JP2008540786A - Method for improving the thermal and light stability of polyesters - Google Patents

Abstract

A method for improving the thermal and light stability of polyesters is provided.
The present invention describes a method for improving the thermal and light stability of a polyester, in particular a polyester fiber, comprising adding a chain extender to the polyester. Especially preferred chain extenders are dianhydrides, alcohols and hindered phenolic aromatic phosphates or mixtures thereof.
[Selection figure] None

Description

  The present invention relates to a method for improving the thermal and light stability of polyesters, especially polyester fibers, comprising adding a chain extender to said polyester.

Patent document 1 describes a method for increasing the molecular weight of a polycondensate during melt processing and / or for improving the polycondensate, wherein the polycondensate is a) at least one multifunctional From adding a blend comprising an anhydride (polyanhydride); b) at least one multifunctional compound whose functional groups can react with the anhydride groups of component a); and c) at least one phosphonate. A method is disclosed.
U.S. Patent No. 6,057,031 discloses master batches that are useful for improving thermoplastic polymers, dispersed polyol branching agents, and / or master batches that contain chain coupling agents such as, for example, dianhydrides. ing.
These known methods for preparing polyesters are not satisfactory for all the high demands that need to be met with respect to the thermal and light stability of the polyesters used especially as polyester fibers. As a result, there continues to be a need for improved methods for the preparation of polyesters with improved thermal and light stability.
US Pat. No. 6,469,078 International Publication No. 2004/101666 Pamphlet

The present invention therefore relates to a method for improving the thermal and light stability of a polyester comprising adding a chain extender to the polyester.
Of interest is a method for improving the thermal and light stability of polyester, a polyester fiber.

The polyester is particularly preferably polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate, polytrimethylene terephthalate (PTT) or copolyester. Particularly preferred is polyethylene terephthalate or polyethylene naphthalate.
The polyester may be a homopolyester or copolyester composed of aliphatic, cycloaliphatic or aromatic dicarboxylic acids and diols or hydroxycarboxylic acids.
Polyesters can be prepared by direct esterification (PTA process) and also by transesterification (DMT process). Any of the known catalyst systems can be used for the preparation.

Preferred diacids are aromatic dicarboxylic acids having 8 to 14 carbon atoms, aliphatic dicarboxylic acids having 4 to 12 carbon atoms, alicyclic dicarboxylic acids having 8 to 12 carbon atoms, and Selected from the group consisting of:
Preferably such diacids are terephthalic acid, isophthalic acid, o-phthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, glutaric acid, adipic acid , Sebacic acid and mixtures thereof.
Particularly preferred are terephthalic acid and 2,6-naphthalenedicarboxylic acid.
Preferred diols are those of formula A

HO-R-OH (A)

(Wherein R represents an aliphatic, alicyclic or aromatic moiety having 2 to 18 carbon atoms.)
It is a compound represented by these.
Preferably such diols are eg ethylene glycol, diethylene glycol, triethylene glycol, propane-1,3-diol, propane-1,2-diol, butane-1,4-diol, pentane-1,5-diol, Hexane-1,6-diol, 1,4-cyclohexanedimethanol, 3-methylpentane-2,4-diol, 2-methylpentane-1,4-diol, 2,2-diethylpropane-1,3-diol 1,4-di- (hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) -propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis -(3-hydroxyethoxyphenyl) propane, 2,2-bis- (4-hydroxypropoxypheny ) Ethane and mixtures thereof.
Most preferably, the diol is ethylene glycol or 1,4-cyclohexanedimethanol.

Various diesters may be used in place of or in addition to the diacid. For example, diesters corresponding to the aforementioned diacids in their acid moieties can be used. Suitable diesters therefore also include aliphatic and aromatic species. Very suitable diesters are, for example, alkyl esters of 1 to 4 carbon atoms of terephthalic acid, isophthalic acid, o-phthalic acid or naphthalenedicarboxylic acid.
Preferably, the esterification and transesterification processes are performed in the presence of a catalyst.
Interesting catalysts for the esterification process are, for example, antimony or germanium compounds, such as antimony (III) oxide (Sb ₂ O ₃ ) or germanium dioxide (GeO ₂ ).
It is. Of interest is also a titanium catalyst as disclosed, for example, in German Offenlegungsschrift 19513066, or cobalt, for example as disclosed in German Offenlegungsschrift 1,195,1943. A titanium-based catalyst combined with a phosphorus-based compound.
An interesting catalyst for the transesterification process is, for example, a titanium compound, such as titanium (IV) butoxide.
The catalyst is preferably used in the production of the polyester in an amount of 0.005 to 0.035% by weight of the total amount of reactants.

  Polyesters can be made in a conventional batch process where the transesterification or esterification product is formed in one vessel and then transferred to a second vessel for polymerization. The second vessel is agitated and the polymerization reaction is continued until the force used by the stirrer reaches a level indicating that the polyester melt has achieved a predetermined intrinsic viscosity and therefore has achieved a predetermined molecular weight. You can continue. For example, in the preparation of polyethylene terephthalate (PET), the esterification or transesterification reaction typically has an intrinsic viscosity of 0.3 to 0.8 dl / g, usually around 0.6 to 0.75 dl / g (phenol 60 At a high temperature of, for example, 200 to 350 ° C. to produce a polyester having a mass% and a tetrachloroethane of 40% by weight at 30 ° C., as determined by ASTM D-4603-86.

Alternatively, these steps can also be performed in a continuous process. For example, the continuous process disclosed in WO 97/44376 involves the diol and diacid or diester at a temperature of approximately 240 to 290 ° C. and at a pressure of approximately 30 to 600 kPa for approximately 1 to 5 hours. Are mixed to obtain a low molecular weight oligomer and water. In general, the continuous feed of reactants is performed using a molar ratio of diol to diacid or diester of approximately 1.0 to 1.6. The water or alcohol thus produced is removed while the reaction proceeds.
In the second stage of the continuous process, typically a polycondensation stage performed in a series of two or more vessels, the oligomer is about 1 to 4 at a temperature of about 240 to 305 ° C. in the presence of a polymerization catalyst. Stir for hours to form a polyester melt.
Typically, the condensation polymerization reaction begins in a first vessel that is operated at a pressure in the range of approximately 0 to 10 kPa. The diol produced in the condensation polymerization is removed from the polyester melt using a suitable vacuum. The polyester melt is typically stirred so that the diol is released from the polyester melt.
As the polyester melt is fed into a series of containers, the molecular weight of the polyester melt increases and therefore the intrinsic viscosity increases. The temperature in each vessel generally increases and the pressure decreases and polymerization proceeds more in each subsequent vessel. The final container is generally operated at a pressure of approximately 0 to 5.5 kPa. Each polymerization vessel is connected to a flash vessel. The retention time in the polymerization vessel and the feed rate of the reactants to the continuous process are based in part on the molecular weight of the desired polyester.
The polymerization catalyst used in the continuous process can generally be added already at the start or during the start of the polymerization stage.
The chain extender used can also be added already at the beginning or during the beginning of the polymerization stage.

When the polymerization process is complete, the resulting polyester, still in the form of a melt, is generally filtered and finished into a specific polyester product or injection molded in the form of a preform or coating, like a bottle. Before being made into a fresh product, it is typically extruded and pelletized. Such a stage is also typically named as “polyester processing”, but of course the final polyester later than the chemical processing stage used to form the polyester in the first stage. Regarding processing.
For example, the polyester melt can be extruded into polyester sheets, filaments, pellets, chips or similar particles (the so-called first extrusion stage). Preferably, the polyester melt is extruded shortly or immediately after finishing the condensation polymerization stage and then cooled, for example in a water tank or cooling unit. The formation of pellets or chips is particularly convenient for storage, transport and handling purposes.
The chips or pellets undergo solid layer polymerization (SSP) and are raised to an intrinsic viscosity of, for example, 0.7 to 1.2 dl / g, preferably approximately 0.83 dl / g.
To produce the final polyester product in the form of fibers, bottles, filaments, sheets, molded articles, etc., the pellets or chips are remelted and reextruded or injection molded. Extrusion and injection molding conditions are conventional. For example, the polyester can be extruded at a temperature in the range of 240 to 315 ° C.

［式中、Ｒは、式（Ｂａ）ないし（ＢＫ）

（式中、
Ｑは、−ＣＨ₂、−ＣＨ（ＣＨ₃）−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−、−Ｓ−、−Ｏ−、−ＳＯ₂−、−ＮＨＣＯ−、−ＣＯ−又は＞Ｐ（Ｏ）（炭素原子数１ないし２０
のアルキル基）を表し、及びここで、式（Ｂａ）ないし（Ｂｅ）中の芳香族環は、未置換であるか又は１個又は幾つかの炭素原子数１ないし６のアルキル基、炭素原子数１ないし６のアルコキシ基又はハロゲン原子により置換されている。）
で表される基を表す。］
で表される化合物である。
Ｒがアルカンテトライル基を表す場合、そのとき、テトラカルボン酸二無水物は例えば、ブタン−１，２，３，４−テトラカルボン酸二無水物であり得る。
好ましいテトラカルボン酸二無水物は、芳香族環を含むものである。
特に好ましくは、ピロメリト酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物及びオキシジフタル酸二無水物である。
必要に応じて、異なった構造のテトラカルボン酸二無水物のブレンドを使用することが
また可能である。 Of interest is a method for improving the thermal and light stability of polyesters comprising the group consisting of anhydrides, epoxides, oxazolines, oxazolones, oxazines, isocyanates, acyllactams, maleimides, alcohols and hindered phenolic aromatic phosphates. A process comprising adding a more selected chain extender or a mixture thereof to the polyester.
In the sense of the present invention, polyfunctional, in particular bifunctional compounds of anhydrides as chain extenders are known and are, for example, those of the formula B

[Wherein R is a group represented by formulas (Ba) to (BK)

(Where
Q is —CH ₂ , —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —S—, —O—, —SO ₂ —, —NHCO—, -CO- or> P (O) (C1-20
Wherein the aromatic rings in formulas (Ba) to (Be) are unsubstituted or one or several alkyl groups of 1 to 6 carbon atoms, carbon atoms It is substituted by an alkoxy group of formula 1 to 6 or a halogen atom. )
Represents a group represented by ]
It is a compound represented by these.
When R represents an alkanetetrayl group, then the tetracarboxylic dianhydride can be, for example, butane-1,2,3,4-tetracarboxylic dianhydride.
Preferred tetracarboxylic dianhydrides are those containing an aromatic ring.
Particularly preferred are pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and oxydiphthalic dianhydride. It is a thing.
If necessary, it is also possible to use a blend of tetracarboxylic dianhydrides of different structures.

  Individual particularly preferred tetracarboxylic dianhydrides are: pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, 1,1,2,2-ethanetetracarboxylic dianhydride, 1,2,3,4- Cyclopentanetetracarboxylic dianhydride, diphenylsulfonetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3cyclohexane-1,2-dicarboxylic dianhydride Bis (3,4-dicarboxylic acid phenyl) ether dianhydride, bis (3,4-dicarboxylic acid phenyl) thioether dianhydride, bisphenol A bis ether dianhydride, 2,2-bis (3,4-dicarboxylic acid) Acid phenyl) hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, bis (3,4-dicar Acid phenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, hydroquinone bisether dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1 -Naphthalene succinic dianhydride, bicyclo (2,2) oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 3,4 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride ( ODP ), Ethylenediaminetetraacetic dianhydride (DDTAH), or a combination thereof dianhydrides.

（式中、Ｒ₂₀₅及びＲ₂₀₇が水素原子を表す場合、Ｒ₂₀₆は水素原子又はメチル基を表し、
及びｐ＝０であり；又はＲ₂₀₅及びＲ₂₀₇が一緒に−ＣＨ₂−ＣＨ₂−又は−ＣＨ₂−ＣＨ₂−ＣＨ₂−を表す場合、Ｒ₂₀₆は水素原子を表し及びｐ＝０又は１である。）
で表されるものを含み、これらの基は、炭素原子、酸素原子、窒素原子又は硫黄原子に直接結合されている。 Epoxides are, for example, two epoxy groups, for example the formula C

(In the formula, when R ₂₀₅ and R ₂₀₇ represent a hydrogen atom, R ₂₀₆ represents a hydrogen atom or a methyl group;
And p = 0; or when R ₂₀₅ and R ₂₀₇ together represent —CH ₂ —CH ₂ — or —CH ₂ —CH ₂ —CH ₂ —, R ₂₀₆ represents a hydrogen atom and p = 0 or 1. )
These groups are directly bonded to a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Examples of epoxides mentioned are:
1. Diglycidyl ester and di (β-methylglycidyl) ester obtainable by reaction of a compound containing two carboxyl groups in the molecule with epichlorohydrin, glycerol dichlorohydrin or β-methylepichlorohydrin. The reaction is beneficially performed in the presence of a base.
The compound containing two carboxyl groups in the molecule can be an aliphatic dicarboxylic acid. Examples of these dicarboxylic acids are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerized or trimerized linoleic acid.
However, it is also possible to use alicyclic dicarboxylic acids such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.
Aromatic dicarboxylic acids such as phthalic acid or isophthalic acid can also be used.

2.2 Acid catalysis of a compound containing two free alcoholic hydroxyl groups and / or phenolic hydroxyl groups and an appropriately substituted epichlorohydrin under alkaline conditions or subsequent treatment with alkali Diglycidyl ether or di (β-methylglycidyl) ether obtainable by reacting in the presence.
Ethers of this type are, for example, ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycol, propane-1,2-diol, or poly (oxypropylene) glycol, propane-1,3-diol, butane-1,4- Derived from diols, poly (oxytetramethylene) glycol, pentane-1,5-diol, hexane 1,6-diol, acyclic alcohols such as sorbitol, and from polyepichlorohydrin.
They are also, for example, 1,3- or 1,4-dihydroxycyclohexane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane or 1,1-bis (hydroxymethyl) cyclohex- Derived from alicyclic alcohols such as 3-enes or they are like N, N-bis (2-hydroxyethyl) aniline or p, p'-bis (2-hydroxyethylamino) diphenylmethane Has a very aromatic nucleus.
Epoxides can also be derived from mononuclear phenols such as resorcinol, pyrocatechol or hydroquinone; or they can be 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 2,2-bis (4- Polynuclear such as hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylsulfone, 9,9′-bis (4-hydroxyphenyl) fluorene Phenols or condensates obtained from phenol and formaldehyde under acid conditions are based, for example, on phenol novolacs.

3. Di (N-glycidyl) compounds can be obtained, for example, by dehydrochlorination of the reaction product of epichlorohydrin and an amine containing two amino hydrogen atoms. These amines are, for example, aniline, toluidine, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane.
Di (N-glycidyl) compounds are also N, N′-diglycidyl derivatives of cycloalkylene ureas such as ethylene urea or 1,3-propylene urea, and N, N ′ of hydantoins such as 5,5-dimethylhydantoin. -Including diglycidyl derivatives.

4). Di (S-glycidyl) compounds such as di-S-glycidyl derivatives derived from dithiols such as ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether.

5. Epoxides containing a group of formula C wherein R ₂₀₅ and R ₂₀₇ together represent —CH ₂ —CH ₂ — and n represents 0, such as bis (2,3-epoxycyclopentyl) ether 2,3-epoxycyclopentyl glycidyl ether or 1,2-bis (2,3-epoxycyclopentoyloxy) ethane; R ₂₀₅ and R ₂₀₇ together are —CH ₂ —C
Epoxides containing a group represented by the formula C, wherein H _2- and n represents 1, for example 3,
4-Epoxy-6-methylcyclohexanecarboxylic acid- (3 ′, 4′-epoxy-6′-methylhexyl) methyl ester.
For example, due to their method of preparation, the difunctional epoxides described above may contain small amounts of mono- or trifunctional components.
Diglycidyl compounds having an aromatic structure are mainly used.
In some cases it is also possible to use blends of epoxides of different structures.
On the other hand, if desired, it is also possible to use tri- and polyfunctional epoxides as adjuvants to obtain branching. Such epoxides include, for example, a) liquid diglycidyl ethers of bisphenol A such as a) Araldit® GY240, Araldit GY250, Araldit GY260, Araldit GY266, Araldit GY2600, Araldit MY790; b) Araldit GT6071 Araldit GT7071, Araldit GT7072, Araldit GT6063, Araldit GT7203, Araldit GT6064, Araldit GT7304, Araldit GT7004, Araldit GT6084, Araldit GT1999, Araldit GT7077, Araldit GT6097, Araldit GT70T8 Solid diglycidyl ether of bisphenol A, such as GT6608, Araldit GT6609, Araldit GT6610; c) liquid glycidyl ether of bisphenol F, such as Araldit GY281, Araldit GY282, Araldit PY302, Araldit PY306; d) CG Epoxy Resin (CG Epoxy) resin) solid polyglycidyl ether of tetraphenylethane such as 0163; e) solid and liquid polyglycidyl ether of phenolformaldehyde novolac such as EPN1138, EPN1139, GY1180, PY307; f) ECN1235, ECN1273, ECN1280 O-cresol formaldehyde novolac solids, such as ECN1299 and Liquid polyglycidyl ethers; g) Shell® glycidyl ether 162, Araldit DY0390, Araldit DY0391, liquid glycidyl ether of alcohol; h) Shell curdra E terephthalate, trimellitate, Araldit PY284, Liquid glycidyl ester of carboxylic acid or a mixture of aromatic glycidyl esters such as Araldit PT910; i) Solid heterocyclic epoxy resin (Triglycidyl isocyanurate) such as Araldit PT810; j) Liquid alicyclic such as Araldit CY179 Epoxy resin; k) liquid N, N, O-triglycidyl ether of p-aminophenol such as Araldit MY0510; l) Araldit MY720, Araldit M 721 such as, tetraglycidyl-4-4'-methylene benzylalkonium Min or N, N, N ', which is N'- tetraglycidyl diaminodiphenyl methane.

Particularly preferred bifunctional epoxides are based on bisphenols, such as 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) sulfone (bisphenol S), bis (ortho / para). -Diglycidyl ether based on a mixture of (hydroxyphenyl) methane (bisphenol F) or a mixture of Araldit MT0163.
Solid epoxides of diglycidyl ether of the bisphenol A type are very particularly preferred, for example: liquid epoxides of the bisphenol F type such as: Araldit GT6071, GT7071, GT7072, GT6097 and GT6099, or Araldit GY281 or PY306.

（式中、
Ｒ₈、Ｒ₉、Ｒ₁₀及びＲ₁₁は、各々互いに独立して、水素原子、ハロゲン原子、炭素原子
数１ないし２０のアルキル基、炭素原子数４ないし１５のシクロアルキル基、未置換の又は炭素原子数１ないし４のアルキル基で置換されたフェニル基；炭素原子数１ないし２０のアルコキシ基又は炭素原子数２ないし２０のカルボキシアルキル基を表し、
ｔ＝３である場合、
Ｒ₁₂は、酸素原子、硫黄又は

により中断されていてもよい１ないし１８個の炭素原子を含む三価の直鎖、枝分れ又は脂環式基を表すか、又はＲ₁₂はまた、未置換の又は炭素原子数１ないし４のアルキル基で置換されたベンゼントリイル基を表し、
ｔ＝２である場合、
Ｒ₁₂は、酸素原子、硫黄又は

により中断されていてもよい１ないし１８個の炭素原子を含む二価の直鎖、枝分れ又は脂環式基を表すか、又はＲ₁₂はまた、未置換の又は炭素原子数１ないし４のアルキル基で置換されたフェニレン基を表し、
Ｒ₁₃は、炭素原子数１ないし８のアルキル基を表し、及び
ｔは２又は３を表す。）
で表される化合物である。 Multifunctional, in particular trifunctional compounds from the class of oxazolines in the sense of the present invention are known and are described inter alia in EP-A-0 583 807 and for example the formula D

(Where
R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 4 to 15 carbon atoms, unsubstituted or A phenyl group substituted by an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 20 carbon atoms or a carboxyalkyl group having 2 to 20 carbon atoms;
If t = 3,
R ₁₂ represents an oxygen atom, sulfur or

Represents a trivalent linear, branched or alicyclic group containing 1 to 18 carbon atoms which may be interrupted by R ₁₂ or R ₁₂ is also unsubstituted or has 1 to 4 carbon atoms A benzenetriyl group substituted with an alkyl group of
If t = 2,
R ₁₂ represents an oxygen atom, sulfur or

Represents a divalent linear, branched or alicyclic group containing 1 to 18 carbon atoms which may be interrupted by R ₁₂ or R ₁₂ is also unsubstituted or has 1 to 4 carbon atoms Represents a phenylene group substituted with an alkyl group of
R ₁₃ represents an alkyl group having 1 to 8 carbon atoms, and t represents 2 or 3. )
It is a compound represented by these.

  The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. A chlorine atom is particularly preferred.

Alkyl groups containing up to 20 carbon atoms are branched or unbranched groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl. Group, tert-butyl group, 2-ethylbutyl group, n-pentyl group, isopentyl group, 1-methylpentyl group, 1,3-dimethylbutyl group, n-hexyl group, 1-methylhexyl group, n-heptyl group, Isoheptyl group, 1,1,3,3-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, n-octyl group, 2-ethylhexyl group, 1,1,3-trimethylhexyl group, 1, 1,3,3-tetramethylpentyl group, nonyl group, decyl group, undecyl group, 1-methylundecyl group, dodecyl group, 1,1,3,3,5,5-hexamethylhexyl group, Rideshiru group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, eicosyl or docosyl. R ₈
, R ₉ , R ₁₀ and R ₁₁ are preferably an alkyl group having 1 to 12 carbon atoms, particularly an alkyl group having 1 to 8 carbon atoms, such as an alkyl group having 1 to 4 carbon atoms.

  The cycloalkyl group having 4 to 15 carbon atoms, particularly the cycloalkyl group having 5 to 12 carbon atoms is, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a cyclododecyl group. A cycloalkyl group having 5 to 8 carbon atoms is preferred, particularly a cyclohexyl group.

A phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, preferably containing 1 to 3, more preferably 1 or 2 alkyl groups is, for example, an o-, m- or p-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2- A methyl-6-ethylphenyl group, a 4-tert-butylphenyl group, a 2-ethylphenyl group or a 2,6-diethylphenyl group;

Alkoxy groups containing up to 20 carbon atoms are branched or unbranched groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy Group, isopentoxy group, hexoxy group, heptoxy group, octoxy group, decyloxy group, tetradecyloxy group, hexadecyloxy group or octadecyloxy group. Preferred meanings of R ₈ , R ₉ , R ₁₀ and R ₁₁ are alkoxy groups having 1 to 12, preferably 1 to 8, for example 1 to 4 carbon atoms.

Carboxyalkyl groups containing 2 to 20 carbon atoms are branched or unbranched groups such as carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxypentyl, carboxy Hexyl group, carboxyheptyl group, carboxyoctyl group, carboxynonyl group, carboxydecyl group, carboxyundecyl group, carboxydodecyl group, 2-carboxy-1-propyl group, 2-carboxy-1-butyl group or 2-carboxy- 1-pentyl group. Preferred meanings of R ₈ , R ₉ , R ₁₀ and R ₁₁ are carboxyalkyl groups having 2 to 12 carbon atoms, especially carboxyalkyl groups having 2 to 8 carbon atoms, such as carboxyalkyl groups having 2 to 4 carbon atoms. It is.

により中断されていてもよい１ないし１８個の炭素原子を含む三価の直鎖、枝分れ又は脂環式基は、三重結合部位が同じ原子に又は異なった原子にあり得ることを意味する。それらの例は、メタントリイル基、１，１，１−エタントリイル基、１，１，１−プロパントリイル基、１，１，１，−ブタントリイル基、１，１，１−ペンタントリイル基、１，１，１−ヘキサントリイル基、１，１，１−ヘプタントリイル基、１，１，１−オクタントリイル基、１，１，１−ノナントリイル基、１，１，１−デカントリイル基、１，１，１−ウンデカントリイル基、１，１，１−ドデカントリイル基、１，２，３−プロパントリイル基、１，２，３−ブタントリイル基、１，２，３−ペンタントリイル基、１，２，３−ヘキサントリイル基、１，１，３−シクロペンタントリイル基、１，３，５−シクロヘキサントリイル基、３−オキソ−１，１，５−ペンタントリイル基、３−チオ−１，１，５−ペンタントリイル基又は３−メチルアミノ−１，１，５−ペンタントリイル基である。 Oxygen atom, sulfur or

A trivalent straight chain, branched or alicyclic group containing 1 to 18 carbon atoms which may be interrupted by means that the triple bond sites may be on the same atom or on different atoms. . Examples thereof are methanetriyl group, 1,1,1-ethanetriyl group, 1,1,1-propanetriyl group, 1,1,1, -butanetriyl group, 1,1,1-pentanetriyl group, , 1,1-hexanetriyl group, 1,1,1-heptanetriyl group, 1,1,1-octanetriyl group, 1,1,1-nonanetriyl group, 1,1,1-decantriyl group, , 1,1-Undecantriyl group, 1,1,1-dodecantriyl group, 1,2,3-propanetriyl group, 1,2,3-butanetriyl group, 1,2,3-pentanetriyl Group, 1,2,3-hexanetriyl group, 1,1,3-cyclopentanetriyl group, 1,3,5-cyclohexanetriyl group, 3-oxo-1,1,5-pentanetriyl group , 3-thio-1,1,5-pentanetriyl group Is 3-methylamino -1,1,5- pentanetricarboxylic yl group.

により中断されていてもよい１ないし１８個の炭素原子を含む二価の直鎖、枝分れ又は脂環式基は、二重結合部位が同じ原子に又は異なった原子にあり得ることを意味する。それらの例は、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシ
レン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基、ウンデシレン基又はドデシレン基である。 Oxygen atom, sulfur or

A divalent linear, branched or alicyclic group containing 1 to 18 carbon atoms which may be interrupted by means that the double bond sites can be on the same atom or on different atoms. To do. Examples thereof are methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group or dodecylene group.

  A benzenetriyl group preferably substituted with an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably containing 1 to 3, more preferably 1 or 2 alkyl groups is, for example, 1,2,4- A benzenetriyl group, a 1,3,5-benzenetriyl group, a 3-methyl-1,2,4-benzoletriyl group or a 2-methyl-1,3,5-benzenetriyl group. A 1,2,4-benzenetriyl group and a 1,3,5-benzenetriyl group are particularly preferred.

Compounds of particular interest are those in which R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently of each other a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁₂ is 1,2, It is represented by Formula D, which represents a 4-benzenetriyl group or a 1,3,5-benzenetriyl group.
Of particular interest are 2,2 ', 2 "-(1,3,5-benzoletriyl) -tris-2-oxazoline; 2,2', 2"-(1,2,4-benzoletriyl) ) -Tris-4,4-dimethyl-2-oxazoline; 2,2 ', 2 "-(1,3,5-benzoletriyl) -tris-4,4-dimethyl-2-oxazoline; 2,2' , 2 "-(1,2,4-Benzoltriyl) -tris-5-methyl-2-oxazoline; or 2,2 ', 2"-(1,3,5-benzoletriyl) -tris-5 -A compound of formula D, such as methyl-2-oxazoline.

で表される化合物である。 Preferred bifunctional compounds from the class of bisoxazolines in the sense of the present invention are T.I. Lootjens et al. , Makromol. Chem. , Macromol. Symp. 75, 211 to 216 (1993) and, for example, the formula

It is a compound represented by these.

（式中、
Ｒ₁₄は、直接結合を表すか、或いは未置換の又は炭素原子数１ないし４のアルキル基で置換されたフェニレン基を表し、及び
Ｒ₁₅及びＲ₁₆は、互いに独立して、水素原子又は炭素原子数１ないし４のアルキル基を表す。）
で表される化合物である。
特に好ましいのは、式中のＲ₁₄が直接結合を表すところの式Ｅａ及びＥｂで表される化合物、特に２，２’−ビス（４Ｈ−３，１−ベンゾキサジノ−４−オン）である。 Multifunctional, in particular bifunctional compounds, from the chain extenders of oxazines or oxazolones in the sense of the invention are known and are described, for example, in H.C. Inata et al. , J .; Appli
d Polymer Science Vol. 32, 4581 to 4594 (1986) and, for example, the formulas Ea and Eb

(Where
R ₁₄ represents a direct bond, or represents a phenylene group which is unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, and R ₁₅ and R ₁₆ are each independently a hydrogen atom or carbon An alkyl group having 1 to 4 atoms is represented. )
It is a compound represented by these.
Particularly preferred are compounds of the formulas Ea and Eb, particularly 2,2′-bis (4H-3,1-benzoxazin-4-one), wherein R ₁₄ represents a direct bond.

In the sense of the present invention, polyfunctional, in particular bifunctional compounds, from the class of isocyanates are known and are, for example, those of the formula F

_{O = C = N-R 23} -N = C = O (F)

(Wherein R ₂₃ represents an alkylene group having 1 to 20 carbon atoms, a polymethylene group, an arylene group, an aralkylene group or a cycloalkylene group.)
It is a compound represented by these.

Preferred diisocyanates are tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, eicosane-1,20-diisocyanate, 4-butylhexamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, OCN (CH ₂ ) ₂ O (CH ₂ ) ₂ NCO, toluene-2,4-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, naphthalene diisocyanate, sulfonyl 3,3′-, 4,4′- and 3,4′-diisocyanates of diisocyanate, diphenylmethane, 2,2-diphenylpropane and diphenyl ether, 3, '- dimethyl-4,4'-diisocyanate diphenyl, 3,3'-dimethoxy-4,4'-diisocyanato diphenyl and 4,4'-diisocyanatodiphenylmethane.
The above listed diisocyanates are commercially available or can be prepared from commercially available amines.
It is also possible to use diisocyanate generators such as polymeric urethanes, urethane dimers and higher oligomers, cyanurate polymers, urethanes of cyanurate polymers and polymeric urethanes, and heat-dissociable adducts of Schiff bases It is.

［式中、ｓは、１ないし１６、特に５ないし１０の数を表し、及び
Ｒ₂₆は、芳香族基、例えば式：

（式中、Ｒ₂₇は、基−ＣＨ₂−、−Ｃ（Ｏ）−、−Ｐ（Ｏ）（炭素原子数１ないし１８の
アルキル）−、−（Ｏ）Ｓ（Ｏ）−、−Ｏ−又は−Ｓ−のうちの１つを表す。）
のうちの１つを表す。］
で表される化合物である。 Multifunctional, in particular bifunctional compounds, from acyllactam chain extenders in the sense of the present invention are known and are, for example, those of the formula G

[Wherein s represents a number from 1 to 16, in particular from 5 to 10, and R ₂₆ represents an aromatic group such as, for example:

Wherein R ₂₇ is a group —CH ₂ —, —C (O) —, —P (O) (C 1 -C 18 alkyl) —, — (O) S (O) —, —O. Represents one of-or -S-.)
Represents one of ]
It is a compound represented by these.

（式中、ｚは、１ないし１６、特に３ないし９の数を表す。）
で表される化合物である。
好ましくは、式中のラクタム環がカプロラクタム又はラウロラクタムであるところの式Ｇａで表される三官能性アシルラクタムである。 Trifunctional compounds from acyllactams in the sense of the present invention are known, for example the formula Ga

(In the formula, z represents a number of 1 to 16, particularly 3 to 9.)
It is a compound represented by these.
Preference is given to trifunctional acyllactams of the formula Ga in which the lactam ring in the formula is caprolactam or laurolactam.

（式中、
Ｒ₂₈は、脂肪族、芳香族、脂環式又はヘテロ環式基を表し；及び
Ｒ₂₉及びＲ₃₀は互いに独立して、水素原子、炭素原子数１ないし４のアルキル基、炭素原子数１ないし６のアルコキシ基、フェニル基又はフェノキシ基を表す。）
で表される化合物である。
脂肪族、芳香族、脂環式又はヘテロ環式基は、最大４０個の炭素原子を有しており、未置換であり得るか又は置換され得、及びまた、−Ｏ−、−Ｓ−、−（ＣＨ₂）_1-6、−Ｃ（Ｏ）−、−Ｐ（Ｏ）（炭素原子数１ないし１８のアルキル）−又は−（Ｏ）Ｓ（Ｏ）−（スルホン）により中断され得る。可能な置換基の例は、炭素原子数１ないし１８のアルキル基、炭素原子数１ないし１８のアルコキシ基、ヒドロキシル基、フェニル基及びフェノキシ基である。 Multifunctional, in particular bifunctional compounds, from maleimides as chain extenders in the sense of the present invention are known, and for example the formula H

(Where
R ₂₈ represents an aliphatic, aromatic, alicyclic or heterocyclic group; and R ₂₉ and R ₃₀ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom. To 6 alkoxy groups, a phenyl group or a phenoxy group; )
It is a compound represented by these.
An aliphatic, aromatic, alicyclic or heterocyclic group has up to 40 carbon atoms and can be unsubstituted or substituted and can also be —O—, —S—, _{- (CH 2) 1-6, -C} (O) -, - P (O) ( alkyl of 1 to 18 carbon atoms) -, or - may be interrupted by (sulfone) - (O) S (O). Examples of possible substituents are alkyl groups having 1 to 18 carbon atoms, alkoxy groups having 1 to 18 carbon atoms, hydroxyl groups, phenyl groups and phenoxy groups.

（式中、Ｒ₃₁は、基−ＣＨ₂、−Ｃ（Ｏ）−、−Ｐ（Ｏ）（炭素原子数１ないし１８のア
ルキル）−又は−（Ｏ）Ｓ（Ｏ）−、−Ｏ−又は−Ｓ−の１つを表す。）
の中の１つの基である。
Ｒ₂₉及びＲ₃₀は、互いに独立して、好ましくは、水素原子又は炭素原子数１ないし４のアルキル基であり；Ｒ₂₉は、特に好ましくは、水素原子であり、及びＲ₃₀は、特に好ましくは、水素原子又はメチル基であり；及びＲ₂₉及びＲ₃₀は、非常に特に好ましくは、水素原子である。 The aromatic group R ₂₈ represents a group having 6 to 40 carbon atoms, such as a phenylene group, a biphenylene group or a naphthylene group, or represents —O—, —S—, — (CH ₂ ). _1-6 , a phenylene group bonded by one of groups such as -C (O)-, -P (O) (C1-C18 alkyl)-or-(O) S (O)- Or represents a biphenylene group.
The alicyclic group R ₂₈ is a group having 5 to 10 carbon atoms such as a cyclopentylene group, a cyclohexylene group or a cyclooctylene group.
The heterocyclic group R ₂₈ is an N-containing 5- or 6-membered ring such as, for example, a pyridylene group, a pyridazylene group or a pyrazolylene group.
R ₂₈ is preferably of the formula:

(Wherein R ₃₁ represents a group —CH ₂ , —C (O) —, —P (O) (alkyl having 1 to 18 carbon atoms) — or — (O) S (O) —, —O—). Or, it represents one of -S-.)
Is one of the groups.
R ₂₉ and R ₃₀ are, independently of one another, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ₂₉ is particularly preferably a hydrogen atom, and R ₃₀ is particularly preferably Is a hydrogen atom or a methyl group; and R ₂₉ and R ₃₀ are very particularly preferably a hydrogen atom.

で表される化合物である。
ビスマレイミドは、ジアミンとマレイン酸無水物とを反応させることにより得られ、及び幾つかは商業上入手可能である。他の適するビスマレイミドは、国際公開第９３／２４４８８号パンフレットに記載されている。 Very particularly preferably, the formula

It is a compound represented by these.
Bismaleimides are obtained by reacting diamines with maleic anhydride, and some are commercially available. Other suitable bismaleimides are described in WO 93/24488.

  Polyfunctional compounds from alcohols as chain extenders in the sense of the present invention are known and, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, bistrimethylolethane, trismethylolpropane, Sorbitol, maltitol, isomaltitol, lactitol, lycasine, mannitol, lactose, leucross, tris (hydroxyethyl) isocyanurate, paratinitol, tetramethylolcyclohexanol, tetramethylolcyclopentanol, tetramethylolcyclopyra Nord, glycerol, diglycerol, polyglycerol or 1-O-α-D-glycopyranosyl-D-mannitol It is a hydrate. Particularly preferred are pentaerythritol, dipentaerythritol and tris (hydroxyethyl) isocyanurate.

（式中、
Ｒ₆は、イソプロピル基、第三ブチル基、シクロヘキシル基又は１ないし３個の炭素原
子数１ないし４のアルキル基により置換されたシクロヘキシル基を表し、
Ｒ₇は、水素原子、炭素原子数１ないし４のアルキル基、シクロヘキシル基又は１ない
し３個の炭素原子数１ないし４のアルキル基により置換されたシクロヘキシル基を表し、
Ｒ₈は、炭素原子数１ないし２０のアルキル基、未置換の又は炭素原子数１ないし４の
アルキル基で置換されたフェニル基又はナフチル基を表し、
Ｒ₉は、水素原子、炭素原子数１ないし２０のアルキル基、未置換の又は炭素原子数１
ないし４のアルキル基で置換されたフェニル基又はナフチル基を表すか；又は

を表し；
Ｍ^r+は、ｒ価の金属カチオンを表し、
ｐは、１、２、３、４、５又は６を表し、及び
ｒは、１、２又は３を表す。）
で表される化合物である。 Preferred hindered phenolic aromatic phosphates are those of formula I

(Where
R ₆ represents an isopropyl group, a tert-butyl group, a cyclohexyl group or a cyclohexyl group substituted by 1 to 3 alkyl groups having 1 to 4 carbon atoms;
R ₇ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group or a cyclohexyl group substituted by 1 to 3 alkyl groups having 1 to 4 carbon atoms;
R ₈ represents an alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted phenyl group or naphthyl group with an alkyl group having 1 to 4 carbon atoms,
R ₉ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, unsubstituted or 1 carbon atom.
Represents a phenyl or naphthyl group substituted with 4 to 4 alkyl groups; or

Represents;
M ^{r +} represents an r-valent metal cation,
p represents 1, 2, 3, 4, 5 or 6, and r represents 1, 2 or 3. )
It is a compound represented by these.

An alkyl substituent of 1 to 20 carbon atoms is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a stearyl group or the corresponding branched isomer; A C2-C4 alkyl group is preferred.
A phenyl group or a naphthyl group which is preferably substituted with an alkyl group having 1 to 3 carbon atoms, especially 1 or 2 alkyl groups containing 1 to 2 carbon atoms, is, for example, an o-, m- or p-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2- Methyl-6-ethylphenyl group, 4-tert-butylphenyl group, 2-ethylphenyl group, 2,6-diethylphenyl group, 1-methylnaphthyl group, 2-methylnaphthyl group, 4-methylnaphthyl group, 1, 6-dimethylnaphthyl group or 4-tert-butylnaphthyl group.
Preferably, a cyclohexyl group substituted with an alkyl group having 1 to 4 carbon atoms including 1 to 3 or 1 or 2 branched or unbranched alkyl groups is, for example, cyclopentyl Group, methylcyclopentyl group, dimethylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, trimethylcyclohexyl group or tert-butylcyclohexyl group.
The monovalent, divalent or trivalent metal cation is preferably an alkali metal cation, alkaline earth metal cation, heavy metal cation or aluminum cation, such as Na ⁺ , K ⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Ba ⁺⁺ , Zn ⁺⁺ or Al ⁺⁺⁺ . Particularly preferred is Ca ⁺⁺ .

Preferred compounds of formula I are those containing at least one tertiary butyl group as R ₆ and R ₇ . Very particular preference is given to compounds in which R ₆ and R ₇ simultaneously represent a tert-butyl group.
p is preferably 1 or 2, very particularly preferably 1.

で表される化合物又はそれらの混合物である。 Very particularly preferred compounds of the formula I are those of the formulas Ia and Ib

Or a mixture thereof.

  Of interest is a method for improving the thermal and light stability of a polyester comprising a chain extender selected from the group consisting of anhydrides, alcohols and hindered phenolic aromatic phosphates or the like. And adding a mixture of:

からなる群より選択される鎖延長剤又はそれらの混合物を添加することを含む、方法である。 Of particular interest is a method for improving the thermal and light stability of a polyester comprising a pyromellitic dianhydride, pentaerythritol, a compound of formula Ia and Ib. Compound

Adding a chain extender selected from the group consisting of or a mixture thereof.

The chain extender is preferably a polyester which is stabilized against degradation induced by heat and light, based on the weight of the polyester, 0.01 to 10%, in particular 0.01 to 5%, for example 0.00. Added in an amount of 01 to 2%.

  A novel method for improving the thermal and light stability of the polyester, including adding a chain extender to the polyester, may include additional co-stabilizers (additives) such as, for example:

1. Antioxidant
1.1. Alkylated monophenols,
For example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 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-tert-butyl-4-methoxymethylphenol, branched in linear or side chain Fractionated nonylphenols such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1′-methylundec-1′-yl) phenol, 2, 4-Dimethyl-6- (1'-methylheptadecy-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof.

1.2. Alkylthiomethylphenol,
For example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthio Methyl-4-nonylphenol.

1.3. Hydroquinone and alkylated hydroquinone,
For example, 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-tertiary Butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherol,
For example, α-, β-, γ-, δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ether,
For example, 2,2′-thiobis (6-tert-butyl-4-methylphenol), 2,2′-thiobis (4-octylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol) ), 4,4′-thiobis (6-tert-butyl-2-methylphenol), 4,4′-thiobis (3,6-di-secondary amylphenol), 4,4′-bis (2,6) -Dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidene bisphenol,
For example, 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-cyclohexylphenol), 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'-methylenebis (6-tert-butyl-2-methylphenol), 1,1 -Bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (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-dodecylme Lucaptobutane, ethylene glycol bis [3,3-bis (3′-tert-butyl-4′-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, 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-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7. O-, N- and S-benzyl compounds ,
For example, 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-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. Hydroxybenzylated malonate ,
For example, dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) -malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) ) Malonate, didodecyl mercaptoethyl-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. Aromatic hydroxybenzyl compounds ,
For example, 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. Triazine compounds ,
For example, 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
Octyl mercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tertiary 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-hydroxyphenylethyl) -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. Acylaminophenol ,
For example, 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1.12. β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid , which is a mono- or polyhydric alcohol, 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, tri Ethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4- Ester with hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.13. β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid , which is a mono- or polyhydric alcohol, 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, tri Ethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4- Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane; 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methyl) Phenyl) propionyloxy Ester} -1,4-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane.

1.14. β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid ester , monohydric or polyhydric alcohol, for example
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-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1- Ester with phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.15.3 Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid , which are mono- or polyhydric alcohols, for example
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-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] Esters with octane.

1.16. β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide , for example
N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, 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-tertiary] (Butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard® XL-1 supplied by Uniroyal).

1.17. Ascorbic acid (vitamin C)

1.18. Amine antioxidants ,
For example, N, N′-di-isopropyl-p-phenylenediamine, N, N′-di-secondary butyl-p-phenylenediamine, N, N′-bis (1,4-dimethylpentyl) -p-phenylene Diamine, 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-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- ( 1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N′-phenyl-p-phenylenediamine, N-cyclohex -N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl-N, N'-di-secondary butyl-p-phenylenediamine, diphenylamine, N -Allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, eg p, p ' -Di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxy) Phenyl) amine, 2,6-di-tert-butyl -4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 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, tertiary octyl N-phenyl-1-naphthylamine, mono- and dialkylated tertiary butyl / tertiary octyl diphenylamine mixtures, mono- and dialkylated nonyl diphenylamine mixtures, mono- and dialkylated dodecyl diphenylamine mixtures, mono- and dialkylated Isopropyl / isohexyldiphenylamine mixtures, mono- and dia Mixtures of killed tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mono- and dialkylated tert-butyl / tertiary octylphenothiazine, mono- and A mixture of dialkylated tertiary octylphenothiazines, N-allylphenothiazine, N, N, N ′, N′-tetraphenyl-1,4-diaminobut-2-ene.

2. UV absorber and light stabilizer
2.1.2- (2′-hydroxyphenyl) benzotriazole ,
For example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) benzotriazole, 2- (5′-th Tributyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5'- Di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3′-tert-butyl-2′-hydroxy-5′-methylphenyl) -5-chlorobenzotriazole, 2- ( 3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-4′-octyloxyphenyl) benzotriazole, 2- (3 ′, 5′- G-second Triamyl-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-chlorobenzotriazole, 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′-hydro Xyl-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-isooctyloxycarbonyl) Ethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazole-2-ylphenol]; 2- [3'-tert-butyl-5 Transesterification of '-(2-methoxycarbonylethyl) -2'-hydroxy-phenyl] -2H-benzotriazole with polyethylene glycol 300 Product; R represents 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl group _{[R-CH 2 CH 2 -COO} -CH 2 CH 2 -] 2 -, 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-hydroxybenzophenone ,
For example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ′, 4′-trihydroxy and 2′-hydroxy-4,4′- Dimethoxy derivative.

2.3. Substituted and unsubstituted esters of benzoic acid ,
For example, 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertiary 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. Acrylate ,
For example, ethyl α-cyano-β, β-diphenyl acrylate, isooctyl α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline and neopentyltetra (α- Cyano-β, β-di-phenyl acrylate.

2.5. Nickel compounds ,
For example, 2,2′-thiobis- [4- (such as 1: 1 or 1: 2 complexes with or without other ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine. 1,1,3,3-tetramethylbutyl) phenol] nickel complex, nickel dibutyldithiocarbamate, monoalkyl ester, eg methyl or ethyl ester, 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid Nickel salts of ketoximes, for example nickel complexes of 2-hydroxy-4-methylphenyl-undecylketoxime, nickel of 1-phenyl-4-lauroyl-5-hydroxypyrazole with or without other ligands Complex.

2.6. A sterically hindered amine ,
For example, 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- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazi Linear or cyclic condensates of 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-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -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-o 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-1,3,5-triazine linear or cyclic condensate, 2-chloro-4,6-bis ( 4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane condensate, 2-chloro-4 , 6-Di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3-aminopropylamino) ethane Condensate of Tyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6) 6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 4- A mixture of hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and Condensation product of 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1
, 3,5-triazine and condensate of 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry Number [136504-96-6]); 1,6-hexanediamine and 2,4,4 6-trichloro-1,3,5-triazine and condensate of N, N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS registration number [192268-64-7]) 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-oxo-spiro [4.5] decane, 7,7,9,9-tetramethyl-2- Cyclo Reaction product of ndecyl-1-oxa-3,8-diaza-4-oxo-spiro [4.5] decane and epichlorohydrin, 1,1-bis (1,2,2,6,6-pentamethyl -4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexa Methylenediamine, diester of 4-methoxymethylenemalonic acid and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6- Tetramethyl-4-piperidyl)] siloxane, maleic anhydride-α-olefin copolymer and 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethy Reaction product with -4-aminopiperidine, 2,4-bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidinine-4-yl) -N-butylamino]- 6- (2-hydroxyethyl) amino-1,3,5-triazine, 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 5- (2-ethylhexanoyl) oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor (Clariant; CAS Registry Number [106917-31-1]), 5- ( 2-ethylhexanoyl) oxymethyl-3,3,5-trimethyl-2-morpholinone, 2,4-bis [(1-cyclohexyloxy-2,2 6,6-piperidin-4-yl) butylamino] -6-chloro-s-triazine and N, N′-bis (3-aminopropyl) ethylenediamine), 1,3,5-tris ( N-cyclohexyl-N- (2,2,6,6-tetramethylpiperidin-3-one-4-yl) amino) -s-triazine, 1,3,5-tris (N-cyclohexyl-N- (1 , 2,2,6,6-Pentamethylpiperazin-3-one-4-yl) amino) -s-triazine.

2.7. Oxamide,
For example, 4,4′-dioctyloxy oxanilide, 2,2′-diethoxy oxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyl Oxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N, N′-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl- 2'-etoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixture of o- and p-methoxy-disubstituted oxanilide and o- and p-ethoxy-2 A mixture of substituted oxanilides.

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-tridecyloxyphenyl) -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-octyloxypropyl) Oxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-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-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (4 − [2- Ethylhexyloxy] -2-hydroxyphenyl) -6- (4-methoxyphenyl) -1,3,5-triazine.

3. Metal deactivators ,
For example, N, N′-diphenyloxamide, N-salicyl-N′-salicyloyl-hydrazine, 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, sebacoyl bisphenyl hydrazide, N, N′-diacetylazi Poil dihydrazide, N, N′-bis (salicyloyl) oxalyl dihydrazide, N, N′-bis (salicyloyl) thiopropionyl dihydrazide.

4). Phosphites and phosphonites,
For example, triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di -Tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methyl) Enyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4, 4'-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphocin, 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-methyl-dibenz [d, g] -1,3,2-dioxaphosphocine, 2,2 ', 2 "-nitrilo [triethyl Tris (3,3 ′, 5,5′-tetra-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-dioxaphosphirane.

5. Hydroxylamine,
For example, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N- N, N-dialkylhydroxylamine derived from dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, hydrogenated tallowamine .

6). Nitron,
For example, N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, N-tetradecyl-α-tridecylnitrone, N -Hexadecyl-α-pentadecyl nitrone, N-octadecyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrone, N -Octadecyl-α-hexadecylnitrone, a nitrone derived from N, N-dialkylhydroxylamine derived from hydrogenated tallowamine.

7). Thio synergist,
For example, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate or distearyl disulfide.

8). Peroxide scavengers,
For example, esters of β-thiodipropionic acid, such as lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole or zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β -Dodecyl mercapto) propionate.

9. Polyamide stabilizers such as copper salts and divalent manganese salts in combination with iodides and / or phosphorus compounds.

10. Basic auxiliary stabilizers such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids such as calcium stearate, stearin Zinc acid, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

11. Nucleating agent ,
For example, inorganic substances such as talc, metal oxides such as titanium dioxide, magnesium oxide, preferably alkaline earth metal phosphates, carbonates or sulfates; organic compounds such as mono- or polycarboxylic acids and Their salts, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers). Particularly preferred are 1,3: 2,4-bis (3 ′, 4′-dimethylbenzylidene) sorbitol, 1,3: 2,4-di (paramethyldibenzylidene) sorbitol, and 1,3: 2,4- Di (benzylidene) sorbitol.

12 Fillers and reinforcing agents ,
For example, calcium carbonate, silicate, glass fiber, glass bulb, asbestos, talc,
Kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and other natural product powders or fibers, synthetic fibers.

13. Other additives such as plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow control agents, optical brighteners, flameproofing agents, antistatic agents and foaming agents.

14 Other benzofuranones and indolinones ,
For example, U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312; U.S. Pat. No. 5,216,052; German Patent Application Publication No. 4316611; German Patent Application Publication No. 4316622; German Patent Application Publication No. 4316876; European Patent Application Publication No. 058989839 or EP-A-0 511 102; those disclosed in EP-A-1291384, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl- Benzofurano-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofurano-2-one, 3,3 ′ -Bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofurano-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) ) Benzofurano-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofurano-2-one, 3- (3,5-dimethyl-4-pi) Valoyloxyphenyl) -5,7-di-tert-butylbenzofurano-2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert-butylbenzofurano-2-one, 3 -(2,3-dimethylphenyl) -5,7-di-tert-butylbenzofurano-2-one, 3- (2-acetyl-5-isooctylphenyl) -5-isooctylbenzofurano-2-one .

The auxiliary stabilizer is added, for example, at a concentration of 0.01 to 10% with respect to the total mass of the polyester to be stabilized.
Another preferred additive is an aldehyde scavenger. These include, for example, polyvinyl alcohol, (meth) acrylamide homo- or copolymers, hydroxylamine, nitrone, amine oxide, poly [glyceryl (meth) acrylate], amine antioxidants, benzofurano-2-one, phosphite, phosphonite, Or a phosphonate or a mixture thereof. Particularly preferred aldehydes are formaldehyde, acetaldehyde or propionaldehyde.

A preferred subject of the present invention is also the use of the chain extenders described above to improve the thermal and light stability of polyesters.
Polyesters having such improved properties are particularly useful in the manufacture of products such as fibers, films, pipes, profiles, bottles, tanks or containers.
Accordingly, a preferred embodiment of the present invention also relates to a product comprising a polyester having improved heat and light stability comprising a chain extender.

  The following examples illustrate the invention in more detail. Parts and percentages are based on mass.

ａ）比較例
ｂ）本発明に従う例
ｃ）イルガモド（Ｉｒｇａｍｏｄ）ＲＡ２０（登録商標）（チバ スペシャルティ ケミカルズ社）（Ｃｉｂａ Ｓｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌｓ Ｉｎｃ．）は、
ポリエステル（ナンヤ（Ｎａｎ Ｙａ）からのタリリン（Ｔａｒｉｌｉｎ））７５．５％
ピロメリト酸二無水物２０．５％
ペンタエリトリトール２％及び
式Ｉａ

で表される化合物（イルガモド１９５，チバ スペシャルティ ケミカルズ社）２％ Example 1: Stabilization of polyester fibers The following procedure was used to evaluate the light and thermal stability performance of PET yarns containing chain extenders:
PET powder [RT21 (Kosa)] was dried in a vacuum oven at 120 ° C. for 8 hours. An appropriate amount of chain extender was added to the dried PET powder. The blend was mixed in a turbomixer and extruded in a twin screw extruder (Berstoff ZE25 33D). The polymer string was then granulated. The resulting granules were dried in a vacuum drying oven at 190 ° C. for 1 hour, followed by 100 ° C. for 1 hour. The granules were then processed through a fiber extruder Spinboy II to produce 40 filament yarns of 4.5 denier each. The fibers were then further tested in a weatherometer (WOM) according to ISO 4892-2 [light stability]. Separately the yarns were tested for their thermal stability in an air circulating oven at 120 ° C. [Thermal stability]. The results are summarized in Table 1.

a) Comparative Example b) Example according to the invention c) Irgamod RA20® (Ciba Specialty Chemicals Inc.) (Ciba Specialty Chemicals Inc.)
75.5% polyester (Tarilin from Nan Ya)
Pyromellitic dianhydride 20.5%
Pentaerythritol 2% and Formula Ia

(Irgamod 195, Ciba Specialty Chemicals) 2%

Claims (12)

A method for improving the thermal and light stability of a polyester comprising adding a chain extender to the polyester. The method of claim 1, wherein the polyester is a polyester fiber. The method according to claim 1, wherein the polyester is polyethylene terephthalate or polyethylene naphthalate. The chain extender is a compound selected from the group consisting of anhydrides, epoxides, oxazolines, oxazolones, oxazines, isocyanates, acyllactams, maleimides, alcohols and hindered phenolic aromatic phosphates, or a mixture thereof. The method according to 1. The method of claim 1, wherein the chain extender is a compound selected from the group consisting of anhydrides, alcohols and hindered phenolic aromatic phosphates, or a mixture thereof. The hindered phenolic aromatic phosphate has the formula I

(Where
R ₆ represents an isopropyl group, a tert-butyl group, a cyclohexyl group or a cyclohexyl group substituted by 1 to 3 alkyl groups having 1 to 4 carbon atoms;
R ₇ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group or a cyclohexyl group substituted by 1 to 3 alkyl groups having 1 to 4 carbon atoms;
R ₈ represents an alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted phenyl group or naphthyl group with an alkyl group having 1 to 4 carbon atoms,
R ₉ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, unsubstituted or 1 carbon atom.
Represents a phenyl or naphthyl group substituted with 4 to 4 alkyl groups; or

Represents;
M ^{r +} represents an r-valent metal cation,
p represents 1, 2, 3, 4, 5 or 6, and r represents 1, 2 or 3. )
The method of Claim 5 which is a compound represented by these. The chain extender comprises pyromellitic dianhydride, pentaerythritol, a compound represented by formula Ia and a compound represented by Ib

The method of claim 1, wherein the compound is a compound selected from the group consisting of: The method of claim 1, wherein the chain extender is present in an amount of 0.01 to 10% based on the weight of the polyester. The method of claim 1 further comprising further additives in addition to the chain extender. 10. A method according to claim 9, comprising an aldehyde scavenger as a further additive. A product comprising a polyester having improved heat and light stability comprising a chain extender. Use of chain extenders to improve the thermal and light stability of polyesters.