KR100816129B1 - Polycarbonate having pronounced shear thinning behaviour - Google Patents

Polycarbonate having pronounced shear thinning behaviour Download PDF

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KR100816129B1
KR100816129B1 KR1020037012464A KR20037012464A KR100816129B1 KR 100816129 B1 KR100816129 B1 KR 100816129B1 KR 1020037012464 A KR1020037012464 A KR 1020037012464A KR 20037012464 A KR20037012464 A KR 20037012464A KR 100816129 B1 KR100816129 B1 KR 100816129B1
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제임스 메이슨
실케 크라쯔쉬머
우베 헉스
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바이엘 악티엔게젤샤프트
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/307—General preparatory processes using carbonates and phenols

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Abstract

본 발명은 현저한 비-뉴톤 유동 거동 (non-Newtonian flow behaviour)을 갖는 신규의 분지된 용융-중합된 폴리카보네이트, 이것을 함유하는 조성물, 및 이들로부터 생산된 성형체에 관한 것이다. The present invention relates to novel branched melt-polymerized polycarbonates having significant non-Newtonian flow behavior, compositions containing them, and shaped bodies produced therefrom.

용융 폴리카보네이트, 전단율, 유동성 Molten Polycarbonate, Shear Rate, Fluidity

Description

현저한 전단희석 거동을 갖는 폴리카보네이트{POLYCARBONATE HAVING PRONOUNCED SHEAR THINNING BEHAVIOUR}POLYCARBONATE HAVING PRONOUNCED SHEAR THINNING BEHAVIOUR}

본 발명은 현저한 비-뉴톤 유동 거동 (non-Newtonian flow behaviour)을 갖는 신규의 분지된 용융-중합된 폴리카보네이트, 이것을 함유하는 조성물, 및 이들로부터 생산된 성형체에 관한 것이다. 본 발명은 또한 이러한 폴리카보네이트를 제조하는 방법에 관한 것이다.
The present invention relates to novel branched melt-polymerized polycarbonates having significant non-Newtonian flow behavior, compositions containing them, and shaped bodies produced therefrom. The invention also relates to a process for producing such polycarbonates.

폴리카보네이트는 산업적으로 계면방법 (interface process)을 이용하거나, 용융물내에서의 트랜스에스테르화방법 (용융중합방법)에 의해서 생산된다. 용융중합방법은 포스겐 또는 염소화된 용매를 사용하지 않고 수행될 수 있기 때문에 그의 중요성이 증가하고 있다. 현재 주로 사용되고 있는 계면방법에 의해서 생산된 폴리카보네이트는 선형이며, 이러한 폴리머는 어떠한 다작용성 구조단위도 함유하지 않는다. 분지화 (branching)을 일으킬 수 있는 다작용성 구조단위가 결여된 이러한 타입의 선형 폴리카보네이트는 단지 미약한 비-뉴톤 유동 거동을 갖는다. 계면방법중에 분지화를 획득하기 위해서는 분지제가 첨가되어야 한다. 다작용성 구조단위를 갖는 생성된 분지물로 인하여 저전단율에서 폴리머의 유동성은 증가하고, 고전단율에서는 감소한다.Polycarbonates are industrially produced using an interface process or by transesterification in a melt (melt polymerization method). The importance of the melt polymerization process is increasing because it can be carried out without using phosgene or chlorinated solvent. Polycarbonates produced by the interfacial methods currently used are linear and these polymers do not contain any polyfunctional structural units. This type of linear polycarbonate lacking multifunctional structural units that can cause branching has only a weak non-Newtonian flow behavior. In order to obtain branching during the interfacial method, a branching agent must be added. The resulting branching with multifunctional structural units increases the fluidity of the polymer at low shear rates and decreases at high shear rates.

용융중합방법을 사용하여 생산된 폴리카보네이트는 필수적으로 다작용성 구조단위를 함유한다. 중합반응중에 불가피한 다작용성 분지화 구조단위의 생성은 공지되어 있으며, 예를들어 문헌 (Angewandte Chemie 20, pp. 633-660, 1956)에 기술되어 있다.Polycarbonates produced using melt polymerization methods contain essentially multifunctional structural units. The creation of inevitable multifunctional branched structural units during polymerization is known and described, for example, in Angelwandte Chemie 20, pp. 633-660, 1956.

US 5 932 683에는 3개의 특정한 구조단위를 갖는 용융 폴리카보네이트가 형성되는 용융방법이 기술되어 있다. 반응시간과 반응온도 사이의 특별한 관계가 해당 폴리카보네이트의 제조에 대한 파라메터로 언급되어 있다. 기술된 폴리카보네이트는 고전단율에서 특별히 준비된 유동 거동을 갖는다. 그러나, 유동 거동은 통상적으로 저전단율에서의 열등한 유동성과 연관된다.
US 5 932 683 describes a melting process in which molten polycarbonates having three specific structural units are formed. A special relationship between reaction time and reaction temperature is mentioned as a parameter for the preparation of the corresponding polycarbonates. The polycarbonates described have a flow behavior specially prepared at high shear rates. However, flow behavior is typically associated with inferior fluidity at low shear rates.

따라서, 본 발명의 목적은 고전단율에서 우수한 유동성을 갖는 것 이외에도 전단율에서 분지되지 않은 폴리카보네이트 보다 유동성이 작지 않은 용융 폴리카보네이트를 개발하는 것이다.Accordingly, it is an object of the present invention to develop molten polycarbonates which are not less fluid than polycarbonates which are not branched at shear rates in addition to having good fluidity at high shear rates.

이러한 목적은 신규의 4작용성 구조단위를 함유하는 용융 폴리카보네이트를 생산하며, US 5 932 683에 언급된 파라메터에 상응하지 않는 용융방법에 의해서 달성되었다. 그러나, 그러한 특정한 분지된 폴리카보네이트는 그럼에도 불구하고 저전단율에서, 분지되지 않은 폴리카보네이트의 계면으로부터의 유동 거동과 동등한 유동 거동을 나타내면서 고전단율에서의 유동 거동은 개선된다. 따라서, 본 발명 에 따르는 폴리카보네이트는 사출성형시에 특히 성공적으로 사용될 수 있으며, 이것은 또한 압출되는 경우에는 분지되지 않은 폴리카보네이트와 동등하다.This object has been achieved by a melting process which produces a molten polycarbonate containing new tetrafunctional structural units and which does not correspond to the parameters mentioned in US Pat. No. 5,932,683. However, such specific branched polycarbonates nevertheless have improved flow behavior at high shear rates while exhibiting flow behavior equivalent to that from the interface of unbranched polycarbonates at low shear rates. Thus, polycarbonates according to the invention can be used particularly successfully during injection molding, which is also equivalent to unbranched polycarbonates when extruded.

본 발명에 따르는 폴리카보네이트는 하기 화학식 1을 갖는다:Polycarbonates according to the invention have the general formula

Figure 112003035457775-pct00001
Figure 112003035457775-pct00001

여기에서, 사각 괄호는 폴리카보네이트의 반복 구조단위를 포함하고 있으며,Here, square brackets include repeating structural units of polycarbonate,

M은 Ar, 또는 다작용성 화합물 A일 수 있고, 여기에서M can be Ar, or multifunctional compound A, wherein

Ar은 화학식 2로 표시되는 화합물, 또는 특히 바람직하게는 화학식 3으로 표시되는 화합물일 수 있으며,Ar may be a compound represented by the formula (2), or particularly preferably a compound represented by the formula (3),

Figure 112003035457775-pct00002
Figure 112003035457775-pct00002

Figure 112003035457775-pct00003
Figure 112003035457775-pct00003

여기에서, Z는 C1-C8-알킬리덴 또는 C5-C12-사이클로알킬리덴, S, SO2 또는 단일결합이고, R은 치환되거나 비치환된 페닐, 메틸, 프로필, 에틸, 부틸, Cl 또는 Br이며, n은 0, 1 또는 2를 나타내고, Wherein Z is C 1 -C 8 -alkylidene or C 5 -C 12 -cycloalkylidene, S, SO 2 or a single bond, R is substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl, Cl or Br, n represents 0, 1 or 2,

Y는 H 또는 화학식 4의 화합물이며,Y is H or a compound of formula 4,

Figure 112003035457775-pct00004
Figure 112003035457775-pct00004

여기에서, R'는 H, C1-C20-알킬, C6H5 또는 C(CH3) 2C6H5일 수 있고, 동일하거나 상이할 수 있으며, n은 0, 1 또는 2를 나타내고,Wherein R ′ may be H, C 1 -C 20 -alkyl, C 6 H 5 or C (CH 3 ) 2 C 6 H 5 , which may be the same or different and n represents 0, 1 or 2 Indicate,

다작용성 화합물 A는 하기 화학식 A의 화합물이고, 폴리카보네이트내에 201 내지 5000 ppm, 바람직하게는 350 내지 2000 ppm, 가장 바람직하게는 300 내지 1000 ppm의 양으로 존재할 수 있다:Multifunctional compound A is a compound of formula A and may be present in the polycarbonate in an amount of 201 to 5000 ppm, preferably 350 to 2000 ppm, most preferably 300 to 1000 ppm:

Figure 112003035457775-pct00005
Figure 112003035457775-pct00005

여기에서, X는 이하의 화합물 B, C 및 D에서와 같이 Y 또는 -(MOCOO)Y이며, 여기에서 M 및 Y는 상기에서 정의한 바와 같다.Here, X is Y or-(MOCOO) Y as in the following compounds B, C and D, where M and Y are as defined above.

화합물 A는 특히 바람직하게는 하기 화학식 A1의 화합물이다:Compound A is particularly preferably a compound of formula A1:

Figure 112003035457775-pct00006
Figure 112003035457775-pct00006

본 발명에 따르는 폴리카보네이트는 추가로 화합물 B, C 및 D를 함유할 수 있다.The polycarbonates according to the invention may further contain compounds B, C and D.

화합물 B는 하기 화학식 B의 다작용성 화합물일 수 있으며, 폴리카보네이트내에 1501 내지 10,000 ppm, 바람직하게는 1550 내지 3000 ppm, 가장 바람직하게는 1600 내지 2000 ppm의 양으로 존재할 수 있다:Compound B may be a multifunctional compound of formula B and may be present in the polycarbonate in an amount of 1501 to 10,000 ppm, preferably 1550 to 3000 ppm, most preferably 1600 to 2000 ppm:

Figure 112003035457775-pct00007
Figure 112003035457775-pct00007

화합물 B는 특히 바람직하게는 하기 화학식 B1의 화합물이다:Compound B is particularly preferably a compound of formula B1:

Figure 112003035457775-pct00008
Figure 112003035457775-pct00008

화합물 C는 하기 화학식 C의 다작용성 화합물일 수 있으며, 폴리카보네이트내에 351 내지 5000 ppm, 바람직하게는 400 내지 2000 ppm, 가장 바람직하게는 450 내지 1000 ppm의 양으로 존재할 수 있다: Compound C may be a multifunctional compound of formula C and may be present in the polycarbonate in an amount of 351 to 5000 ppm, preferably 400 to 2000 ppm, most preferably 450 to 1000 ppm:                 

Figure 112003035457775-pct00009
Figure 112003035457775-pct00009

화합물 C는 특히 바람직하게는 하기 화학식 C1의 화합물이다:Compound C is particularly preferably a compound of formula C1:

Figure 112003035457775-pct00010
Figure 112003035457775-pct00010

화합물 A1, B, B1, C 및 C1에서 X는 화합물 A에 대해서 정의한 바와 같다.X in compounds A1, B, B1, C and C1 is as defined for compound A.

화합물 D는 하기 화학식 D의 화합물일 수 있으며, 폴리카보네이트내에 751 내지 5000 ppm, 바람직하게는 800 내지 2000 ppm, 가장 바람직하게는 850 내지 1500 ppm의 양으로 존재할 수 있다:Compound D may be a compound of Formula D and may be present in the polycarbonate in an amount of 751 to 5000 ppm, preferably 800 to 2000 ppm, most preferably 850 to 1500 ppm:

Figure 112003035457775-pct00011
Figure 112003035457775-pct00011

화합물 D는 특히 바람직하게는 하기 화학식 D1의 화합물이다: Compound D is particularly preferably a compound of formula D1:                 

Figure 112003035457775-pct00012
Figure 112003035457775-pct00012

본 발명에 따르는 폴리카보네이트는 겔투과 크로마토그라피에 의해서 측정된 것으로 5,000 내지 80,000, 바람직하게는 10,000 내지 60,000, 가장 바람직하게는 15,000 내지 40,000의 중량평균분자량을 가질 수 있다.The polycarbonate according to the present invention is measured by gel permeation chromatography and may have a weight average molecular weight of 5,000 to 80,000, preferably 10,000 to 60,000, most preferably 15,000 to 40,000.

본 발명에 따르는 폴리카보네이트는 또한, 하기 수학식 1에 따르는 전단희석비 y로 정의될 수도 있다:The polycarbonate according to the invention may also be defined by the shear dilution ratio y according to the following equation:

Figure 112003035457775-pct00013
Figure 112003035457775-pct00013

여기에서, x는 폴리카보네이트의 상대점도이다. 전단희석비는 유동 거동을 정량화하는 작용을 한다. 전단희석비는 고전단율에서의 점도에 대한 저전단율에서의 점도의 비이다. 본 발명에 따르면, 전단희석비는 280℃에서 측정된 5000 s-1의 전단율에서의 점도에 대한 50 s-1의 전단율에서의 점도의 비이다.Where x is the relative viscosity of the polycarbonate. Shear dilution ratio serves to quantify the flow behavior. Shear dilution ratio is the ratio of the viscosity at low shear rate to the viscosity at high shear rate. According to the invention, the shear dilution ratio is the ratio of the viscosity at a shear rate of 50 s −1 to the viscosity at a shear rate of 5000 s −1 measured at 280 ° C.

큰 수의 분지화 및 이와 연관된 현저한 비-뉴톤 유동 거동에도 불구하고, 본 발명에 따르는 폴리카보네이트는 사출성형중에 탁월한 색상 및 색상 안정성을 갖는다. 이것은 공지의 용융 폴리카보네이트 보다 현저하게 더 작은 황변현상 (yellowing)을 나타낸다. Despite the large number of branching and associated non-Newtonian flow behaviors, the polycarbonates according to the invention have excellent color and color stability during injection molding. This exhibits significantly smaller yellowing than known molten polycarbonates.                 

용융 트랜스에스테르화 방법에 의한 방향족 폴리카보네이트의 제조는 공지되어 있으며, 예를들어 문헌 ("Schnell", Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York, London, Sydney 1964)에 기술되어 있으며, 문헌 (D.C. Prevorsek, B.T. Debona and Y. Kesten, Corporate Research Center, Allied Chemical Corporation, Moristown, New Jersey 07960, "Synthesis of Poly(ester)carbonate Copolymers" in Journal of Polymer Science, Polymer Chemistry Edition, Vol. 19, 75-90 (1980); D. Freitag, U. Grigo, P.R. Muller, N. Nouvertne, Bayer AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Vol. 11, Second Edition, 1988, pp. 648-718; 마지막으로 Des. U. Grigo, K. Kircher and P.R. Muller "Polycarbonate" in Becker/Braun, Kunststoff-Handbuch, Vol. 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna, 1992, pp. 117-299)을 참고로 한다.The preparation of aromatic polycarbonates by melt transesterification methods is known and described, for example, in "Schnell", Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York, London, Sydney 1964. DC Prevorsek, BT Debona and Y. Kesten, Corporate Research Center, Allied Chemical Corporation, Moristown, New Jersey 07960, "Synthesis of Poly (ester) carbonate Copolymers" in Journal of Polymer Science, Polymer Chemistry Edition , Vol. 19, 75-90 (1980); D. Freitag, U. Grigo, PR Muller, N. Nouvertne, Bayer AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Vol. 11, Second Edition, 1988, pp. 648-718; finally Des. U. Grigo, K. Kircher and PR Muller "Polycarbonate" in Becker / Braun, Kunststoff-Handbuch, Vol. 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich , Vienna, 1992, pp. 117-299).

폴리에스테르 카보네이트일 수도 있는 본 발명에 따르는 폴리카보네이트는 적합한 촉매의 존재하에서 적합한 디페놀과 카본산 디아릴 에스테르의 용융 트랜스에스테르화 반응에 의해서 생산된다. 폴리카보네이트는 또한, 하이드록시 또는 카보네이트 말단그룹을 함유하는 카보네이트 올리고머와 적합한 디페놀 및 카본산 디아릴 에스테르의 축합반응에 의해서 제조될 수도 있다.The polycarbonates according to the invention, which may be polyester carbonates, are produced by melt transesterification of suitable diphenols and carboxylic acid diaryl esters in the presence of a suitable catalyst. Polycarbonates may also be prepared by condensation of carbonate oligomers containing hydroxy or carbonate endgroups with suitable diphenols and carboxylic acid diaryl esters.

본 발명과 관련하여 적합한 카본산 디아릴 에스테르는 디-C6- 내지 C14-아릴 에스테르, 바람직하게는 페놀 또는 알킬-치환된 페놀의 디에스테르, 즉 디페닐 카보네이트, 디크레실 카보네이트 및 디-4-3급-부틸페닐 카보네이트이다. 디페닐 카보네이트가 가장 바람직하다.Suitable carboxylic acid diaryl esters in the context of the present invention are diesters of di-C 6 -to C 14 -aryl esters, preferably phenols or alkyl-substituted phenols, ie diphenyl carbonate, dicresyl carbonate and di- 4-tert-butylphenyl carbonate. Most preferred is diphenyl carbonate.

적합한 카보네이트 올리고머는 220 내지 15,000의 분자량을 갖는 상기 화학식 1로 기술된 것이다.Suitable carbonate oligomers are those described in Formula 1 above having a molecular weight of 220 to 15,000.

적합한 디-C6-C14-아릴 에스테르에는 또한 아릴 치환체의 혼합물을 함유하는 비대칭 디아릴 에스테르가 포함된다. 가장 바람직한 것은 페닐크레실 카보네이트 및 4-3급-부틸페닐 카보네이트이다.Suitable di-C 6 -C 14 -aryl esters also include asymmetric diaryl esters containing a mixture of aryl substituents. Most preferred are phenylcresyl carbonate and 4-tert-butylphenyl carbonate.

적합한 디아릴 에스테르는 또한, 하나 이상의 디-C6-C14-아릴 에스테르의 혼합물을 포함한다. 가장 바람직한 혼합물은 디페닐 카보네이트, 디크레실 카보네이트 및 디-4-3급-부틸페닐 카보네이트의 혼합물이다.Suitable diaryl esters also include mixtures of one or more di-C 6 -C 14 -aryl esters. Most preferred mixtures are mixtures of diphenyl carbonate, dicresyl carbonate and di-4-tert-butylphenyl carbonate.

디페놀 1 몰에 대하여, 카본산 디아릴 에스테르는 1.00 내지 1.30 몰의 양으로, 특히 바람직하게는 1.02 내지 1.20 몰의 양으로, 가장 바람직하게는 1.05 내지 1.15 몰의 양으로 사용될 수 있다.With respect to 1 mole of diphenol, the carboxylic acid diaryl esters can be used in amounts of 1.00 to 1.30 moles, particularly preferably in amounts of 1.02 to 1.20 moles, most preferably in amounts of 1.05 to 1.15 moles.

본 발명과 관련하여 적합한 디하이드록시벤젠 화합물은 하기 화학식 5에 상응하는 화합물이다:Suitable dihydroxybenzene compounds in the context of the present invention are compounds corresponding to formula (5):

Figure 112003035457775-pct00014
Figure 112003035457775-pct00014

상기 식에서,Where

R은 치환되거나 비치환된 페닐, 메틸, 프로필, 에틸, 부틸, Cl 또는 Br이며,R is substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl, Cl or Br,

n은 0, 1 또는 2를 나타낸다.n represents 0, 1 or 2.

가장 바람직한 디하이드록시벤젠 화합물은 1,3-디하이드록시벤젠, 1,4-디하이드록시벤젠 및 1,2-디하이드록시벤젠이다.Most preferred dihydroxybenzene compounds are 1,3-dihydroxybenzene, 1,4-dihydroxybenzene and 1,2-dihydroxybenzene.

본 발명과 관련하여 적합한 디페놀은 하기 화학식 6에 상응하는 화합물이다:Suitable diphenols in the context of the present invention are compounds corresponding to formula (6)

Figure 112003035457775-pct00015
Figure 112003035457775-pct00015

상기 식에서,Where

Z는 C1-C8-알킬리덴 또는 C5-C12-사이클로알킬리덴, S, SO2 또는 단일결합이며,Z is C 1 -C 8 -alkylidene or C 5 -C 12 -cycloalkylidene, S, SO 2 or a single bond,

R은 치환되거나 비치환된 페닐, 메틸, 프로필, 에틸, 부틸, Cl 또는 Br이고,R is substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl, Cl or Br,

n은 0, 1 또는 2를 나타낸다.n represents 0, 1 or 2.

바람직한 디페놀은 4,4'-디하이드록시디페닐, 4,4'-디하이드록시디페닐 설파이드, 1,1-비스(4-하이드록시페닐)사이클로헥산, 1,2-비스(4-하이드록시페닐)벤젠, 1,3-비스(4-하이드록시페닐)벤젠, 1,4-비스(4-하이드록시페닐)벤젠, 비스(4-하이드록시페닐)메탄, 2,2-비스(4-하이드록시페닐)프로판, 2,4-비스(4-하이드록시페닐)-2-메틸부탄, 2,2-비스(3-메틸-4-하이드록시페닐)프로판, 2,2-비스(3-클로로-4-하이 드록시페닐)프로판, 비스(3,5-디메틸-4-하이드록시페닐)메탄, 2,2-비스(3,5-디메틸-4-하이드록시페닐)프로판, 비스(3,5-디메틸-4-하이드록시페닐)설폰, 비스(4-하이드록시페닐)설폰, 1,2-비스[2-(4-하이드록시페닐)이소프로필]벤젠, 1,3-비스[2-(4-하이드록시페닐)이소프로필]벤젠, 1,4-비스[2-(4-하이드록시페닐)이소프로필]벤젠, 1,1-비스(4-하이드록시페닐)-1-페닐에탄, 2,4-비스(4-하이드록시페닐)-2-메틸부탄, 2,2-비스(3,5-디클로로-4-하이드록시페닐)프로판, 2,2-비스(3,5-디브로모-4-하이드록시페닐)프로판 및 1,1-비스(4-하이드록시페닐)-3,3,5-트리메틸사이클로헥산이다.Preferred diphenols are 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl sulfide, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,2-bis (4- Hydroxyphenyl) benzene, 1,3-bis (4-hydroxyphenyl) benzene, 1,4-bis (4-hydroxyphenyl) benzene, bis (4-hydroxyphenyl) methane, 2,2-bis ( 4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis ( 3-chloro-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, 1,2-bis [2- (4-hydroxyphenyl) isopropyl] benzene, 1,3-bis [2- (4-hydroxyphenyl) isopropyl] benzene, 1,4-bis [2- (4-hydroxyphenyl) isopropyl] benzene, 1,1-bis (4-hydroxyphenyl) -1- Phenylethane, 2,4-bis (4- Idoxyphenyl) -2-methylbutane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) Propane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

가장 바람직한 디페놀은 1,1-비스(4-하이드록시페닐)-1-페닐에탄, 2,2-비스(4-하이드록시페닐)프로판, 4,4'-디하이드록시디페닐, 1,1-비스(4-하이드록시페닐)-3,3,5-트리메틸사이클로헥산, 2,2-비스(3,5-디브로모-4-하이드록시페닐)프로판 및 1,3-비스[2-(4-하이드록시페닐)이소프로필]벤젠이다.Most preferred diphenols are 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl, 1, 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and 1,3-bis [2 -(4-hydroxyphenyl) isopropyl] benzene.

적합한 디페놀에는 또한 하나 이상의 디페놀의 혼합물이 포함되며, 이 경우에는 코폴리카보네이트가 형성될 수 있다. 가장 바람직한 혼합물은 1,3-비스[2-(4-하이드록시페닐)이소프로필]벤젠, 1,1-비스(4-하이드록시페닐)-3,3,5-트리메틸사이클로헥산, 2,2-비스(4-하이드록시페닐)프로판, 4,4'-디하이드록시디페닐 및 2,2-비스(3,5-디브로모-4-하이드록시페닐)프로판이다.Suitable diphenols also include mixtures of one or more diphenols, in which case copolycarbonates may be formed. Most preferred mixtures are 1,3-bis [2- (4-hydroxyphenyl) isopropyl] benzene, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2 -Bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

또한, 3개의 작용성 페놀 OH 그룹을 함유하는 화합물과 같은 분지제 (branching agent)가 첨가될 수 있다. 이것은 명백하게 폴리머를 분지시킬 수 있으며, 비-뉴톤 폴리머를 증가시킬 수 있다. 적합한 분지제에는 플로로글루시놀, 3,3-비스(3-메틸-4-하이드록시페닐)-2-옥소-2,3-디하이드로인돌, 4,6-디메틸-2,4,6-트리스(4-하이드록시페닐)헵트-2-엔, 4,6-디메틸-2,4,6-트리스(4-하이드록시페닐)헵탄, 1,3,5-트리스(4-하이드록시페닐)벤젠, 1,1,1-트리스(4-하이드록시페닐)에탄, 트리스(4-하이드록시페닐)페닐메탄, 2,2-비스[4,4-비스(4-하이드록시페닐)사이클로헥실]프로판, 2,4-비스(4-하이드록시페닐이소프로필)페놀, 2,6-비스(2-하이드록시-5'-메틸벤질)-4-메틸페놀, 2-(4-하이드록시페닐)-2-(2,4-디하이드록시페닐)프로판, 헥사키스(4-(4-하이드록시페닐이소프로필)페닐)오르토테레프탈레이트, 테트라키스(4-하이드록시페닐)메탄, 테트라키스(4-(4-하이드록시페닐이소프로필)페녹시)메탄 및 1,4-비스(4',4"-디하이드록시트리페닐)메틸)벤젠, 이사틴비스크레졸, 펜타에리트리톨, 2,4-디하이드록시벤조산, 트리메신산 및 시아누르산이 포함된다.In addition, branching agents such as compounds containing three functional phenol OH groups can be added. This can obviously branch polymers and increase non-Newtonian polymers. Suitable branching agents include phloroglucinol, 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole, 4,6-dimethyl-2,4,6- Tris (4-hydroxyphenyl) hept-2-ene, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) Benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] Propane, 2,4-bis (4-hydroxyphenylisopropyl) phenol, 2,6-bis (2-hydroxy-5'-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) 2- (2,4-dihydroxyphenyl) propane, hexakis (4- (4-hydroxyphenylisopropyl) phenyl) ortho terephthalate, tetrakis (4-hydroxyphenyl) methane, tetrakis (4 -(4-hydroxyphenylisopropyl) phenoxy) methane and 1,4-bis (4 ', 4 "-dihydroxytriphenyl) methyl) benzene, isatin biscresol, pentaerytri Tol, 2,4-dihydroxybenzoic acid, trimesic acid and cyanuric acid.

본 발명에 따르는 폴리카보네이트의 제조에 적합한 촉매는 예를들어, 하기 화학식 7의 촉매이다:Suitable catalysts for the preparation of the polycarbonates according to the invention are, for example, catalysts of the formula:

Figure 112003035457775-pct00016
Figure 112003035457775-pct00016

상기 식에서,Where

R1, R2, R3 및 R4는 동일하거나 상이한 C1- 내지 C8-알킬렌, C6- 내지 C10-아릴 또는 C5- 내지 C6-사이클로알킬을 나타낼 수 있고, R 1 , R 2 , R 3 and R 4 may represent the same or different C 1 -C 8 -alkylene, C 6 -C 10 -aryl or C 5 -C 6 -cycloalkyl,

X-는 음이온 (여기에서 상응하는 산-염기 쌍 H+ + X ↔ HX-는 < 11의 pKb를 갖는다) 뿐만 아니라 공촉매를 나타낼 수 있다.X − can represent a cocatalyst as well as an anion (where the corresponding acid-base pair H + + X ↔ HX − has a pK b of <11).

바람직한 촉매는 테트라페닐포스포늄 플루오라이드, 테트라페닐포스포늄 테트라페닐보레이트 및 테트라페닐포스포늄 페놀레이트이다. 테트라페닐포스포늄 페놀레이트가 가장 바람직하다. 포스포늄 염 촉매의 바람직한 양은 디페놀의 몰 당, 10-2 내지 10-8 몰이며, 가장 바람직한 촉매의 양은 디페놀의 몰 당, 10-4 내지 10-6 몰이다. 중합반응의 속도를 증가시키기 위해서 포스포늄 염 이외에 추가의 공촉매가 사용된다. 이러한 공촉매에는 알칼리 금속 및 알칼리 토금속의 염, 예를들어 리튬, 나트륨 및 칼륨의 하이드록사이드, 알콕사이드 및 아릴 옥사이드, 바람직하게는 나트륨의 하이드록사이드, 알콕사이드 또는 아릴 옥사이드가 포함된다. 가장 바람직한 것은 수산화나트륨 및 나트륨 페놀레이트이다. 공촉매의 양은 각각의 경우에 나트륨으로 계산하여 201 내지 10,000 ppb, 바람직하게는 220 내지 1500 ppb, 가장 바람직하게는 240 내지 500 ppb의 범위이다.Preferred catalysts are tetraphenylphosphonium fluoride, tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium phenolate. Tetraphenylphosphonium phenolate is most preferred. The preferred amount of phosphonium salt catalyst is 10 -2 to 10 -8 moles, per mole of diphenol, and the most preferred amount of catalyst is 10 -4 to 10 -6 moles, per mole of diphenol. Additional cocatalysts are used in addition to the phosphonium salts to increase the rate of polymerization. Such cocatalysts include salts of alkali and alkaline earth metals, for example hydroxides, alkoxides and aryl oxides of lithium, sodium and potassium, preferably hydroxides, alkoxides or aryl oxides of sodium. Most preferred are sodium hydroxide and sodium phenolate. The amount of cocatalyst is in each case in the range of 201 to 10,000 ppb, preferably 220 to 1500 ppb, most preferably 240 to 500 ppb, calculated as sodium.

폴리카보네이트는 150℃ 내지 400℃의 온도로 단계적으로 수행되는 반응조건하에서 제조될 수 있으며, 각 단계에서의 체류시간은 15분 내지 5시간일 수 있고, 압력은 1000 내지 0.01 mbar이다.The polycarbonate may be prepared under reaction conditions carried out stepwise at a temperature of 150 ° C. to 400 ° C., the residence time in each step may be 15 minutes to 5 hours, and the pressure is 1000 to 0.01 mbar.

본 발명은 또한, 본 발명에 따르는 폴리카보네이트를 함유하는 폴리카보네이트 조성물 뿐만 아니라, 이러한 조성물을 함유하는 성형체를 제공한다.The present invention also provides a polycarbonate composition containing the polycarbonate according to the present invention, as well as a molded article containing such a composition.

본 발명에 따르는 조성물은 폴리카보네이트 또는 폴리에스테르 카보네이트 이외에도 추가의 폴리머 구성성분 및 통상적인 첨가제를 함유할 수 있다. 이용할 수 있는 폴리머 구성성분은 예를들어 스티렌/아크릴/니트릴 터폴리머 (SAN), 아크릴/부타디엔/스티렌 터폴리머 (ABS), 폴리메틸 메타크릴레이트 (PMMA), 불소화된 폴리올레핀 (PTFE), 폴리페닐스티렌 (PPS), 폴리에틸렌, 폴리프로필렌 및 에틸렌/프로필렌 고무와 같은 폴리올레핀, 에폭시 수지, 폴리부틸렌 테레프탈레이트 (PBT), 폴리에틸렌 테레프탈레이트 (PET), 폴리사이클로헥센디메탄올 (PCT), 두가지 구성성분의 비가 1:4로 된 에틸렌글리콜과 사이클로헥센 디메탄올 테레프탈산의 코폴리에스테르 (PCTG), 두가지 구성성분의 비가 4:1로 된 에틸렌글리콜과 사이클로헥센 디메탄올 테레프탈산의 코폴리에스테르 (PETG)와 같은 폴리에스테르, 및 계면방법에 의해서 생산된 그밖의 다른 폴리카보네이트, 및 또한 전술한 성분들의 혼합물이다. 추가의 첨가제는 이형제, 안정화제, 항산화제, 내화제 (flame-proofing agents), 착색제 및 안료, 대전방지제, 핵형성제, 항-드립핑제 (anti-dripping agents), 및 유기 및 추가의 무기 충진제 및 보강제를 포함한다.The composition according to the invention may contain further polymer components and customary additives in addition to polycarbonates or polyester carbonates. Polymer components that can be used are, for example, styrene / acryl / nitrile terpolymer (SAN), acrylic / butadiene / styrene terpolymer (ABS), polymethyl methacrylate (PMMA), fluorinated polyolefin (PTFE), polyphenyl Polyolefins such as styrene (PPS), polyethylene, polypropylene and ethylene / propylene rubber, epoxy resins, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polycyclohexene dimethanol (PCT), Copolyester (PCTG) of ethylene glycol and cyclohexene dimethanol terephthalic acid in a 1: 4 ratio, and copolyester (PETG) of ethylene glycol and cyclohexene dimethanol terephthalic acid in a two-component ratio of 4: 1 Esters, and other polycarbonates produced by interfacial processes, and also mixtures of the aforementioned components. Additional additives include release agents, stabilizers, antioxidants, flame-proofing agents, colorants and pigments, antistatic agents, nucleating agents, anti-dripping agents, and organic and additional inorganic fillers and Adjuvants.

본 발명에 따르는 폴리카보네이트는 본 발명에 따르는 조성물내에 조성물의 중량을 기준으로하여 바람직하게는 5 내지 95 wt.%, 특히 바람직하게는 10 내지 90 wt.%, 가장 특히 바람직하게는 20 내지 80 wt.%의 양으로 존재할 수 있다. 본 발명에 따르는 조성물의 추가의 폴리머 구성성분은 조성물의 중량을 기준으로하여 바람직하게는 1 내지 60 wt.%, 특히 바람직하게는 1 내지 40 wt.%, 가장 바람직하게는 2 내지 30 wt.%의 양으로 존재할 수 있다.The polycarbonates according to the invention are preferably 5 to 95 wt.%, Particularly preferably 10 to 90 wt.%, Most particularly preferably 20 to 80 wt, based on the weight of the composition in the composition according to the invention. It may be present in an amount of.%. The further polymer component of the composition according to the invention is preferably 1 to 60 wt.%, Particularly preferably 1 to 40 wt.%, Most preferably 2 to 30 wt.%, Based on the weight of the composition. It may be present in an amount of.

조성물은 충진되거나 보강된 성형조성물을 기준으로하여 60 wt.% 이하, 바람 직하게는 10 내지 40 wt.%의 충진제 및/또는 보강제와 같은 무기물질을 함유할 수 있다. 내화제는 본 발명에 따르는 조성물내에 조성물의 중량을 기준으로하여 35 wt.% 이하, 바람직하게는 10 내지 25 wt.%의 양으로 존재할 수 있다.The composition may contain up to 60 wt.%, Preferably 10 to 40 wt.% Of inorganic materials, such as fillers and / or reinforcing agents, based on the filled or reinforced molding composition. The refractory agent may be present in the composition according to the invention in an amount of up to 35 wt.%, Preferably from 10 to 25 wt.%, Based on the weight of the composition.

폴리카보네이트/폴리에스테르 카보네이트 이외에, 본 발명에 따르는 조성물내에 아마도 포함될 수 있는 이들 및 추가의 구성성분 또는 첨가제는 이하에 예를들어 설명하였다.In addition to polycarbonate / polyester carbonates, these and further components or additives which may possibly be included in the compositions according to the invention are described by way of example below.

이들 물질은 예를들어, 문헌 (Additives for Plastics Handbook, John Murphy, 1999)과 같은 다수의 문헌들에서 볼 수 있으며, 시판품으로 이용할 수 있다.These materials can be found in a number of documents, such as, for example, Additives for Plastics Handbook, John Murphy, 1999, and are available commercially.

1. 적합한 항산화제는 예를들어 다음과 같다: 1. Suitable antioxidants are for example:

1.1. 알킬화된 모노페놀, 예를들어 2,6-디-3급-부틸-4-메틸페놀, 2-3급-부틸-4,6-디메틸페놀, 2,6-디-3급-부틸-4-에틸, 2,6-디-3급-부틸-4-n-부틸페놀, 2,6-디-3급-부틸-4-이소부틸페놀, 2,6-디사이클로펜틸-4-메틸페놀, 2-(α-메틸사이클로헥실)-4,6-디메틸페놀, 2,6-디옥타데실-4-메틸페놀, 2,4,6-트리사이클로헥실페놀, 2,6-디-3급-부틸-4-메톡시메틸페놀, 측쇄에서 선형이거나 분지될 수 있는 노닐페놀, 예를들어 2,6-디노닐-4-메틸페놀, 2,4-디메틸-6-(1'-메틸운데크-1'-일)페놀, 2,4-디메틸-6-(1'-메틸헵타데크-1'-일)페놀, 2,4-디메틸-6-(1'-메틸트리데크-1'-일)페놀.1.1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-3-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4 -Ethyl, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol , 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tertiary -Butyl-4-methoxymethylphenol, nonylphenol which may be linear or branched in the side chain, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylun Deck-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1 ' -Yl) phenol.

1.2. 알킬티오메틸페놀, 예를들어 2,4-디옥틸티오메틸-6-3급-부틸페놀, 2,4-디옥틸티오메틸-6-메틸페놀, 2,4-디옥틸티오메틸-6-에틸페놀, 2,6-디도데실티오메 틸-4-노닐페놀.1.2. Alkylthio methyl phenols, such as 2,4-di-octyl thiomethyl -6-3-tert-butylphenol, 2,4-di-octyl-thio-6-methylphenol, 2,4-octylthio-6- Ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

1.3. 하이드로퀴논 및 알킬화된 하이드로퀴논, 예를들어 2,6-디-3급-부틸-4-메톡시페놀, 2,5-디-3급-부틸하이드로퀴논, 2,5-디-3급-아밀하이드로퀴논, 2,6-디페닐-4-옥타데실옥시페놀, 2,6-디-3급-부틸하이드로퀴논, 2,5-디-3급-부틸-4-하이드록시아니솔, 3,5-디-3급-부틸-4-하이드록시아니솔, 3,5-디-3급-부틸-4-하이드록시페닐 스테아레이트 및 비스(3,5-디-3급-부틸-4-하이드록시페닐)아디페이트.1.3. Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert- Amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3 , 5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and bis (3,5-di-tert-butyl-4 Hydroxyphenyl) adipate.

1.4. 토코페롤, 예를들어 α-토코페롤, β-토코페롤, γ-토코페롤, δ-토코페롤 및 이들의 혼합물 (비타민 E).1.4. Tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

1.5. 하이드록실화 티오디페닐 에테르, 예를들어 2,2'-티오비스(6-3급-부틸-4-메틸페놀), 2,2'-티오비스(4-옥틸페놀), 4,4'-티오비스(6-3급-부틸-3-메틸-페놀), 4,4'-티오비스(6-3급-부틸-2-메틸페놀), 4,4'-티오비스(3,6-디-2급-아밀-페놀), 4,4'-비스(2,6-디메틸-4-하이드록시-페놀)디설파이드.1.5. Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4 ' -Thiobis (6-tert-butyl-3-methyl-phenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6 Di-tert-amyl-phenol), 4,4'-bis (2,6-dimethyl-4-hydroxy-phenol) disulfide.

1.6. 알킬리덴비스페놀, 예를들어 2,2'-메틸렌비스(6-3급-부틸-4-메틸페놀), 2,2'-메틸렌비스(6-3급-부틸-4-에틸페놀), 2,2'-메틸렌비스[4-메틸-6-(α-메틸사이클로헥실)페놀], 2,2'-메틸렌비스(4-메틸-6-사이클로헥실-페놀), 2,2'-메틸렌비스(6-노닐-4-메틸페놀), 2,2'-메틸렌비스(4,6-디-3급-부틸페놀), 2,2'-에틸리덴비스(4,6-디-3급-부틸페놀), 2,2'-에틸리덴비스(6-3급-부틸-4-이소부틸페놀), 2,2'-메틸렌비스[6-(α-메틸벤질)-4-노닐페놀], 2,2'-메틸렌비스[6-(α,α-디메틸벤질)-4-노닐페놀], 4,4'-메틸렌비스(2,6-디-3급-부틸페놀), 4,4'-메틸렌 비스(6-3급-부틸-2-메틸페놀), 1,1-비스(5-3급-부틸-4-하이드록시-2-메틸페닐)부탄, 2,6-비스(3-3급-부틸-5-메틸-2-하이드록시벤질)-4-메틸페놀, 1,1,3-트리스(5-3급-부틸-4-하이드록시-2-메틸페닐)부탄, 1,1-비스(5-3급-부틸-4-하이드록시-2-메틸페닐)-3-n-도데실머캅토부탄, 에틸렌글리콜-비스[3,3-비스(3'-3급-부틸-4'-하이드록시페닐)부티레이트], 비스(3-3급-부틸-4-하이드록시-5-메틸페닐)디사이클로펜타디엔, 비스[2-(3'-3급-부틸-2'-하이드록시-5'-메틸벤질)-6-3급-부틸-4-메틸페닐]-테레프탈레이트, 1,1-비스(3,5-디메틸-2-하이드록시페닐)부탄, 2,2-비스(3,5-디-3급-부틸-4-하이드록시페닐)프로판, 2,2-비스(5-3급-부틸-4-하이드록시-2-메틸페닐)-4-n-도데실머캅토부탄, 1,1,5,5-테트라-(5-3급-부틸-4-하이드록시-2-메틸페닐)펜탄.1.6. Alkylidenebisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2 , 2'-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexyl-phenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert- Butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4 ' Methylene bis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-3) Tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1- Bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercapto Butane, ethylene glycol-bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (tert-butyl-4-hydroxy-5-methylphenyl) di Cyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] -terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tertiary -Butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane .

1.7. O-, N- 및 S-벤질 화합물, 예를들어 3,5,3',5'-테트라-3급-부틸-4,4'-디하이드록시디벤질 에테르, 옥타데실-4-하이드록시-3,5-디메틸벤질 머캅토아세테이트, 트리데실-4-하이드록시-3,5-디-3급-부틸벤질 머캅토아세테이트, 트리스(3,5-디-3급-부틸-4-하이드록시벤질)아민, 비스(4-3급-부틸-3-하이드록시-2,6-디메틸벤질)디티오테레프탈레이트, 비스(3,5-디-3급-부틸-4-하이드록시벤질)설파이드, 이소옥틸-3,5-디-3급-부틸-4-하이드록시벤질 머캅토아세테이트.1.7. O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy -3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydrate Hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) Sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

1.8. 하이드록시벤질화된 말로네이트, 예를들어 디옥타데실-2,2-비스(3,5-디-3급-부틸-2-하이드록시벤질)말로네이트, 디옥타데실-2-(3-3급-부틸-4-하이드록시-5-메틸벤질)말로네이트, 디도데실머캅토에틸-2,2-비스(3,5-디-3급-부틸-4-하이드록시벤질)말로네이트, 비스[4-(1,1,3,3-테트라메틸부틸)페닐]-2,2-비스(3,5-디-3급-부틸-4-하이드록시벤질)말로네이트.1.8. Hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3- Tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, Bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.9. 방향족 하이드록시벤질 화합물, 예를들어 1,3,5-트리스-(3,5-디-3급-부틸-4-하이드록시벤질)-2,4,6-트리메틸벤젠, 1,4-비스(3,5-디-3급-부틸-4-하이드록시벤질)-2,3,5,6-테트라메틸벤젠, 2,4,6-트리스(3,5-디-3급-부틸-4-하이드록시벤질)페놀.1.9. Aromatic hydroxybenzyl compounds such as 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) phenol.

1.10. 트리아진 화합물, 예를들어 2,4-비스(옥틸머캅토)-6-(3,5-디-3급-부틸-4-하이드록시아닐리노)-1,3,5-트리아진, 2-옥틸머캅토-4,6-비스(3,5-디-3급-부틸-4-하이드록시아닐리노)-1,3,5-트리아진, 2-옥틸머캅토-4,6-비스(3,5-디-3급-부틸-4-하이드록시페녹시)-1,3,5-트리아진, 2,4,6-트리스(3,5-디-3급-부틸-4-하이드록시페녹시)-1,2,3-트리아진, 1,3,5-트리스(3,5-디-3급-부틸-4-하이드록시벤질)이소시아누레이트, 1,3,5-트리스(4-3급-부틸-3-하이드록시-2,6-디메틸벤질)이소시아누레이트, 2,4,6-트리스(3,5-디-3급-부틸-4-하이드록시페닐에틸)-1,3,5-트리아진, 1,3,5-트리스(3,5-디-3급-부틸-4-하이드록시-페닐프로피오닐)-헥사하이드로-1,3,5-트리아진, 1,3,5-트리스(3,5-디사이클로헥실-4-하이드록시벤질)이소시아누레이트.1.10. Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2 -Octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4- Hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5 -Tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy Phenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) -hexahydro-1,3,5 Triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11. 아실아미노페놀, 예를들어 4-하이드록시라우라닐리드, 4-하이드록시스테아라닐리드, 옥틸-N-(3,5-디-3급-부틸-4-하이드록시페닐)카바메이트.1.11. Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1.12. 일가 또는 다가 알콜, 예를들어 메탄올, 에탄올, n-옥탄올, i-옥탄올, 옥타데칸올, 1,6-헥산디올, 1,9-노난디올, 에틸렌글리콜, 1,2-프로판디올, 네오펜 틸글리콜, 티오디에틸렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 펜타에리트리톨, 트리스(하이드록시에틸)이소시아누레이트, N,N'-비스(하이드록시에틸)-옥사미드, 3-티아운데칸올, 3-티아펜타데칸올, 트리메틸헥산디올, 트리메틸올프로판, 4-하이드록시메틸-1-포스파-2,6,7-트리옥사비사이클로[2.2.2]옥탄과 β-(3,5-디-3급-부틸-4-하이드록시페닐)프로피온산과의 에스테르.1.12. Monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, Neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) -oxamide, 3- Thioundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and β- ( Ester with 3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid .

1.13. 일가 또는 다가 알콜, 예를들어 메탄올, 에탄올, n-옥탄올, i-옥탄올, 옥타데칸올, 1,6-헥산디올, 1,9-노난디올, 에틸렌글리콜, 1,2-프로판디올, 네오펜틸글리콜, 티오디에틸렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 펜타에리트리톨, 트리스(하이드록시에틸)이소시아누레이트, N,N'-비스(하이드록시에틸)-옥사미드, 3-티아운데칸올, 3-티아펜타데칸올, 트리메틸헥산디올, 트리메틸올프로판, 4-하이드록시메틸-1-포스파-2,6,7-트리옥사비사이클로[2.2.2]옥탄과 β-(5-3급-부틸-4-하이드록시-3-메틸페닐)프로피온산과의 에스테르.1.13. Monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, Neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) -oxamide, 3-thia Undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and β- (5 Ester with tert-butyl-4-hydroxy-3-methylphenyl) propionic acid .

1.14. 일가 또는 다가 알콜, 예를들어 메탄올, 에탄올, 옥탄올, 옥타데칸올, 1,6-헥산디올, 1,9-노난디올, 에틸렌글리콜, 1,2-프로판디올, 네오펜틸글리콜, 티오디에틸렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 펜타에리트리톨, 트리스(하이드록시에틸)이소시아누레이트, N,N'-비스(하이드록시에틸)-옥사미드, 3-티아운데칸올, 3-티아펜타데칸올, 트리메틸헥산디올, 트리메틸올프로판, 4-하이드록시메틸-1-포스파-2,6,7-트리옥사비사이클로[2.2.2]옥탄과 β-(3,5-디사이클로헥실-4-하이드록시페닐)프로피온산과의 에스테르.1.14. Monohydric or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene Glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) -oxamide, 3-thiaoundanol, 3-thiapenta Decanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and β- (3,5-dicyclohexyl- Ester with 4-hydroxyphenyl) propionic acid .

1.15. 일가 또는 다가 알콜, 예를들어 메탄올, 에탄올, 옥탄올, 옥타데칸올, 1,6-헥산디올, 1,9-노난디올, 에틸렌글리콜, 1,2-프로판디올, 네오펜틸글리콜, 티오디에틸렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 펜타에리트리톨, 트리스(하이드록시에틸)이소시아누레이트, N,N'-비스(하이드록시에틸)-옥사미드, 3-티아운데칸올, 3-티아펜타데칸올, 트리메틸헥산디올, 트리메틸올프로판, 4-하이드록시메틸-1-포스파-2,6,7-트리옥사비사이클로[2.2.2]옥탄과 3,5-디-3급-부틸-4-하이드록시페닐아세트산과의 에스테르.1.15. Monohydric or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene Glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) -oxamide, 3-thiaoundanol, 3-thiapenta Decanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and 3,5-di-tert-butyl- Esters with 4-hydroxyphenylacetic acid .

1.16. β-(3,5-디-3급-부틸-4-하이드록시페닐)프로피온산의 아미드, 예를들어 N,N'-비스(3,5-디-3급-부틸-4-하이드록시페닐프로피오닐)헥사메틸렌디아미드, N,N'-비스(3,5-디-3급-부틸-4-하이드록시페닐프로피오닐)트리메틸렌디아미드, N,N'-비스(3,5-디-3급-부틸-4-하이드록시페닐프로피오닐)하이드라지드, N,N'-비스[2-(3-[3,5-디-3급-부틸-4-하이드록시페닐]프로피오닐옥시)에틸]옥사미드 (유니로얄사 (Uniroyal)의 나우가드 (Naugard™) XL-1).1.16. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid , for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenyl Propionyl) hexamethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamide, N, N'-bis (3,5- Di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propy Onyloxy) ethyl] oxamide (Naugard ™ XL-1 from Uniroyal).

1.17. 아스코르빈산 (비타민 C)1.17. Ascorbic acid (vitamin C)

1.18. 아민-타입 항산화제, 예를들어 N,N'-디이소프로필-p-페닐렌디아민, N,N'-디-2급-부틸-p-페닐렌디아민, N,N'-비스(1,4-디메틸펜틸)-p-페닐렌디아민, N,N'-비스(1-에틸-3-메틸펜틸)-p-페닐렌디아민, N,N'-비스(1-메틸헵틸)-p-페닐렌디아민, N,N'-디사이클로헥실-p-페닐렌디아민, N,N'-디페닐-p-페닐렌디아민, N,N'-비스(2-나프틸)-p-페닐렌디아민, N-이소프로필-N'-페닐-p-페닐렌디아민, N-(1,3-디메틸부틸)-N'-페닐-p-페닐렌디아민, N-(1-메틸헵틸)-N'-페닐-p-페닐렌디아민, N-사이클로헥실-N'-페닐-p-페닐렌디아민, 4-(p-톨루엔설파모일)디페닐아민, N,N'-디메틸- N,N'-디-2급-부틸-p-페닐렌디아민, 디페닐아민, N-알릴-디페닐아민, 4-이소프로폭시디페닐아민, N-페닐-1-나프틸아민, N-(4-3급-옥틸페닐)-1-나프틸아민, N-페닐-2-나프틸아민, 옥틸화된 디페닐아민, 예를들어 p,p'-디-3급-옥틸디페닐아민, 4-n-부틸아미노페놀, 4-n-부티릴아미노페놀, 4-노나노일아미노페놀, 4-도데카노일아미노페놀, 4-옥타데카노일아미노페놀, 비스(4-메톡시페놀)아민, 2,6-디-3급-부틸-4-디메틸아미노메틸페놀, 2,4'-디아미노디페닐메탄, 4,4'-디아미노-디페닐메탄, N,N,N',N'-테트라메틸-4,4'-디아미노디페닐메탄, 1,2-비스[(2-메틸페닐)아미노]에탄, 1,2-비스(페닐아미노)프로판, (o-톨릴)비구아니드, 비스[4-(1',3'-디메틸부틸)페닐]아민, 3급-옥틸화된 N-페닐-1-나프틸아민, 모노알킬화 및 디알킬화된 3급-부틸/3급-옥틸디페닐아민의 혼합물, 모노알킬화 및 디알킬화된 노닐디페닐아민의 혼합물, 모노알킬화 및 디알킬화된 도데실디페닐아민의 혼합물, 모노알킬화 및 디알킬화된 이소프로필/이소헥실디페닐아민의 혼합물, 모노알킬화 및 디알킬화된 3급-부틸디페닐아민의 혼합물, 2,3-디하이드로-3,3-디메틸-4H-1,4-벤조티아진, 페노티아진, 모노알킬화 및 디알킬화된 3급-부틸/3급-옥틸 페노티아진의 혼합물, 모노알킬화 및 디알킬화된 3급-옥틸 페노티아진의 혼합물, N-알릴페노티아진, N,N,N',N'-테트라페닐-1,4-디아미노부트-2-엔, N,N-비스(2,2,6,6-테트라메틸피페리드-4-일)-헥사메틸렌디아민, 비스(2,2,6,6-테트라메틸피페리드-4-일)세바케이트, 2,2,6,6-테트라메틸피페리딘-4-온, 2,2,6,6-테트라메틸피페리딘-4-올. 각각의 화합물 또는 이들의 혼합물이 사용될 수도 있다.1.18. Amine-type antioxidants such as N, N'-diisopropyl-p-phenylenediamine, N, N'-di-tert-butyl-p-phenylenediamine, N, N'-bis (1 , 4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p -Phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenyl Rendiamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl)- N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl- N, N '-Di-tert-butyl-p-phenylenediamine, diphenylamine, N-allyl-diphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4 -Tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-n-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenol) amine , 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diamino-diphenylmethane, N, N, N ', N '-Tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide , Bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, monoalkylated and dialkylated tert-butyl tert-octa Mixtures of tildiphenylamine, mixtures of monoalkylated and dialkylated nonyldiphenylamines, mixtures of monoalkylated and dialkylated dodecyldiphenylamines, mixtures of monoalkylated and dialkylated isopropyl / isohexyldiphenylamines, mono Mixtures of alkylated and dialkylated tert-butyldiphenylamines, 2,3-dihi Rho-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, monoalkylated and dialkylated mixtures of tert-butyl / 3-octyl phenothiazine, monoalkylated and dialkylated 3 Mixtures of rapid-octyl phenothiazines, N-allylphenothiazines, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2 , 6,6-tetramethylpiperid-4-yl) -hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetra Methylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol. Individual compounds or mixtures thereof may be used.

1.19. 적합한 티오상승제 (thiosynergists)는 예를들어 디라우릴 티오디프로 피오네이트 및/또는 디스테아릴 티오디프로피오네이트이다.1.19. Suitable thiosynergists are, for example, dilauryl thiodipropionate and / or distearyl thiodipropionate.

2. UV-흡수제 및 광안정화제가 본 발명에 따르는 조성물내에서 조성물의 중량을 기준으로하여 0.1 내지 15 wt.%, 바람직하게는 3 내지 8 wt.%의 양으로 사용될 수 있다. 적합한 UV-흡수제 및 광안정화제는 예를들어 다음과 같다:2. UV-absorbers and light stabilizers can be used in the compositions according to the invention in amounts of 0.1 to 15 wt.%, Preferably 3 to 8 wt.%, Based on the weight of the composition. Suitable UV-absorbers and light stabilizers are for example:

2.1. 2-(2'-하이드록시페닐)벤조트리아졸, 예를들어 2-(2'-하이드록시-5'-메틸페닐)벤조트리아졸, 2-(3',5'-디-3급-2'-하이드록시페닐)벤조트리아졸, 2-(5'-3급-부틸-2'-하이드록시페닐)벤조트리아졸, 2-(2'-하이드록시-5'-(1,1,3,3-테트라메틸-부틸페닐)벤조트리아졸, 2-(3',5'-디-3급-부틸-2'-하이드록시페닐)-5-클로로벤조트리아졸, 2-(3'-3급-부틸-2'-하이드록시-5'-메틸페닐)-5-클로로벤조트리아졸, 2-(3'-2급-부틸-5'-3급-부틸-2'-하이드록시페닐)벤조트리아졸, 2-(2'-하이드록시-4'-옥틸옥시페닐)벤조트리아졸, 2-(3',5'-디-3급-아밀-2'-하이드록시페닐)벤조트리아졸, 2-(3',5'-비스(α,α-디메틸벤질)-2'-하이드록시페닐)벤조트리아졸, 2-(3'-3급-부틸-2'-하이드록시-5'-(2-옥틸옥시카보닐에틸)페닐)-5-클로로벤조트리아졸, 2-(3'-3급-부틸-5'-[2-(2-에틸헥실옥시)카보닐에틸]-2'-하이드록시페닐)-5-클로로벤조트리아졸, 2-(3'-3급-부틸-2'-하이드록시-5'-(2-메톡시카보닐에틸)-페닐)-5-클로로벤조트리아졸, 2-(3'-3급-부틸-2'-하이드록시-5'-(2-메톡시카보닐에틸)페닐)벤조트리아졸, 2-(3'-3급-부틸-2'-하이드록시-5'-(2-옥틸옥시카보닐에틸)페닐)벤조트리아졸, 2-(3'-3급-부틸-5'-[2-(2-에틸헥실옥시)카보닐에틸]-2'-하이드록시페닐)벤조트리아졸, 2-(3'-도데실-2'-하이드록시-5'-메틸페닐)벤조트리아졸, 2-(3'-3급-부틸-2'-하이드록시-5'-(2-이소옥틸옥시카보닐에틸)페닐)벤조트리아졸, 2,2'-메틸렌비스[4-(1,1,3,3-테트라메틸부틸)-6-벤조트리아졸-2-일페놀]; 2-[3'-3급-부틸-5'-(2-메톡시카보닐에틸)-2'-하이드록시페닐]-2H-벤조트리아졸과 폴리에틸렌글리콜 300의 트랜스에스테르화 생성물; [R-CH2CH2-COO-CH2CH2] 2 (여기에서, R은 3'-3급-부틸-4'-하이드록시-5'-2H-벤조트리아졸-2-일-페닐이다), 2-[2'-하이드록시-3'-(α,α-디메틸벤질)-5'-(1,1,3,3-테트라메틸부틸)페닐]벤조트리아졸, 2-[2'-하이드록시-3'-(1,1,3,3-테트라메틸부틸)-5'-(α,α-디메틸벤질)페닐]벤조트리아졸.2.1. 2- (2'-hydroxyphenyl) benzotriazole , for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tertiary-2 '-Hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-(1,1,3 , 3-tetramethyl-butylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'- Tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5'-tert-butyl-2'-hydroxyphenyl) Benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole , 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' -(2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl]- 2'-hydroxyphenyl) -5-chloro Benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) -phenyl) -5-chlorobenzotriazole, 2- (3'- Tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-( 2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl ) Benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-( 2-isooctyloxycarbonylethyl) phenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol] Transesterification products of 2- [3'-tert-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; -CH 2 CH 2 -COO-CH 2 CH 2 ] 2 , wherein R is 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl , 2-[ 2'-hydroxy-3 '-(α, α-dimethylbenzyl) -5'-(1,1,3,3-tetramethylbutyl) phenyl] benzotriazole, 2- [2'-hydroxy-3 '-(1,1,3,3-tetramethylbutyl) -5'-(α, α-dimethylbenzyl) phenyl] benzotriazole.

2.2. 2-하이드록시벤조페논, 예를들어 4-하이드록시, 4-메톡시, 4-옥틸옥시, 4-데실옥시, 4-도데실옥시, 4-벤질옥시, 4,2',4'-트리하이드록시 및 2'-하이드록시-4,4'--디메톡시 유도체.2.2. 2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'- Trihydroxy and 2'-hydroxy-4,4 '-dimethoxy derivatives.

2.3. 치환 및 비치환된 벤조산의 에스테르, 예를들어 4-3급-부틸페닐 살리실레이트, 페닐 살리실레이트, 옥틸페닐 살리실레이트, 디벤조일 레조르시놀, 비스(4-3급-부틸벤조일)레조르시놀, 벤조일 레조르시놀, 2,4-디-3급-부틸페닐-3,5-디-3급-부틸-4-하이드록시벤조에이트, 헥사데실-3,5-디-3급-부틸-4-하이드록시벤조에이트, 옥타데실-3,5-디-3급-부틸-4-하이드록시벤조에이트, 2-메틸-4,6-디-3급-부틸페닐-3,5-디-3급-부틸-4-하이드록시벤조에이트.2.3. Esters of substituted and unsubstituted benzoic acids , for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) Resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert -Butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl-3,5 Di-tert-butyl-4-hydroxybenzoate.

2.4. 아크릴레이트, 예를들어 에틸-α-시안-β,β-디페닐 아크릴레이트, 이소옥틸-α-시안-β,β-디페닐 아크릴레이트, 메틸-α-카보메톡시 신나메이트, 메틸-α-시안-β-메틸-p-메톡시 신나메이트, 부틸-α-시안-β-메틸-p-메톡시 신나 메이트, 메틸-α-카보메톡시-p-메톡시 신나메이트 및 N-(β-카보메톡시-β-시안비닐)-2-메틸인돌린.2.4. Acrylates such as ethyl-α-cyan-β, β-diphenyl acrylate, isooctyl-α-cyan-β, β-diphenyl acrylate, methyl-α-carbomethoxy cinnamate, methyl-α -Cyan-β-methyl-p-methoxy cinnamate, butyl-α-cyan-β-methyl-p-methoxy cinnamate, methyl-α-carbomethoxy-p-methoxy cinnamate and N- (β Carbomethoxy-β-cyanvinyl) -2-methylindolin.

2.5. 니켈 화합물, 예를들어 n-부틸아민, 트리에탄올아민 또는 N-사이클로헥실디에탄올아민과 같은 추가의 리간드 존재 또는 부재하의 2,2'-티오비스[4-(1,1,3,3-테트라메틸부틸)페놀]의 1:1 컴플렉스 또는 1:2 컴플렉스와 같은 니켈 컴플렉스, 니켈 디부틸 디티오카바메이트, 4-하이드록시-3,5-디-3급-부틸벤질포스폰산의 모노알킬 에스테르, 예를들어 메틸 또는 에틸 에스테르의 니켈 염, 케톡심, 예를들어 2-하이드록시-4-메틸페닐운데실 케톡심의 니켈 컴플렉스, 추가의 리간드 존재 또는 부재하의 1-페닐-4-라우로일-5-하이드록시피라졸의 니켈 컴플렉스.2.5. 2,2'-thiobis [4- (1,1,3,3-tetra) with or without further ligands such as nickel compounds such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine Methylbutyl) phenol] nickel complex such as 1: 1 complex or 1: 2 complex, nickel dibutyl dithiocarbamate, monoalkyl ester of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid For example nickel salts of methyl or ethyl esters, ketoximes, for example nickel complexes of 2-hydroxy-4-methylphenylundecyl ketoxime, 1-phenyl-4-lauroyl- with or without further ligands Nickel complex of 5-hydroxypyrazole.

2.6. 입체적으로 장애된 아민, 예를들어 비스(2,2,6,6-테트라메틸-4-피페리딜)세바케이트, 비스(2,2,6,6-테트라메틸-4-피페리딜)석시네이트, 비스(1,2,2,6,6-펜타메틸-4-피페리딜)세바케이트, 비스(1-옥틸옥시-2,2,6,6-테트라메틸-4-피페리딜)세바케이트, 비스(1,2,2,6,6-펜타메틸-4-피페리딜), n-부틸-3,5-디-3급-부틸-4-하이드록시벤질 말로네이트, 1-(2-하이드록시에틸)-2,2,6,6-테트라메틸-4-하이드록시피페리딘과 석신산의 축합물, N,N'-비스(2,2,6,6-테트라메틸-4-피페리딜)헥사메틸렌디아민과 4-3급-옥틸아미노-2,6-디클로로-1,3,5-트리아진의 선형 또는 사이클릭 축합물, 트리스(2,2,6,6-테트라메틸-4-피페리딜)-니트릴로트리아세테이트, 테트라키스(2,2,6,6-테트라메틸-4-피페리딜)-1,2,3,4-부탄테트라카복실레이트, 1,1'-(1,2-에탄디일)비스(3,3,5,5-테트라메틸피페라지논), 4-벤조일-2,2,6,6-테트라메틸피페리딘, 4-스테아릴옥시-2,2,6,6-테트라메틸피페리딘, 비스(1,2,2,6,6-펜타메틸 피페리딜)-2-n-부틸-2-(2-하이드록시-3,5-디-3급-부틸벤질)말로네이트, 3-n-옥틸-7,7,9,9-테트라메틸-1,3,8-트리아자스피로[4.5]데칸-2,4-디온, 비스(1-옥틸옥시-2,2,6,6-테트라메틸피페리딜)세바케이트, 비스(1-옥틸옥시-2,2,6,6-테트라메틸피페리딜)석시네이트, N,N'-비스(2,2,6,6-테트라메틸-4-피페리딜)헥사메틸렌디아민과 4-모르폴리노-2,6-디클로로-1,3,5-트리아진의 선형 또는 사이클릭 축합물, 2-클로로-4,6-비스(4-n-부틸아미노-2,2,6,6-테트라메틸피페리딜)-1,3,5-트리아진과 1,2-비스(3-아미노프로필아미노)에탄의 축합물, 2-클로로-4,6-비스(4-n-부틸아미노-1,2,2,6,6-펜타메틸피페리딜)-1,3,5-트리아진과 1,2-비스(3-아미노프로필아미노)에탄의 축합물, 8-아세틸-3-도데실-7,7,9,9-테트라메틸-1,3,8-트리아자스피로[4.5]데칸-2,4-디온, 3-도데실-1-(2,2,6,6-테트라메틸-4-피페리딜)피롤리딘-2,5-디온, 3-도데실-1-(1,2,2,6,6-펜타메틸-4-피페리딜)피롤리딘-2,5-디온, 4-헥사데실옥시- 및 4-스테아릴옥시-2,2,6,6-테트라메틸피페리딘의 혼합물, N,N'-비스(2,2,6,6-테트라메틸-4-피페리딜)헥사메틸렌디아민과 4-사이클로헥실아미노-2,6-디클로로-1,3,5-트리아진의 축합생성물, 1,2-비스(3-아미노프로필아미노)에탄과 2,4,6-트리클로로-1,3,5-트리아진 및 4-부틸아미노-2,2,6,6-테트라메틸피페리딘의 축합생성물 (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-테트라메틸-4-피페리딜)-n-도데실석신이미드, N-(1,2,2,6,6-펜타메틸-4-피페리딜)-n-도데실석신이미드, 2-운데실-7,7,9,9-테트라메틸-1-옥사-3,8-디아자-4-옥소스피로[4.5]데칸, 7,7,9,9-테트라메틸-2-사이클로운데실-1-옥사-3,8-티아자-4-옥소스피로[4.5]데칸과 에피클로로하이드린의 반응생성물, 1,1-비스(1,2,2,6,6-펜타메틸-4-피페리딜옥소카보닐)-2-(4-메톡시페닐)에 텐, N,N'-비스(포르밀)-N,N'-비스(2,2,6,6-테트라메틸-4-피페리딜)헥사메틸렌디아민, 4-메톡시메틸렌말론산과 1,2,2,6,6-펜타메틸-4-하이드록시피페리딘과의 디에스테르, 폴리[메틸프로필-3-옥시-4-(2,2,6,6-테트라메틸-4-피페리딜)]실옥산, 말레산 무수물/α-올레핀 코폴리머와 2,2,6,6-테트라메틸-4-아미노피페리딘 또는 1,2,2,6,6-펜타메틸-4-아미노피페리딘의 반응생성물.2.6. Stericly hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) Succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl ) Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl), n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, 1 Condensate of-(2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, N, N'-bis (2,2,6,6-tetra Linear or cyclic condensates of methyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6, 6-tetramethyl-4-piperidyl) -nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 '-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tet Lamethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl piperidyl) -2-n-butyl 2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6- Tetramethylpiperidyl) succinate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1 Linear or cyclic condensates of, 3,5-triazine, 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3 Condensate of, 5-triazine with 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-bis (4-n-butylamino-1,2,2,6,6-penta Condensate of methyl piperidyl) -1,3,5-triazine with 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl -1,3,8-tria Jaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3- Dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 4-hexadecyloxy- and 4-stearyloxy-2 A mixture of 2,6,6-tetramethylpiperidine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2 Condensation products of, 6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine and 4 Condensation products of -butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl ) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospyro [4.5] decane, 7,7, Reaction product of 9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-thiaza-4-oxospyro [4.5] decane with epichlorohydrin, 1,1-bis (1,2 , 2,6,6-pentamethyl-4-piperidyloxocarbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bis (formyl) -N, N'-bis ( 2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 4-methoxymethylenemalonic acid and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine Diester, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, maleic anhydride / α-olefin copolymer with 2,2, Reaction product of 6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. 옥사미드, 예를들어 4,4'-디옥틸옥시옥사닐리드, 2,2'-디에톡시옥사닐리드, 2,2'-디옥틸옥시-5,5'-디-3급-부톡사닐리드, 2,2'-디도데실옥시-5,5'-디-3급-부톡사닐리드, 2-에톡시-2'-에톡시아닐리드, N,N'-비스(3-디메틸아미노프로필)옥사미드, 2-에톡시-5-3급-부틸-2'-에톡시아닐리드 및 그의 2-에톡시-2'-에틸-5,5'-디-3급-부톡사닐리드와의 혼합물, o- 및 p-메톡시-이치환된 옥사닐리드의 혼합물, 및 o- 및 p-에톡시-이치환된 옥사닐리드의 혼합물.2.7. Oxamides , for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanyl Reed, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethoxyanilide, N, N'-bis (3-dimethylaminopropyl ) Oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxyanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,5'-di-tert-butoxanilide , a mixture of o- and p-methoxy-disubstituted oxanilides, and a mixture of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2-(2-하이드록시페닐)-1,3,5-트리아진, 예를들어 2,4,6-트리스(2-하이드록시-4-옥틸옥시페닐)-1,3,5-트리아진, 2-(2-하이드록시-4-옥틸옥시페닐)-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진, 2-(2,4-디하이드록시페닐)-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진, 2,4-비스(2-하이드록시-4-프로필옥시페닐)-6-(2,4-디메틸페닐)-1,3,5-트리아진, 2-(2-하이드록시-4-옥틸옥시페닐)-4,6-비스(4-메틸페닐)-1,3,5-트리아진, 2-(2-하이드록시-4-도데실옥시페닐)-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진, 2-(2-하이드록시-4-트리데실옥시페닐)-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진, 2-[2-하이드록시-4-(2-하이드록시-3-부틸옥시프로폭시)페닐]-4,6-비스(2,4-디메틸)-1,3,5-트리아진, 2-[2-하이드록시-4-(2-하이드록시-3-옥틸옥시프 로필옥시)페닐]-4,6-비스(2,4-디메틸)-1,3,5-트리아진, 2-[4-도데실옥시/트리데실옥시-2-하이드록시프로폭시)-2-하이드록시페닐]-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진, 2-[2-하이드록시-4-(2-하이드록시-3-도데실옥시프로폭시)페닐]-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진, 2-(2-하이드록시-4-헥실옥시)페닐-4,6-디페닐-1,3,5-트리아진, 2-(2-하이드록시-4-메톡시페닐)-4,6-디페닐-1,3,5-트리아진, 2,4,6-트리스[2-하이드록시-4-(3-부톡시-2-하이드록시프로폭시)페닐]-1,3,5-트리아진, 2-(2-하이드록시페닐)-4-(4-메톡시페닐)-6-페닐-1,3,5-트리아진, 2-{2-하이드록시-4-[3-(2-에틸헥실-1-옥시)-2-하이드록시프로필옥시]페닐}-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진.2.8. 2- (2-hydroxyphenyl) -1,3,5-triazine , for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine , 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4- Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxy Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl ] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4-dodecyloxy / tridecyloxy-2-ha Idoxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy Oxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) Phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2 , 4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4 -(4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxy Propyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

이러한 화합물은 개별적으로 또는 혼합물의 형태로 사용될 수 있다.These compounds can be used individually or in the form of mixtures.

3. 적합한 금속 유도체는 예를들어 N,N'-디페닐옥사미드, N-살리실알-N'-살리실로일하이드라진, N,N'-비스(살리실로일)하이드라진, N,N'-비스(3,5-디-3급-부틸-4-하이드록시페닐프로피오닐)하이드라진, 3-살리실로일아미노-1,2,4-트리아졸, 비스(벤질리덴)옥살릴 디하이드라지드, 옥사닐리드, 이소프탈로일 디하이드라지드, 세바코일비스페닐 하이드라지드, N,N'-디아세틸아디포일 디하이드라지드, N,N'-비스(살리실로일)옥살릴 디하이드라지드, N,N'-비스(살리실로일)티오프로피오닐 디하이드라지드이다. 이러한 화합물은 개별적으로 또는 혼합물의 형태로 사용될 수 있다.3. Suitable metal derivatives are, for example, N, N'-diphenyloxamide, N-salicyl-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'- Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide , Oxanilide, isophthaloyl dihydrazide, sebacoylbisphenyl hydrazide, N, N'-diacetyladipoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihay Drazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide. These compounds can be used individually or in the form of mixtures.

4. 열안정화제로 사용될 수 있는 적합한 포스파이트 및 포스포나이트에는 예 를들어 트리페닐 포스파이트, 디페닐알킬 포스파이트, 페닐디알킬 포스파이트, 트리(노닐페닐)포스파이트, 트리라우릴 포스파이트, 트리옥타데실 포스파이트, 디스테아릴펜타에리트리톨 디포스파이트, 트리스(2,4-디-3급-부틸페닐)포스파이트, 디이소데실펜타에리트리톨 디포스파이트, 비스(2,4-디-3급-부틸페닐)펜타에리트리톨 디포스파이트, 비스(2,6-디-3급-부틸-4-메틸페닐)펜타에리트리톨 디포스파이트, 디이소데실옥시펜타에리트리톨 디포스파이트, 비스(2,4-디-3급-부틸-6-메틸페닐)펜타에리트리톨 디포스파이트, 비스(2,4,6-트리스(3급-부틸페닐)펜타에리트리톨 디포스파이트, 트리스테아릴소르비톨 트리포스파이트, 테트라키스(2,4-디-3급-부틸페닐)-4,4'-비페닐렌 디포스포나이트, 6-이소옥틸옥시-2,4,8,10-테트라-3급-부틸-12H-디벤즈[d,g]-1,3,2-디옥사포스포사인, 6-플루오로-2,4,8,10-테트라-3급-부틸-12-메틸디벤즈[d,g]-1,3,2-디옥사포스포사인, 비스(2,4-디-3급부틸-6-메틸페닐)메틸 포스파이트, 비스(2,4-디-3급-부틸-6-메틸페닐)에틸 포스파이트, 6-플루오로-2,4,8,10-테트라-3급-부틸-12-메틸디벤즈[d,g]-1,3,2-디옥사포스포사인, 2,2',2"-니트릴로[트리에틸트리스(3,3',5,5'-테트라-3급-부틸-1,1'-비페닐-2,2'-디일)포스파이트], 2-에틸헥실(3,3',5,5'-테트라-3급-부틸-1,1'-비페닐-2,2'-디일)포스파이트, 5-부틸-5-에틸-2-(2,4,6-트리-3급-부틸페녹시)-1,3,2-디옥사포스피레인이 포함된다. 이러한 화합물은 개별적으로 또는 혼합물의 형태로 사용될 수 있다.4. Suitable phosphites and phosphonites that can be used as thermal stabilizers include, for example, triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tri (nonylphenyl) phosphite, trilauryl phosphite, Trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-3 Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4- Di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis ( 2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphona Yit, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphosine, 6-fluoro- 2,4,8,10-tetra-tert-butyl-12-methyldibenz [d, g] -1,3,2-dioxaphosphosine, bis (2,4-di-tert-butyl) 6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12 -Methyldibenz [d, g] -1,3,2-dioxaphosphosine, 2,2 ', 2 "-nitrilo [triethyltris (3,3', 5,5'-tetra-3) Tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3 ', 5,5'-tetra-tert-butyl-1,1'- Biphenyl-2,2'-diyl) phosphite, 5-butyl-5-ethyl-2- (2,4,6-tri-tert-butylphenoxy) -1,3,2-dioxaphosphore Phosphorus is included Such compounds may be used individually or in the form of mixtures.

특히 바람직한 것은 트리스(2,4-디-3급-부틸페닐)포스파이트 (이르가포스 (Irgafos™) 168; Ciba-Geigy), 트리페닐포스핀, 또는 (2,4,6-트리-3급-부틸페닐)-(2-부틸-2-에틸프로판-1,3-디일)포스파이트 (울트라녹스 (Ultranox™) 641; GE Specialty Chemicals)이다.Especially preferred are tris (2,4-di-tert-butylphenyl) phosphite (Irgafos ™ 168; Ciba-Geigy), triphenylphosphine, or (2,4,6-tri-3 Tert-butylphenyl)-(2-butyl-2-ethylpropane-1,3-diyl) phosphite (Ultranox ™ 641; GE Specialty Chemicals).

적합한 포스파이트 및 포스포나이트의 예는 또한 하기 화학식 8 내지 14의 화합물이다:Examples of suitable phosphites and phosphonites are also compounds of the formulas 8-14:

Figure 112003035457775-pct00017
Figure 112003035457775-pct00017

5. 적합한 퍼옥사이드 캣쳐 (catchers)는 예를들어 β-티오디프로피온산의 에스테르, 예를들어 라우릴, 스테아릴, 미리스틸 또는 트리데실 에스테르, 머캅토벤즈이미다졸 또는 2-머캅토벤즈이미다졸의 아연 염, 아연디부틸 디티오카바메이트, 디옥타데실 디설파이드, 펜타에리트리톨 테트라키스(도데실머캅토)프로피오네이트이다. 이러한 화합물은 개별적으로 또는 혼합물의 형태로 사용될 수 있다.5. Suitable peroxide catchers are, for example, esters of β-thiodipropionic acid, for example lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazoles or 2-mercaptobenzimidazoles. Zinc salt, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (dodecyl mercapto) propionate. These compounds can be used individually or in the form of mixtures.

6. 적합한 염기성 공안정화제는 예를들어 멜라민, 폴리(비닐피롤리돈), 디시안디아미드, 트리알릴 시아누레이트, 우레아 유도체, 하이드라진 유도체, 아민, 폴리아미드, 폴리우레탄, 고급 지방산의 알칼리 금속 염 및 알칼리 토금속 염, 예를들어 칼슘 스테아레이트, 아연 스테아레이트, 마그네슘 베헤네이트, 마그네슘 스테아레이트, 나트륨 리시놀리에이트 및 칼륨 팔미테이트, 안티몬 피로카테콜레이트 또는 아연 피로카테콜레이트이다. 이러한 화합물은 개별적으로 또는 혼합물의 형태로 사용될 수 있다.6. Suitable basic co-stabilizing agents are for example alkali metal salts of melamine, poly (vinylpyrrolidone), dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, higher fatty acids. And alkaline earth metal salts, such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate. These compounds can be used individually or in the form of mixtures.

7. 적합한 핵형성제는 예를들어 탈크와 같은 무기물질, 이산화티탄 또는 산화마그네슘과 같은 금속 옥사이드, 바람직하게는 알칼리 토금속의 포스페이트, 카보네이트 또는 설페이트; 모노카복실산 또는 폴리카복실산 및 이들의 염과 같은 유기화합물, 예를들어 4-3급-부틸벤조산, 아디프산, 디페닐아세트산, 나트륨 석시네이트 또는 나트륨 벤조에이트; 이온성 코폴리머 (이오노머 (ionomers))와 같은 폴리머 화합물이다. 특히 바람직한 것은 1,3:2,4-비스(3',4'-디메틸벤질리덴)소르비톨, 1,3:2,4-디(파라메틸-디벤질리덴)소르비톨 및 1,3:2,4-디(벤질리덴)소르비톨이다. 이러한 화합물은 개별적으로 또는 혼합물의 형태로 사용될 수 있다.7. Suitable nucleating agents include, for example, inorganic materials such as talc, metal oxides such as titanium dioxide or magnesium oxide, preferably phosphates, carbonates or sulfates of alkaline earth metals; Organic compounds such as monocarboxylic acids or polycarboxylic acids and salts thereof, such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; Polymeric compounds such as ionic copolymers (ionomers). Especially preferred are 1,3: 2,4-bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1,3: 2,4-di (paramethyl-dibenzylidene) sorbitol and 1,3: 2, 4-di (benzylidene) sorbitol. These compounds can be used individually or in the form of mixtures.

8. 적합한 충진제 및 보강제는 예를들어 탄산칼슘, 실리케이트, 유리섬유, 유리볼, 석면, 탈크, 카올린, 운모, 황산바륨, 금속 옥사이드 및 하이드록사이드, 카본블랙, 흑연, 규회석, 톱밥 및 그밖의 다른 천연산물의 분말 또는 섬유, 합성섬유이다. 이러한 화합물은 개별적으로 또는 혼합물의 형태로 사용될 수 있다.8. Suitable fillers and reinforcing agents are, for example, calcium carbonate, silicates, glass fibers, glass balls, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wollastonite, sawdust and other Powders or fibers of other natural products, synthetic fibers. These compounds can be used individually or in the form of mixtures.

9. 그밖의 다른 적합한 첨가제는 예를들어 가소제, 윤활제, 유화제, 안료, 점도변형제, 촉매, 유동-조절제, 광학증백제, 난연제, 대전방지제 및 팽창제 (blowing agents)이다.9. Other suitable additives are, for example, plasticizers, lubricants, emulsifiers, pigments, viscosity modifiers, catalysts, flow-controlling agents, optical brighteners, flame retardants, antistatic agents and blowing agents.

10. 적합한 벤조푸라노논 및 인돌리논은 예를들어 US 4,325,863; US 4,338,244; US 5,175,312; US 5,216,052; US 5,252,643; DE-A-43 16 611; DE-A-43 16 622; DE-A-43 16 876; EP-A-0 589 839 또는 EP-A-0 591 102에 기술된 것, 또는 3-[4-(2-아세톡시에톡시)페닐]-5,7-디-3급-부틸벤조푸란-2-온, 5,7-디-3급-부틸-3-[4-(2-스테아로일옥시에톡시)페닐]벤조푸란-2-온, 3,3'-비스-[5,7-디-3급-부틸-3-(4-[2-하이드록시에톡시]페닐)벤조푸란-2-온], 5,7-디-3급-부틸-3-(4-에톡시페닐)벤조푸란-2-온, 3-(4-아세톡시-3,5-디메틸페닐)-5,7-디-3급-부틸벤조푸란-2-온, 3-(3,5-디메틸-4-피발로일옥시페닐)-5,7-디-3급-부틸벤조푸란-2-온, 3-(3,4-디메틸페닐)-5,7-디-3급-부틸벤조푸란-2-온, 3-(2,3-디메틸페닐)-5,7-디-3급-부틸벤조푸란-2-온, 화학식 15와 같은 락톤 항산화제이다: 10. Suitable benzofuranones and indolinones are described, for example, in US 4,325,863; US 4,338,244; US 5,175,312; US 5,216,052; US 5,252,643; DE-A-43 16 611; DE-A-43 16 622; DE-A-43 16 876; Those described in EP-A-0 589 839 or EP-A-0 591 102, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran- 2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis- [5,7 -Di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl ) Benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl- 4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert-butylbenzofuran- 2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, a lactone antioxidant such as Formula 15:

Figure 112003035457775-pct00018
Figure 112003035457775-pct00018

이들 화합물은 예를들어, 항산화제로 작용한다. 이러한 화합물은 개별적으로 또는 혼합물의 형태로 사용될 수 있다.These compounds, for example, act as antioxidants. These compounds can be used individually or in the form of mixtures.

11. 적합한 형광성 가소제 (fluorescing plasticisers)는 문헌 ("Plastics Additives Handbook", Eds. R. Gachter and H. Muller, Hanser Verlag, 3rd Edition, 1990, pp. 775-789)에 기술되어 있다.11. Suitable fluorescent plasticizers (fluorescing plasticisers) is described in the literature ( "Plastics Additives Handbook", Eds . R. Gachter and H. Muller, Hanser Verlag, 3 rd Edition, 1990, pp. 775-789).

12. 적합한 이형제는 지방족산과 알콜의 에스테르, 예를들어 펜타에리트리톨 테트라스테아레이트 및 글리세롤 모노스테아레이트이며, 이들은 단독으로 또는 혼합물로서, 바람직하게는 조성물의 중량을 기준으로하여 0.02 내지 1 wt.%의 양으로 사용된다.12. Suitable release agents are esters of aliphatic acids with alcohols, for example pentaerythritol tetrastearate and glycerol monostearate, which are alone or as a mixture, preferably 0.02 to 1 wt.%, Based on the weight of the composition. It is used in the amount of.

13. 적합한 난연성 첨가제는 포스페이트 에스테르, 즉 트리페닐 포스페이트, 레조르시놀 디인산 에스테르, 브롬화된 인산 에스테르, 브롬화된 올리고카보네이트 및 폴리카보네이트와 같은 브롬-함유 화합물, 및 C4F9SO3 -Na +와 같은 염이다.13. Suitable flame retardant additives are phosphate esters, i.e. triphenyl phosphate, resorcinol di-phosphoric acid esters, brominated phosphate esters, bromine, such as brominated oligonucleotide carbonate and polycarbonate-containing compound, and C 4 F 9 SO 3 - Na + And salts.

14. 충격내성을 부여하는 적합한 성분은 스티렌-아크릴로니트릴 또는 메틸 메타크릴레이트가 그래프트된 부타디엔 고무, 말레산 무수물이 그래프트된 에틸렌- 프로필렌 고무, 메틸 메타크릴레이트 또는 스티렌-아크릴로니트릴이 그래프트된 에틸 아크릴레이트 및 부틸 아크릴레이트 고무, 투입성 (interpenetrating) 실옥산 및 메틸 메타크릴레이트 또는 스티렌-아크릴로니트릴이 그래프트된 아크릴레이트 네트워크이다.14. Suitable components for imparting impact resistance are butadiene rubbers grafted with styrene-acrylonitrile or methyl methacrylate, ethylene-propylene rubbers grafted with maleic anhydride, methyl methacrylate or styrene-acrylonitrile grafted Acrylate networks grafted with ethyl acrylate and butyl acrylate rubbers, interpenetrating siloxanes and methyl methacrylate or styrene-acrylonitrile.

15. 적합한 폴리머는 SAN, ABS, PMMA, PTFE, PSU, PPS, 폴리에틸렌, 폴리프로필렌 및 에틸렌-프로필렌 고무와 같은 폴리올레핀, 에폭시 수지, PBT, PET, PCT, PCTG 및 PETG와 같은 폴리에스테르, 및 계면방법에서 생성된 그밖의 다른 폴리카보네이트이다.15. Suitable polymers include SAN, ABS, PMMA, PTFE, polyolefins such as PSU, PPS, polyethylene, polypropylene and ethylene-propylene rubber, epoxy resins, polyesters such as PBT, PET, PCT, PCTG and PETG, and interfacial methods. Other polycarbonates produced in.

16. 적합한 대전방지제는 설포네이트 염, 예를들어 C12H25SO3- 또는 C8F17SO3-의 테트라에틸암모늄 염이다.16. Suitable antistatic agents are sulfonate salts, for example tetraethylammonium salts of C 12 H 25 SO 3- or C 8 F 17 SO 3- .

17. 적합한 착색제는 안료 및 유기 및 무기염료이다.17. Suitable colorants are pigments and organic and inorganic dyes.

18. 에폭시 그룹을 함유하는 화합물, 예를들어 3,4-에폭시사이클로헥실메틸-3,4-에폭시사이클로헥실카복실레이트, 글리시딜 메타크릴레이트와 에폭시실란의 코폴리머.18. Compounds containing epoxy groups , such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, copolymers of glycidyl methacrylate and epoxysilane.

19. 무수그룹을 함유하는 화합물, 예를들어 말레산 무수물, 석신산 무수물, 벤조아세트산 무수물 및 프탈산 무수물.19. Compounds containing anhydride groups such as maleic anhydride, succinic anhydride, benzoacetic anhydride and phthalic anhydride.

그룹 18 및 19의 화합물은 용융 안정화제로서 작용한다. 이들은 개별적으로 또는 혼합물로 사용될 수 있다.Compounds of groups 18 and 19 act as melt stabilizers. These can be used individually or in mixtures.

본 발명에 따르는 조성물 (성형조성물)은 각각의 구성성분들을 공지의 방식 으로 혼합시키고, 생성된 혼합물을 내부반죽기 (internal kneaders), 압출기 및 이축 스크류 (double-shaft screw)와 같은 통상적인 장치내에서 약 200℃의 온도, 예를들어 200℃ 내지 300℃의 온도로 용융 배합 및 용융 압출시킴으로써 생성된다. 개개 구성성분들은 연속적으로 또는 동시에, 약 20℃ (실온) 또는 더 고온에서 혼합시킬 수 있다.The composition according to the invention (molding composition) mixes the respective components in a known manner and the resulting mixture is mixed in conventional devices such as internal kneaders, extruders and double-shaft screws. It is produced by melt compounding and melt extrusion at a temperature of about 200 ° C., for example between 200 ° C. and 300 ° C. Individual components may be mixed continuously or simultaneously, at about 20 ° C. (room temperature) or higher.

본 발명에 따르는 성형조성물은 모든 형태의 성형체를 생산하는데 사용될 수 있다. 이들 성형체는 사출성형, 압출 및 취입성형방법에 의해서 생산될 수 있다. 추가의 가공형태는 미리 제조된 쉬트 또는 필름으로부터 딥드로잉 (deep-drawing)함으로써 성형체를 생산하는 것이다.The molding compositions according to the invention can be used to produce shaped articles of all forms. These molded bodies can be produced by injection molding, extrusion and blow molding methods. A further form of processing is the production of shaped bodies by deep-drawing from previously prepared sheets or films.

본 발명에 따르는 성형체의 예로는, 예를들어 착즙기, 커피제조기, 믹서와 같은 가전제품용; 모니터, 프린터, 복사기와 같은 사무기기용; 건설구역, 내장재 및 외장재를 위한 쉬트, 튜브, 전기설비 도관, 창, 문 및 프로파일 절편 (profile section)용; 스위치 및 플러그와 같은 전기기술 분야에서 프로파일 절편, 필름 및 모든 형태의 케이싱 부품 (casing parts)이 포함된다. 또한, 본 발명에 따르는 성형제품은 궤도 비히클 (railway vehicle), 배, 항공기, 버스 및 그밖의 모터 비히클 (motor vehicles)용의 내부 장착물 및 구조적 부품, 및 모터 비히클 동체부품용으로 사용될 수 있다.Examples of the molded article according to the present invention include, for example, for home appliances such as juicers, coffee makers, mixers; For office equipment such as monitors, printers, copiers; For sheets, tubes, electrical installation conduits, windows, doors and profile sections for construction areas, interior and exterior materials; Profile sections, films and all forms of casing parts are included in the electrotechnical field such as switches and plugs. In addition, the molded articles according to the invention can be used for internal installations and structural parts for rail vehicles, ships, aircraft, buses and other motor vehicles, and motor vehicle fuselage parts.

본 발명에 따르는 성형제품은 투명하거나 불투명할 수 있다. 추가의 성형제품에는 특히 미니디스크 (mini disks), 컴팩트 디스크 (compact disks; CD) 또는 디지탈 다목적 디스크 (digital versatile discs; DVD)와 같은 광학적 및 자기-광 학적 데이타 저장매체, 식품 및 음료 포장, 광학렌즈 및 프리즘, 조명 목적의 렌즈, 모터 비히클 헤드램프 (headlamp) 렌즈, 건물 및 모터 비히클용 창유리, 온실과 같은 다른 형태의 창유리, 소위 웹처리된 이중 쉬트 또는 중공 쉬트가 포함된다.Molded articles according to the invention may be transparent or opaque. Additional molded articles include, in particular, optical and magneto-optical data storage media, such as mini disks, compact disks (CD) or digital versatile discs (DVD), food and beverage packaging, optical Lenses and prisms, lenses for illumination purposes, motor vehicle headlamp lenses, window panes for buildings and motor vehicles, other forms of panes such as greenhouses, so-called webped double sheets or hollow sheets.

이하의 실시예는 본 발명을 더 상세히 설명하기 위해서 제공된다.
The following examples are provided to further illustrate the present invention.

실시예Example

실시예 1 내지 3의 폴리머는 촉매로 테트라페닐포스포늄 페놀레이트, 및 나트륨으로 계산하여 250 ppb의 나트륨 페놀레이트를 사용하여 용융물중에서 디페닐카보네이트와 비스페놀 A를 용융중합시킴으로써 제조되었다. 모노머 및 촉매의 양은 표 1에 제시되어 있다. 반응조건은 표 2에 제시되어 있다. 용액의 측정된 상대점도, 황변지수 (yellowing index; YI), 용융점도, 전단희석비 및 다작용성 화합물의 양은 표 3에 제시되어 있다.The polymers of Examples 1-3 were prepared by melt polymerizing diphenylcarbonate and bisphenol A in the melt using tetraphenylphosphonium phenolate as the catalyst and 250 ppb sodium phenolate as calculated by sodium. The amounts of monomers and catalysts are shown in Table 1. Reaction conditions are shown in Table 2. The measured relative viscosity, yellowing index (YI), melt viscosity, shear dilution ratio and amount of multifunctional compound of the solution are shown in Table 3.

비교실시예 1, 2 및 3은 선형 폴리카보네이트이며, 통상적인 계면중합방법에 의해서 제조되었다. 이들은 상품명 마크롤론 (Makrolon™) 2808, 2408 및 3108 (Bayer AG)로 시판되고 있다. 비교실시예 4 및 5는 계면중합방법에 의해서 제조된 분지된 폴리카보네이트이다. 상응하는 제품은 상품명 마크롤론 (Makrolon™) 1243 및 1239 (Bayer AG)로 시판되고 있다. 비교실시예 7, 8 및 9는 촉매로 테트라페닐포스포늄 페놀레이트를 사용하여 용융물중에서 디페닐 카보네이트와 비스페놀 A의 반응에 의해 제조되었다. 실시예 6의 폴리카보네이트는 촉매로 테트라페닐포스포늄 페놀레이트, 및 나트륨으로 계산하여 100 ppb의 나트륨 페놀레이트를 사용하여 용융물중에서 디페닐카보네이트와 비스페놀 A를 반응시킴으로써 제조되었다.Comparative Examples 1, 2 and 3 are linear polycarbonates and were prepared by conventional interfacial polymerization. These are sold under the trade names Makrolon ™ 2808, 2408 and 3108 (Bayer AG). Comparative Examples 4 and 5 are branched polycarbonates prepared by the interfacial polymerization method. Corresponding products are sold under the trade names Makrolon ™ 1243 and 1239 (Bayer AG). Comparative Examples 7, 8 and 9 were prepared by the reaction of diphenyl carbonate with bisphenol A in the melt using tetraphenylphosphonium phenolate as catalyst. The polycarbonate of Example 6 was prepared by reacting diphenylcarbonate and bisphenol A in the melt using tetraphenylphosphonium phenolate as the catalyst and 100 ppb sodium phenolate calculated as sodium.

중합반응을 위해서는 물질의 가열 및 배기에 적합하며 충분히 긴 혼합 및 체류시간이 가능한 통상적인 트랜스에스테르화 용기를 사용할 수 있다.For the polymerization, conventional transesterification vessels suitable for heating and evacuating the material and capable of sufficiently long mixing and residence times can be used.

상대점도는 20℃에서 메틸렌클로라이드의 0.5% 용액중에서 측정되었다.Relative viscosity was measured at 0.5 ° C. in 0.5% solution of methylene chloride.

황변지수 (YI)는 CIELAB 방법에 따라서 4 ㎜ 두께의 사출성형된 샘플에 대해서 측정하였다. 사출성형은 270℃, 300℃ 및 330℃에서 수행하였다.The yellowing index (YI) was measured on 4 mm thick injection molded samples according to the CIELAB method. Injection molding was performed at 270 ° C, 300 ° C and 330 ° C.

용융점도는 ISO 11443에 따르는 시험방법을 사용하여 280℃에서 측정하였다. 비-뉴톤 유동 거동은 전단희석비를 계산함으로써 정량화되었다. 전단희석비는 5,000 s-1의 전단율에서의 용융점도로 나눈 50 s-1의 전단율에서의 용융점도로 계산되었다.Melt viscosity was measured at 280 ° C. using the test method according to ISO 11443. Non-Newtonian flow behavior was quantified by calculating the shear dilution ratio. The shear dilution ratio was calculated as the melt viscosity at a shear rate of 50 s −1 divided by the melt viscosity at a shear rate of 5,000 s −1 .

다작용성 화합물의 양은 폴리카보네이트를 완전 가수분해시킨 후에 HPLC (고압액체 크로마토그라피)를 사용하여 모노머 화합물을 분리시킴으로써 측정되었다. 이들 화합물은 자기공명분광기술에 의해서 특정화되었다.The amount of multifunctional compound was measured by separating the monomer compound using HPLC (high pressure liquid chromatography) after complete hydrolysis of the polycarbonate. These compounds have been characterized by magnetic resonance spectroscopy.

실시예Example C6C6 C7C7 C8C8 C9C9 1One 22 33 DPC, 몰DPC, Mall 1.181.18 1.1731.173 1.1871.187 1.1681.168 1.1781.178 1.2141.214 1.2091.209 BPA, 몰BPA, Mall 1.01.0 1.01.0 1.01.0 1.01.0 1.01.0 1.01.0 1.01.0 나트륨페놀레이트 (ppb), 나트륨으로 계산Sodium phenolate (ppb), calculated as sodium 100100 0.00.0 0.00.0 0.00.0 250250 250250 250250 테트라페닐포스포늄 페놀레이트, 몰Tetraphenylphosphonium Phenolate, Mole 0.000040.00004 0.000040.00004 0.000040.00004 0.000040.00004 0.000040.00004 0.000040.00004 0.000040.00004 DPC: 디페닐카보네이트; BPA: 비스페놀 A DPC: diphenyl carbonate; BPA: Bisphenol A

비교실시예 6 내지 9 및 실시예 1 내지 3에 대한 반응조건Reaction Conditions for Comparative Examples 6-9 and Examples 1-3 시간 (분)Time (min) 온도 (℃)Temperature (℃) 압력 (mbar)Pressure (mbar) 전-축합반응Pre-condensation reaction 4545 190190 10001000 반응기 I Reactor I 2020 190190 200200 반응기 II Reactor II 2020 230230 8080 반응기 III Reactor III 1010 250250 5050 반응기 IV Reactor IV 1010 270270 2525 비교실시예 6에 대한 반응조건Reaction Conditions for Comparative Example 6 증발기 I Evaporator I 4545 275275 7.47.4 증발기 II Evaporator II 130130 310310 1.401.40 비교실시예 7에 대한 반응조건Reaction Conditions for Comparative Example 7 증발기 I Evaporator I 4545 275275 7.37.3 증발기 II Evaporator II 130130 312312 1.001.00 비교실시예 8에 대한 반응조건Reaction Conditions for Comparative Example 8 증발기 I Evaporator I 4545 275275 5.55.5 증발기 II Evaporator II 130130 312312 0.50.5 비교실시예 9에 대한 반응조건Reaction Conditions for Comparative Example 9 증발기 I Evaporator I 4545 275275 7.37.3 증발기 II Evaporator II 130130 312312 0.980.98 실시예 1에 대한 반응조건Reaction Conditions for Example 1 증발기 I Evaporator I 4545 275275 8.58.5 증발기 II Evaporator II 120120 310310 2.252.25 실시예 2에 대한 반응조건Reaction Conditions for Example 2 증발기 I Evaporator I 4545 275275 6.56.5 증발기 II Evaporator II 120120 310310 0.900.90 실시예 3에 대한 반응조건Reaction Conditions for Example 3 증발기 I Evaporator I 4545 275275 6.56.5 증발기 II Evaporator II 120120 310310 1.261.26

Figure 112003035457775-pct00019
Figure 112003035457775-pct00019

이들 신규한 용융-중합된 폴리카보네이트는 다작용성 구조단위를 함유하고, 높은 분지도를 가지며, 현저한 비-뉴톤 유동특성을 갖지만, 폴리카보네이트는 놀랍게도 우수한 유동 거동을 나타낸다. 250 ppb의 나트륨 페놀레이트가 사용된 실시예들의 폴리카보네이트는 전단희석비로 표시되는 높은 분지도를 갖는다. 단지 100 ppb의 나트륨 페놀레이트 만을 갖는 비교실시예는 동일한 점도를 갖는 선형 폴리카보네이트의 전단희석비와 동등한 전단희석비를 갖는다. 따라서, 현저한 비-뉴톤 유동특성은 단지, 비교적 대량의 분지성 화합물이 존재하는 경우에만 수득되었다. 높은 분지도는 높은 황변도를 갖는 화합물의 통상적인 형성이 없이 획득되었다.These new melt-polymerized polycarbonates contain multifunctional structural units, have a high degree of branching and have significant non-Newtonian flow properties, but polycarbonates exhibit surprisingly good flow behavior. The polycarbonates of the examples where 250 ppb of sodium phenolate were used have a high degree of branching, expressed in shear dilution ratio. The comparative example with only 100 ppb sodium phenolate has a shear dilution ratio equivalent to the shear dilution ratio of linear polycarbonate with the same viscosity. Thus, significant non-Newtonian flow characteristics were obtained only in the presence of relatively large amounts of branched compounds. High branching was obtained without the conventional formation of compounds with high yellowness.

Claims (10)

하기 화학식 1의 용융-중합된 폴리카보네이트:Melt-Polymerized Polycarbonate of Formula 1: <화학식 1><Formula 1>
Figure 112003035457775-pct00020
Figure 112003035457775-pct00020
 상기 식에서,Where 사각 괄호는 반복 구조단위를 나타내며,Square brackets indicate repeating structural units, M은 Ar, 또는 다작용성 화합물 A일 수 있고, 여기에서M can be Ar, or multifunctional compound A, wherein Ar은 화학식 2로 표시되는 화합물, 또는 화학식 3으로 표시되는 화합물일 수 있으며,Ar may be a compound represented by Formula 2, or a compound represented by Formula 3, <화학식 2><Formula 2>
Figure 112003035457775-pct00021
Figure 112003035457775-pct00021
 <화학식 3><Formula 3>
Figure 112003035457775-pct00022
Figure 112003035457775-pct00022
 여기에서, Z는 C1-C8-알킬리덴 또는 C5-C12-사이클로알킬리덴, S, SO2 또는 단일결합이고, R은 치환되거나 비치환된 페닐, 메틸, 프로필, 에틸, 부틸, Cl 또는 Br이며, n은 0, 1 또는 2를 나타내고,Wherein Z is C 1 -C 8 -alkylidene or C 5 -C 12 -cycloalkylidene, S, SO 2 or a single bond, R is substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl, Cl or Br, n represents 0, 1 or 2, 다작용성 화합물 A는 하기 화학식 A의 화합물이며, 폴리카보네이트내에 200 내지 5000 ppm의 양으로 존재할 수 있고,Multifunctional compound A is a compound of formula A, which may be present in the polycarbonate in an amount of 200 to 5000 ppm, <화학식 A><Formula A>
Figure 112003035457775-pct00023
Figure 112003035457775-pct00023
 Y는 H 또는 화학식 4의 화합물이며,Y is H or a compound of formula 4, <화학식 4><Formula 4>
Figure 112003035457775-pct00024
Figure 112003035457775-pct00024
 여기에서,From here, R은 H, C1-C20-알킬, C6H5 또는 C(CH3)2C 6H5일 수 있고, 동일하거나 상이할 수 있으며,R may be H, C 1 -C 20 -alkyl, C 6 H 5 or C (CH 3 ) 2 C 6 H 5 , may be the same or different, n은 0, 1, 2 또는 3을 나타내고,n represents 0, 1, 2 or 3, X는 Y 또는 -(MOCOO)Y이며, 여기에서 M 및 Y는 상기에서 정의한 바와 같다.X is Y or-(MOCOO) Y, where M and Y are as defined above. 제 1 항에 있어서, M이 하기 화학식 B의 화합물 B를 더 포함하는 것인 용융-중합된 폴리카보네이트:The melt-polymerized polycarbonate of claim 1, wherein M further comprises Compound B of Formula B: <화학식 B><Formula B>
Figure 112007068543669-pct00025
Figure 112007068543669-pct00025
 상기 식에서, Ar 및 X는 상기 정의한 바와 같다.Wherein Ar and X are as defined above. 제 1 항 또는 2 항에 있어서, M이 하기 화학식 C의 화합물 C를 더 포함하는 것인 용융-중합된 폴리카보네이트:The melt-polymerized polycarbonate according to claim 1 or 2, wherein M further comprises compound C of formula C: <화학식 C><Formula C>
Figure 112007068543669-pct00026
Figure 112007068543669-pct00026
 상기 식에서, Ar 및 X는 상기 정의한 바와 같다.Wherein Ar and X are as defined above. 제 1 항 또는 제 2 항에 있어서, M이 하기 화학식 D의 화합물 D를 더 포함하는 것인 용융-중합된 폴리카보네이트:3. The melt-polymerized polycarbonate according to claim 1, wherein M further comprises compound D of formula D: <화학식 D><Formula D>
Figure 112007068543669-pct00027
Figure 112007068543669-pct00027
 상기 식에서, Ar는 상기 정의한 바와 같다.Wherein Ar is as defined above. 제 1 항 또는 제 2 항에 있어서, 하기 수학식 1에 따르는 전단희석비 y를 갖는 폴리카보네이트:The polycarbonate according to claim 1 or 2, having a shear dilution ratio y according to the following formula: <수학식 1><Equation 1>
Figure 112006092562712-pct00028
Figure 112006092562712-pct00028
 여기에서, x는 폴리카보네이트의 상대점도이다.Where x is the relative viscosity of the polycarbonate. 제 1 항 또는 제 2 항에 따르는 용융-중합된 폴리카보네이트를 함유하는 조성물.A composition containing the melt-polymerized polycarbonate according to claim 1. 제 6 항에 따르는 조성물을 함유하는 성형체.A molded article containing the composition according to claim 6. 하이드록시 또는 카보네이트 말단기를 갖는 디페놀 및/또는 카보네이트 올리고머가 촉매의 존재하에 150℃ 내지 400℃의 온도 및 1,000 mbar 내지 0.01 mbar의 압력에서 제조되며, 여기에서 촉매로는 하기 화학식 7의 4급 화합물이 사용되고, 공촉매로는 아민 염, 나트륨으로 계산하여 201 내지 10,000 ppb의 양으로 실리콘, 나트륨 및 칼륨의 하이드록사이드, 알콕사이드 및 아릴옥사이드와 같은 알칼리 금속 및 알칼리 토금속의 염으로 이루어진 군으로부터 선택된 공촉매가 사용되는, 폴리카보네이트의 제조를 위한 용융중합방법:Diphenols and / or carbonate oligomers having hydroxy or carbonate end groups are prepared at a temperature of 150 ° C. to 400 ° C. and a pressure of 1,000 mbar to 0.01 mbar in the presence of a catalyst, wherein the catalyst is quaternary Compounds are used and the cocatalyst is selected from the group consisting of salts of alkali and alkaline earth metals such as hydroxides, alkoxides and aryloxides of silicon, sodium and potassium in amounts of 201 to 10,000 ppb calculated as amine salts, sodium Melt polymerization method for the production of polycarbonate, in which a cocatalyst is used: <화학식 7><Formula 7>
Figure 112007068543669-pct00029
Figure 112007068543669-pct00029
 상기 식에서,Where R1, R2, R3 및 R4는 동일하거나 상이한 C1- 내지 C18-알킬렌, C6- 내지 C10-아릴 또는 C5- 내지 C6-사이클로알킬을 나타낼 수 있고,R 1 , R 2 , R 3 and R 4 may represent the same or different C 1 -to C 18 -alkylene, C 6 -to C 10 -aryl or C 5 -to C 6 -cycloalkyl, X-는 음이온을 나타낼 수 있으며, 여기에서 상응하는 산-염기 쌍 H+ + X- ↔ HX는 11 미만의 pKb를 갖는다.X − may represent an anion, where the corresponding acid-base pair H + + X − ↔ HX has a pK b of less than 11. 제 8 항에 있어서, 촉매가 테트라페닐포스포늄 페놀레이트 및 나트륨 페놀레이트의 혼합물인 용융중합방법.The melt polymerization method according to claim 8, wherein the catalyst is a mixture of tetraphenylphosphonium phenolate and sodium phenolate. 제 9 항에 있어서, 촉매가 테트라페닐포스포늄 페놀레이트 및 나트륨 페놀레이트의 혼합물이고, 210 내지 500 ppb의 나트륨이 존재하는 용융중합방법.10. The melt polymerization process according to claim 9, wherein the catalyst is a mixture of tetraphenylphosphonium phenolate and sodium phenolate, and 210 to 500 ppb sodium is present.
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