JP3279427B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION This invention relates to specific compounds is 2,5-bis [5'-t-Buchirubenzo thia Zoriru (2)] polycarbonate resin composition without coloration containing thiophene .

[0002]

BACKGROUND OF THE INVENTION The high molecular weight polycarbonates of the present invention are general purpose engineering thermoplastics having a wide range of uses, particularly for injection molding or as glass sheets in place of window glass. Polycarbonate is generally said to be excellent in heat resistance, transparency, and impact resistance.

[0003] As a method for producing polycarbonate, a phosgene method in which a divalent hydroxy compound and phosgene are interfacially polycondensed and reacted, and a transesterification method in which a divalent hydroxy compound and a diester carbonate are reacted in a molten state are generally known. ing.

[0004] A typical example of the transesterification method is to add a transesterification catalyst to dihydric phenol and carbonic acid diester, synthesize a prepolymer while distilling phenol under heating and reduced pressure, and finally prepare a high polymer under high vacuum. And heating to 290 ° C. or higher to distill phenol to obtain a high molecular weight polycarbonate (US Pat. No. 4,345,062).

[0005] In the transesterification method, in order to promote the reaction efficiently, in the initial stage of the reaction, a prepolymer is synthesized in a tank-type reactor having ordinary stirring blades, and subsequently a device such as a horizontal extruder with a vent is used. It is known to carry out a polycondensation reaction to produce a high molecular weight polycarbonate.

However, since high molecular weight polycarbonates have extremely high melt viscosities unlike other engineering plastics, they require a high temperature of 280 ° C. or higher as a reaction condition and distill off monohydric hydroxy compounds having a high boiling point. Therefore, a high vacuum (1 to 10 ^-2 torr) is required, which has a problem of adversely affecting the hue of the produced polycarbonate.

"Polycarbonate resin", 3rd edition, Nikkan Kogyo Shimbun P.64, describes that bisphenol A, which is a monomer, is decomposed when an alkaline catalyst is used to produce a colored substance or a resinous substance. In addition, the produced polycarbonate is subjected to the action of alkali at high temperature, and Kolbe-
It is also described that a side reaction similar to the Schmitt reaction produces branching and crosslinking.

For this reason, it has been strongly desired that the polycarbonate obtained by subjecting a divalent hydroxy compound and a carbonic acid diester to a polycondensation reaction in the presence of a transesterification catalyst has an excellent hue.

[0009]

Means for Solving the Problems The present inventors have developed a compound 2,5 specific to a polycarbonate resin obtained by melt polycondensation.
- by adding bis [5'-t-Buchirubenzo thia Zoriru (2)] thiophene was found that polycarbonate resin composition having excellent hue can be obtained.

[0010] Namely, the present invention is a polycarbonate, characterized in that it contains 2,5-bis [5'-t-Buchirubenzo thia Zoriru (2)] thiophene shown in the polycarbonate resin by the following general formula (I) The present invention relates to a resin composition.

[0011]

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Furthermore, the present invention relates to a polycarbonate resin composition characterized by containing the polycarbonate resin 2,5-bis [5'-t-Buchirubenzo thia Zoriru (2)] thiophene and plasticizers.

[0013] The addition amount of 2,5-bis [5'-t-Buchirubenzo thiazolium <br/> Lil (2)] thiophene, the polycarbonate resin 100 parts by weight, range of 5~500ppm is preferred. If the addition amount is less than 5 ppm, there is no effect of improving the hue, and if it exceeds 500 ppm, not only a bluish color tone is obtained but also the film becomes slightly cloudy and impairs transparency.

When forming a film or sheet, it is preferable to use a plasticizer. Representative examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, 2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, and tri-2-ethylhexyl trimellit. Tate, dicyclohexyl phthalate and the like can be mentioned, and particularly preferred is dicyclohexyl phthalate.

The amount of the plasticizer added is preferably in the range of 50 to 5,000 ppm based on 100 parts by weight of the polycarbonate resin. If the added amount is less than 50 ppm, the uniform dispersibility deteriorates, and if the added amount exceeds 5,000 ppm, not only the bleeding from the polycarbonate resin, not only impairing the appearance but also the glass transition point is too low and the mechanical properties as the polycarbonate resin are too low. Impair.

In the presence of a general transesterification catalyst,
A method for producing a polycarbonate resin obtained by melt polycondensation will be specifically described.

Representative examples of the divalent hydroxy compound include:
Examples include compounds selected from the compounds represented by the following general formulas (1) to (4).

[0018]

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As bisphenols classified into the general formula (1), 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) octane, 4,4′-dihydroxy-2,2,2-
Triphenylethane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and the like.

As bisphenols classified into the general formula (2), 2,2-bis (4-hydroxy-3-methylphenyl) propane and 2,2-bis (4-hydroxy-3-
Isopropylphenyl) propane, 2,2-bis (4-
(Hydroxy-3-sec-butylphenyl) propane, 2,
2-bis (4-hydroxy-3-tert-butylphenyl) propane and the like.

As bisphenols classified into the general formula (3), 1,1'-bis (4-hydroxyphenyl) -p
-Diisopropylbenzene, 1,1'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, and the like.

Examples of bisphenols classified into the general formula (4) include 1,1'-bis (4-hydroxyphenyl) cyclohexane.

Among these, in particular, 2,2-bis (4-
(Hydroxyphenyl) propane is preferred.

Further, it is possible to produce a copolymerized polycarbonate obtained by combining two or three or more divalent hydroxy compounds selected from the compounds represented by the above general formulas (1) to (4). is there.

Further, typical examples of the carbonic acid diester include:
Diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate,
Dicyclohexyl carbonate and the like are used. Of these, diphenyl carbonate is particularly preferred.

In producing a polycarbonate in the present invention, the above-mentioned carbonic acid diester is required to be equimolar to the divalent hydroxy compound present in the reaction system. Generally, in order to produce a high molecular weight polycarbonate, one mole of a carbonate compound and one mole of a divalent hydroxy compound must react. When diphenyl carbonate is used, 2 moles of phenol are formed by the reaction. These two moles of phenol are distilled out of the reaction system. The viscosity [η] of the polycarbonate thus obtained is 0.2 to 0.8 dl / g.

However, when distilling the produced monovalent hydroxy compound out of the system in order to proceed with the reaction, the diester carbonate used as a monomer may be distilled off at the same time. 1.01 to 1.5 mol, preferably 1.015 to 1 mol of phenol
Preferably, it is used in an amount of 〜1.20 mol.

Examples of the transesterification catalyst that can be used in the present invention include an electron-donating amine compound, an alkali metal compound and an alkaline earth metal compound, and a borate. And Na, K, Be, Ca, Sr, Ba, Zn, C
d, Al, Cr, Mo, Fe, Co, Ni, Ag, A
Metals such as u, Sn, Sb, Pb, Pt, and Pd and alcoholates, oxides, carbonates, acetates, hydrides, and the like can also be used.

Representative examples of the electron donating amine compound include 4-dimethylaminopyridine, 4-diethylaminopyridine, 4-pyrrolidinopyridine, 4-aminopyridine, 2-hydroxypyridine, 4-hydroxypyridine, and 2-methoxypyridine. , 4-methoxypyridine, 2
-Methoxyimidazole, 1-methylimidazole, imidazole, aminoquinoline, 4-methylimidazole, diazabicyclooctane (DABCO) and the like.

Representative examples of the alkali metal compound and the alkaline earth metal compound include sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium hydrogen carbonate, lithium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, lithium carbonate, and potassium carbonate. , Sodium acetate, lithium acetate, potassium acetate, sodium stearate, lithium stearate, potassium stearate, sodium borohydride, lithium borohydride, potassium borohydride, sodium benzoate, lithium benzoate, potassium benzoate, water Barium oxide, calcium hydroxide, magnesium hydroxide, barium hydrogen carbonate, calcium hydrogen carbonate, magnesium hydrogen carbonate, barium carbonate, calcium carbonate, magnesium carbonate, barium acetate, calcium acetate, magnesium acetate , Barium stearate, calcium stearate, magnesium stearate, and the like.

Representative examples of borates include sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate, lithium metaborate, lithium tetraborate, lithium pentaborate , Potassium metaborate, potassium tetraborate, potassium pentaborate,
Potassium hexaborate, potassium octaborate, ammonium metaborate, ammonium tetraborate, ammonium pentaborate, ammonium octaborate, ammonium borate, tetramethylammonium borate, aluminum potassium borate, cadmium borate, boric acid Examples include silver, copper borate, lead borate, nickel borate, magnesium borate, and manganese borate.

These transesterification catalysts may be used alone or in combination of two or more. When a plurality of catalysts are used in combination, the catalyst may be added at the same time as the monomer is charged, or may be added stepwise during the reaction.

The amount of the transesterification catalyst to be used ranges from 10 ^-1 mol to 10 ^-8 mol per mol of the dihydric phenol present in the reaction system.
A mole is required, but preferably from 10 ^-2 to 10 ^-7 mole. When the amount is less than 10 ^-8 mol, the catalytic action is small and the polymerization rate of the polycarbonate is slowed. When the amount is 10 ^-1 mol or more, the rate of remaining in the produced polycarbonate is increased, so that the physical properties of the polycarbonate are deteriorated.

Further, boric acid added to the reaction mixture and / or
Or typical examples of borate esters, boric acid, triphenyl borate, trimethyl borate, triethyl borate,
Examples thereof include butyl borate and tolyl borate.
These boric acids and / or boric esters may be added at the beginning of the reaction, or during or after the reaction. These boric acids and / or borate esters have the effect of deactivating the basic polymerization catalyst and increasing the thermal stability of the polymer. The amount of the boric acid and / or boric ester used is based on 1 mol of the basic group and / or the alkali metal atom and the alkaline earth metal atom of the catalyst used.
It is preferably from 0.01 to 500 mol. If it is less than 0.01 mol, there is no effect on heat stabilization, and if it exceeds 500 mol, the degree of polymerization cannot be increased, which is not preferable.

Next, as a typical method of adding the additive, an extruder having a feeder capable of feeding the additive is used, and the additive is continuously added to the molten resin through a feeder. There is a method of kneading with an extruder.

Examples of the additives include a heat stabilizer, a light stabilizer, an ultraviolet absorber, a pigment, and a moldability improver. Examples of the heat stabilizer include organic phosphorus compounds and hindered phenol compounds. Examples of the light stabilizer include a hindered amine compound, and examples of the ultraviolet absorber include a benzotriazole compound.

Representative examples of the phosphorus compound that can be used in the present invention include triethyl phosphite, triisopropyl phosphite, triisodecyl phosphite, tridodecyl phosphite, phenyl diisodecyl phosphite,
Diphenylisodecyl phosphite, triphenyl phosphite, tris-tolyl phosphite, phenyl-bis (4-nonylphenyl) phosphite, tris (4-
Octylphenyl) phosphite, tris (4- (1-
Phenylethyl) phenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenyl represented by the following formula: Range phosphonite,

[0038]

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Pentaerythritol represented by the following formula:
Di [(2,6-di-t-butyl-4-methylphenyl)
Phosphite),

[0040]

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Pentaerythritol represented by the following formula:
Di [(2,4-di-t-butylphenyl) phosphite],

[0042]

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Tetrakis (2,4-di-t-butylphenyl) -4,4 '-(2,2-diphenylpropane) phosphonite represented by the following formula:

[0044]

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Dialkoxyphenylphosphoric acid represented by the following formula

[0046]

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(R ₆ and R _{7 each} represent a linear or branched alkyl group having 1 to 20 carbon atoms, and Ph represents a phenyl group.). The amount of phosphorus compound added is based on the dihydric phenol
10-1000 ppm is preferred. If it is less than 10 ppm, there is no effect on heat stabilization, and if it exceeds 1000 ppm, physical properties are adversely affected.

Representative examples of the hindered phenol compound that can be used in the present invention include octadecylpropionate-3- (3,5-di-t-butyl-4-hydroxyphenyl), N, N'-hexamethylene Bis (3,5-di-
t-butyl-4-hydroxy-hydrocinnamamide),
Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, and compounds represented by the following formulas (A) to (C).

[0049]

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The amount of the hindered phenol compound to be added is preferably 10 to 2000 ppm based on the dihydric phenol. Less than 10ppm has no effect on thermal stabilization, 2000pp
If it exceeds m, physical properties are adversely affected, which is not preferable.

Representative examples of the hindered amine compound which can be used in the present invention include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis-succinic acid
(2,2,6,6-tetramethyl-4-piperidinyl) ester, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid bis (1,2,
2,6,6-ventamethyl-4-piperidyl) and the like.

Representative examples of the benzotriazole compound that can be used in the present invention include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- (3,5-di-t-butyl-2-hydroxyphenyl). ) Benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole,
-(2'-hydroxy-5'-t-octylphenyl)
Benzotriazole and the like.

All of the additives described herein may be used alone or in combination of two or more.

[0054]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples.

First, methods for measuring the viscosity average molecular weight (Mv) and the hue described in the examples and comparative examples will be described.

Viscosity average molecular weight (Mv): The intrinsic viscosity [η] of a methylene chloride solution of the polymer at 20 ° C. was measured using an Ubbelohde viscometer and calculated from the following equation. [Η] = 1.11 × 10 ⁻⁴ (Mv) ^0.82 Hue (YI): Measured using Nippon Denshoku 300A.

Synthesis Example In a nickel-plated tank-type reactor, 4,560 g (20 mol) of 2,2-bis (4-hydroxyphenyl) propane, 4391.5 g (20.5 mol) of diphenyl carbonate and 38 mg (1 × 10 4) of sodium tetraborate were added. ^-4 mol) and 30.9 mg of boric acid (5 × 10 ^-4 mol), dissolved at 160 ° C. under nitrogen, stirred for 1 hour, and then gradually heated under reduced pressure. Polycondensation was carried out for 4 hours, phenol produced was distilled off, and the mixture was further reacted for 50 minutes in a vertical twin-screw self-cleaning reactor to obtain a colorless and transparent polycarbonate. When the viscosity average molecular weight (Mv) of the obtained polycarbonate is measured, it is 2
9,000.

[0058] 2,5-bis shown in polycarbonate 1kg obtained in Example 1 Synthesis Example by the general formula (I) [5'-t-Buchirubenzo thia Zoriru
(2)] 50 mg of thiophene was added and kneaded. The hue (YI) of the obtained polycarbonate resin composition was 9.6.

Comparative Example 1 The hue (YI) of the polycarbonate obtained in the synthesis example was 18.3.

[0060] 2,5-bis represented by the general formula (I) in the polycarbonate 1kg obtained in Example 2 Synthesis Example [5'-t-Buchirubenzo thia Zoriru
(2)] A mixture previously mixed with 50 mg of thiophene and 500 mg of dicyclohexyl phthalate was added and kneaded. The obtained polycarbonate resin composition was extruded from a T-die to form a sheet having a thickness of 2 mm. The hue (YI) of this sheet was 1.9.

Comparative Example 1 The polycarbonate obtained in the synthesis example was extruded from a T-die to form a sheet having a thickness of 2 mm. Hue of this sheet (Y
I) was 4.3.

Claims (12)

(57) [Claims] 1. A polycarbonate resin having the following general formula
Represented by (I) 2,5-bis [5'-t-Buchirubenzo thia <br/> Zoriru (2)] polycarbonate resin composition characterized by containing the thiophene. Embedded image Wherein the polycarbonate resin 100 parts by weight of 2,5-bis [5'-t-Buchirubenzo thia Zoriru (2)
] The polycarbonate resin composition according to claim 1, which contains 5 to 500 ppm of thiophene. 3. The polycarbonate resin composition according to claim 1, further comprising a plasticizer in the polycarbonate resin. 4. The polycarbonate resin composition according to claim 3, which contains 50 to 5,000 ppm of a plasticizer based on 100 parts by weight of the polycarbonate resin. 5. The polycarbonate resin composition according to claim 3, wherein the plasticizer is dicyclohexyl phthalate. 6. The polycarbonate according to claim 1, wherein the polycarbonate resin is a polycarbonate resin obtained by melt polycondensation of a divalent hydroxy compound and a carbonic acid diester in the presence of a transesterification catalyst. -Based resin composition. 7. The polycarbonate resin composition according to claim 6, wherein the transesterification catalyst is an electron donating amine compound and / or an alkali metal compound or an alkaline earth metal compound. 8. The polycarbonate resin composition according to claim 6, wherein the transesterification catalyst is a borate. 9. The polycarbonate resin composition according to claim 1, further comprising boric acid in the polycarbonate resin. 10. The polycarbonate resin composition according to claim 1, further comprising a boric acid ester in the polycarbonate resin. 11. A divalent hydroxy compound represented by the following general formula:
The polycarbonate resin composition according to any one of claims 6 to 10, which is selected from the compounds represented by (1) to (4). Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ represent hydrogen, an alkyl group having 1 to 8 carbon atoms or a linear or branched alkyl group, or a phenyl group, X represents a halogen atom, and n = 0 to 4, m = 1 to 4.) 12. A method comprising using two or three or more selected from the divalent hydroxy compounds according to claim 11.
11. The copolymerized polycarbonate resin composition according to any one of 10 above.