Patent Description:
Exposure to sunlight and other sources of ultraviolet (UV) radiation (also referred to as UV light) is known to cause degradation of a wide variety of materials. For example, polymeric materials such as plastics often discolor, lose gloss and/or become brittle as a result of prolonged exposure to UV light due primarily to a reduction in the molecular weight of the polymer. Accordingly, a large body of art has been developed directed towards compositions such as UV light absorbers and stabilizers, which are capable of inhibiting such degradation in polymeric articles.

Exposure to heat is also known to cause degradation of materials, especially polymeric materials. While compositions that reduce or prevent degradation caused by heat have been developed, combining these compositions with UV light stabilizer systems has not always yielded the desired result since the UV light stabilization properties are often hindered or completely relinquished (i.e., antagonistic) when combined with the heat stabilizer composition(s). <CIT> relates to stabilizing compositions suitable for protecting materials from degradation against UV light and thermal exposure. However, the compositions disclosed therein do not include ortho-hydroxy tris-aryl-triazines. <CIT> refers to blends of phosphites and phenols and their use as stabilizer compositions for polymer compositions. <CIT> discloses stabilizing compositions for protecting materials from degradation only against UV light. There remains an unmet need in the market for a stabilizer composition that can protect materials from degradation due to both UV light and thermal exposure. This invention is believed to be an answer to the foregoing need.

In one aspect, the invention is directed to thermal and ultraviolet (UV) light stabilizing compositions that include an ortho-hydroxyl tris-aryl-s-triazine compound; a hindered amine light stabilizer compound; a hindered hydroxybenzoate compound; an acid scavenger; a phosphite compound; a hindered phenol antioxidant compound comprising a molecular fragment according to one or more of Formula (IVa), (IVb), or (IVc):
<CHM>
wherein.

In another aspect, the invention is directed to stabilized compositions that include any of the thermal and UV light stabilizing compositions described herein and a material to be stabilized.

In yet a further aspect, the invention is directed to a process for achieving stability against thermal and UV light degradation of a material selected from the group consisting of polyolefins, polyesters, polyethers, polyketones, polyamides, natural and synthetic rubbers, polyurethanes, polystyrenes, high-impact polystyrenes, polyacrylates, polymethacrylates, polyacetals, polyacrylonitriles, polybutadienes, polystyrenes, acrylonitrile-butadiene-styrene, styrene acrylonitrile, acrylate styrene acrylonitrile, cellulosic acetate butyrate, cellulosic polymers, polyimides, polyamideimides, polyetherimides, polyphenylsulfides, polyphenyloxidepolysulfones, polyethersulfones, polyvinylchlorides, polycarbonates, polyketones, aliphatic polyketones, thermoplastic olefins, aminoresin cross-linked polyacrylates and polyesters, polyisocyanate cross-linked polyesters and polyacrylates, phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins, drying and non-drying alkyd resins, alkyd resins, polyester resins, acrylate resins cross-linked with melamine resins, urea resins, isocyanates, isocyanurates, carbamates, and epoxy resins, cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl compounds, which are cross-linked with anhydrides or amines, polysiloxanes, Michael addition polymers, amines, blocked amines with activated unsaturated and methylene compounds, ketimines with activated unsaturated and methylene compounds, polyketimines in combination with unsaturated acrylic polyacetoacetate resins, polyketimines in combination with unsaturated acrylic resins, radiation curable compositions, epoxymelamine resins, organic dyes, cosmetic products, cellulose-based paper formulations, photographic film paper, fibers, waxes, inks, and blends thereof, the process comprising adding a stabilizing amount of a stabilizing composition as described herein to the material.

These and other aspects of the invention are described in more detail herein.

As summarized above, the compositions and processes using the same that have now been discovered and disclosed herein for the first time are surprisingly useful for achieving optimal stability against thermal and UV light degradation compared to current commercially available stabilizer packages. Furthermore, the processes and compositions disclosed herein additionally (and surprisingly) provide a stabilizer package that has a low release of volatile organic compounds (VOCs), low odor and low blooming as compared to current commercially available polymer stabilizer packages.

As employed above and throughout the disclosure, the following terms and definitions are provided to assist the reader. Unless otherwise defined, all terms of art, notations and other scientific terminology used herein are intended to have the meanings commonly understood by those of skill in the chemical arts. As used herein and in the appended claims, the singular forms include plural referents unless the context clearly dictates otherwise. Additionally, as used herein and in the appended claims, the disclosure of any ranges of amounts or concentrations includes the disclosure of any amount or value in the given range.

Throughout this specification the terms and substituents retain their definitions. A comprehensive list of abbreviations utilized by organic chemists (i.e. persons of ordinary skill in the art) appears in the first issue of each volume of the Journal of Organic Chemistry. The list, which is typically presented in a table entitled "Standard List of Abbreviations", is incorporated herein by reference.

The term "hydrocarbyl" is a generic term encompassing aliphatic, alicyclic and aromatic groups having an all-carbon backbone and consisting of carbon and hydrogen atoms. In certain cases, as defined herein, one or more of the carbon atoms making up the carbon backbone may be replaced or interrupted by a specified atom or group of atoms, such as by one or more heteroatom of N, O, and/or S. Examples of hydrocarbyl groups include alkyl, cycloalkyl, cycloalkenyl, carbocyclic aryl, alkenyl, alkynyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkenylalkyl, and carbocyclic aralkyl, alkaryl, aralkenyl and aralkynyl groups. Such hydrocarbyl groups can also be optionally substituted by one or more substituents as defined herein. Accordingly, the chemical groups or moieties discussed in the specification and claims should be understood to include the substituted or unsubstituted forms. The examples and preferences expressed below also apply to each of the hydrocarbyl substituent groups or hydrocarbyl-containing substituent groups referred to in the various definitions of substituents for compounds of the formulas described herein unless the context indicates otherwise.

Preferred non-aromatic hydrocarbyl groups are saturated groups such as alkyl and cycloalkyl groups. Generally, and by way of example, the hydrocarbyl groups can have up to fifty carbon atoms, unless the context requires otherwise. Hydrocarbyl groups with from <NUM> to <NUM> carbon atoms are preferred. Within the sub-set of hydrocarbyl groups having <NUM> to <NUM> carbon atoms, particular examples are C<NUM>-<NUM> hydrocarbyl groups, such as C<NUM>-<NUM> hydrocarbyl groups (e.g. C<NUM>-<NUM> hydrocarbyl groups or C<NUM>-<NUM> hydrocarbyl groups), specific examples being any individual value or combination of values selected from C<NUM> through C<NUM> hydrocarbyl groups.

Alkyl is intended to include linear, branched, or cyclic hydrocarbon structures and combinations thereof. Lower alkyl refers to alkyl groups of from <NUM> to <NUM> carbon atoms. Examples of lower alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, s-and t-butyl and the like. Preferred alkyl groups are those of C<NUM> or below.

Alkoxy or alkoxyalkyl refers to groups of from <NUM> to <NUM> carbon atoms of a straight, branched, cyclic configuration and combinations thereof attached to the parent structure through an oxygen. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, cyclohexyloxy and the like.

Acyl refers to formyl and to groups of <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> and <NUM> carbon atoms of a straight, branched, cyclic configuration, saturated, unsaturated and aromatic and combinations thereof, attached to the parent structure through a carbonyl functionality. Examples include acetyl, benzoyl, propionyl, isobutyryl, t-butoxycarbonyl, benzyloxycarbonyl and the like. Lower-acyl refers to groups containing one to six carbons.

References to "carbocyclic" or "cycloalkyl" groups as used herein shall, unless the context indicates otherwise, include both aromatic and non-aromatic ring systems. Thus, for example, the term includes within its scope aromatic, non-aromatic, unsaturated, partially saturated and fully saturated carbocyclic ring systems. In general, such groups may be monocyclic or bicyclic and may contain, for example, <NUM> to <NUM> ring members, more usually <NUM> to <NUM> ring members. Examples of monocyclic groups are groups containing <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM> ring members, more usually <NUM> to <NUM>, and preferably <NUM> or <NUM> ring members. Examples of bicyclic groups are those containing <NUM>, <NUM>, <NUM>, <NUM> and <NUM> ring members, and more usually <NUM> or <NUM> ring members. Examples of non-aromatic carbocycle/cycloalkyl groups include c-propyl, c-butyl, c-pentyl, c-hexyl, and the like. Examples of C<NUM> to C<NUM> polycyclic hydrocarbons include ring systems such as norbornyl and adamantyl.

Aryl (carbocyclic aryl) refers to a <NUM>- or <NUM>-membered aromatic carbocycle ring containing; a bicyclic <NUM>- or <NUM>-membered aromatic ring system; or a tricyclic <NUM>- or <NUM>-membered aromatic ring system. The aromatic <NUM>- to <NUM>-membered carbocyclic rings include, e.g., substituted or unsubstituted phenyl groups, benzene, naphthalene, indane, tetralin, and fluorene.

Substituted hydrocarbyl, alkyl, aryl, cycloalkyl, alkoxy, etc. refer to the specific substituent wherein up to three H atoms in each residue are replaced with alkyl, halogen, haloalkyl, hydroxy, alkoxy, carboxy, carboalkoxy (also referred to as alkoxycarbonyl), carboxamido (also referred to as alkylaminocarbonyl), cyano, carbonyl, nitro, amino, alkylamino, dialkylamino, mercapto, alkylthio, sulfoxide, sulfone, acylamino, amidino, phenyl, benzyl, halobenzyl, heteroaryl, phenoxy, benzyloxy, heteroaryloxy, benzoyl, halobenzoyl, or lower alkylhydroxy.

As summarized above, this invention relates to a thermal and ultraviolet (UV) light stabilizing composition that includes an ortho-hydroxyl tris-aryl-s-triazine compound, a hindered amine light stabilizer (HALS) compound, a hindered hydroxybenzoate compound, a phosphite compound, an acid scavenger, a hindered phenol antioxidant compound comprising a molecular fragment according to one or more of Formula (IVa), (IVb), or (IVc):
<CHM>
wherein.

Preferably, the ortho-hydroxy tris-aryl-s-triazine compound is <NUM>-(<NUM>'-hydroxyphenyl)-<NUM>,<NUM>,<NUM>-triazine compound according to Formula (I):
<CHM>
wherein each of R<NUM> and R<NUM> in Formula (I) is independently chosen from C<NUM>-C<NUM> aryl optionally substituted, C<NUM>-C<NUM> hydrocarbyl-substituted amino, C<NUM>-C<NUM> acyl and C<NUM>-C<NUM> alkoxyl; and wherein R<NUM> in Formula (I) is a substituent that is the same or different at from <NUM> to <NUM> positions of the phenoxy portion of Formula I and is independently chosen from hydroxyl, C<NUM>-C<NUM> hydrocarbyl, C<NUM>-C<NUM> alkoxyl, C<NUM>-C<NUM> alkoxyester, and C<NUM>-C<NUM> acyl.

Examples of the <NUM>-(<NUM>'-hydroxyphenyl)-<NUM>,<NUM>,<NUM>-triazine include <NUM>,<NUM>-bis-(<NUM>,<NUM>-dimethylphenyl)-<NUM>-(<NUM>-hydroxy-<NUM>-octyloxyphenyl)-s-triazine; <NUM>,<NUM>-bis-(<NUM>,<NUM>-dimethylphenyl)-<NUM>-(<NUM>,<NUM>-- dihydroxyphenyl)-s-triazine; <NUM>,<NUM>-bis(<NUM>,<NUM>-dihydroxyphenyl)-<NUM>-(<NUM>-chlorophenyl)-s-triazine; <NUM>,<NUM>-bis[<NUM>-hydroxy-<NUM>-(<NUM>-hydroxy-ethoxy)phenyl]-<NUM>-(<NUM>-chlorophenyl)-s-triazine; <NUM>,<NUM>-bis[<NUM>-hydroxy-<NUM>-(<NUM>-hydroxy-<NUM>-(<NUM>-hydroxy-ethoxy)phenyl]-<NUM>-(<NUM>,<NUM>-dimethylphenyl)-s-triazine; <NUM>,<NUM>-bis[<NUM>-hydroxy-<NUM>-(<NUM>-hydroxyethoxy)phenyl]-<NUM>-(<NUM>-bromophenyl)-s-triazine; <NUM>,<NUM>-bis[<NUM>-hydroxy-<NUM>-(<NUM>-acetoxyethoxy)phenyl]-<NUM>-(<NUM>-chlorophenyl)-s-triazine; <NUM>,<NUM>-bis(<NUM>,<NUM>-dihydroxyphenyl)-<NUM>-(<NUM>,<NUM>-dimethylphenyl)-s-triazine; <NUM>,<NUM>-bis(<NUM>-biphenylyl)-<NUM>-[<NUM>-hydroxy-<NUM>-[(octyloxycarbonyl)ethylideneoxy]phenyl]-s-triazine; <NUM>,<NUM>-bis(<NUM>-biphenylyl)-<NUM>-[<NUM>-hydroxy-<NUM>-(<NUM>-ethylhexyloxy)phenyl]-s-triazine; <NUM>-phenyl-<NUM>-[<NUM>-hydroxy-<NUM>-(<NUM>-sec-butyloxy-<NUM>-hydroxypropyloxy)phenyl]-<NUM>-[<NUM>-hydroxy-<NUM>-(<NUM>-sec-amyloxy-<NUM>-hydroxypropyloxy)phenyl]-s-triazine; <NUM>,<NUM>-bis(<NUM>,<NUM>-dimethylphenyl)-<NUM>-[<NUM>-hydroxy-<NUM>(- <NUM>-benzyloxy-<NUM>-hydroxypropyloxy)phenyl]-s-triazine; <NUM>,<NUM>-bis(<NUM>-hydroxy-<NUM>-n-butyloxyphenyl)-<NUM>-(<NUM>,<NUM>-di-n-butyloxyphenyl)-s-triazine; <NUM>,<NUM>-bis(<NUM>,<NUM>-dimethylphenyl)-<NUM>-[<NUM>-hydroxy-<NUM>-(<NUM>-nonyloxy-<NUM>-hydroxypropylox- y)-<NUM>-α-cumylphenyl]-s-triazine; methylenebis-{<NUM>,<NUM>-bis(<NUM>,<NUM>-dimethylphenyl)-<NUM>-[<NUM>-hydroxy-<NUM>-(<NUM>-butyloxy-<NUM>-hydroxypropoxy)phenyl]-s-triazine}; methylene bridged dimer mixture bridged in the <NUM>:<NUM>', <NUM>:<NUM>' and <NUM>:<NUM>' positions in a <NUM>:<NUM>:<NUM> ratio; <NUM>,<NUM>,<NUM>-tris(<NUM>-hydroxy-<NUM>-isooctyloxycarbonyliso-propylideneoxy-phenyl)-s-triazine; <NUM>,<NUM>-bis(<NUM>,<NUM>-dimethylphenyl)-<NUM>-(<NUM>-bydroxy-<NUM>-hexyloxy-<NUM>-α-cumylphenyl)-s-triazine; <NUM>-(<NUM>,<NUM>,<NUM>-trimethylphenyl)-<NUM>,<NUM>-bis[<NUM>-hydroxy-<NUM>-(<NUM>-butyloxy-<NUM>-hydroxypropyloxy)phenyl]-s-triazine; <NUM>,<NUM>,<NUM>-tris[<NUM>-hydroxy-<NUM>-(<NUM>-sec-butyloxy-<NUM>-hydroxypropyloxy)-phenyl]-s-triazine; mixture of <NUM>,<NUM>-bis-(<NUM>,<NUM>-dimethylphenyl)-<NUM>-(<NUM>-hydroxy-<NUM>-(<NUM>-dodecyloxy-<NUM>-hydroxypropoxy)phenyl)-s-triazine and <NUM>,<NUM>-bis-(<NUM>,<NUM>-dimethylphenyl)-<NUM>-(<NUM>-hydroxy-<NUM>-(<NUM>-tridecyloxy-<NUM>-hydroxypropoxy)phenyl)-s-triazine; <NUM>,<NUM>-bis-(<NUM>,<NUM>-dimethylphenyl)-<NUM>-(<NUM>-hydroxy-<NUM>(<NUM>-(<NUM>-ethylhexyloxy)-<NUM>-hydroxypropoxy)-phenyl)-s-triazine; <NUM>,<NUM>-diphenyl-<NUM>-(<NUM>-hexyloxy-<NUM>-hydroxyphenyl)-s-triazine; <NUM>-(<NUM>,<NUM>-Diphenyl-<NUM>,<NUM>,<NUM>-triazin-<NUM>-yl)-<NUM>-[<NUM>-(<NUM>-ethylhexanoyloxy)ethoxy]phenol; <NUM>,<NUM>,<NUM>-tris(<NUM>-hydroxy-<NUM>-octyloxyphenyl)-<NUM>,<NUM>,<NUM>-triazine; propanoic acid, <NUM>,<NUM>',<NUM>"-[<NUM>,<NUM>,<NUM>-triazine-<NUM>,<NUM>,<NUM>-triyltris[(<NUM>-hydroxy-<NUM>, <NUM>-phenylene)oxy]]tris-<NUM>,<NUM>',<NUM>" -trioctyl ester; propanoic acid, <NUM>-[<NUM>-[<NUM>,<NUM>-bis([<NUM>,<NUM>'-biphenyl]-<NUM>-yl)-<NUM>,<NUM>,<NUM>-triazin-2y1]-<NUM>-hydroxyphenoxyl]-isooctyl ester; and combinations thereof.

The HALS compound includes a molecular fragment according to Formula (II):
<CHM>.

The hindered hydroxybenzoate compound is a compound according to Formula (III):
<CHM>
wherein R<NUM> in Formula (III) is a C<NUM>-C<NUM> alkyl and R<NUM> in Formula (III) is a C<NUM>-C<NUM> alkyl or substituted or unsubstituted C<NUM>-C<NUM> aryl. In particular, the hindered hydroxybenzoate compound is <NUM>,<NUM>-di-tert-butylphenyl <NUM>,<NUM>-di-tert-butyl-<NUM>-hydroxybenzoate; hexadecyl <NUM>,<NUM>-di-tert-butyl-<NUM>-hydroxybenzoate; octadecyl <NUM>,<NUM>-di-tert-butyl-<NUM>-hydroxybenzoate; octyl <NUM>,<NUM>-di-tert-butyl-<NUM>-hydroxybenzoate; tetradecyl <NUM>,<NUM>-di-tert-butyl-<NUM>-hydroxybenzoate; behenylyl <NUM>,<NUM>-di-tert-butyl-<NUM>-hydroxybenzoate; <NUM>-methyl-<NUM>,<NUM>-di-tert-butylphenyl <NUM>,<NUM>-di-tert-butyl-<NUM>-hydroxybenzoate or butyl <NUM>-[<NUM>-t-butyl-<NUM>-(<NUM>,<NUM>-di-t-butyl-<NUM>-hydroxybenzoyloxy)phenyl]propionate.

The acid scavenger used in the thermal and UV light stabilizing composition may include one or more of the following compounds: zinc oxide, calcium lactate, natural and synthetic hydrotalcites, natural and synthetic hydrocalumites, alkali metal salts and alkaline earth metal salts of higher fatty acids, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate, zinc pyrocatecholate. In one example, the acid scavenger includes magnesium oxide, aluminum oxide, magnesium hydroxide, aluminum hydroxide, carbonates thereof or mixtures thereof. A specific example of an acid scavenger includes DHT-4A (<NPL>), a magnesium aluminum hydroxide carbonate hydrate that is a synthetic hydrotalcite compound.

The hindered phenol antioxidant compound includes a molecular fragment according to one or more of Formula (IVa), (IVb), or (IVc):
<CHM>
wherein R<NUM> in Formulae (IVa), (IVb) and (IVc) is chosen from hydrogen and a C<NUM>-<NUM> hydrocarbyl; R<NUM> and R<NUM> in Formulae (IVa), (IVb) and (IVc) are each individually chosen from hydrogen and a C<NUM>-C<NUM> hydrocarbyl; and R<NUM> in Formulae (IVa), (IVb) and (IVc) is chosen from C<NUM>-C<NUM> hydrocarbyl. In one embodiment, R<NUM> in Formulae (IVa), (IVb) and (IVc) and R<NUM> are chosen from methyl and t-butyl. Examples of the hindered phenol antioxidant compound include (<NUM>,<NUM>,<NUM>-Tris(<NUM>-t-butyl-<NUM>-hydroxy-<NUM>,<NUM>-dimethylbenzyl)-<NUM>,<NUM>,<NUM>-triazine-<NUM>,<NUM>,<NUM>-(<NUM>,<NUM>,<NUM>)-trione; <NUM>,<NUM>,<NUM>-tris(<NUM>,<NUM>-di-tert-butyl-<NUM>-hydroxybenzyl)-<NUM>,<NUM>,<NUM>-triazine-<NUM>,<NUM>,<NUM>(<NUM>,<NUM>,SH)-trione; <NUM>,<NUM>,<NUM>-Tris(<NUM>'-methyl-<NUM>'-hydroxy-<NUM>'-t-butylphenyl)butane; Triethylene glycol bis[<NUM>-(<NUM>-t-butyl-<NUM>-hydroxy-<NUM>-methylphenyl)propionate]; <NUM>,<NUM>'-Thiobis(<NUM>-t-butyl-<NUM>-methylphenol); <NUM>,<NUM>'-Thiodiethylene bis[<NUM>-(<NUM>-t-butyl-<NUM>-hydroxyl-<NUM>-methylphenyl)propionate]; Octadecyl <NUM>-(<NUM>'-t-butyl-<NUM>'-hydroxy-<NUM>'-methylphenyl)propionate; Tetrakismethylene(<NUM>-t-butyl-<NUM>-hydroxy-<NUM>-methylhydrocinnamate)methane; N,N'-Hexamethylene bis[<NUM>-(<NUM>-t-butyl-<NUM>-hydroxy-<NUM>-methylphenyl)propionamide]; Di(<NUM>-tertiarybutyl-<NUM>-hydroxy-<NUM>,<NUM>-dimethyl benzyl) thiodipropionate; and octadecyl <NUM>,<NUM>-di-(tert)-butyl-<NUM>-hydroxyhydrocinnamate.

The phosphite used in the thermal and UV light stabilizing composition may be a hindered arylalkyl phosphite or a trisarylphosphite, or mixtures thereof. The hindered arylalkyl phosphite is a compound according to Formula (V):
<CHM>
wherein R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, and R<NUM> in Formula (V) are each individually selected from hydrogen, C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> cycloalkyl, C<NUM>-C<NUM> alkyl cycloalkyl, C<NUM>-C<NUM> aryl, and C<NUM>-C<NUM> alkylaryl, wherein R<NUM> and R<NUM> together comprise at least <NUM> carbons and at least one of R<NUM> and R<NUM> comprises a tertiary carbon, wherein R<NUM> and R<NUM> together comprise at least <NUM> carbons and at least one of R<NUM> and R<NUM> comprises a tertiary carbon. Examples of the hindered arylalkyl phosphite include: bis-(<NUM>,<NUM>-di-t-butyl-<NUM>-methlphenyl)pentaerythritol diphosphite, (bis-(<NUM>,<NUM>-dicumylphenyl)pentaerythritol diphosphite, bis-(<NUM>,<NUM>-di-t-butyl-phenyl)pentaerythritol diphosphite, and bis-(<NUM>,<NUM>,<NUM>-tri-t-butyl-phenyl)pentaerythritol diphosphate.

The trisarylphosphite is a compound according to Formula (VI):
<CHM>
wherein R<NUM>, R<NUM>, R<NUM>, R<NUM>, and R<NUM> in Formula (VI) are each individually selected from hydrogen, C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> cycloalkyl, C<NUM>-C<NUM> alkyl cycloalkyl, C<NUM>-C<NUM> aryl, and C<NUM>-C<NUM> alkylaryl. Examples of the trisarylphosphite include: tris-(<NUM>,<NUM>-di-t-butylphenyl)phosphite, tris(<NUM>-nonylphenyl) phosphite and triphenyl phosphite.

The thioester compound is dilauryl thiodipropionate, distearyl thiodipropionate, pentaerythrithol tetrakis-(<NUM>-dodecylthipropionate), tetra-alkyl thioethyl thiodisuccinate, <NUM>,<NUM>-dihydroxy-<NUM>,<NUM>-dithia-<NUM>-oxatridecamethylene bis[<NUM>-(dodecylthio)propionate], polyalkanol esters of alkylthio-alkanoic acids, or dialkyl <NUM>,<NUM>'-thiodipropionate.

In anembodiment, a formulation of the thermal and UV light stabilizing composition includes between about <NUM> wt. % to about <NUM> wt. % (preferably about <NUM> wt. % to about <NUM> wt. %) of the ortho-hydroxyl tris-aryl-s-triazine compound, between about <NUM> wt. % to about <NUM> wt. % (preferably about <NUM> wt. % to about <NUM> wt. %) of the hindered amine light stabilizer compound, between about <NUM> wt. % to about <NUM> wt. % (preferably about <NUM> wt. % to about <NUM> wt. %) of the hindered hydroxybenzoate compound, between <NUM> wt. % to about <NUM> wt. % (preferably about <NUM> wt. % to about <NUM> wt. %) of the acid scavenger, between about <NUM> wt. % to about <NUM> wt. % (preferably about <NUM> wt. % to about <NUM> wt. %) of the hindered phenol antioxidant compound, between about <NUM> wt. % to about <NUM> wt. % (preferably about <NUM> wt. % to about <NUM> wt. %) of the phosphite compound, and between about <NUM> wt. % to about <NUM> wt. % (preferably about <NUM> wt. % to <NUM> wt. %) of the thioester compound, where the wt. % of each component is based on the total weight of the thermal and UV light stabilizing composition.

In a particular embodiment, a formulation of the thermal and UV light stabilizing composition includes about <NUM> wt. % of the ortho-hydroxyl tris-aryl-s-triazine compound, about <NUM> wt. % of the hindered amine light stabilizer compound, about <NUM> wt. % of the hindered hydroxybenzoate compound, about <NUM> wt. % of the acid scavenger, about <NUM> wt. % of the hindered phenol antioxidant compound, about <NUM> wt. % of the phosphite compound and about <NUM> wt. % of the thioester compound, where the wt. % of each component is based on the total weight of the thermal and UV light stabilizing composition.

The thermal and UV light stabilizing composition can be combined with a material to be stabilized, e.g., a polymer, in any manner known in the art, thus forming a composition that is a stabilized material (also referred to herein as a stabilized composition or a composition). Materials to be stabilized, to which the thermal and UV light stabilizing composition may be combined with, include, but are not limited to, polymers such as polyolefins, polyesters, polyethers, polyketones, polyamides, natural and synthetic rubbers, polyurethanes, polystyrenes, high-impact polystyrenes, polyacrylates, polymethacrylates, polyacetals, polyacrylonitriles, polybutadienes, polystyrenes, acrylonitrile-butadiene-styrene, styrene acrylonitrile, acrylate styrene acrylonitrile, cellulosic acetate butyrate, cellulosic polymers, polyimides, polyamideimides, polyetherimides, polyphenylsulfides, polyphenyloxidepolysulfones, polyethersulfones, polyvinylchlorides, polycarbonates, polyketones, aliphatic polyketones, thermoplastic olefins, aminoresin cross-linked polyacrylates and polyesters, polyisocyanate cross-linked polyesters and polyacrylates, phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins, drying and non-drying alkyd resins, alkyd resins, polyester resins, acrylate resins cross-linked with melamine resins, urea resins, isocyanates, isocyanurates, carbamates, and epoxy resins, cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl compounds, which are cross-linked with anhydrides or amines, polysiloxanes, Michael addition polymers, amines, blocked amines with activated unsaturated and methylene compounds, ketimines with activated unsaturated and methylene compounds, polyketimines in combination with unsaturated acrylic polyacetoacetate resins, polyketimines in combination with unsaturated acrylic resins, radiation curable compositions, epoxymelamine resins, as well as organic dyes, cosmetic products, cellulose-based paper formulations, photographic film paper, fibers, waxes, inks, and blends thereof.

Preferably, the material to be stabilized is a polymer, such as thermoplastic olefins, acrylonitrile-butadiene-styrene, polyesters, polyvinylchloride, polyamides, polyurethanes, or homo- and copolymers of propylene, isobutylene, butene, methylpentene, hexene, heptene, octene, isoprene, butadiene, hexadiene, dicyclopentadiene, ethylidene, cyclopentene and norbornene. More preferably, the material to be stabilized is polypropylene and thermoplastic olefins.

In one embodiment, it is contemplated that the material to be stabilized may be a material or item used in the construction or renovation of buildings, e.g., homes, offices, warehouses, and the like. For example, the material to be stabilized may include vinyl siding, vinyl siding trim, shutters, gable vents, eaves, fascia, soffits, moldings, roofing shingles, roofing underlayment or base sheets, roofing membranes, batten systems, batten extenders, flashing, tile pans, ridge vents, weather blocks, hip and ridge systems (also known as hip and ridge shingles), eave risers, taper strips, gable end wedges, rake trim, geomembranes, composite deck materials, railings, window frames, and other materials and items used in the construction or renovation of buildings.

In one embodiment, the material to be stabilized, and thermal and UV light stabilizing composition are combined to form a "master batch" composition. In one embodiment, the master batch composition includes between <NUM> wt. % to about <NUM> wt. % of the thermal and UV light stabilizing compound, based on the total weight of the master batch composition, with the remainder being the material to be stabilized. In a more preferred embodiment, the master batch composition includes between <NUM> wt. % to about <NUM> wt. % of the thermal and UV light stabilizing composition, based on the total weight of the master batch composition, with the remainder being the material to be stabilized. In another embodiment, the master batch composition includes between <NUM> wt. % to about <NUM> wt. % of the thermal and UV light stabilizing composition, based on the total weight of the master batch composition, with the remainder being the material to be stabilized.

One embodiment includes a masterbatch concentrate comprising a stabilizing composition according to any of the embodiments described herein and at least one organic material identical or compatible with a material to be stabilized, wherein the stabilizing composition is present in an amount from <NUM> wt. % to <NUM> wt. % based on the total weight of the master batch concentrate.

In certain embodiments, the amount of thermal and UV stabilizing composition as described herein in the stabilized composition for end-use is present at any point in the range from <NUM> wt. % to <NUM> wt. %, based on the total weight of the material to be stabilized. In a particular embodiment, the amount of thermal and UV stabilizing composition in the stabilized composition for end-use is present at any point in the range from <NUM> wt. % to <NUM> wt. %, based on the total weight of the material to be stabilized.

The specific components of the thermal and UV stabilizing composition as described herein can be present in the stabilized composition in various amounts depending on the material to be stabilized and/or the level of desired protection. For example, the amount of the ortho-hydroxyl tris-aryl-s-triazine compound in the stabilized composition for end-use can range from about <NUM> wt. % to about <NUM> wt. %, preferably <NUM> wt. % to about <NUM> wt. %, more preferably <NUM> wt. % to about <NUM> wt. % based on the total weight of stabilized composition.

The amount of the hindered amine light stabilizer compound in the stabilized composition is from about <NUM> wt. % to about <NUM> wt. %, preferably from about <NUM> wt. % to about <NUM> wt. %, more preferably from <NUM> wt. % to about <NUM> wt. %, based on the total weight of the stabilized composition.

The amount of the hindered hydroxybenzoate compound in the stabilized composition is from about <NUM> wt. % to about <NUM> wt. %, preferably from about <NUM> wt. % to about <NUM> wt. %, more preferably from about <NUM> wt. % to about <NUM> wt. %, based on the total weight of the stabilized composition.

The amount of the acid scavenger in the stabilized composition is from about <NUM> wt. % to about <NUM> wt. %, preferably from about <NUM> wt. % to about <NUM> wt. %, more preferably from <NUM> wt. % to about <NUM> wt. %, based on the total weight of the stabilized composition.

The amount of the hindered phenol antioxidant compound in the stabilized composition is from about <NUM> wt. % to about <NUM> wt. %, preferably from about <NUM> wt. % to about <NUM> wt. %, more preferably from about <NUM> wt. % to about <NUM> wt. %, based on the total weight of the stabilized composition.

The amount of the phosphite compound in the stabilized composition is from about <NUM> wt. % to about <NUM> wt. %, preferably from about <NUM> wt. % to about <NUM> wt. %, more preferably from about <NUM> wt. % to about <NUM> wt. %, based on the total weight of the stabilized composition.

The amount of the thioester compound in the stabilized composition is from about <NUM> wt. % to about <NUM> wt. %, preferably from about <NUM> wt. % to about <NUM> wt. %, more preferably from about <NUM> wt. % to about <NUM> wt. %, based on the total weight of the stabilized composition.

This application also contemplates a method of preparing the composition above by combining the thermal and UV light stabilizing composition with the material to be stabilized. The term "combining" or "combined" is intended to include all manners in which the thermal and UV light stabilizing compositions can be combined, and includes, for example, intermixing, admixing, integrating, mixing, blending, and the like. Additionally, it is noted that the thermal and UV light stabilizing composition and the material to be stabilized may be combined in any order, i.e., the thermal and UV light stabilizing composition can be added to the material to be stabilized, or vice versa, or the thermal and UV light stabilizing composition and the material to be stabilized can be simultaneously added to a vessel.

The material to be stabilized and the thermal and UV light stabilizing composition can be combined by blending or compounding the components in a kneading apparatus such as a single or twin screw extruder, Banbury mixer, or hot rollers. The processing parameters and the use of such kneading apparatus are well known to those skilled in the art.

As would be apparent to those skilled in the art of making plastic materials, in addition to the material to be stabilized and the thermal and UV light stabilizing composition, the composition of the present invention may also include conventional additives including, but not limited to, metal deactivators, nitrones, lactones, co-stabilizers, nucleating agents, clarifying agents, neutralizers, metallic stearates, metal oxides, hydrotalcites, fillers and reinforcing agents, plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, level agents, optical brighteners, flame retardant agents, anti-static agents and blowing agents.

The invention includes at least the following embodiments:.

The compositions disclosed herein may be used in a variety of applications, including, but not limited to automotive applications such as air vents, instrument panels, control consoles, battery house, and exterior parts such as bumpers, side moldings and mirror housings. The compositions may also be used in geomembrane applications such as, for example, pond liners, ground covers, underlayment, water barriers, erosion control membranes, and the like. Other applications that would benefit from thermal and UV stabilization are also contemplated herein.

The invention will now be illustrated by the following examples. The examples are not intended to limit the scope of the present invention. In conjunction with the general and detailed descriptions above, the examples provide further understanding of the present invention.

Materials: Thermoplastic olefin (TPO) number AHXPT053A1100NT101 from Asahi Kasei Corporation is used as base polymer. The various additives (designated A - H) and their wt. % loading are listed in Table <NUM> below, which will be used henceforth. The additives are used as received.

Melt Mixing of Polymer Additives: First, the additives are weighed and mixed with polymer pellets. The solid mixture is vigorously shaken to achieve uniform mixing of additives. The solid mixture is then fed into the twin screw extruder hopper. The compounding of additives is performed using a Twin Screw extruder. The conditions during compounding are as follows: rotor speed: <NUM> rpm; melt temperature: <NUM>; feed rate: <NUM> rpm; temperature profile range: <NUM>-<NUM>. The average pressure reading during compounding is <NUM>-<NUM> %. Compounded samples are pelletized using a Conair pelletizer. The pellets are air dried for <NUM> hrs. before further use.

Sample Preparation: Samples for thermal and weathering tests are prepared using an Arburg injection molder. The conditions during injection molding are as follows: nozzle temperature: <NUM>; injection pressure: <NUM>, shot size: <NUM>. For tensile testing, tensile bars according to ASTM638-Type <NUM> are prepared. Plaques having standard <NUM> x <NUM> x <NUM> inch dimension are used for both thermal and weathering tests.

Thermal and Weathering Test Conditions: For thermal performance, samples (Tensile bars and plaques) are kept at <NUM> for a total of <NUM> hrs. Samples are analyzed for gloss retention, Delta E, and mechanical strength (stress at break) at <NUM> hr. Surface gloss is measured using micro-TRI-Gloss from BYK-Gardner under ASTM Test Procedure D523 with a <NUM>° angle. The gloss retention value is calculated based on unexposed sample. Change in sample color is measured using a Macbeth Color Eye Colorimeter using ASTM D2244-<NUM> with <NUM>" view and D65/<NUM>° observer. From the raw data, Delta E, which is the difference between total color change before and after exposure, is calculated. Lower Delta E indicates less color change respectively, indicating better performance. For tensile strength, five tensile bars for each data point are tested on an Instron Engineering Company Tensile Tester (Model TTB). The average tensile strength of the five test samples are measured using ASTM D638 type-<NUM> method. The cross-head speed of the tensile tester is <NUM> inch (<NUM>. ) per minute.

For UV weathering, samples are exposed to Xenon Weather-ometer under ASTM-G-<NUM> testing conditions, PV1303, SAEJ1885 (J2412) and SAEJ1960 (J2527). Samples are analyzed for gloss retention and Delta E after set exposure interval.

Thirteen samples with various stabilizer additive combinations are formulated as described above and then tested for extreme thermal performance (tensile strength, gloss and color change) and extreme weathering performance (gloss and color change) against a control sample (no stabilizer composition added). Those samples denoted by a "C" are comparative and represent control samples (i.e., no stabilizing compositions added), or samples containing formulations previously known to those skilled in the art. Example 2C, for example, is based on a formulation described in <CIT>. Results of the thermal and weathering tests for the samples as prepared above are presented in Tables <NUM>-<NUM> below.

Examples 1C - 4C performed poorly with regard to retaining tensile strength under extreme thermal conditions as compared to certain compositions as described herein (e.g., Examples <NUM>-<NUM>).

Compositions according to the invention as described herein (e.g., Examples <NUM> and <NUM>) provide the best extreme thermal performance in terms of highest gloss retention and lowest color change as compared to control samples and samples containing formulations known to those skilled in the art (i.e., Examples 1C - 4C). This result is also visually demonstrated by <FIG>. Plaques with no stabilizer composition (<FIG>) or with stabilizer composition based on <CIT> (<FIG>) show blooming under extreme thermal conditions, whereas plaques with stabilizing compositions according to the invention as described herein (<FIG>) show significantly less, or no blooming under the same conditions.

Compositions according to the invention as described herein (Examples <NUM>, and <NUM>) do not adversely affect the good weathering performance in terms of highest gloss retention when compared to control samples and samples containing formulations known to those skilled in the art (i.e., Examples 1C - 4C).

Compositions according to the invention as described herein (Examples <NUM>, and <NUM>) do not adversely affect the good weathering performance in terms of lowest color change when compared to control samples and samples containing formulations known to those skilled in the art (i.e., Examples 1C - 4C).

Thus, based on the results above, it is surprisingly shown that compositions according to the invention as described herein not only display a synergistic effect and provide enhanced thermal performance in terms of retaining tensile strength under extreme conditions as compared to control samples and samples containing formulations known to those skilled in the art, but the compositions according to the invention as described herein also do not have any antagonistic effect against the good weathering performance demonstrated by samples containing formulations known to those skilled in the art.

In Examples <NUM>-<NUM>, the additives listed in Table <NUM> are utilized to conduct a multipass processing stabilization study.

Melt Mixing of Polymer Additives: First, the additives are weighed and mixed with polypropylene (Profax <NUM>) resin. The solid mixture is vigorously shaken to achieve uniform mixing of additives. The solid mixture is fed into the single screw extruder hopper. The compounding of additives is performed using a single screw extruder. The conditions during compounding are as follows: rotor speed: <NUM> rpm; melt temperature: <NUM>; feed rate: <NUM>-<NUM> rpm; temperature profile range: <NUM>-<NUM>. The average pressure reading during compounding is <NUM>-<NUM>%. Compounded samples are pelletized using a Conair pelletizer.

Multipass Extrusion Processing: The pellets are passed through the single screw extruder five times and about <NUM> of sample are collected from the first, third, and fifth passes. To determine the processing characteristics, the relative melt flow of the compounded polypropylene pellets are measured using the Dynisco Melt Flow Indexer (MFI). This procedure is specific for ASTM D1238 Method B - Automatically Timed Flow Rate Measurement. A lower Melt flow rate (MFR - g/<NUM>) indicates higher viscosity properties, demonstrating better stability performance of the polymer. The results are shown in Table <NUM> below as well as in a graph presented in <FIG>.

Claim 1:
A thermal and ultraviolet (UV) light stabilizer composition comprising :
an ortho-hydroxyl tris-aryl-s-triazine compound;
a hindered amine light stabilizer compound;
a hindered hydroxybenzoate compound;
an acid scavenger;
a phosphite compound;
a hindered phenol antioxidant compound comprising a molecular fragment according to one or more of Formula (IVa), (IVb), or (IVc):
<CHM>
wherein
R<NUM> in Formulae (IVa), (IVb) and (IVc) is chosen from hydrogen and a C<NUM>-<NUM> hydrocarbyl;
R<NUM> and R<NUM> in Formulae (IVa), (IVb) and (IVc) are each individually chosen from hydrogen and a C<NUM>-C<NUM> hydrocarbyl; and
R<NUM> in Formulae (IVa), (IVb) and (IVc) is chosen from C<NUM>-C<NUM> hydrocarbyl, and
a thioester compound.