilitated, the industrial production is easily adapted, and the heat resistance of the silicone compound is not easily lowered. On the other hand, when the weight average molecular weight of the silicone compound is 5000 or less, the dispersibility in the polycarbonate resin composition is less likely to decrease, and the flame retardancy and mechanical properties of the aromatic polycarbonate resin composition are further reduced. It tends to be effectively suppressed.

When compounded, the flame retardant aid is added in an amount of, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more, and 7.5 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. Hereafter, it is preferably 5 parts by mass or less. If the addition ratio of the flame retardant auxiliary is less than the lower limit, flame retardancy may be insufficient, and if the addition ratio of the flame retardant auxiliary exceeds the upper limit, appearance defects such as delamination occur and transparency As the flame retardancy decreases, the flame retardancy may reach the ceiling and may become uneconomical.

As an ultraviolet absorber, in addition to inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, a benzotriazole compound, a benzophenone compound, a salicylate compound, a cyanoacrylate compound, a triazine compound, an oxazanilide compound, a malonic acid ester compound, a hindered amine compound, a phenyl salicylate compound Organic UV absorbers such as compounds can be mentioned. Of these, benzotriazole-based and benzophenone-based organic ultraviolet absorbers are preferable. In particular, specific examples of the benzotriazole compound include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-[2'-hydroxy-3',5'-bis(α,α-
Dimethylbenzyl)phenyl]-benzotriazole, 2-(2'-hydroxy-3',5
'-Di-tert-butyl-phenyl)-benzotriazole, 2-(2'-hydroxy-
3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-
(2'-Hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole), 2-(2'-hydroxy-3',5'-di-tert-amyl)-benzo Triazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6
-(2N-benzotriazol-2-yl)phenol], 2-(4,6-diphenyl-
1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-
[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-
5-(octyloxy)phenol, 2,2'-(1,4-phenylene)bis[4H-3,
1-benzoxazin-4-one], [(4-methoxyphenyl)-methylene]-propanedioic acid-dimethyl ester, 2-(2H-benzotriazol-2-yl)
-P-cresol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-
Methyl-1-phenylmethyl)phenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, 2,4-di-t
ert-Butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 2-(
2H-benzotriazol-2-yl)-4-(1,1,3,3-tetrabutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(
1,1,3,3-Tetrabutyl)phenol], [methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate-polyethylene glycol] condensate Etc. can be mentioned. You may use these 2 or more types together. Among the above, 2-(2'-hydroxy-5'-tert- is preferable.
Octylphenyl)benzotriazole, 2,2'-methylene-bis[4-(1,1,3
,3-Tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol]
Is. Further, as a specific example of the benzophenone-based ultraviolet absorber, 2,4-dihydroxy-
Benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4
-N-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4 , 4'-dimethoxy-benzophenone, 2,2',4,4'-tetrahydroxy-benzophenone and the like. Specific examples of the phenyl salicylate-based ultraviolet absorber include phenyl salicylate and 4-tert-butyl-phenyl salicylate. Furthermore,
Specific examples of the triazine-based ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol and 2-[4,6- Examples include bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol. Moreover, bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate etc. can be mentioned as a specific example of a hindered amine ultraviolet absorber.

When compounded, the addition ratio of the ultraviolet absorber is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and 3 parts by mass or less, with respect to 100 parts by mass of the aromatic polycarbonate resin. Is 1 part by mass or less. If the addition ratio of the ultraviolet absorber is less than the lower limit value, the effect of improving the weather resistance may be insufficient, and if the addition ratio of the ultraviolet absorber exceeds the upper limit value, mold devogit, etc. occur, and the mold or Can cause chill roll contamination.

Examples of the release agent include carboxylic acid ester, polysiloxane compound, paraffin wax (polyolefin type) and the like. Specific examples include at least one compound selected from the group of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oil. be able to. As the aliphatic carboxylic acid, a saturated or unsaturated aliphatic monovalent, divalent or trivalent
A carboxylic acid may be mentioned. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable.
Specific examples of the aliphatic carboxylic acid include palmitic acid, stearic acid, valeric acid, caproic acid,
Examples thereof include capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetrariacontanoic acid, montanic acid, glutaric acid, adipic acid and azelaic acid. Specific examples of the ester of an aliphatic carboxylic acid and an alcohol include beeswax (mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate. , Glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like. Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, alicyclic hydrocarbon is also included in the aliphatic hydrocarbon. Further, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable. The number average molecular weight is preferably 200 to
It is 5000. These aliphatic hydrocarbons may be a single substance or a mixture of constituent components and various molecular weights, as long as the main component is within the above range. Examples of the polysiloxane-based silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. You may use these 2 or more types together.
When compounded, the addition ratio of the release agent is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and 2 parts by mass or less, relative to 100 parts by mass of the aromatic polycarbonate resin. , And more preferably 1 part by mass or less. If the addition ratio of the release agent is less than the lower limit value, the effect of releasability may not be sufficient, and if the addition ratio of the release agent exceeds the upper limit value,
There is a possibility that the hydrolysis resistance may decrease and that the mold may be contaminated during injection molding.

Examples of dyes and pigments as colorants include inorganic pigments, organic pigments, and organic dyes. Examples of the inorganic pigments include sulfide pigments such as carbon black, cadmium red and cadmium yellow; silicate pigments such as ultramarine; titanium oxide, zinc oxide, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron. -Based brown, titanium-cobalt-based green, cobalt-green, cobalt-blue, copper-chromium-based black, copper-iron-based black and other oxide-based pigments; chrome-based pigments such as yellow lead and molybdate orange; ferrocyanines such as navy blue Examples thereof include pigments. Examples of organic pigments and organic dyes as colorants include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone. And condensed polycyclic dyes such as dioxazine, isoindolinone, and quinophthalone; quinoline, anthraquinone, heterocyclic, and methyl dyes and pigments. And among these, from the viewpoint of thermal stability, titanium oxide, carbon black, cyanine-based,
Quinoline-based, anthraquinone-based, phthalocyanine-based dyes and pigments are preferred. The dyes and pigments are
One kind may be contained, and two kinds or more may be contained in optional combination and ratio. The dyes and pigments may be used as master batches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handleability at the time of extrusion and improving dispersibility in the resin composition. Good.
When compounded, the addition ratio of the colorant is, for example, 5 parts by mass or less, preferably 3 parts by mass or less, and more preferably 2 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin. If the proportion of the colorant added is too large, the impact resistance may be insufficient.

<Manufacturing method>
Examples of the method for producing the polycarbonate resin used in the present invention include various synthetic methods including an interfacial polymerization method, a pyridine method, and a transesterification method.

In the reaction by the interfacial polymerization method, the pH is usually maintained at 10 or higher in the presence of an organic solvent inert to the reaction and an alkaline aqueous solution, and the aromatic dihydroxy compound and the terminal terminator, and if necessary, the aromatic dihydroxy compound are used. To obtain an aromatic polycarbonate resin by reacting with phosgene, then adding a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt, and carrying out interfacial polymerization. You can The addition of the terminal stopper is
There is no particular limitation as long as it is from the time of phosgenation to the start of the polymerization reaction. The reaction temperature is 0 to 35° C., and the reaction time is several minutes to several hours.

Here, as the organic solvent inert to the reaction, dichloromethane, 1,2-dichloroethane,
Examples thereof include chlorinated hydrocarbons such as chloroform, monochlorobenzene and dichlorobenzene, aromatic hydrocarbons such as benzene, toluene and xylene. As a polymerization catalyst, tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, pyridine; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Can be mentioned.

Flakes of a polycarbonate resin can be obtained, for example, by dropping a dichloromethane solution containing an aromatic polycarbonate resin obtained by an interfacial polymerization method into warm water kept at 45° C. and removing the solvent by evaporation, or Alternatively, a dichloromethane solution containing an aromatic polycarbonate resin obtained by the interfacial polymerization method may be added to methanol, and the precipitated polymer may be obtained by filtration and drying, or alternatively, it may be obtained by the interfacial polymerization method. A dichloromethane solution containing the obtained polycarbonate resin can be obtained by stirring and pulverizing while maintaining the temperature at 40° C. with stirring with a kneader, and then removing the solvent with hot water at 95° C. or higher.

The reaction by the transesterification method is a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound. Usually, the molecular weight and the amount of terminal hydroxyl groups of the desired aromatic polycarbonate resin are determined by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound or adjusting the degree of pressure reduction during the reaction. The amount of the terminal hydroxyl group has a great influence on the thermal stability, hydrolysis stability, color tone and the like of the aromatic polycarbonate resin, and in order to have practical physical properties, it is preferably 1000 ppm or less, more preferably 7 ppm.
It is below 00 ppm. It is general to use the carbonic acid diester in an equimolar amount or more with respect to 1 mol of the aromatic dihydroxy compound, and it is preferably used in an amount of 1.01 to 1.30 mol.

Examples of carbonic acid diesters include dimethyl carbonate, diethyl carbonate, di-
Examples thereof include dialkyl carbonate compounds such as tert-butyl carbonate, diphenyl carbonate or substituted diphenyl carbonates such as di-p-tolyl carbonate, phenyl-p-tolyl carbonate and di-p-chlorophenyl carbonate. Among them, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. These carbonic acid diester compounds may be used alone or in combination of two or more.

When synthesizing an aromatic polycarbonate resin by a transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, but an alkali metal compound and/or an alkaline earth metal compound is mainly used, and a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine-based compound is auxiliary. It is also possible to use basic compounds such as compounds in combination. In the transesterification reaction using such raw materials,
A mixture of a dihydric phenol, a monohydric phenol (end terminating agent) and a carbonic acid diester is supplied to a reactor while being melted, a reaction is carried out at a temperature of 100 to 320° C., and finally 2.7×10 ^2. P
A method of performing the melt polycondensation reaction while removing by-products such as aromatic hydroxy compounds under a reduced pressure of a (2 mmHg) or less can be mentioned. The melt polycondensation can be carried out batchwise or continuously, but the aromatic polycarbonate resin used in the present invention is preferably carried out continuously from the viewpoint of stability and the like. In the transesterification method, as a catalyst deactivator in the aromatic polycarbonate resin, it is preferable to use a compound that neutralizes the catalyst, for example, a sulfur-containing acidic compound, or a derivative formed therefrom, and the amount thereof is It is added in an amount of 0.5 to 10 equivalents, preferably 1 to 5 equivalents, relative to the alkali metal of the catalyst, and usually 1 to 100 ppm, preferably 1 to 20 ppm relative to the aromatic polycarbonate resin.

As described above, the polycarbonate resin of the present invention can be produced according to the conventional method, and the present invention is an industrially useful invention.

The polycarbonate resin of the present invention may contain a resin other than the polycarbonate resin of the present invention, if necessary. Examples of such other resins include polycarbonate resins other than the polycarbonate resin used in the present invention, polyethylene terephthalate resin (P
ET resin), polytrimethylene terephthalate (PTT resin), polybutylene terephthalate resin (PBT resin) and other thermoplastic polyester resins; polystyrene resin (PS resin)
, High impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), methyl methacrylate-styrene copolymer (MS resin) and other styrene resins; methyl methacrylate-acrylic rubber-styrene copolymer (MAS) Core/shell type elastomers such as, elastomers such as polyester elastomers; polyolefin resins such as cyclic cycloolefin resins (COP resins) and cyclic cycloolefin (COP) copolymer resins; polyamide resins (PA resins); polyimide resins ( 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); polycaprolactone and the like.
The blending ratio of the other resin component in the polycarbonate resin of the present invention is preferably 10% by mass or less of the total resin component, and more preferably 1% or less. If the component ratio of the other resin exceeds 10% by mass, various physical properties may be impaired.

Various additives are added to the polycarbonate resin of the present invention at an arbitrary ratio, and the cold cut method of the well-known strand method (the aromatic polycarbonate resin composition once melted is formed into a strand shape, and after cooling, a predetermined shape is obtained. Method of cutting and pelletizing), hot cutting method of hot cutting method in air (method of cutting aromatic polycarbonate resin composition once melted into pellets while not touching water in air), hot in water Polycarbonate resin pellets can be obtained by a hot-cutting method (a method in which an aromatic polycarbonate resin composition once melted is cut in water and simultaneously cooled to form a pellet).
The obtained polycarbonate resin pellets are preferably dried by a method such as drying using a hot air drying oven, a vacuum drying oven, or a dehumidifying drying oven.

<Molecular weight>
The viscosity average molecular weight (Mv) of the polycarbonate resin of the present invention is measured under the following measurement conditions.

<Conditions for measuring viscosity average molecular weight (Mv)>
Measuring instrument: Ubbelohde capillary viscometer Solvent: Dichloromethane resin solution concentration: 0.5 g/deciliter Measuring temperature: 25°C
The intrinsic viscosity [η] deciliter/gram is calculated with the Huggins constant of 0.45 under the above conditions, and calculated by the following formula.

The viscosity average molecular weight of the polycarbonate resin of the present invention is 18,000 to 35,000.
0 is preferable, 20,000 to 30,000 is more preferable, 22,000 to 28.0
00 is particularly preferred.

The glass transition point, melt flowability, and drawdown resistance are physical properties that are affected by the molecular weight, and when the viscosity average molecular weight of the polycarbonate resin is in the above range, all of these properties are applicable to the production of sheets, films, and thermoformed products. preferable. That is, the polycarbonate resin of the present invention,
It can be said to be particularly suitable for thermoforming applications.
If the viscosity average molecular weight is larger than 35,000, the melt fluidity may decrease. In addition, the glass transition point of the polycarbonate resin does not become a low value, and the thermoformability may deteriorate.
If the viscosity average molecular weight is less than 18,000, the drawdown resistance may decrease.

Glass transition point The glass transition point of the polycarbonate resin of the present invention is measured using a differential scanning calorimeter under the following conditions.

<Glass transition temperature measurement conditions>
Measuring equipment: Differential scanning calorimeter (DSC)
Heating rate: 10°C/min
Gas flow environment: Nitrogen 20 ml/min
Sample pretreatment: heat melting at 300℃

The polycarbonate resin of the present invention has a glass transition point of 100°C to 13 from the viewpoint of thermoformability.
It is preferably in the range of 5°C. The glass transition point of the polycarbonate resin of the present invention is 11
The range of 0° C. to 130° C. is more preferable, and the range of 115° C. to 130° C. is particularly preferable.
If the glass transition point is lower than 100° C., the polycarbonate resin powder may aggregate during the granulation and drying steps in the production of the polycarbonate resin, and the productivity may be significantly reduced.
For the above reason, a glass transition point having a higher glass transition has a wider process margin for producing a polycarbonate resin, and a high quality polycarbonate resin can be produced efficiently and stably. Therefore, the glass transition point of the polycarbonate resin of the present invention is more preferably 105° C. or higher, and particularly preferably 110° C. or higher.
If the glass transition temperature is higher than 135°C, it is necessary to soften the resin at high temperature during thermoforming,
Energy consumption may increase.

The melt fluidity of the polycarbonate resin of the present invention is evaluated by the Q value measured using the Koka type flow tester under the following conditions. A high Q value indicates high melt fluidity, and a low Q value indicates low melt fluidity.

<Q value measurement conditions>
Measuring equipment: Flow characteristic evaluation equipment Flow tester load: 160 kgf/cm ²
Orifice: diameter 1 mm x length 10 mm
Measurement temperature: 280°C

When the Q value of the polycarbonate resin measured under the above measurement conditions is less than 1×10 ⁻² cm ³ /s, even if the glass transition point is low, the melt fluidity is too low, and thus the sheet is heated at a higher temperature than usual, It is necessary to manufacture a film or a thermoformed body, which may increase energy consumption or decompose the resin.
From the viewpoint of sheet film production stability and energy consumption during production, Q value is 1 x 10
^-2 cm ^{< 3} >/s or more, and more preferably 2*10 ^<-2 > cm ^{< 3} >/s or more.

On the contrary, even if the glass transition point is in the preferable range of 100° C. to 135° C., if the Q value of the polycarbonate resin measured under the above measurement conditions is 35×10 ⁻² cm ³ /s or more, the melt fluidity is high. Since it is too much, the drawdown resistance is low, and significant drawdown occurs during thermoforming, which may cause defective molding. Glass transition point is 100°C to 135°C, and Q
When the value is 30×10 ⁻² cm ³ /s or less, drawdown is hardly observed during thermoforming, which is particularly preferable.
Due to the above reasons, the Q value of the polycarbonate resin of the present invention is 1×10 ⁻² cm ³ /s or more.
The range is preferably 35×10 ⁻² cm ³ /s, and is preferably 2×10 ⁻² cm ³ /s to 35.
It is more preferably in the range of ×10 ⁻² cm ³ /s, and preferably 2×10 ⁻² cm ³ /s to 30.
It is particularly preferable that it be in the range of ×10 ⁻² cm ³ /s.

<Sheets, films>
The method for producing the sheet or film of the present invention is not particularly limited, but extrusion molding and cast molding are preferable.
As an example of extrusion molding, pellets, flakes or powder of the polycarbonate resin of the present invention or a resin composition obtained by adding an additive thereto is melted and kneaded by an extruder and then extruded from a T-die or the like to obtain a semi-molten state. There is a method in which the sheet is cooled and solidified while being pressed by a polishing roll or the like to obtain a product. The extruder may be uniaxial or biaxial, and both vented and non-vented can be used.

<Thermoformed body>
The thermoformed article of the present invention is a formed article produced by thermoforming a polycarbonate resin. Specific molding methods include vacuum molding and compressed air pressure molding.

<Thermoformability>
The thermoformability of the polycarbonate resin of the present invention is evaluated by pressure forming the polycarbonate resin film of the present invention. Specifically, the polycarbonate resin film is 200 mm x
Cut into 300 mm × 180 μm, attach the obtained sample film to the mold of a pressure molding machine, preheat to a predetermined temperature with an infrared heater, and pressure mold into a mold (cube type) with high pressure air of 2.5 MPa. Carry out. The height of the diaphragm is 5 mm.

<Drawdown resistance>
The polycarbonate resin film of the present invention is attached to the frame of a pressure molding machine, heated to a predetermined temperature with an infrared heater, and the drawdown resistance is visually observed.

<Use>
The sheet, film and thermoformed article of the present invention are thermoformed articles containing the polycarbonate resin of the present invention including the above-described various preferable forms and configurations. Shape, pattern, color of thermoformed body,
There is no limitation on the size and the like, and it may be set arbitrarily according to the application. Specific examples of the thermoformed body include electrical and electronic equipment, office automation equipment, information terminal equipment, machine parts, home appliances, vehicle parts, construction materials, various containers, leisure goods/general goods, parts such as lighting equipment, and various households. Examples thereof include parts for electric appliances, housings of electric appliances, containers, covers, housings, cases, covers and cases of lighting appliances, and the like. Examples of electric and electronic devices include personal computers, game machines, television receivers, display devices such as liquid crystal display devices and plasma display devices, printers, copiers, scanners, fax machines, electronic organizers and PDAs, electronic desk calculators, electronic devices. Dictionary, camera, camcorder, mobile phone, smartphone, tablet, battery pack,
Examples thereof include a recording medium drive and reading device, a mouse, a numeric keypad, a CD player, an MD player, and a portable radio/audio player. Also, as a molded body,
Illuminated signboards, liquid crystal backlights, lighting displays, traffic signs, signboards, screens, automobile parts such as reflectors and meter parts, toys, and ornaments can also be mentioned.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the examples, and various numerical values and materials in the examples are examples.

The viscosity average molecular weight (Mv) of the polycarbonate resin of the present invention was measured under the following measurement conditions.

<Conditions for measuring viscosity average molecular weight (Mv)>
Measuring instrument: Ubbelohde capillary viscometer Solvent: Dichloromethane resin solution concentration: 0.5 g/deciliter Measuring temperature: 25°C
The intrinsic viscosity [η] deciliter/gram was measured with the Huggins constant of 0.45 under the above conditions, and calculated by the following formula.

The glass transition point of the polycarbonate resin of the present invention was measured using a differential scanning calorimeter under the following conditions.

<Glass transition temperature measurement conditions>
Measuring instrument: differential scanning calorimeter (DSC) Shimadzu DSC-50
Heating rate: 10°C/min
Gas flow environment: Nitrogen 20 ml/min
Sample pretreatment: heat melting at 300℃

The melt fluidity of the polycarbonate resin of the present invention was evaluated by a Q value measured using a Koka type flow tester under the following conditions.

<Q value measurement conditions>
Measuring device: Flow characteristic evaluation device Flow Tester CFT-500D made by Shimadzu Corporation
Load: 160 kgf/cm ²
Orifice: diameter 1 mm x length 10 mm
Measurement temperature: 280°C

<Extrusion molding conditions>
Film formation by extrusion molding of the polycarbonate resin of the present invention uses a twin-screw extruder,
It carried out on the conditions shown below.
Extruder: TEM26DS manufactured by Toshiba Machine Co., Ltd.
Extruder temperature: 280°C
Die width: 330mm
Die temperature: 260℃

<Thermoformability>
The thermoformability of the polycarbonate resin of the present invention was evaluated by pressure forming the polycarbonate resin film of the present invention. Specifically, the polycarbonate resin film is 200 mm x
The sample film was cut into 300 mm×180 μm, and the obtained sample film was attached to the mold of VAP-30MT (feed rate 900 mm/s) manufactured by NK Enterprise Co., Ltd., and 150° C., 170° C., 190° C. by an infrared heater. It was preheated to 0° C. and pressure-molded into a mold (cube type) by high-pressure air of 2.5 MPa. The drawing height is 5
A height of mm was used.

The surface condition (cracks, wrinkles, unevenness, shape) of the obtained thermoformed body was observed, and the following 3
The grade was evaluated. When the shape is imprinted and no cracks, wrinkles, or unevenness are observed,
It was evaluated as "especially good", and when the cube-shaped corners had a slightly round shape, it was evaluated as "good", and when the cube-shaped corners had a round shape.

<Drawdown resistance>
The polycarbonate resin film of the present invention was attached to the mold of a pressure molding machine, heated to 150° C., 170° C., and 190° C. by an infrared heater, and the drawdown resistance was visually observed.
When almost no drawdown was observed, it was evaluated as "especially good", when some drawdown was observed, it was evaluated as "good", and when significant drawdown was observed, it was evaluated as "poor".

<Production Example 1>
Based on Organic Chemistry Handbook P143-150, esterification by dehydration reaction was performed using 4-hydroxybenzoic acid manufactured by Tokyo Chemical Industry Co., Ltd. and 1-hexadecanol manufactured by Tokyo Chemical Industry Co., Ltd., and hexahydroxy parahydroxybenzoate was used. Decyl ester (CEPB) was obtained.

<Production Example 2>
Para-benzoic acid 2- was produced in the same manner as in Production Example 1 except that 1-hexadecanol was changed to 2-hexyldecanol (trade name: NJGECOL 160BR) manufactured by Shin Nippon Rika Co., Ltd. Hexyldecyl ester (HDPB) was obtained.

<Example 1>
To 57.2 kg of 9 w/w% sodium hydroxide aqueous solution, 7.1 kg (31.14 mol) of bisphenol A (BPA) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and 30 g of hydrosulfite were added and dissolved. To this, 40 kg of dichloromethane was added, and the solution temperature was adjusted to 15 while stirring.
4.33 kg of phosgene was blown in over 30 minutes while maintaining the temperature in the range of 25°C to 25°C.

After the completion of blowing phosgene, 6 kg of a 9 w/w% sodium hydroxide aqueous solution, 11 kg of dichloromethane, and 443 g (1.22 mol) of CEPB were added to 10 k of dichloromethane.
The solution dissolved in g was added, and the mixture was vigorously stirred to emulsify, and then 10 ml of triethylamine was added as a polymerization catalyst to polymerize for about 40 minutes.

The polymerization liquid was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with pure water was repeated until the pH of the washing liquid became neutral. Polycarbonate resin powder was obtained by evaporating the organic solvent from this purified polycarbonate resin solution by evaporation.

The polycarbonate resin powder obtained was used in a twin-screw extruder having a screw diameter of 35 mm,
The mixture was melt-kneaded at a cylinder temperature of 260° C., extruded in a strand shape and pelletized by a pelletizer.

Using the obtained polycarbonate resin pellets, viscosity average molecular weight, glass transition point, Q
As a result of carrying out the value measurement, the viscosity average molecular weight is 27600, the glass transition point (Tg) is 127° C., and the Q is Q.
The value was 7.7×10 ⁻² cm ³ /s.

Furthermore, using a 40 mm single-screw extruder having a T-die, the obtained polycarbonate resin pellets are melt-extruded at a discharge rate of 40 kg/h and a cylinder temperature of 260° C., extruded in a film form from the T-die, and then a mirror surface of 120° C. It cooled using the roll and the 180-micrometer-thick film was obtained.

Using the obtained polycarbonate resin film, as a result of evaluating thermoformability and drawdown resistance, the thermoformability was 150° C., 170° C., 190° C., and the shape was imprinted and cracked. Neither wrinkles nor unevenness was observed, and "especially good",
Regarding the drawdown resistance, drawdown was hardly observed under any of the temperature conditions of 150° C., 170° C. and 190° C., and it was “particularly good”.

<Comparative Example 1>
Product name "Upilon (registered trademark) S-" manufactured by Mitsubishi Engineering Plastics Co., Ltd.
Using 3000 (the terminal structure is paratertiary butylphenol (PTBP)), the same procedure as in Example 1 was carried out to obtain a polycarbonate resin pellet and a film.

The viscosity average molecular weight of the obtained polycarbonate resin is 21,500, the glass transition point (Tg)
Is 146° C., the Q value is 10×10 ⁻² cm ³ /s, and the thermoformability is “poor” because the cube-shaped corners are rounded at 150° C., and the cube is 170° C. The shape of the mold was slightly round and the shape was “good”, and the shape was shaped at 190° C., and no cracks, wrinkles, or unevenness were observed, and “good”. Regarding drawdown resistance, drawdown was hardly observed under any of the temperature conditions of 150° C., 170° C., and 190° C., and was “especially good”.

From Table 1, the polycarbonate resin of the present invention gives a sheet or film which has better thermoformability at low temperatures and excellent drawdown resistance during thermoforming, as compared with conventional general polycarbonate resins. It can be said that it is a thing.

<Example 2>
Polycarbonate resin pellets and films were obtained in the same manner as in Example 1, except that the amount of CEPB was changed to 551 g (1.52 mol).

The viscosity average molecular weight of the obtained polycarbonate resin is 23600, the glass transition point (Tg)
Is 119[deg.] C., the Q value is 17*10 ^<-2 > cm ^{< 3} >/s, and the thermoformability is "particularly good", with no shape, no cracks, wrinkles, and unevenness observed. Regarding the drawdown property, almost no drawdown was observed, and the result was "particularly good".

<Example 3>
Polycarbonate resin pellets and a film were obtained in the same manner as in Example 1, except that the amount of CEPB was changed to 502 g (1.38 mol).

The obtained polycarbonate resin has a viscosity average molecular weight of 25,000 and a glass transition point (Tg).
Is 123° C., the Q value is 13×10 ⁻² cm ³ /s, the thermoformability is a shape, and no cracks, wrinkles, or unevenness are observed, which is “particularly good” and Regarding the drawdown property, almost no drawdown was observed, and the result was "particularly good".

<Example 4>
In Example 1, CEPB was changed to the above HDPB, and the amount of HDPB was 383 g (1
． Polycarbonate resin pellets and film were obtained in the same manner as in Example 1 except that the amount was set to 05 mol).

The viscosity average molecular weight of the obtained polycarbonate resin is 27100, the glass transition point (Tg)
Is 130° C., the Q value is 8.7×10 ⁻² cm ³ /s, and the thermoformability is “particularly good” because the shape is imprinted, and cracks, wrinkles, and unevenness are not observed. Regarding drawdown resistance, drawdown was hardly observed, and the result was "particularly good".

<Example 5>
Polycarbonate resin pellets and a film were obtained in the same manner as in Example 4, except that the amount of HDPB was changed to 452 g (1.25 mol).

The viscosity average molecular weight of the obtained polycarbonate resin is 24600, the glass transition point (Tg)
Is 126° C., the Q value is 12×10 ⁻² cm ³ /s, and the thermoformability is “particularly good” with no shape, no cracks, wrinkles, and unevenness observed. Regarding the drawdown property, almost no drawdown was observed, and the result was "particularly good".

<Example 6>
A polycarbonate resin pellet and a film were obtained in the same manner as in Example 4, except that the amount of HDPB was 525 g (1.45 mol).

The viscosity average molecular weight of the obtained polycarbonate resin is 22000, the glass transition point (Tg)
Is 122° C., the Q value is 25×10 ⁻² cm ³ /s, the thermoformability is a shape, and no cracks, wrinkles, or unevenness are observed, which is “especially good” and Regarding the drawdown property, almost no drawdown was observed, and the result was "particularly good".

<Example 7>
In the same manner as in Example 1, except that CEPB was changed to parahydroxybenzoic acid dodecyl ester (PODB) manufactured by Tokyo Chemical Industry Co., Ltd., and the amount of PODB was changed to 443 g (1.45 mol). To obtain a polycarbonate resin pellet and a film.

The viscosity average molecular weight of the obtained polycarbonate resin is 20,700, the glass transition point (Tg)
Is 128° C., the Q value is 21×10 ⁻² cm ³ /s, the thermoformability is a shape, and no cracks, wrinkles, or unevenness are observed, which is “especially good” and Regarding the drawdown property, almost no drawdown was observed, and the result was "particularly good".

<Example 8>
In Example 1, CEPB was changed to para-hydroxybenzoic acid 2-ethylhexyl ester (EHPB) manufactured by Tokyo Chemical Industry Co., Ltd., and the amount of EHPB was 376 g (1.50 mol).
A polycarbonate resin pellet and a film were obtained in the same manner as in Example 1 except for the above.

The viscosity average molecular weight of the obtained polycarbonate resin is 22,700, the glass transition point (Tg)
Is 132° C., the Q value is 11×10 ⁻² cm ³ /s, and cracks, wrinkles, and unevenness are not observed in the thermoformability, but the cube-shaped corners are slightly rounded. "Good", almost no drawdown was observed for drawdown resistance,
Especially good”.

<Example 9>
A polycarbonate resin pellet and a film were obtained in the same manner as in Example 8 except that the amount of EHPB was changed to 426 g (1.70 mol).

The viscosity average molecular weight of the obtained polycarbonate resin is 20100, and the glass transition point (Tg)
Is 128° C., the Q value is 28×10 ⁻² cm ³ /s, the thermoformability is a shape, and no cracks, wrinkles or unevenness are observed, which is “especially good”, Regarding the drawdown property, almost no drawdown was observed, and the result was "particularly good".

<Example 10>
Example 8 was repeated except that the amount of EHPB was changed to 445 g (1.78 mol) to obtain a polycarbonate resin pellet and a film.

The viscosity average molecular weight of the obtained polycarbonate resin is 19,200, the glass transition point (Tg)
Is 127° C., the Q value is 34×10 ⁻² cm ³ /s, the thermoformability is a shape, and no cracks, wrinkles, or unevenness are observed, which is “particularly good” and Regarding drawdown property, a slight drawdown was observed, which was “good”.

<Comparative example 2>
Polycarbonate resin pellets and films were obtained in the same manner as in Example 7, except that the amount of PODB was 630 g (2.06 mol).

The viscosity average molecular weight of the obtained polycarbonate resin is 16700, the glass transition point (Tg)
Was 120° C., the Q value was 64×10 ⁻² cm ³ /s, and the drawdown resistance was “poor” because a remarkable drawdown was observed. The thermoformability was "poor" because the thermoformability could not be thermoformed due to the remarkable drawdown.

<Comparative example 3>
A polycarbonate resin pellet and film were obtained in the same manner as in Example 8 except that the amount of EHPB was 514 g (2.06 mol).

The viscosity average molecular weight of the obtained polycarbonate resin is 16500, and the glass transition point (Tg)
Was 124° C., the Q value was 60×10 ⁻² cm ³ /s, and remarkable drawdown was observed with respect to the drawdown resistance, which was “poor”. The thermoformability was "poor" because the thermoformability could not be thermoformed due to the remarkable drawdown.

<Comparative example 4>
In Comparative Example 2, the same operation as in Comparative Example 2 was performed except that PODB was parahydroxybenzoic acid butyl ester (POBB) manufactured by Tokyo Chemical Industry Co., Ltd. and the amount of POBB was 241.5 g (1.24 mol). To obtain a polycarbonate resin pellet and a film.

The viscosity average molecular weight of the obtained polycarbonate resin is 24300, glass transition point (Tg)
Is 141° C., Q value is 7.1×10 ⁻² cm ³ /s, and the thermoformability is “cube” with rounded corners of the cube type, “poor”, and the drawdown resistance is Almost no drawdown was observed, which was "especially good".

<Comparative Example 5>
In Comparative Example 2, except that PODB was parahydroxybenzoic acid propyl ester (POPB) manufactured by Tokyo Chemical Industry Co., Ltd. and the amount of POPB was 224 g (1.24 mol),
The same operation as in Comparative Example 2 was carried out to obtain a polycarbonate resin pellet and a film.

The viscosity average molecular weight of the obtained polycarbonate resin is 23900, glass transition point (Tg)
Is 141° C., the Q value is 7.3×10 ⁻² cm ³ /s, and the thermoformability is “poor” because the cube-shaped corners are rounded, and the drawdown resistance is low. The drawdown was “notably good” with almost no drawdown observed.

<Comparative example 6>
Polycarbonate resin pellets and films were obtained in the same manner as in Example 1 except that the amount of CEPB was 188 g (0.52 mol).

The viscosity average molecular weight of the obtained polycarbonate resin is 46800, the glass transition point (Tg)
Is 146° C., the Q value is 0.5×10 ⁻² cm ³ /s, and the thermoformability is “poor” because the cube-shaped corners are rounded, and the drawdown resistance is low. The drawdown was “notably good” with almost no drawdown observed.

<Comparative Example 7>
A polycarbonate resin pellet and a film were obtained in the same manner as in Comparative Example 6 except that 188 g (0.52 mol) of HDPB was used instead of CEPB in Comparative Example 6.

The viscosity average molecular weight of the obtained polycarbonate resin is 47,000 and the glass transition point is 146.
C, Q value is 0.5×10 ⁻² cm ³ /s, cube shape is rounded and shaped for thermoformability, “poor”, and drawdown resistance is for drawdown. Almost no down was observed, which was “especially good”.

<Comparative Example 8>
Polycarbonate resin pellets and films were obtained in the same manner as in Example 7, except that the amount of PODB was 159 g (0.52 mol).

The obtained polycarbonate resin has a viscosity average molecular weight of 47,700 and a glass transition point of 147.
C, Q value is 0.5×10 ⁻² cm ³ /s, cube shape is rounded and shaped for thermoformability, “poor”, and drawdown resistance is for drawdown. Almost no down was observed, which was “especially good”.

<Comparative Example 9>
A polycarbonate resin pellet and a film were obtained in the same manner as in Example 1, except that the amount of CEPB was changed to 732 g (2.39 mol).

The obtained polycarbonate resin has a viscosity average molecular weight of 16900 and a glass transition point of 112.
° C., Q value is ^{67 × 10 -2 cm 3 / s} , since a significant drawdown was observed for drawdown resistance, it was "poor". The thermoformability was "poor" because the thermoformability could not be thermoformed due to the remarkable drawdown.

<Comparative Example 10>
Polycarbonate resin pellets and a film were obtained in the same manner as in Comparative Example 9, except that CDPB was changed to HDPB732g (2.39 mol) in Comparative Example 9.

The obtained polycarbonate resin has a viscosity average molecular weight of 16800 and a glass transition point of 112.
° C., Q value is ^{67 × 10 -2 cm 3 / s} , since a significant drawdown was observed for drawdown resistance, it was "poor". The thermoformability was "poor" because the thermoformability could not be thermoformed due to the remarkable drawdown.

As shown in Table 2, the polycarbonate resin of the present invention has better thermoformability at low temperatures and better drawdown resistance than conventional polycarbonate resins.
That is, in the polycarbonate resin of each example, EHPB having 8 carbon atoms, CEPB having 16 carbon atoms, HDPB, or the like having a glass transition point of 100° C. to 135° C. and Q The value is 1×10 ⁻² cm ³ /s to 35×10 ⁻² cm ³ /
By adjusting within the range of s, excellent thermoformability and drawdown resistance are realized.
On the other hand, the polycarbonate resins of Comparative Examples 1, 2, 9, and 10 having a large Q value and too high fluidity at high temperature were inferior in drawdown resistance, and PO having a small carbon number of 4 as an end terminating agent.
In Comparative Examples 4 to 8 including Comparative Examples 4 and 5 using BB or POPB, the glass transition point was as high as 141° C. or higher, resulting in poor thermoformability.
Further, as described above, the polycarbonate resin of the present invention, which is excellent in thermoformability and drawdown resistance, can provide a sheet, a film and a molded article having good drawdown resistance.

Claims (8)

A polycarbonate resin obtained by reacting a monohydric phenol represented by the following general formula (1), a dihydric phenol represented by the general formula (2), and a carbonate binder, having a glass transition point of 100°C to 135°C. And a Q value showing melt fluidity is 1×10 ⁻² cm ³ /s to 35×10 ⁻² cm ³ /s,
The Q value is a value measured under the conditions that the load is 160 kgf/cm ² , the orifice is 1 mm in diameter×10 mm in length, and the measurement temperature is 280° C.,
The dihydric phenol represented by the formula (2) contains at least 2,2-bis(4-hydroxyphenyl)propane,
A polycarbonate resin in which the monohydric phenol represented by the formula (1) contains either parahydroxybenzoic acid 2-hexyldecyl ester or parahydroxybenzoic acid hexadecyl ester.
(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms,
R _{2 to} R ₅ each independently represent hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may have a substituent. .. )

(In the formula, R _{6 to} R ₉ are each independently hydrogen, halogen, an alkoxyl group having 1 to 5 carbon atoms which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent. Group, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, and an aryl group having 7 to 17 carbon atoms which may have a substituent An aralkyl group or an alkenyl group having 2 to 15 carbon atoms which may have a substituent,
X is, -O -, - S -, - SO -, - SO 2 -, - CO- and the following formula (3) to (6) of the group selected from is any structure. )
(In the formula, R ₁₀ and R ₁₁ are each hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, a substituent A C6-12 aryl group which may have a group, a C2-5 alkenyl group which may have a substituent, or a C7-17 aralkyl group which may have a substituent. Represents
R ₁₀ and R ₁₁ may be bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms,
c represents an integer of 0 to 20)
(In the formula, R ₁₂ and R ₁₃ are each hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, and a substituent. A C6-12 aryl group which may have a group, a C2-5 alkenyl group which may have a substituent, or a C7-17 aralkyl group which may have a substituent. Represents
R ₁₂ and R ₁₃ may be bonded to each other to form a carbocycle or a heterocycle having 1 to 20 carbon atoms. )
(In the formula, R _{14 to} R ₁₇ are each hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, and a substituent. A C6-12 aryl group which may have a group, a C2-5 alkenyl group which may have a substituent, or a C7-17 aralkyl group which may have a substituent. Represents
R ₁₄ and R ₁₅ , and R ₁₆ and R ₁₇ may be bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms. )
(In formula, R< ₁₈ >-R< ₂₇ > is a hydrogen atom or a C1-C3 alkyl group, respectively. The polycarbonate resin according to claim 1, wherein R _{1 in} the monohydric phenol represented by the formula (1) has 12 to 22 carbon atoms. The polycarbonate resin according to claim 2, wherein the monohydric phenol represented by the formula (1) is selected from para-hydroxybenzoic acid 2-hexyldecyl ester and para-hydroxybenzoic acid hexadecyl ester. The polycarbonate resin according to any one of claims 1 to 3, wherein the dihydric phenol represented by the formula (2) is 2,2-bis(4-hydroxyphenyl)propane. The polycarbonate resin according to any one of claims 1 to 4, having a viscosity average molecular weight of 18,000 to 35,000. The polycarbonate resin according to claim 5, having a viscosity average molecular weight of 22,000 to 28,000. A sheet or film using the polycarbonate resin according to any one of claims 1 to 6 as a raw material. The dihydric phenol represented by the formula (2) is
2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)-p-diisopropylbenzene, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxy-3,5-dimethylphenyl) ) Propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-3) -Ethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diphenylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 2,2-bis(4- Hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, Bis-(4-hydroxy-3-methylphenyl)methane, bis-(4-hydroxy-3-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxy) -3-methylphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane [=bisphenol Z], bis(4-hydroxyphenyl)sulfone, 2, 4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxy-2,5- Diethoxydiphenyl ether, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1-phenyl-1,1-bis(4- Hydroxy-3-methylphenyl)ethane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxy-3-methylphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis( 4-hydroxy-3-methylphenyl)fluorene and 2,2-bis(4-hydroxyphenyl)hexafluoropropane,
At least 2,2-bis (4-hydroxyphenyl) including propane, claim 1 3, 5 and 6 or polycarbonate resin according to one of.