JPH11323100A - Ultraviiolet-stabilized polyester molding composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition exhibiting improved stability to discoloration and luster loss caused by being continuously exposed to ultraviolet radiation, therefore useful in the automotive industry by combining a polyester resin with an ultraviolet-stabilizing system. SOLUTION: This composition is obtained by combining (A) a thermoplastic polyester resin with (B) such an effective amount of an ultraviolet-stabilizing system as to be enough to attain a color difference of about <2.25 as calculated with CIELab unit under the light source D-65 in accordance with ASTM Standard D-2244 when this composition is exposed to an irradiation of 601.6 kj/m<2> using a xenon arc weather-O-meter operated in accordance with SAEJ1885, and present a surface gloss retainability of at least about 7.5; wherein the component B comprises (i) an ultraviolet absorber, (ii) a hindered amine-based light stabilizer and (iii) an antioxidant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a UV-stabilized thermoplastic polyester molding composition suitable for preparing molded articles. A molding composition is prepared by combining the polyester resin with an ultraviolet light stabilizing system comprising a hindered amine light stabilizer and an ultraviolet light absorber. Molded articles prepared from the composition exhibit improved stability against discoloration and loss of gloss caused by continuous UV exposure.

[0002]

BACKGROUND OF THE INVENTION For many years, the automotive industry has painted molded articles from many different polymer systems, including polyester resins. Historically, all of these polymers have not previously had sufficient UV stability to eliminate the painting process. Painting (pain
t) and the application layer of the optional UV coating protected the polymer from UV degradation which caused undesirable discoloration and reduced surface gloss. The automotive industry is interested in eliminating the painting process, lowering costs, and reducing emissions to the atmosphere from the use of paints and solvents.

[0003]

It is known that polyester resins such as copolyester elastomers and polyalkylene terephthalates decompose when exposed to ultraviolet light for a long period of time. This decomposition is typically exhibited in the form of a distinct and undesirable discoloration from the desired color of the molded article. Specifically, upon exposure to ultraviolet light and other environmental factors found inside automobiles, the color of the polyester resin usually changes from its initial color to distinct yellow and tan. In the automotive industry, continue painting the part to prevent this UV-induced discoloration and loss of gloss, or select another polymer system that has desirable performance characteristics that are important for UV exposure applications Was needed.

[0004] There is a need for an ultraviolet stabilizing system that eliminates the need to apply surface paints and additives to molded articles to prevent discoloration and loss of gloss when combined with polyester resins. The stabilizing system should not adversely affect the physical or molding properties of the composition,
It is necessary to add a small amount and combine with the polyester.

[0005]

SUMMARY OF THE INVENTION The present invention is directed to a thermoplastic polyester resin and a xenon arc weatherometer operated in accordance with SAE J1885.
When exposed to 1.6 kj / m ² of radiation, CIE under light source “D-65” according to ASTM standard D-2244
Combined with the polyester resin in an effective amount sufficient to achieve a color difference of less than about 2.25, calculated in Lab units, and exhibit at least about 7.5% surface gloss retention after irradiation. And a UV-stabilized molding composition comprising a UV-stabilizing system. The UV stabilizing system comprises: (i) a UV absorber; (ii) a hindered amine light stabilizer; and (iii) an antioxidant. The composition is capable of withstanding discoloration, loss of gloss and surface degradation when exposed to prolonged extreme ultraviolet conditions, for example, automotive interior components, such as: dash board con
trols), suitable for preparing molded articles for the automotive industry, such as instrument panel mounted airbag covers and side impact airbag covers.

According to the present invention, it is characterized by containing a polyester resin and an ultraviolet light stabilizing system, and is suitable for preparing a molded article which is resistant to decomposition and discoloration when exposed to ultraviolet light for a long period of time. The plastic polyester molding composition will be described. The polyester resin can be characterized as comprising a polyalkylene terephthalate, a copolyester elastomer, and optionally a polycarbonate, or a blend thereof. The ultraviolet light stabilizing system added to the polyester resin may include a hindered amine light stabilizer and an ultraviolet light stabilizer. In addition to the stabilizing system, the composition can also include antioxidants and other additive components known in the art.

[0007]

DETAILED DESCRIPTION OF THE INVENTION Copolyester Elastomers A preferred class of thermoplastic polyesters suitable for use in the present invention are copolyester elastomers, such as copolyetheresters. A property of copolyester elastomers is the multiplicity of repeating internal linear long and short chain ester units linked head-to-tail by ester linkages. The linkage chain ester unit has the following structure:

Embedded image Wherein the short-chain ester unit is represented by the following structure:

Embedded image [In the above formula, (i) G is a molecular weight of about 600 and about 55 ° C.
Divalent groups remaining after removing terminal hydroxyl groups from long chain polymer glycols, having a melting point of less than;
(Ii) R ₁ and R ₂ are each different divalent groups remaining after removal of the carboxyl group from different dicarboxylic acids, each having a molecular weight of less than about 300; and (iii) D
₁ and D ₂ are different divalent groups remaining after removal of hydroxyl groups from different low molecular weight diols, each having a molecular weight of less than about 250].

[0008] The "short-chain ester unit" in the copolyetherester means that the copolyetherester has a content of about 25% by weight or less.
95% by weight, and about 50-100% by weight of the short-chain ester units in the copolyetherester may be the same. The term "long chain ester unit" as applied to units in the polymer chain refers to the reaction product of a long chain glycol and a dicarboxylic acid. The “long-chain ester unit”, which is a repeating unit in the copolyester elastomer, corresponds to the above formula I (a) or I (b). Long chain glycols are polymeric glycols having terminal (or near terminal) hydroxy groups and a molecular weight of about 600 to about 6,000. The long-chain glycols used to prepare the copolyesters of the present invention are generally poly (alkylene oxide) glycols or glycol esters of poly (alkylene oxide) dicarboxylic acids. The chemical structure of the long chain polymer portion of the long chain glycol is not critical and does not interfere with the formation of the polyesters of the present invention by polymerizing the compound with glycol (s) or dicarboxylic acid (s). Optional substituents can be present. Thus, the chain may be a single divalent acrylate, cycloaliphatic, or aromatic hydrocarbon group that satisfies other requirements described herein.
It can be a poly (alkylene oxide) group, a polyester group, or a combination thereof. Any of the foregoing compounds can include substituents that do not substantially interfere with the polymerization to form the copolyester. The term "short-chain ester unit" applied to units in the polyester chain
Means a low molecular weight compound or polymer chain unit having a molecular weight of less than about 550. They are made, for example, by reacting a low molecular weight diol of less than about 250 with a dicarboxylic acid to form a repeating unit corresponding to Formulas I (c), (d), (e) or (f) above. .
As used herein, the term "dicarboxylic acid" refers to a condensation polymerization equivalent of a dicarboxylic acid, i.e., an ester or ester-forming derivative thereof, such as, for example, acid chlorides and acid anhydrides, or substantially in a polymerization reaction with a glycol. And their derivatives that behave like dicarboxylic acids.

Suitable copolyesters in the compositions of the present invention include (a) one or more dicarboxylic acids or their equivalents (and esters or ester-forming derivatives such as, for example, acid chlorides, acid anhydrides and the like); (B) one or more linear long-chain glycols; and (c) one or more low molecular weight diols. The polymerization reaction can be initiated by conventional procedures, for example in bulk, or in a solvent that dissolves one or more of the monomers.

"Dicarboxylic acid monomer" useful in the present invention
Is, for example, aromatic, aliphatic or cycloaliphatic, having a molecular weight of less than about 300. The dicarboxylic acids can include any substituents or combinations thereof that do not interfere with the polymerization reaction. Representative dicarboxylic acids include terephthalic acid, isophthalic acid, dibenzoic acids such as bis (p-carboxyphenyl) methane, p-oxy- (p-carboxyphenyl) benzoic acid, 2,7-naphthalenedicarboxylic acid, Nantes La dicarboxylic acid, anthranilamide dicarboxylic acid, 4,4'-sulfonyl-disubstituted dicarboxy compounds with benzene nuclei such as benzoic acid, and C ₁ -C ₁₀ alkyl ring-substituted derivatives thereof or such as halo, alkoxy, Or other ring substituted derivatives such as aryl derivatives. If a dicarboxylic acid is also present, a hydroxy acid such as, for example, p (β-hydroxyethoxy) benzoic acid can be used.

"Aromatic dicarboxylic acids" are dicarboxylic acids in which each carboxy group is bonded to a carbon atom in, for example, an independent benzene ring or a fused benzene ring as described above. "Aliphatic dicarboxylic acids" are acids in which each carboxy group is attached to a fully saturated carbon atom or to a carbon atom that is part of an olefinic double bond. If the carbon atom is in a ring, the acid is cycloaliphatic, otherwise it is aliphatic. Representative aliphatic and cycloaliphatic acids are sebacic acid, 1,3- or 1,4
-Cyclohexanedicarboxylic acid, adipic acid, glutaric acid, succinic acid, carbonic acid, oxalic acid, itaconic acid, azelaic acid,
Diethylmalonic acid, fumaric acid, citraconic acid, allylmalinate acid, 4-cyclohexane-1,2-dicarboxylate acid, pimelic acid, suberic acid, 2,5-diethyladipate, 2-ethylsuberin Acid, 2,2,3,3-tetramethylsuccinic acid, cyclopentanedicarboxylic acid, decahydro-1,5- (or 2,6-) naphthylic acid, the different isomers being present in the copolyester It should be considered as different compounds forming different short chain ester units with the same diol.

Generally, the short chain ester units of formula II should provide from about 25 to about 95% by weight of the copolyester, and from about 50 to about 1 of all short chain ester units.
00% is the same, that is, the reaction product of a single low molecular weight diol and a single low molecular weight dicarboxylic acid.
The short chain ester units are usually statistically dispersed throughout the polymer backbone.

[0013] Copolyester elastomers can be prepared by conventional transesterification reactions. A preferred procedure is to convert a dimethyl ester of terephthalic acid, or a mixture of terephthalic acid and isophthalic acid, to a long chain glycol with a molar excess of butanediol and butenediol in the presence of a catalyst at a temperature of about 50C to about 260C. And removing methanol produced by the exchange by distillation. Heating is continued until the evolution of methanol is complete. Depending on the reaction temperature, catalyst and excess glycol, the polymerization
It may be completed within a range of several minutes to several hours. This procedure prepares low molecular weight prepolymers that can produce high molecular weight copolyesters by distilling excess short chain diol units in a conventional polycondensation reaction. Additional transesterification occurs during the distillation, increasing the molecular weight and randomizing the arrangement of the copolyester units. Usually, the best results are, for example, sym-di-β-naphthyl-p-phenylenediamine and 1,3,5-trimethyl-2,4-tris- (3,5-di-t-butyl-4
Obtained if this final distillation or polycondensation is carried out in the presence of an antioxidant such as -hydroxybenzyl) benzene at a temperature of about 225 ° C. to 260 ° C. and a pressure of less than 1 mm for less than about 2 hours. The most practical polymerization technique is by transesterification to complete the polymerization reaction. It is advantageous to use a catalyst for the transesterification reaction in order to avoid excessive reaction times at elevated temperatures with possible irreversible temperature decomposition. A wide variety of catalysts can be used, but organic titanates such as, for example, tetrabutyl titanate or tetraisopropyl titanate, used alone or in combination with magnesium acetate or calcium acetate, are preferred. Titanate complexes such as those derived from alkali metal or alkaline earth metal alkoxides and titanate esters are also very effective.
Inorganic titanates such as lanthanum titanate, calcium acetate / antimony trioxide mixtures, lithium alkoxides and magnesium alkoxides are representative catalysts that can be used.

The prepolymer can also be prepared by a number of alternative esterification or transesterification methods. For example, a long chain glycol may be reacted with a high or low molecular weight short chain ester homopolymer or copolymer in the presence of a catalyst until randomization occurs. Short chain ester homopolymers or copolymers can be prepared by transesterification from the dimethyl esters and low molecular weight diols described above, or from the free acid with acetic acid diol. Alternatively, short chain ester copolymers are prepared, for example, by direct esterification of the diol with the appropriate acid, acid anhydride or acid chloride, or by other methods such as, for example, reacting the acid with a cyclic ester or carbonate. You may. Obviously, it is believed that the prepolymer is also prepared by performing these methods in the presence of a long chain glycol.

Transesterification polymerization is generally carried out in the melt without the addition of a solvent, but the use of an inert solvent facilitates the removal of volatile components from the mass at low temperatures. can do. The method is particularly useful, for example, during prepolymer preparation by direct esterification.
However, certain low molecular weight diols, such as butanediol in terphenyl, are conveniently removed just during the polymerization by azeotropic distillation. Other special polymerization techniques, such as the interfacial polymerization of bisphenols with bisacyl halides and bisacyl halide-capped linear diols, may prove useful in preparing certain polymers. Both batch and continuous processes may be used for any stage of copolyester polymer preparation. Polycondensation of the prepolymer can also be achieved in the solid phase by heating the finely divided solid prepolymer under vacuum or under an inert gas stream to remove free low molecular weight diols. This method has the advantage of suppressing decomposition since it must be performed at a temperature below the softening point of the prepolymer. The main disadvantage is that it takes a long time to react at any degree of polymerization.

Polyalkylene terephthalate Another class of polyesters that can be useful in making the UV stabilized thermoplastic molding compositions of the present invention is the linear polyalkylene terephthalate, generally polyethylene terephthalate (PET). , Polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), and ethylene-1,4-cyclohexylene dimethylene terephthalate (PETG). Among these, polybutylene terephthalate (PBT) is particularly preferred. Polybutylene terephthalate can be prepared by conventional methods such as, for example, transesterification and polycondensation of dimethyl terephthalate or terephthalic acid or its lower alcohol esters and 1,4-butanediol. Polymers based on polybutylene terephthalate are not strictly limited to PBT homopolymers, but also include copolymers predominantly composed of polybutylene terephthalate units. Thus, as used herein, the term "copolymer" refers to terephthalic acid or its lower alcohol ester as the major dibasic acid component and the major glycol, under the condition that less than 40 mole% of the ester-forming monomer is present. It means a polymer obtained by polycondensation with 1,4-butanediol as a component. The comonomer components that can be used in the present invention include, for example, dibasic acid components such as isophthalic acid and orthophthalic acid and their lower alcohols; and, for example, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, hexamethylene glycol, 1,4 like pentyl glycol
-Other common glycol components such as alkylene glycols other than butanediol, and cyclohexane, dimethanol, and aromatic diols, such as bisphenol A and the ethylene oxide (2 mole) adduct of bisphenol A. Hydroxy acids such as, for example, hydroxybenzoic acid and hydroxynaphthoic acid, and their ester-forming derivatives may also be used as suitable comonomers. The intrinsic viscosity number (IV) and melt index of the PBT are not critical, and changes in the melt index of the PBT or elastomer do not appear to affect the mechanical properties of the compositions of the present invention, although typical IVs are From about 0.7 to about 2.0. Typically, PBTs useful in the present invention have a pH of about 6 to about 6 to about 2 to about 10% as measured by ASTM method D-1238 at 250 ° C. with a load of 2160 g.
It has a melt index of about 90 and an intrinsic viscosity of about 0.6 to about 1.2 dl / g when measured in orthochlorophenol at 25 ° C.

Polycarbonate Optionally, polycarbonate may be combined with the thermoplastic polymer resin of the present invention. Polycarbonates may be added to individual polymers or blends thereof. The polycarbonate resin of the present invention can be uniformly blended with polyester and polyalkylene terephthalate.
Polycarbonates are prepared by reacting a dihydric phenol with a carbonate precursor such as phosgene in the presence of a known acid acceptor and a molecular weight modifier, for example, in a solvent such as methylene chloride, or For example, by transesterification with a carbonate precursor such as diphenyl carbonate.

Suitable examples of dihydric phenols include bisphenols, of which 2,2-bis- (4-
Hydroxyphenyl) -propane, bisphenol A, is particularly preferred. Bisphenol A can be partially or completely replaced by other dihydric phenols. Other dihydric phenols other than bisphenol A include, for example, hydroquinone, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) cycloalkane, bis (4
Compounds such as -hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, and bis (4-hydroxyphenyl) ether; and for example, bis (3,5
Halogenated bisphenols such as -dibromo-4-hydroxyphenyl) propane and bis (3,5-dichloro-4-hydroxyphenyl) propane.
The dihydric phenol may be a homopolymer of a dihydric phenol or a copolymer of two or more dihydric phenols. Further, the polycarbonate resin used in the present invention may be a thermoplastic, randomly branched polycarbonate prepared by reacting a polyfunctional aromatic compound with a dihydric phenol and / or a carbonate precursor. good.

Polycarbonates suitable for use in the present invention have an IV of at least about 0.4 or more (2 in methyl chloride).
(At 0 ° C.).

Generally, the thermoplastic polyester resin of the present invention comprises 0 to about 30% by weight of polyalkylene terephthalate, about 35 to about 70% by weight of polyester elastomer, 0 to about 30% by weight of polycarbonate, and about 30% by weight of MBS. 10 to about 50% by weight, and about 0.2 to about 1.0% by weight of antioxidant. Typically, the polyester composition of the present invention comprises from 0 to about 30% by weight of a polyalkylene terephthalate, from about 55 to about 65% by weight of a polyester elastomer, and from 0 to about 65% by weight, based on the total weight of the composition. 15% by weight, about 15 to about 45% by weight of MBS, and about 0.2 to about 0.8% by weight of antioxidant; preferably, 0 to about 25% by weight of polyalkylene terephthalate and about 60% of polyester elastomer. 0% to about 10% by weight of polycarbonate,
It contains about 20 to about 40% by weight of MBS and about 0.6% by weight of antioxidants.

UV Stabilizing System The UV stabilizing system of the present invention contains a hindered amine light stabilizer, a UV absorber, and an antioxidant. The components of the stabilizer system can be added to the polymer resin after being combined together, or the components can be incorporated directly into the polymer resin. The thermoplastic polyester resin of the present invention, when combined with the UV stabilizer system described herein, significantly increased UV stability and weatherability.

The UV stabilization system comprises a UV absorber which, when exposed to a xenon arc weatherometer operated according to SAE J1885, is compatible with sufficient composition to achieve an acceptable UV exposure result. Including.
In general, UV absorbers have the formula:

Embedded image Wherein R ′ is hydrogen or an alkyl group having 1 to 8 carbon atoms, based on benzophenones. More specifically, the benzophenones are 2-hydroxybenzophenones, for example, 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-t-butoxybenzophenone; 2-hydroxy-4-octoxy. Benzophenone; 2-hydroxy-4-dodecyloxybenzophenone; 2-hydroxy-4-stearoxybenzophenone; 2-hydroxy-4-phenoxybenzophenone; 2-hydroxy-4- (β-hydroxyethoxy) benzophenone; 2-hydroxy-4 -(2'-hydroxy-3'-acryloxypropoxy) benzophenone; 2-hydroxy-4- (2'-hydroxy-3
'-Methacryloxypropoxyl) benzophenone;
2,2'-dihydroxybenzophenone;2,2'-dihydroxy-4-methoxybenzophenone;2,2'-
Dihydroxy-4-butoxybenzophenone; 2,2
'-Dihydroxy-4-octoxybenzophenone;
2,2'-dihydroxy-4-lauroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone;2,2',4'-trihydro-4-methoxybenzophenone; 2-hydroxy-4-methoxy- 4'-chlorobenzophenone;2,2'-dihydroxy-4,4
'-Dimethyloxybenzophenone; 2-hydroxy-
4-methoxy-2'-methyl-4'-hydroxybenzophenone;2-hydroxy-4-methoxy-4'-t-
Butyl benzophenone; 2-hydroxy-4-methoxy-4'-methyl-benzophenone; 2-hydroxy-
4,4'-dimethoxybenzophenone; 2-hydroxy-4,4 ', 2'-trimethoxybenzophenone; 2-
And hydroxy-4-N-octoxybenzophenone.

The UV absorber is based on benzotriazole, more particularly 2-hydroxybenzotriazole, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole; 2- (2'-hydroxy-3) '-5'-di-t-butylphenyl) benzotriazole; 2- (2'-hydroxy-3'-5'-di-t
-Butylphenyl) -5-chlorobenzotriazole;
2- (2'-hydroxy-3 ', 5'-diphenyl)-
5-benzotriazole; 2- (2'-hydroxy-3
'-T-butyl-5'-methylphenyl) -5-chlorobenzotriazole; 2- (2'-hydroxy-5'
-T-butyl-5'-methylphenyl) benzotriazole; 2- (2'-hydroxy-3'-s-butyl-5
'-T-butylphenyl) benzotriazole; 2-
(2′-hydroxy-5-t-octylphenyl) benzotriazole; 2- (2H-benzotriazole-2
-Yl) -4,6-bis (1-methyl-1-phenylethyl) -phenyl; 2- (3 ', 5'-bis (1-
Methyl-1-phenylethyl) -2'-hydroxyphenyl) benzotriazole and the like.

Generally, the effective amount of UV absorber in the molding composition is from about 0.5 to about 0.5, based on the total weight of the composition.
About 5% by weight. Commercially available benzotriazoles useful in the present invention include Cyasorb® UV 5411, 2- (2-hydroxy-5-t-octylphenyl) -benzotriazole, commercially available from American Cyanamid Company; 2- (3'-5'-bis (1-methyl-) commercially available from Geigy Corporation.
Tinuvin® 234, which is 1-phenylethyl) -2′-hydroxyphenyl) benzotriazole. Commercially available benzophenones useful in the present invention include those commercially available from American Cyanamid Company.
Cyasorb® UV 531 which is -hydroxy-4-N-octoxybenzophenone.

Hindered amine light stabilizers (HALS) useful in ultraviolet light stabilizing systems include 1,1 '-[1,2-
Ethanediyl] -bis [3,3,5,5-tetramethylpoperadione]; dimethyl succinate polymer and 4-
Hydroxy-2,2,6,6-tetramethyl-1-piperdinethanol; bis (1,2,2,6,6-pentamethyl-4-piperdinyl) sebacate; bis [2
2,6,6-tetramethyl-4-piperidinyl] decandioate; bis (1,2,2,6,6-pentamethyl-4-piperidinyl) -2-[[3,5-bis (1,1
-Dimethylethyl) -4-hydroxyphenyl] methyl] -2-butylpropanedioate; poly [(2,
2,6,6-tetramethyl-4-piperidinyl) iminomethylene (2,2,6,6-tetramethyl-4-piperidinyl) imino [6- (octylamino) -1,3,5
-Triazine-4,2-diyl]]; 2,2,6,6-
Tetramethyl-4-piperidinyl benzoate; tetrakis (2,2,6,6-tetramethyl-4-piperidinyloxy) silane; Preferred commercially available HALS for the present invention include bis (1,2,2,2)
6,6-pentamethyl) -4-piperidinyl- (3,5
Tinuvin 144, which is -di-t-butyl-4-hydroxybenzyl) butyl propane diate, Hoechst AG, Fr.
high melt polymer / oligomer hindered amine light stabilizer commercially available from ankfurt am Main, Germany
Hostavin® N20 and Hostavin N30; 2,
Sanol® LS770, a 2,6,6-tetramethylpiperidine; Goodrite 3150, a hindered amine light stabilizer commercially available from BF Goodrich

Embedded image And [1,2,2,6,6-pentamethyl-4-piperidiyl / β, β, β ′, β′-tetramethyl-3,9;
-(2,4,8,10-tetraoxaspiro (5,5)
Adka Stab LA-63 which is undecane) diethyl] -1,2,3,4-butanetetracarboxylate.

In general, an effective amount of HALS is included in the UV stabilization system to prevent surface degradation of the thermoplastic polyester resin as a result of UV exposure. An effective amount of HALS in the molding composition is from about 0.5 to about 5% by weight based on the total weight of the composition. Typically, the relative ratio of HALS: UVA in the stabilizing system is from about 1: 1 to about 1: 2, preferably about 1: 1.
It is one.

Also, the ultraviolet light stabilizing system of the present invention may contain an antioxidant in an amount of about 0.5 to about 1.5 based on the total weight of the composition.
% By weight. Typically, the antioxidant is Ciba Geigy C
tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane commercially available from Orporation under the name Irganox 1010; and
It is commercially available from Sandos under the name Sandostab P-EPQ [tetrakis (2,4-di-t-butylphenyl) -4,4-biphenyldiphosphonite].

Further, as lubricants and fillers, for example, minerals such as talc, calcium carbonate, mica and the like, release agents,
Plasticizers, nucleating agents, impact modifiers, pigments, and colorants; glass, amorphous carbon, graphite carbon, aramid, stainless steel, ceramic, alumina, titanium, magnesium, metal-coated carbon, rock wool, and the like. And continuous length reinforcing fibers selected from the group consisting of the following combinations:

[0029]

EXAMPLES The following examples are presented as specific descriptions of the claimed invention, but it is to be understood that the invention is not limited by the specific descriptions set forth in the following examples. It is. The polyester resin was pre-blended in dry form with various additives and post-blended prior to molding as shown in the table below. The dry formulation is then added to about 100 to about 1
Extruded and pelletized by a single or twin screw extruder operating at 50 revolutions per minute and a temperature of about 300 ° C. Pelletized sample,
Test plaques were injection molded on a VanDorn using a barrel temperature of about 470 ° F and a molding temperature of about 180 ° F.

The test plaques were used to determine the physical properties of the polyester resin composition, particularly "color difference" and "percent gloss retention". In this regard,
Exposure of the test plaque to ultraviolet light and heat in a xenon arc weatherometer operated according to the automated test procedure SAE J1885 resulted in the "color difference" data listed in Tables 1 and 2 below.

SAE J1885 Conditions Light Cycle Dark Cycle Irradiation, W / m ² 0.55-Black Panel Temperature, ° C. 89 38 Relative Humidity,% 50 95 Cycle Time, h 3.8 1.0 Exposure is based on total exposure received by test plaque Measured, Kilojoules per square meter (kJ / m ² )
It was expressed by.

The degree of color change was determined by measuring the color of the exposed test piece with respect to the color of the unexposed test piece using an apparatus. The degree of color change is AS
Quantified as total color difference (ΔE *) calculated in all cases for light source “D-65”, 10 ° observer, specular content, expressed in CIELab units, according to TM D-2244. When the values of L, a and b of the Hunter colorimeter system are measured, the color difference value ΔE of the polyester composition of the present invention is calculated by the following formula: ΔE = [(L−L ₀ ) ² + (a−a ₀ ) ² + (B−b ₀ ) ² ] ^1/2 (where L ₀ , a ₀ and b ₀ are color values measured before irradiation, and L, a and b are color values measured after irradiation. Yes,
ΔL = L−L ₀ is the light and dark difference between the exposed and unexposed samples, Δa = a−a ₀ is the red and green difference between the exposed and unexposed samples, and Δb = b
−b ₀ is the yellow and blue difference between the exposed and unexposed samples). "Percent Retention of Gloss" (% gloss 60 °) is the 60 ° gloss of test plaques before and after exposure to a Xenon arc weatherometer using a Gardner multi-angle gloss meter operated according to ASTM 523. Determined by measuring. The gloss retention of each test plaque was obtained by dividing the gloss measurement of the exposed specimen by the gloss measurement of the unexposed specimen. The unit of the obtained value is%.

Example 1 Various amounts of the components of the stabilizer system were incorporated into a polyester resin. It comprises about 25% by weight of polybutylene terephthalate, about 15% by weight of copolyester elastomer, about 30% by weight of olefin elastomer and about 30% by weight of MBS.
Wt%, about 0.1% by weight of Irganox 1010, and Irgaph
It is characterized by containing about 0.2% by weight of os. Samples 1-16 were prepared by mixing the component amounts measured in g according to the above procedure. In addition to a number of UV absorbers and HALS, a colorant MC3123K20 3
A sample was prepared using 9292-04-21.

Sample 1 Polyester 2000.0 g MC3123K20 39292-04-21 00.0 g Sample 2 Polyester 1979.0 g MC3123K2029292-04-21 00.0 g Cyasorb UV5411 0.5 g Sanol LS770 10.5 g Sample 3 Polyester 1979.0 g MC3123K2029292- 04-21 100.0 g Cyasorb UV5411 10.5 g Hostavin N20 10.5 g Sample 4 polyester 1979.0 g MC3123K2029292-04-21 100.0 g Cyasorb UV5411 10.5 g Hostavin N30 10.5 g Sample 5 polyester 1799.0 g MC3123K2029292-04- 21 100.0 g Cyasorb UV5411 10.5 g Adkastab LA63 10.5 g Sample 6 polyester 1979.0 g MC3123K2029292-04-21 100.0 g Sanol LS770 10.5 g Tinuvin 234 10.5 g Sample 7 polyester 1979.0 g MC3123K2029292-04-21 100 0.0g Sanol LS770 10.5 Cyasorb UV531 10.5 g Sample 8 Polyester 1968.50 g MC3123K2029292-04-21 100.0 g Cyasorb UV5411 10.5 g Sanol LS770 10.5 g Sample 9 Polyester 1968.5 g MC3123K2029292-04-21 100.0 g Cyasorb UV5411 10.5 g Sanol LS770 10.5 g Irganox 1010 10.5 g Sample 10 Polyester 1968.5 g MC3123K2029292-04-21 100.0 g Cyasorb UV5411 10.5 g Sanol LS770 10.5 g Sandostab P-EPQ 10.5 g Sample 11 polyester 1958.5 g MC3123K2029292-04-21 100.0 g Cyasorb UV5411 10.5 g Sanol LS770 10.5 g Irganox 1010 10.5 g Sandostab P-EPQ 10.5 g Sample 12 polyester 1978.9 g MC3123K2029292-04-21 100.0 g Cyasorb UV5411 10.5 g Sanol LS770 5.3 g Hostavin N30 5.3g Sample 13 POLYS 1968.5 g MC3123K2029292-04-21 100.0 g Cyasorb UV5411 10.5 g Sanol LS770 10.5 g Hostavin N30 10.5 g Sample 14 polyester 1968.5 g MC3123K2029292-04-21 100.0 g Cyasorb UV5411 10.5 g Hostavin N20 3 g Hostavin N30 5.3 g sample 15 polyester 1968.4 g MC3123K2029292-04-21 100.0 g Cyasorb UV5411 10.5 g Hostavin N20 5.3 g Hostavin N30 5.3 g Sandostab P-EQP 10.5 g sample 16 polyester 1947.5 g MC3123K2029292- 04-21 100.0 g Cyasorb UV5411 21.0 g Sanol LS770 10.5 g Hostavin N30 10.5 g Sandostab P-EQP 10.5 g

Test plaques prepared from these compositions were exposed to a xenon arc weatherometer according to SAEJ 1885, as previously described. The data obtained is shown in Table 1 as "color difference" or ΔE *. In general, the greater the change in measured color, the more visually the sample becomes visually objectionable.
As can be seen from Table 1, the color difference after exposure was
From about 2,16 to about 3.31 for the control without UV stabilizer (Sample 1). The new and unexpected result of the molding composition is that the low molecular weight monomer H
Samples containing ALS (eg, Sanol LS770 or Hostavin N20) generally exhibited a surface gloss value equal to or greater than the blank control, ie, sample 1. This increase in gloss is completely unexpected,
Visually the least desirable. Only samples 4 and 5, which did not contain any one of these additives, visually appeared to have less change in overall appearance as compared to control sample 1. Specifically, Sample 4, which contains the oligomer HALS Hostavin N30,
The visual change was the least and most stable.

[0036]

[Table 1] Table 1Sample No. 1 2 3 4 5 6 7 8  Polyester resin 95.24 94.24 94.24 94.24 94.24 94.24 94.24 93.7 Colorant 4.76 4.76 4.76 4.76 4.76 4.76 4.76 4.7 Cyasorb UV5411 0.50 0.50 0.50 0.50 0.7 Sanol LS770 0.50 0.50 0.50 0.7 Hostavin N20 0.50 Hostavin N30 0.50 Adkastab LA63 0.50 0.50 Tinuvin ＠ 601.6kJ / m^Two 3.31 2.63 2.96 2.66 2.95 2.57 3.06 2.3 ΔL * -2.43 -1.78 -1.95 -1.72 -2.21 -1.93 -2.12 -1.5 Δb * 2.24 1.93 2.23 2.02 1.95 1.69 2.21 1.760 ° gloss (%) 8.0 8.3 8.6 4.3 4.0 8.0 7.4 6.1  Table 1 (continued)Sample No. 9 10 11 12 13 14 Polyester 93.74 93.74 93.24 94.24 93.74 94.24 Colorant 4.76 4.76 4.76 4.76 4.76 4.76 Cyasorb UV5411 0.50 0.50 0.50 0.50 0.50 0.50 Sanol LS770 0.50 0.50 0.50 0.25 0.50 Hostavin N20 0.25 Hostavin N30 0.25 0.50 0.25 Adkastab LA63 Tinuvin 0.50 Irganstab P-EPQ 0.50 0.50 ΔE*＠601.6kJ/m^Two 2.79 2.47 2.51 2.61 2.89 3.01 ΔL * -1.80 -1.50 -1.33 -1.64 -1.98 -2.14 Δb * 2.13 1.96 2.12 2.03 2.11 2.1260 ° gloss (%) 8.3 11.8 12.5 8.5 9.3 7.9  Table 1 (continued)Sample No. 15 16 Polyester resin 93.74 92.74 Colorant 4.76 4.76 Cyasorb UV5411 0.50 1.00 Sanol LS770 0.50 Hostavin N20 0.25 Hostavin N30 0.25 0.50 Adkastab LA63 Tinuvin 234 Cyasorb UV531 Irganox 1010 Sandostab P-EPQ 0.50 0.50 ΔE*＠601.6kJ/m^Two 2.38 2.16 ΔL * -1.46 -1.29 Δb * 1.88 1.7360 ° gloss (%) 8.7 7.1

Another surprising and unexpected result was that the type of UV absorber had substantially no effect on resin UV performance. Samples 2, 6 and 7 were low molecular weight benzotriazoles (Cyasor
b UV5411), high molecular weight benzotriazole (Tinuvin 23
4), and benzophenone (Cyasorb UV5311). The UV performance of these three samples was substantially the same, both visually and as measured by color difference and gloss change.

Example 2 This set of samples was prepared and tested to further investigate the effect of the hindered amine light stabilizer component on the UV stability of the polyester polymer system. In this example, various monomer and polymer / oligomer hindered amines were evaluated to fully understand the effect of primarily molecular weight on the UV performance of all resin systems. In addition, various groups substituted on the HALS structure were studied.
As in Example 1 and Example 2, Vandar (registered trademark) 91
18 Natural thermoplastic polyester, colorant RC3097K2
UV stabilized samples were prepared using 0 and various parts of the stabilization system (except sample 17). Ho
echst Celanese Corporation, Hoechst Technical Polym
Vandar 91 commercially available from ers, Summit, NJ 07901
18 The thermoplastic polyester resin can
0% by weight, about 40% by weight of MBS modifier, Irganox B215
About 0.1% by weight, Irgaphos 168 about 0.2% by weight,
And about 0.5% by weight of Sandostab P-EPQ.

Sample 17 Polyester 2000.0 g RC3097K20 100.0 g Sample 18 Polyester 1979 g RC3097K20 100.0 g Cyasorb UV5411 10.5 g Hostavin N30 10.5 g Sample 19 polyester 1947.5 RC3097K20 100 Cyasorb UV5411 42 Hostavin N30 10.5 Sample 20 Polyester 1947.5 RC3097K20 100 Cyasorb UV5411 10.5 Hostavin N30 42 Sample 21 Polyester 1947.5 RC3097K20 100 Cyasorb UV5411 26.3 Hostavin N30 26.3 Sample 22 Polyester 1916 RC3097K20 100 Cyasorb UV5411 42 Hostavin N30 42 Sample 23 Polyester 1916 Polyester N30 42 Tinuvin 234 42 Sample 24 Polyester 1979 RC3097K20 100 Cyasorb UV5411 10.5 Tinuvin 144 10.5 Sample 25 Polyester Tel 1947.5 RC3097K20 100 Cyasorb UV5411 42 Tinuvin 144 10.5 Sample 26 Polyester 1947.5 RC3097K20 100 Cyasorb UV5411 10.5 Tinuvin 144 42 Sample 27 Polyester 1947.4 RC3097K20 100 Cyasorb UV5411 26.3 Tinuvin 144 26.3 Sample 28 Polyester 1916 RC3097K20 100 Cyasorb UV5411 42 Tinuvin 144 42 Sample 29 Polyester 1916 RC3097K20 100 Tinuvin 144 42 Tinuvin 234 42 Sample 30 Polyester 1979 RC3097K20 100 Cyasorb UV5411 10.5 Goodrite 3150 10.5 Sample 31 Polyester 1947.5100 3150 10.5 sample 32 polyester 1947.5 RC3097K20 100 Cyasorb UV5411 10.5 Goodrite 3150 42 sample 33 polyester 1947.4 RC3 097K20 100 Cyasorb UV5411 26.3 Goodrite 3150 26.3 Sample 34 Polyester 1916 RC3097K20 100 Cyasorb UV5411 42 Goodrite 3150 42 Sample 35 Polyester 1916 RC3097K20 100 Goodrite 3150 42 Tinuvin 234 42 Sample 36 Polyester 1979 RC3097K20 100 Cyasorb UV 5.5 Sample 37 Polyester 1979 RC3097K20 100.0 Cyasorb UV5411 42.0 Adkastab LA63 10.5 Sample 38 Polyester 1947.5 RC3097K20 100.0 Cyasorb UV5411 41.5 Adkastab LA63 10.5 Sample 39 Polyester 1947.5 RC3097K20 100.0 Cyasorb UV5411 41.5 Adkastab LA63 42.0 Sample 40 polyester 1947.5 RC3097K20 100 Cyasorb UV5411 26.3 Adkastab LA63 26.3 Sample 41 polyester 1 916.0 RC3097K20 100 Cyasorb UV5411 42.0 Adkastab LA63 42.0 Sample 42 polyester 1916.0 RC3097K20 100 Adkastab LA63 42.0 Tinuvin 234 42.0

Table 2 below sets forth the weight percent of components present in the sample, based on 100 weight percent of the sample.

[0041]

[Table 2] Table 2Ingredients 17 18 19 20 21 22 23  Polyester resin 95.24 94.24 92.74 92.74 92.74 91.24 91.24 Colorant 4.76 4.76 4.76 4.76 4.76 4.76 4.76 Cyasorb UV5411 0.50 2.00 0.50 1.25 2.00 Hostavin N30 0.50 0.50 2.00 1.25 2.00 2.00 Tinuvin 234 2.00 ΔE*＠601.1kJ/m^Two 3.93 3.70 2.79 2.07 1.76 1.89 2.23 ΔL * -2.39 -1.65 -1.06 -1.01 -1.01 -1.45 -1.84 Δb * 2.99 3.31 2.57 1.79 1.41 1.19 1.2660 ° gloss (%) 3.2 6.4 6.1 25.9 12.8 7.9 9.2  Table 2 (continued)Ingredients 24 25 26 27 28 29 Polyester resin 94.24 92.74 92.74 92.74 91.24 91.24 Colorant 4.76 4.76 4.76 4.76 4.76 4.76 Cyasorb UV5411 0.50 2.00 0.50 1.25 2.00 Tinuvin 144 0.50 0.50 2.00 1.25 2.00 2.00 Tinuvin 234 2.00 ΔE*＠601.6kJ/m^Two 1.90 1.35 2.87 2.47 1.34 0.87 ΔL * -0.69 -1.00 -2.36 -2.11 -0.97 -0.50 Δb * 1.74 0.87 1.61 1.25 0.89 0.6360 ° gloss (%) 21.4 12.5 7.2 6.8 7.7 6.7  Table 2 (continued)Ingredients 30 31 32 33 34 35 Polyester resin 94.24 92.74 92.74 92.74 91.24 91.24 Colorant 4.76 4.76 4.76 4.76 4.76 4.76 Cyasorb UV5411 0.50 2.00 0.50 1.25 2.00 Good-Rite 3150 0.50 0.50 2.00 1.25 2.00 2.00 Tinuvin 234 2.00 ΔE*＠601.6kJ/m^Two 1.35 1.43 1.76 1.21 0.52 0.62 ΔL * -0.21 -1.23 -1.40 -0.88 -0.08 -0.05 Δb * 1.27 0.62 1.01 0.75 0.45 0.5160 ° gloss (%) 18.8 5.2 5.6 6.5 5.5 5.6  Table 2 (continued)Ingredients 36 37 38 39 40 40 41 Polyester resin 94.24 92.74 92.74 92.74 91.24 91.24 Colorant 4.76 4.76 4.76 4.76 4.76 4.76 Cyasorb UV5411 0.50 2.00 0.50 1.25 2.00 Adkastab LA-63 0.50 0.50 2.00 1.25 2.00 2.00 Tinuvin 234 2.00 ΔE*＠601.6kJ/m^Two 2.33 1.51 1.93 1.56 1.76 1.86 ΔL * -0.86 -1.17 -1.45 -1.27 -1.54 -1.65 Δb * 2.14 0.93 1.24 0.87 0.83 0.8560 ° gloss (%) 11.5 15.5 19.4 14.2 3.8 3.9

It was determined that Hostavin N30 and Adkastab LA63 continued to perform well (Table 2, samples 20 and 21). Further, Tinuvin 144 having a hindered phenol antioxidant group and Go having a triazine group
The odrite 3150 also performed well. These four
Two HALS compounds were further evaluated to study their concentration effects on stability.

The results in Table 2 show that the high molecular weight HALS compounds and / or the highly substituted compounds are important in achieving good UV stability of the polyester resin. In addition, an unexpected result from this experiment was the effect of polymer / oligomer HALS concentration and UV absorber on increasing surface gloss. Low level polymer / oligomer HALS, ie Hosta
Samples 18 and 19 with vin N30 showed no increase in gloss. High level of polymer / oligomer HA
Sample 20 with LS showed a very substantial increase in gloss, but even at high levels of HALS, a 1: 1 ratio of polymer / oligomer HALS with UV absorber was used.
With, the increase in surface gloss was eliminated. Sample 2
² , 28, 34 and 40 all passed the exposure requirement of 601.6 kJ / m2. This is the color change (ΔE *)
Was small and no significant increase in surface gloss was observed.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/5393 C08K 5/5393 C08L 67/02 C08L 67/02 // C08L 9/06 C08L 9/06 71/02 71/02 (C08L 67/02 69:00 9:06)

Claims (23)

[Claims] 1. A thermoplastic polyester resin, comprising:
When exposed to 601.6 kj / m ² of radiation in a Xenon arc weatherometer operated in accordance with J1885, when calculated in CIELab units under light source “D-65” according to ASTM standard D-2244. Ultraviolet light comprising an effective amount of an ultraviolet light stabilizing system in combination with the polyester resin to achieve a color difference of less than 2.25 and to exhibit a surface gloss retention of at least about 7.5% after irradiation. A stabilized molding composition, wherein the ultraviolet light stabilizing system comprises: (i) an ultraviolet light absorber; (ii) a hindered amine light stabilizer; and (iii) an antioxidant. Stuff. 2. A thermoplastic polyester, comprising: a linear polyalkylene terephthalate, a copolyester elastomer;
The composition of claim 1 selected from the group consisting of polycarbonates and mixtures thereof. 3. A linear polyalkylene terephthalate,
Polybutylene terephthalate, polypropylene terephthalate, polyethylene terephthalate, and ethylene-
3. The composition of claim 2, wherein the composition is selected from the group consisting of 1,4-cyclohexylene dimethylene terephthalate. 4. The composition according to claim 3, wherein the copolyester elastomer is a copolyetherester. 5. The method of claim 1 wherein the thermoplastic polyester comprises polybutylene terephthalate from 0 to about 3 based on the total weight of the composition.
0% by weight, polyester elastomer about 35 to about 70% by weight, polycarbonate 0 to about 30% by weight, MBS about 1
0 to about 50% by weight, and about 0.2 to about 1.0 of an antioxidant.
5. The composition of claim 4, which is a weight percent formulation. 6. The composition of claim 5, wherein the ultraviolet light stabilizing system is present in an amount from about 0.5 to about 5.0% by weight based on the total weight of the composition. 7. The composition of claim 6, wherein the ultraviolet light stabilizing system is present in an amount of about 0.1 to about 2.0% by weight based on the total weight of the composition. 8. The composition of claim 6, wherein the hindered amine is present in an amount from about 0.1 to about 2.0% by weight based on the total weight of the composition. 9. The ratio of hindered amine to UV absorber is from about 1: 1 to about 1: 2, respectively.
A composition as described. 10. The composition of claim 9, wherein the antioxidant is present in an amount from about 0.1 to about 1.0% by weight based on the total weight of the composition. 11. An ultraviolet absorber comprising: 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-t-butoxybenzophenone; 2-hydroxy-4-octoxybenzophenone; 2-hydroxy -4-dodecyloxybenzophenone; 2-hydroxy-4-stearoxybenzophenone; 2-hydroxy-4-phenoxybenzophenone;
2-hydroxy-4- (β-hydroxyethoxy) benzophenone; 2-hydroxy-4- (2′-hydroxy-3′-acryloxypropoxy) benzophenone;
2-hydroxy-4- (2'-hydroxy-3'-methacryloxypropoxyl) benzophenone; 2,2 '
-Dihydroxybenzophenone; 2,2'-dihydroxy-4-methoxybenzophenone;2,2'-dihydroxy-4-butoxybenzophenone;2,2'-dihydroxy-4-octoxybenzophenone;2,2'-
Dihydroxy-4-lauroxybenzophenone; 2,2
', 4,4'-tetrahydroxybenzophenone; 2,
2 ', 4'-trihydro-4-methoxybenzophenone;2-hydroxy-4-methoxy-4'-chlorobenzophenone;2,2'-dihydroxy-4,4'-dimethyloxybenzophenone; 2-hydroxy-4-methoxy -2'-methyl-4'-hydroxybenzophenone;2-hydroxy-4-methoxy-4'-t-butylbenzophenone; 2-hydroxy-4-methoxy-4 '
-Methyl-benzophenone; 2-hydroxy-4,4 '
-Dimethoxybenzophenone; 2-hydroxy-4,4
The composition of claim 10, which is a benzophenone selected from the group consisting of ', 2'-trimethoxybenzophenone; and 2-hydroxy-4-N-octoxybenzophenone. 12. The method according to claim 12, wherein the ultraviolet absorbent is 2- (2′-hydroxy-5′-methylphenyl) benzotriazole;
-(2'-hydroxy-3'-5'-di-t-butylphenyl) benzotriazole; 2- (2'-hydroxy-3'-5'-di-t-butylphenyl) -5-chlorobenzotriazole 2- (2′-hydroxy-3 ′,
5'-diphenyl) -5-benzotriazole; 2-
(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole; 2- (2
'-Hydroxy-5'-t-butyl-5'-methylphenyl) benzotriazole; 2- (2'-hydroxy-
3'-s-butyl-5'-t-butylphenyl) benzotriazole; 2- (2'-hydroxy-5-t-octylphenyl) benzotriazole; 2- (2H-benzotriazol-2-yl) -4 2,6-bis (1-methyl-1-phenylethyl) -phenyl; and 2-
The ultraviolet stabilizing system according to claim 11, which is a benzotriazole selected from the group consisting of (3 ', 5'-bis (1-methyl-1-phenylethyl) -2'-hydroxyphenyl) benzotriazole. 13. A hindered amine light stabilizer comprising:
'-[1,2-ethanediyl] -bis [3,3,5,5
Dimethyl succinate polymer and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol; bis (1,2,2
6,6-pentamethyl-4-piperdinyl) sebacate; bis [2,2,6,6-tetramethyl-4-piperidinyl] decandioate; bis (1,2,2,6,6
-Pentamethyl-4-piperidinyl) -2-[[3,5
-Bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -2-butylpropanediate; poly [(2,2,6,6-tetramethyl-4-piperidinyl) iminomethylene (2,2 , 6,6-tetramethyl-
4-piperidinyl) imino [6- (octylamino)-
1,3,5-triazine-4,2-diyl]]; 2,
2,6,6-tetramethyl-4-piperidinyl benzoate; tetrakis (2,2,6,6-tetramethyl-4
-Piperidinyloxy) silane; bis (1,2,2,
6,6-pentamethyl) -4-piperidinyl- (3,5
-Di-t-butyl-4-hydroxybenzyl) butylpropane diate; high melt polymer / oligomer hindered amines; 2,2,6,6-tetramethylpiperidine; [1,2,2,6,6-pentamethyl-4 -Piperidiyl / β, β, β ', β'-tetramethyl-3,9-
13. The composition of claim 12, wherein the composition is selected from the group consisting of (2,4,8,10-tetraoxaspiro (5,5) undecane) diethyl] -1,2,3,4-butanetetracarboxylate. 14. An antioxidant comprising tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane and [tetrakis (2,4-di-t)
-Butylphenyl) -4,4-biphenyldiphosphonite]. 15. The composition of claim 14, further comprising an impact modifier.
A composition as described. 16. The composition according to claim 15, wherein the molding composition is suitable for preparing a molded article suitable for an ultraviolet environment. 17. The method of claim 1 wherein the polyalkylene terephthalate is 0 to
About 30% by weight, about 55 to about 65% by weight polyester elastomer, 0 to about 15% by weight polycarbonate, M
About 15 to about 45% by weight of BS and about 0.1% of antioxidant are used.
A thermoplastic polyester resin containing from 2 to about 0.8% by weight;
When exposed to 601.6 kj / m ² radiation in a Xenon arc weatherometer operated according to SAE J1885, when calculated in CIELab under light source “D-65” according to ASTM standard D-2244. An ultraviolet light stabilizer comprising an effective amount of an ultraviolet light stabilizing system combined with the polyester resin in an effective amount sufficient to achieve a color difference of about 2.16 and exhibit about 7.1% surface gloss retention after irradiation. A molding composition, wherein the UV stabilizing system comprises: (i) about 0.5 to about 5.0 wt% of a UV absorber selected from the group consisting of benzotriazole and benzophenone; (ii) 1,1 ′-[1,2-ethanediyl] -bis [3,3,5,5-tetramethylpoperadione]; dimethyl succinate polymer and 4-hydroxy-2,2
6,6-tetramethyl-1-piperidineethanol; bis (1,2,2,6,6-pentamethyl-4-piperdinyl) -sebacate; bis [2,2,6,6-tetramethyl-4-piperidinyl] Decandioate; bis (1,2,2,6,6-pentamethyl-4-piperidinyl) -2-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -2 -Butyl propane diate; poly [(2,2,6,6-tetramethyl-4-piperidinyl) iminomethylene (2,2,
6,6-tetramethyl-4-piperidinyl) imino [6
-(Octylamino) -1,3,5-triazine-4,
2-diyl]]; 2,2,6,6-tetramethyl-4-
Piperidinyl benzoate; tetrakis (2,2,6,
6-tetramethyl-4-piperidinyloxy) silane;
Bis (1,2,2,6,6-pentamethyl) -4-piperidinyl- (3,5-di-tert-butyl-4-hydroxybenzyl) butylpropanediate; high melt polymer / oligomer hindered amine; 2,2 , 6,6-tetramethylpiperidine; Goodrite 3150; and [1,
2,2,6,6-pentamethyl-4-piperidiyl /
β, β, β ′, β′-tetramethyl-3,9- (2,
A hindered amine light stabilizer selected from the group consisting of 4,8,10-tetraoxaspiro (5,5) undecane) diethyl] -1,2,3,4-butanetetracarboxylate from about 0.5 to about 5 And (iii) tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane and [tetrakis (2,4-di-tert-butylphenyl)-
4,4-biphenyldiphosphonite], from about 0.1 to about 1.0% by weight of an antioxidant selected from the group consisting of: 18. The benzophenone is 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-t-butoxybenzophenone; 2-hydroxy-4-octoxybenzophenone; 2-hydroxy-4. -Dodecyloxybenzophenone; 2-hydroxy-4-stearoxybenzophenone; 2-hydroxy-4-phenoxybenzophenone; 2-hydroxy-4- (β-hydroxyethoxy)
Benzophenone; 2-hydroxy-4- (2'-hydroxy-3'-acryloxypropoxy) benzophenone; 2-hydroxy-4- (2'-hydroxy-3'-
Methacryloxypropoxyl) benzophenone; 2,
2,2'-dihydroxybenzophenone;2,2'-dihydroxy-4-methoxybenzophenone;2,2'-dihydroxy-4-butoxybenzophenone;2,2'-
Dihydroxy-4-octoxybenzophenone; 2,2
'-Dihydroxy-4-lauroxybenzophenone;
2,2 ', 4,4'-tetrahydroxybenzophenone;2,2',4'-trihydro-4-methoxybenzophenone;2-hydroxy-4-methoxy-4'-chlorobenzophenone;2,2'-dihydroxy- 4,4 '
-Dimethyloxybenzophenone; 2-hydroxy-4
-Methoxy-2'-methyl-4'-hydroxybenzophenone;2-hydroxy-4-methoxy-4'-t-butylbenzophenone; 2-hydroxy-4-methoxy-
4'-methyl-benzophenone; 2-hydroxy-4,
4'-dimethoxybenzophenone; 2-hydroxy-
4,4 ', 2'-trimethoxybenzophenone; and 2
18. The composition of claim 17, wherein the composition is selected from the group consisting of -hydroxy-4-N-octoxybenzophenone. 19. A method for converting benzotriazole into 2- (2′-
(Hydroxy-5'-methylphenyl) benzotriazole; 2- (2'-hydroxy-3'-5'-di-tert-butylphenyl) benzotriazole; 2- (2'-hydroxy-3'-5'-di -T-butylphenyl) -5-
Chlorobenzotriazole; 2- (2'-hydroxy-
3 ', 5'-diphenyl) -5-benzotriazole;
2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole; 2-
(2'-hydroxy-5'-t-butyl-5'-methylphenyl) benzotriazole; 2- (2'-hydroxy-3'-s-butyl-5'-t-butylphenyl) benzotriazole; 2- (2′-hydroxy-5-t-
Octylphenyl) benzotriazole; 2- (2H-
Benzotriazol-2-yl) -4,6-bis (1-
Methyl-1-phenylethyl) -phenyl; and 2
20. The composition of claim 18, wherein the composition is selected from the group consisting of-(3 ', 5'-bis (1-methyl-1-phenylethyl) -2'-hydroxyphenyl) benzotriazole. 20. The method according to claim 19, further comprising an impact modifier.
A composition as described. 21. The composition of claim 20, wherein the molding composition is suitable for preparing a molded article suitable for an ultraviolet environment. 22. A polyalkylene terephthalate,
About 25% by weight, about 60% by weight of polyester elastomer, 0 to about 10% by weight of polycarbonate, about 20 to about 40% by weight of MBS, and about 0.6% by weight of antioxidant
AST when exposed to 601.6 kj / m ² in a Xenon arc weatherometer operated in accordance with SAE J1885.
Light source "D-65" according to M standard D-2244
Below, an effective amount of UV light combined with the polyester to achieve a color difference of about 2.16 as calculated in CIELab units and exhibit a surface gloss retention of about 7.1% after irradiation. A UV-stabilized molding composition comprising: (i) 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-t. -Butoxybenzophenone; 2-hydroxy-
4-octoxybenzophenone; 2-hydroxy-4-
Dodecyloxybenzophenone; 2-hydroxy-4-
Stearoxybenzophenone; 2-hydroxy-4-phenoxybenzophenone; 2-hydroxy-4- (β-
2-hydroxy-4- (2'-hydroxy-3'-acryloxypropoxy) benzophenone; 2-hydroxy-4- (2 '
-Hydroxy-3'-methacryloxypropoxyl)
Benzophenone; 2,2'-dihydroxybenzophenone;2,2'-dihydroxy-4-methoxybenzophenone;2,2'-dihydroxy-4-butoxybenzophenone;2,2'-dihydroxy-4-octoxybenzophenone; 2, 2'-dihydroxy-4-lauroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone;2,2',4'-trihydro-4
-Methoxybenzophenone; 2-hydroxy-4-methoxy-4'-chlorobenzophenone;2,2'-dihydroxy-4,4'-dimethyloxybenzophenone; 2
-Hydroxy-4-methoxy-2'-methyl-4'-hydroxybenzophenone;2-hydroxy-4-methoxy-4'-t-butylbenzophenone;2-hydroxy-4-methoxy-4'-methyl-benzophenone; −
Hydroxy-4,4'-dimethoxybenzophenone; 2
-Hydroxy-4,4 ', 2'-trimethoxybenzophenone;2-hydroxy-4-N-octoxybenzophenone; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole; 2- (2'- Hydroxy-3
'-5'-di-t-butylphenyl) benzotriazole; 2- (2'-hydroxy-3'-5'-di-t-butylphenyl) -5-chlorobenzotriazole; 2-
(2'-hydroxy-3 ', 5'-diphenyl) -5
Benzotriazole; 2- (2'-hydroxy-3'-
t-butyl-5'-methylphenyl) -5-chlorobenzotriazole; 2- (2'-hydroxy-5'-t-
Butyl-5'-methylphenyl) benzotriazole;
2- (2'-hydroxy-3'-s-butyl-5'-t
-Butylphenyl) benzotriazole; 2- (2'-
(Hydroxy-5-t-octylphenyl) benzotriazole; 2- (2H-benzotriazol-2-yl)
-4,6-bis (1-methyl-1-phenylethyl)-
Phenyl; and an ultraviolet absorber selected from the group consisting of 2- (3 ', 5'-bis (1-methyl-1-phenylethyl) -2'-hydroxyphenyl) benzotriazole from about 0.5 to about 5.0% by weight; (ii) 1,1 '-[1,2-ethanediyl] -bis [3,3,5,5-tetramethylpoperadione]; dimethyl succinate polymer and 4-hydroxy-2, 2,
6,6-tetramethyl-1-piperidineethanol; bis (1,2,2,6,6-pentamethyl-4-piperdinyl) -sebacate; bis [2,2,6,6-tetramethyl-4-piperidinyl] Decandioate; bis (1,2,2,6,6-pentamethyl-4-piperidinyl) -2-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -2 -Butyl propane diate; poly [(2,2,6,6-tetramethyl-4-piperidinyl) iminomethylene (2,2,
6,6-tetramethyl-4-piperidinyl) imino [6
-(Octylamino) -1,3,5-triazine-4,
2-diyl]]; 2,2,6,6-tetramethyl-4-
Piperidinyl benzoate; tetrakis (2,2,6,
6-tetramethyl-4-piperidinyloxy) silane;
Bis (1,2,2,6,6-pentamethyl) -4-piperidinyl- (3,5-di-tert-butyl-4-hydroxybenzyl) butylpropanediate; high melt polymer / oligomer hindered amine; 2,2 , 6,6-tetramethylpiperidine; Goodrite 3150; and [1,
2,2,6,6-pentamethyl-4-piperidiyl /
β, β, β ′, β′-tetramethyl-3,9- (2,
A hindered amine light stabilizer selected from the group consisting of 4,8,10-tetraoxaspiro (5,5) undecane) diethyl] -1,2,3,4-butanetetracarboxylate from about 0.5 to about 5 And (iii) tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane and [tetrakis (2,4-di-tert-butylphenyl)-
4,4-biphenyldiphosphonite], from about 0.1 to about 1.0% by weight of an antioxidant selected from the group consisting of: 23. (i) 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-t-butoxybenzophenone; 2-hydroxy-4-octoxybenzophenone;
2-hydroxy-4-dodecyloxybenzophenone;
2-hydroxy-4-stearoxybenzophenone; 2
-Hydroxy-4-phenoxybenzophenone; 2-hydroxy-4- (β-hydroxyethoxy) benzophenone; 2-hydroxy-4- (2′-hydroxy-3 ′
-Acryloxypropoxy) benzophenone; 2-hydroxy-4- (2'-hydroxy-3'-methacryloxypropoxyl) benzophenone; 2,2'-dihydroxybenzophenone;2,2'-dihydroxy-4
-Methoxybenzophenone; 2,2'-dihydroxy-
4-butoxyiobenzophenone; 2,2′-dihydroxy-4-octoxybenzophenone; 2,2′-dihydroxy-4-lauroxybenzophenone; 2,2 ′,
4,4'-tetrahydroxybenzophenone; 2,2
', 4'-trihydro-4-methoxybenzophenone;
2-hydroxy-4-methoxy-4'-chlorobenzophenone;2,2'-dihydroxy-4,4'-dimethyloxybenzophenone;2-hydroxy-4-methoxy-2'-methyl-4'-hydroxybenzophenone;
-Hydroxy-4-methoxy-4'-t-butylbenzophenone;2-hydroxy-4-methoxy-4'-methyl-benzophenone;2-hydroxy-4,4'-dimethoxybenzophenone; 2-hydroxy-4,4 ' , 2
'-Trimethoxybenzophenone; 2-hydroxy-4
-N-octoxybenzophenone; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole; 2
-(2'-hydroxy-3'-5'-di-t-butylphenyl) benzotriazole; 2- (2'-hydroxy-3'-5'-di-t-butylphenyl) -5-chlorobenzotriazole 2- (2′-hydroxy-3 ′,
5'-diphenyl) -5-benzotriazole; 2-
(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole; 2- (2
'-Hydroxy-5'-t-butyl-5'-methylphenyl) benzotriazole; 2- (2'-hydroxy-
3'-s-butyl-5'-t-butylphenyl) benzotriazole; 2- (2'-hydroxy-5-t-octylphenyl) benzotriazole; 2- (2H-benzotriazol-2-yl) -4 2,6-bis (1-methyl-1-phenylethyl) -phenyl; and 2-
About 0.5 to about 5.0% by weight of an ultraviolet absorber selected from the group consisting of (3 ', 5'-bis (1-methyl-1-phenylethyl) -2'-hydroxyphenyl) benzotriazole; (Ii) 1,1 ′-[1,2-ethanediyl] -bis [3,3,5,5-tetramethylpoperadione]; dimethyl succinate polymer and 4-hydroxy-2,2
6,6-tetramethyl-1-piperidineethanol; bis (1,2,2,6,6-pentamethyl-4-piperdinyl) -sebacate; bis [2,2,6,6-tetramethyl-4-piperidinyl] Decandioate; bis (1,2,2,6,6-pentamethyl-4-piperidinyl) -2-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -2 -Butyl propane diate; poly [(2,2,6,6-tetramethyl-4-piperidinyl) iminomethylene (2,2,
6,6-tetramethyl-4-piperidinyl) imino [6
-(Octylamino) -1,3,5-triazine-4,
2-diyl]]; 2,2,6,6-tetramethyl-4-
Piperidinyl benzoate; tetrakis (2,2,6,
6-tetramethyl-4-piperidinyloxy) silane;
Bis (1,2,2,6,6-pentamethyl) -4-piperidinyl- (3,5-di-tert-butyl-4-hydroxybenzyl) butylpropanediate; high melt polymer / oligomer hindered amine; 2,2 , 6,6-tetramethylpiperidine; Goodrite 3150; and [1,
2,2,6,6-pentamethyl-4-piperidiyl /
β, β, β ′, β′-tetramethyl-3,9- (2,
A hindered amine light stabilizer selected from the group consisting of 4,8,10-tetraoxaspiro (5,5) undecane) diethyl] -1,2,3,4-butanetetracarboxylate from about 0.5 to about 5 And (iii) tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane and [tetrakis (2,4-di-tert-butylphenyl)-
4,4-biphenyldiphosphonite] from about 0.1 to about 1.0% by weight of an antioxidant selected from the group consisting of:
An ultraviolet light stabilizing system suitable for thermoplastic polyester resin compositions, the system comprising 6 in a xenon arc weatherometer operated according to SAE J1885.
When exposed to irradiation of 01.6kj / m ^2, the light source "D-65" according to ASTM Standard D-2244 under, CI
Characterized by achieving a color difference of about 2.16 when calculated in ELab units and at least about 7.1 after irradiation.
% Of the ultraviolet light stabilizing system exhibiting a retention of surface gloss of 1%.