A thermoplastic composition comprising a poly(arylene ether), a polyamide, a compatibilizing agent, and a polyester ionomer exhibits reduced moisture absorption, improved paint adhesion, and improved stability. Use of the polyester ionomer allows use of lower amounts of conductive fillers. The compositions of the present invention comprise an amount of a stabilizer package effective to enhance the morphological stability of the thermoplastic composition wherein the stabilizer package comprises at least one phenolic species in combination with at one thioester species, at least one one organo-phosphite species, or at least one thioester species in combination with at least one organo-phosphite species.

Not Applicable
The present invention relates to a thermoplastic blend. In particular, the invention relates to an improved thermoplastic blend comprising a poly(arylene ether) and a polyamide and having an enhanced retention of physical properties.
Thermoplastic blends comprising poly(arylene ether)s and polyamides are commercially available materials that combine the heat resistance, stiffness and impact strength of the amorphous poly(arylene ether) phase with the chemical resistance and processability of the crystalline polyamide phase. Their exceptional balance of thermal and mechanical properties has led to adoption of these blends by the automotive industry for use in painted body panels. Body panels are large parts and are often commercially formed using injection molding techniques. These injection molding techniques often subject the thermoplastic blends to elevated temperatures for long periods of time and often result in diminished morphological stability and reduced physical properties.
There therefore remains a need for poly(arylene ether)/polyamide blends with retention of physical properties and having reduced water retention and improved paint adhesion.
A poly(arylene ether)/polyamide blend having reduced water absorption comprises:
about 5 to about 95 weight percent of a poly(arylene ether);
about 5 to about 95 weight percent of a polyamide;
about 0.01 to about 10 weight percent of a compatibilizing agent;
about 0.1 to about 20 weight percent of a polyester ionomer which is the polycondensation product of (1) an aromatic dicarboxylic acid or its ester-forming derivative; (2) a diol compound or its ester-forming derivative; and (3) an ester-forming compound containing an ionic sulfonate group; and
an amount of a stabilizer package effective to enhance the morphological stability of the poly(arylene ether)/polyamide blend wherein the stabilizer package comprises at least one phenolic species in combination with at one thioester species, at least one one organo-phosphite species, or at least one thioester species in combination with at least one organo-phosphite species,
wherein weight percentages are based on the total weight of the composition.
Thermoplastic blends exhibiting reduced water absorption, improved paint adhesion, and improved conductivity comprise:
about 5 to about 95 weight percent of a poly(arylene ether);
about 5 to about 95 weight percent of a polyamide;
about 0.01 to about 10 weight percent of a compatibilizing agent;
about 0.1 to about 20 weight percent of a polyester ionomer which is the polycondensation product of (1) an aromatic dicarboxylic acid or its ester-forming derivative; (2) a diol compound or its ester-forming derivative; and (3) an ester-forming compound containing an ionic sulfonate group; and
an amount of a stabilizer package effective to enhance the morphological stability of the thermoplastic blends wherein the stabilizer package comprises at least one phenol species in combination with at one thioester species, at least one one organo-phosphite species, or at least one thioester material in combination with at least one organo-phosphite species,
wherein weight percentages are based on the total weight of the composition.
The composition may comprise any conventional poly(arylene ether). The term poly(arylene ether) includes polyphenylene ether (PPE) and poly(arylene ether) copolymers; graft copolymers; poly(arylene ether) ether ionomers; and block copolymers of alkenyl aromatic compounds, vinyl aromatic compounds, and poly(arylene ether), and the like; and combinations comprising at least one of the foregoing; and the like. Poly(arylene ether)s per se, are known polymers comprising a plurality of structural units of the formula:
wherein for each structural unit, each Q1 is independently halogen, primary or secondary lower alkyl having 1 to about 7 carbon atoms, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and each Q2 is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q1. Preferably, each Q1 is alkyl or phenyl, especially C14 alkyl, and each Q2 is hydrogen.
Both homopolymer and copolymer poly(arylene ether)s are included. The preferred homopolymers are those containing 2,6-dimethylphenylene ether units. Suitable copolymers include random copolymers containing, for example, such units in combination with 2,3,6-trimethyl-1,4-phenylene ether units or copolymers derived from copolymerization of 2,6-dimethylphenol with 2,3,6-trimethylphenol. Also included are poly(arylene ether)s containing moieties prepared by grafting vinyl monomers or polymers such as polystyrenes, as well as coupled poly(arylene ether) in which coupling agents such as low molecular weight polycarbonates, quinones, heterocycles and formals undergo reaction in known manner with the hydroxy groups of two poly(arylene ether) chains to produce a higher molecular weight polymer. Poly(arylene ether)s of the present invention further include combinations of any of the above.
The poly(arylene ether) generally has a number average molecular weight within the range of about 3,000 to about 40,000 and a weight average molecular weight within the range of about 20,000 to about 80,000, as determined by gel permeation chromatography. The poly(arylene ether) generally has an intrinsic viscosity of about 0.10 to about 0.60 deciliters per gram (dl/g), preferably in the range of about 0.29 to about 0.48 dl/g, all as measured in chloroform at 25xc2x0 C. It is also possible to utilize a high intrinsic viscosity poly(arylene ether) and a low intrinsic viscosity poly(arylene ether) in combination. Determining an exact ratio, when two intrinsic viscosities are used, will depend somewhat on the exact intrinsic viscosities of the poly(arylene ether) used and the ultimate physical properties desired.
The poly(arylene ether)s are typically prepared by the oxidative coupling of at least one monohydroxyaromatic compound such as 2,6-xylenol or 2,3,6-trimethylphenol. Catalyst systems are generally employed for such coupling; they typically contain at least one heavy metal compound such as a copper, manganese or cobalt compound, usually in combination with various other materials.
Particularly useful poly(arylene ether)s for many purposes are those that comprise molecules having at least one aminoalkyl-containing end group. The aminoalkyl radical is typically located in an ortho position to the hydroxy group. Products containing such end groups may be obtained by incorporating an appropriate primary or secondary monoamine such as di-n-butylamine or dimethylamine as one of the constituents of the oxidative coupling reaction mixture. Also frequently present are 4-hydroxybiphenyl end groups, typically obtained from reaction mixtures in which a by-product diphenoquinone is present, especially in a copper-halide-secondary or tertiary amine system. A substantial proportion of the polymer molecules, typically constituting as much as about 90% by weight of the polymer, may contain at least one of said aminoalkyl-containing and 4-hydroxybiphenyl end groups.
It will be apparent to those skilled in the art from the foregoing that suitable poly(arylene ether)s include all those presently known, irrespective of variations in structural units or ancillary chemical features.
The composition may comprise poly(arylene ether) in an amount of about 5 to about 95 weight percent, based on the total weight of the composition. It is preferred to use the poly(arylene ether) in an amount of about 20 to about 60 weight percent, more preferably about 30 to about 45 weight percent.
Suitable polyamide resins are a generic family of resins known as nylons, characterized by the presence of an amide group (xe2x80x94C(O)NHxe2x80x94). Nylon-6 and nylon-6,6 are the generally preferred polyamides and are available from a variety of commercial sources. Other polyamides, however, such as nylon-4,6, nylon-12, nylon-6,10, nylon-6,9, nylon-6/6T and nylon-6,6/6T with triamine contents below about 0.5 weight percent, as well as others, such as the amorphous nylons may be useful for particular poly(arylene ether)-polyamide applications. Mixtures of various polyamides, as well as various polyamide copolymers, are also useful. A highly preferred polyamide is nylon-6,6.
The polyamides can be obtained by a number of well known processes such as those described in U.S. Pat. Nos. 2,071,250; 2,071,251; 2,130,523; 2,130,948; 2,241,322; 2,312,966; and 2,512,606. Nylon-6, for example, is a polymerization product of caprolactam. Nylon-6,6 is a condensation product of adipic acid and 1,6-diaminohexane. Likewise, nylon-4,6 is a condensation product of adipic acid and 1,4-diaminobutane. Besides adipic acid, other useful diacids for the preparation of nylons include azelaic acid, sebacic acid, dodecane diacid, as well as terephthalic and isophthalic acids, and the like. Other useful diamines include m-xylyene diamine, di-(4-aminophenyl)methane, di-(4-aminocyclohexyl)methane, 2,2-di-(4-aminophenyl)propane, 2,2-di-(4-aminocyclohexyl)propane, among others. Copolymers of caprolactam with diacids and diamines are also useful.
Polyamides having viscosity of up to about 400 milliliters per gram (ml/g) can be used, with a viscosity of about 90 to about 350 ml/g preferred, and about 110 to about 240 ml/g especially preferred, as measured in a 0.5 weight percent solution in 96 weight percent sulfuric acid in accordance with ISO 307.
The composition may comprise polyamide in an amount of about 5 to about 95 weight percent, based on the total weight of the composition. It is preferred to use the polyamide in an amount of about 30 to about 70 weight percent, more preferably about 40 to about 60 weight percent.
The composition may further comprise a compatibilizing agent. Compatibilizing agents generally improve the physical properties of the poly(arylene ether)-polyamide resin blend, and they enable the use of a greater proportion of the polyamide component. When used herein, the expression xe2x80x9ccompatibilizing agentxe2x80x9d refers to those polyfunctional compounds that interact with either the poly(arylene ether), the polyamide resin, or both. This interaction may be chemical (e.g., grafting) or physical (e.g., affecting the surface characteristics of the dispersed phases). In either instance the resulting poly(arylene ether)-polyamide composition appears to exhibit improved compatibility, particularly as evidenced by enhanced impact strength, mold knit line strength and/or elongation. As used herein, the expression xe2x80x9ccompatibilized poly(arylene ether)-polyamide base resinxe2x80x9d refers to those compositions that have been physically or chemically compatibilized with an agent as discussed above, as well as those compositions that are physically compatible without such agents, as described in, for example, U.S. Pat. No. 3,379,792.
Examples of the various non-polymeric compatibilizing agents that may be employed include: a) liquid diene polymers, b) epoxy compounds, c) oxidized polyolefin waxes, d) quinones, e) organosilane compounds, f) polyfunctional compounds, and g) functionalized poly(arylene ether)s obtained by reacting one or more of the previously mentioned compatibilizing agents with poly(arylene ether)s as described below.
Suitable liquid diene polymers (a) include homopolymers of a conjugated diene, as well as copolymers of a conjugated diene with at least one monomer selected from other conjugated dienes; vinyl monomers such as styrene and alphamethyl styrene; olefins such as ethylene, propylene, butene-1, isobutylene, hexene-1, octene-1 and dodecene-1, and mixtures thereof. The liquid diene polymer preferably have a number average molecular weight of about 150 to about 10,000 preferably about 150 to about 5,000. These homopolymers and copolymers can be produced by the methods described in, for example, U.S. Pat. Nos. 4,054,612; 3,876,721; and 3,428,699 and include, among others, polybutadiene, polyisoprene, poly(1,3-pentadiene), poly(butadiene-isoprene), poly(styrene-butadiene), polychloroprene, poly(butadiene-alpha methylstyrene), poly(butadiene-styrene-isoprene), poly(butylene-butadiene), and the like.
Epoxy compounds (b) suitable for use include: (1) epoxy resins produced by condensing polyhydric phenols (e.g. bisphenol A, tetrabromobisphenol A, resorcinol and hydroquinone) and epichlorohydrin; (2) epoxy resins produced by condensing polyhydric alcohols (e.g., ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, trimethylolethane, and the like) and epichlorohydrin; (3) glycidyletherified products of monohydric alcohols and monohydric phenols, including phenyl glycidylether, butyl glycidyl ether, and cresyl glycidylether; (4) glycidyl derivatives of amino compounds, including the diglycidyl derivatives of aniline; and (5) epoxidized products of higher olefins, cycloalkenes, natural unsaturated oils (e.g. soybean oil), and the foregoing liquid diene polymers; and the like.
Oxidized polyolefin waxes (c) are well known and an illustrative description thereof and processes for their production are found in U.S. Pat. Nos. 3,822,227 and 3,756,999. Generally, these are prepared by an oxidation or suspension is oxidation of polyolefin. An especially preferred polyolefin wax is xe2x80x9cHoechst Wachsxe2x80x9d.
Suitable quinone compounds (d) are characterized as having in the molecule of the unsubstituted derivative at least one six-membered carbon ring; at least two carbonyl groups in the ring structure, both of which may be in the same or, if more than one ring, different rings, provided that they occupy positions corresponding to the 1,2- or 1,4-orientation of the monocyclic quinone; and at least two carbon-carbon double bonds in the ring structure, said carbon-carbon double bonds and carbonyl carbon-oxygen double bonds being conjugated with respect to each other. Where more than one ring is present in the unsubstituted quinone, the rings may be fused, non-fused, or both: non-fused rings may be bound by a direct carbon-carbon double bond or by a hydrocarbon radical having conjugated unsaturation such as xe2x80x94Cxe2x95x90Cxe2x80x94Cxe2x95x90Cxe2x80x94.
Substituted quinones are also within the scope of the present invention. The degree of substitution, where substitution is desired, may be from one to the maximum number of replaceable hydrogen atoms. Exemplary of the various substituents that may be present on the quinone nucleus include halogen (e.g. chlorine, bromine, and fluorine), hydrocarbon radicals including branched and unbranched, saturated and unsaturated alkyl, aryl, alkylaryl and cycloalkyl radicals and halogenated derivatives thereof; and similar hydrocarbons having heteroatoms therein, particularly oxygen, sulfur, or phosphorus, and wherein the heteroatom connects the radical to the quinone ring.
Exemplary quinones include 1,2- and 1,4-benzoquinone; 2,6-diphenyl-1,4-benzoquinone; 3,3xe2x80x2,5,5xe2x80x2-tetramethyl-4,4xe2x80x2-diphenoquinone; 2,2xe2x80x2- and 4,4xe2x80x2-diphenoquinone; 1,2-, 1,4-, and 2,6-naphthoquinone; 2,3,5,6-tetrachloro-2,5-cyclohexadiene-1,4-dione (chloranil); 2-chloro-1,4-benzoquinone; 2,6-dimethyl benzoquinone; and the like.
Organosilane compounds (e) suitable as compatibilizing agents are characterized as having in the molecule (1) at least one silicon atom bonded to a carbon through an oxygen link and (2) at least one carbon-carbon double bond or carbon-carbon triple bond and/or a functional group selected from an amine group or a mercapto group provided that the functional group is not directly bonded to the silicon atom.
In such compounds, the Cxe2x80x94Oxe2x80x94Si component is generally present as an alkoxy or acetoxy group bonded directly to the silicon atom, wherein the alkoxy or acetoxy group generally has fewer than about 15 carbon atoms and may also contain hetero atoms (e.g., oxygen). Additionally, there may also be more than one silicon atom in the compound, such multiple silicon atoms, if present, being linked through an oxygen atom (e.g., siloxanes), a silicon-silicon bond, or a divalent organic radical (e.g., methylene or phenylene), or the like.
Examples of suitable organosilane compounds include gamma-aminopropyltriethoxy silane, 2-(3-cyclohexyl)ethyltrimethoxy silane, 1,3-divinyltetraethoxy silane, vinyl tris-(2-methoxyethoxy)silane, 5-bicycloheptenyl triethoxy silane, and gamma-mercaptopropyl trimethoxy silane.
Polyfunctional compounds (f) that may be employed as compatibilizer are of three types. The first type includes molecules having both a carbon-carbon double bond or a carbon-carbon triple bond and at least one carboxylic acid, anhydride, amide, ester, imide, amino, epoxy, orthoester, or hydroxy group. Examples of such polyfunctional compounds include maleic acid; maleic anhydride; fumaric acid; glycidyl acrylate; itaconic acid; aconitic acid; maleimide; maleic hydrazide; products resulting from the reaction of a diamine with maleic anhydride, maleic acid, fumaric acid, or the like; dichloromaleic anhydride; maleic acid amide; unsaturated dicarboxylic acids (e.g., acrylic acid, butenoic acid, methacrylic acid, pentenoic acid, decenoic acids, undecenoic acids, dodecenoic acids, linoleic acid, and the like); esters, acid amides or anhydrides of the foregoing unsaturated carboxylic acids; unsaturated alcohols (e.g., crotyl alcohol, methyl vinyl carbinol, 4-pentene-1-ol, 1,4-hexadiene-3-ol, 3-butene-1,4-diol, 2,5-dimethyl-3-hexene-2,5-diol and alcohols of the formulae CnH2nxe2x88x921OH, CnH2nxe2x88x923OH, CnH2nxe2x88x925OH, CnH2nxe2x88x927OH, and CnH2nxe2x88x929OH, a positive integer not greater than about 30); unsaturated amines resulting from replacing the xe2x80x94OH group(s) of the above unsaturated alcohols with xe2x80x94NH2 groups; functionalized diene polymers and copolymers; and the like. Of these, maleic acid, fumaric acid, and maleic anhydride are preferred.
The second group of polyfunctional compatibilizer compounds suitable for use herein are characterized as having both a group represented by the formula (OG) wherein G is hydrogen or an alkyl, aryl, acyl or carbonyl dioxy group, and at least two groups, each of which may be the same or different, selected from carboxylic acid, acid halide, anhydride, acid halide anhydride, ester, orthoester, amide, imido, amino, and various salts thereof. Typical examples of this group include aliphatic polycarboxylic acids, acid esters and acid amides represented by the formula:
(RIO)mR(COORII)n(CONRIIIRIV)s
wherein R is a linear or branched chain, saturated aliphatic hydrocarbon of from 2 to 20, preferably 2 to 10, carbon atoms; RI is hydrogen or an alkyl, aryl, acyl or carbonyl 20 dioxy group of 1 to 10, preferably 1 to 6, most preferably 1 to 4, carbon atoms; each RII is independently hydrogen or an alkyl or aryl group having from 1 to about 20 carbon atoms, preferably from 1 to about 10 carbon atoms; each RIII and RIV are independently hydrogen or an alkyl or aryl group having from 1 to about 10, preferably from 1 to about 6, more preferably 1 to about 4, carbon atoms; m is equal to 1; (n+s) is greater than or equal to 2, preferably equal to 2 or 3, and n and s are each greater than or equal to zero; and (ORI) is alpha or beta to a carbonyl group and at least two carbonyl groups are separated by 2 to 6 carbon atoms. RI, RII, RIII and RIV cannot be aryl when the respective substituent has less than 6 carbon atoms.
Exemplary members of this second group include citric acid, malic acid, agaricic acid, and the like, including the various commercial forms thereof, such as for example, the anhydrous and hydrated acids. Illustrative of useful esters include, for example, acetyl citrate and mono- and/or distearyl citrates, and the like. Suitable amides include, for example, N,N-diethyl citric acid amide; N-phenyl citric acid amide; N-dodecyl citric acid amide; N,N-didodecyl citric acid amide and N-dodecyl malic acid. Especially preferred derivates are the salts thereof, including the salts with amines and preferably, the alkali and alkaline earth metal salts. Exemplary salts include calcium malate, calcium citrate, potassium malate, and potassium citrate.
The third group of polyfunctional compatibilizer compounds are characterized as having in the molecule both (1) an acid halide group, most preferably an acid chloride group, and (2) at least one carboxylic acid, anhydride, ester, epoxy, orthoester, or amide group, preferably a carboxylic acid or anhydride group. Examples of compatibilizers within this group include trimellitic anhydride acid chloride, chloroformyl succinic anhydride, chloroformyl succinic acid, chloroformyl glutaric anhydride, chloroformyl glutaric acid, chloroacetyl succinic anhydride, chloroacetylsuccinic acid, trimellitic acid chloride, and chloroacetyl glutaric acid. Among these, trimellitic anhydride acid chloride is preferred. Furthermore, it is especially preferred that compatibilizers of this group be pre-reacted with at least a portion of the poly(arylene ether) whereby the compatibilizing agent is a poly(arylene ether)-functionalized compound.
The foregoing compatibilizing agents are more fully described in U.S. Pat. Nos. 4,315,086; 4,600,741; 4,642,358; 4,826,933; 4,927,894; 4,980,424; 5,041,504; and 5,115,042.
The foregoing compatibilizing agents may be used alone or in various combinations. Furthermore, they may be added directly to the melt blend or pre-reacted with either or both the poly(arylene ether) and polyamide, as well as with other resinous materials. With many of the foregoing compatibilizing agents, particularly the polyfunctional compounds, even greater improvement in compatibility is found where at least a portion of the compatibilizing agent is pre-reacted, either in the melt or in a solution of a suitable solvent, with all or a part of the poly(arylene ether). It is believed that such pre-reacting may cause the compatibilizing agent to react with the polymer and, consequently, functionalize the poly(arylene ether) For example, the poly(arylene ether) may be pre-reacted with maleic anhydride to form an anhydride functionalized poly(arylene ether) that has improved compatibility with the polyamide compared to a non-functionalized poly(arylene ether).
Where the compatibilizing agent is employed, the amount used will depend on the specific compatibilizing agent chosen and the specific polymeric system to which it is added. Such amounts may be readily determined by one of ordinary skill in the art. In the preferred embodiment in which the compatibilizing agent is maleic acid, maleic anhydride, citric acid, or fumaric acid, a suitable amount is about 0.01 to about 10 weight percent, preferably about 0.1 to about 3 weight percent, more preferably about 0.3 to about 1.5 weight percent, based on the weight of the entire composition.
It is possible to use in the composition according to the invention any other known compatibilization system. Other systems have been described, for example, in U.S. Pat. No. 4,866,114.
The term polyester ionomer as used herein refers to the polycondensation reaction product of an aromatic dicarboxylic acid or its ester-forming derivative, a diol or its ester-forming derivative, and an ester-forming compound comprising an ionic sulfonate group.
The polyester ionomer may comprise a monovalent and/or divalent aryl carboxylic sulfonate salt units represented by the formula:
wherein p=1-3; d=1-3; p+d=2-6; M is a metal; n=1-5; and A is an aryl group containing one or more aromatic rings, for example, benzene, naphthalene, anthracene, biphenyl, terphenyl, oxy diphenyl, sulfonyl diphenyl, or alkyl diphenyl, where the sulfonate substituent is directly attached to an aryl ring. These groups are incorporated into the polyester through carboxylic ester linkages. The aryl groups may contain one or more sulfonate substituents (d=1-3) and may have one or more carboxylic acid linkages (p=1-3). Groups with one sulfonate substituent (d=1) and two carboxylic linkages (p=2) are preferred.
Preferred metals are alkali or alkaline earth metals where n=1-2. Zinc and tin are also preferred metals.
The polyester ionomer may alternatively comprise sulfonate salt units represented by the formula:
xe2x80x83(1/nMn+xe2x88x92O3S)dxe2x80x94Axe2x80x94(ORxe2x80x3OH)p
wherein p, d, M, n, and A are as defined above, and wherein Rxe2x80x3 is a divalent alkylene or alkyleneoxy group, for example,
xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH2OCH2CH2xe2x80x94, xe2x80x94CH(CH3)CH2xe2x80x94, xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2CH2xe2x80x94, and the like.
A preferred polyester ionomer comprises divalent ionomer units represented by the formula:
wherein R is hydrogen, halogen, alkyl having from one to about twenty carbons, or aryl having from one to about twenty carbons; M is a metal, and n=1-5.
Typical sulfonate substituents that can be incorporated into the metal sulfonate polyester copolymer may be derived from the following carboxylic acids or their ester forming derivatives: sodium 5-sulfoisophthalic acid, potassium sulfoterephthalic acid, sodium sulfonaphthalene dicarboxylic acid, calcium 15 -sulfoisophthalate, potassium 4,4xe2x80x2-di(carbomethoxy) biphenyl sulfonate, lithium 3,5-di(carbomethoxy)benzene sulfonate, sodium p-carbomethoxybenzenesulfonate, dipotassium 5-carbomethoxy-1,3-disulfonate, sodio 4-sulfonaphthalene-2,7-dicarboxylic acid, 4-lithio sulfophenyl-3,5-dicarboxy benzene sulfonate, 6-sodiosulfo-2-naphthyl-3,5-dicarbomethoxy benzene sulfonate, and dimethyl 5-[4-(sodiosulfo)phenoxy] isophthalate.
Other suitable sulfonate carboxylic acids and their ester forming derivatives are described in U.S. Pat. Nos. 3,018,272 and 3,546,008 which are included herein by reference. Preferred sulfonate polyesters include those derived from sodium 3,5-dicarbomethoxybenzene sulfonate
the bis(ethylene glycol) ester of sodium 5-sulfoisophthalate
the bis(diethylene glycol) ester of sodium 5-sulfoisophthalate
Typical diol reactants are aliphatic diols, including straight chain, branched, or cycloaliphatic alkane diols and may contain from 2 to 12 carbon atoms. Examples of such diols include ethylene glycol; propylene glycol, i.e., 1,2- and 1,3-propylene glycol; butane diol, i.e., 1,2-, 1,3- and 1,4-butane diol; diethylene glycol; 2,2-dimethyl-1,3-propane diol; 2-ethyl- and 2-methyl-1,3-propane diol; 1,3- and 1,5-pentane diol; dipropylene glycol; 2-methyl-1,5-pentane diol; 1,6-hexane diol; dimethanol decalin, dimethanol bicyclo octane; 1,4-cyclohexane dimethanol and particularly its cis- and trans-isomers; triethylene glycol; 1,10-decane diol; and mixtures of any of the foregoing. A preferred cycloaliphatic diol is 1,4-cyclohexane dimethanol or its chemical equivalent. When cycloaliphatic diols are used as the diol component, a mixture of cis- to trans-isomers may be used, it is preferred to have a trans isomer content of 70% or more. Chemical equivalents to the diols include esters, such as dialkyl esters, diaryl esters, and the like.
Examples of aromatic dicarboxylic acid reactants are isophthalic or terephthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4xe2x80x2-dicarboxydiphenyl ether, 4,4xe2x80x2-bisbenzoic acid and mixtures thereof. All of these acids contain at least one aromatic nucleus. Acids containing fused rings can also be present, such as in 1,4-, 1,5-, or 2,6-naphthalene dicarboxylic acids. Preferred dicarboxylic acids include terephthalic acid, isophthalic acid or mixtures thereof.
A highly preferred polyester ionomer comprises repeating units of the formula:
wherein R is hydrogen, halogen, alkyl having from one to about twenty carbons, or aryl having from one to about twenty carbons; M is a metal; n=1-5; R1 is an alkylene radical having from one to about twelve carbon atoms; A1 is a 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene radical; and the mole fraction, x, of sulfonate-substituted units, is about 0.1 to about 50 percent of the sum of x and y, with about 0.2 to about 20 mole percent being preferred, about 0.5 to about 10 mole percent being more preferred, and about 1 to about 5 mole percent being even more preferred. Preferably R is hydrogen. Preferably R1 is alkylene having from one to about six carbon atoms; more preferably R1 is ethylene or butylene. M is preferably an alkali or alkaline earth metal; M is more preferably sodium or potassium.
Highly preferred ionomer polyesters include poly(ethylene terephthalate) (PET) ionomers, and poly(1,4-butylene terephthalate) (PBT) ionomers, and poly(1,3-propylene terephthalate) (PPT) ionomers.
Also contemplated herein are the above polyester ionomers with minor amounts, e.g., from about 0.5 to about 15 percent by weight, of units derived from aliphatic acid and/or aliphatic polyols to form copolyesters. The aliphatic polyols include glycols, such as poly(ethylene glycol) or poly(butylene glycol). Such polyesters can be made following the teachings of, for example, U.S. Pat. Nos. 2,465,319 and 3,047,539.
The preferred poly(1,4-butylene terephthalate) ionomer resin is one obtained by polymerizing an ionomer component comprising a glycol component comprising at least 70 mole percent, preferably at least 90 mole percent, of tetramethylene glycol; and an acid component comprising about 1 to about 10 mole percent of a dimethyl 5-sodium sulfo-1,3-phenylenedicarboxylate, and at least 70 mole percent, preferably at least 90 mole percent, of terephthalic acid, and polyester-forming derivatives thereof.
The glycol component preferably comprises not more than 30 mole percent, more preferably not more than 20 mole percent, of another glycol, such as ethylene glycol, trimethylene glycol, 2-methyl-1,3-propane glycol, hexamethylene glycol, decamethylene glycol, cyclohexane dimethanol, or neopentylene glycol.
The acid component preferably comprises not more than 30 mole percent, preferably not more than 20 mole percent, of another acid such as isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 4,4xe2x80x2-diphenyldicarboxylic acid, 4,4xe2x80x2-diphenoxyethane dicarboxylic acid, p-hydroxy benzoic acid, sebacic acid, adipic acid and polyester-forming derivatives thereof.
It is also possible to use a branched polyester ionomer comprising a branching agent, for example, a glycol having three or more hydroxyl groups or an aromatic carboxylic acid having three or more carboxylic acid groups. Furthermore, it is sometimes desirable to have various concentrations of acid and hydroxyl end groups on the polyester, depending on the ultimate end-use of the composition.
In some instances, it is desirable to reduce the number of acid end groups, typically to less than about 30 micro equivalents per gram, with the use of acid reactive species. In other instances, it is desirable that the polyester has a relatively high carboxylic end group concentration.
Preferred polyester ionomers will possess sufficient thermal stability to withstand compounding temperatures of at least about 250xc2x0 C., preferably at least about 275xc2x0 C., more preferably at least about 300xc2x0 C.
Blends of polyesters ionomers with non sulfonate salt polyesters may also be employed as the polyester ionomer composition. For example, a blend of a sulfonate salt PBT and the unmodified PBT resin may be used. Preferred non sulfonate salt polyesters are the alkylene phthalate polyesters. It is preferred that the sulfonate salt polyester be present in an amount greater than or equal to the amount of the non sulfonate salt polyester.
A useful amount of polyester ionomer is about 0.01 to about 15 weight percent, with about 1 to about 10 weight percent preferred, and about 2 to about 8 weight percent especially preferred, wherein the weight percentages are based on the total weight of the composition.
The composition optionally comprises an impact modifier. All impact modifiers as generally used for compositions comprising a poly(arylene ether), a polyamide, or a combination of a poly(arylene ether) and a polyamide can be used. Particularly suitable are the so called block copolymers, for example, Axe2x80x94Bxe2x80x94A triblock copolymers and Axe2x80x94B diblock copolymers. The Axe2x80x94B and Axe2x80x94Bxe2x80x94A type block copolymer rubber additives which may be used are thermoplastic rubbers comprising one or two alkenyl aromatic blocks which are typically styrene blocks and a rubber block, e.g., a butadiene block which may be partially hydrogenated. Mixtures of these triblock copolymers and diblock copolymers are especially useful. In a preferred embodiment, the poly(arylene ether) phase comprises at least 50%, preferably at least 75%, more preferably at least 90%, of the block copolymer.
Suitable Axe2x80x94B and Axe2x80x94Bxe2x80x94A type block copolymers are disclosed in, for example, U.S. Pat. Nos. 3,078,254, 3,402,159, 3,297,793, 3,265,765, and 3,594,452 and U.K. Patent 1,264,741. Examples of typical species of Axe2x80x94B and Axe2x80x94Bxe2x80x94A block copolymers include polystyrene-polybutadiene, polystyrene-poly(ethylene-propylene), polystyrene-polyisoprene, poly(xcex1-methylstyrene)-polybutadiene, polystyrene-polybutadiene-polystyrene, polystyrene-poly(ethylene-propylene)-polystyrene, polystyrene-polyisoprene-polystyrene, poly(xcex1-methylstyrene)-polybutadiene-poly(xcex1-methylstyrene), polystyrene-poly(ethylene-butadiene)-polystyrene, as well as the selectively hydrogenated versions thereof, and the like.
Polystyrene-poly(ethylene-propylene) and polystyrene-poly(ethylene-butadiene)-polystyrene are presently preferred. Mixtures of the aforementioned block copolymers are also useful. Such Axe2x80x94B and Axe2x80x94Bxe2x80x94A block copolymers are available commercially from a number of sources, including Phillips Petroleum under the trademark SOLPRENE(copyright), Shell Chemical Co. under the trademark KRATON(copyright), Dexco under the trademark VECTOR(copyright), and Kuraray under the trademark SEPTON(copyright).
Other useful impact modifiers include functionalized elastomeric polyolefins such as elastomeric polyolefins comprising functional groups such as anhydride, epoxy, oxazoline, orthoester, and the like. The essential structural units of the elastomeric polyolefin are derived from ethylene and at least one C3-8 1-olefin, such as, propylene, 1-butene, 1-hexene and 1-octene. The proportions of ethylene and C3-8 1-olefin are not critical provided that they together constitute the major portion of the polymer. An example of a functionalized elastomeric polyolefin is a functionalized ethylene-propylene rubber or a functionalized ethylene-propylene-diene elastomer. The diene portion is at least one non-conjugated diene, such as ethylidene norbornene, 1,4-hexadiene, or dicyclopentadiene. These elastomeric polyolefins are known in the art as EPR and EPDM elastomers, and they are described more fully in U.S. application Ser. No. 09/064,270 filed Apr. 22, 1998, and U.S. application Ser. No. 09/307,194, filed May 7, 1999. In a preferred embodiment, the polyamide phase of the thermoplastic composition comprises at least 50%, preferably at least 75%, more preferably at least 90%, of the functionalized elastomeric polyolefin.
A useful amount of impact modifier is up to about 20 weight percent, with about 1 to about 15 weight percent preferred, and about 5 to about 12 weight percent especially preferred, wherein the weight percentages are based on the total weight of the composition. Various mixtures of the previous described impact modifiers are also useful.
The composition optionally comprises a conductive filler. The conductive filler may be any filler that enhances the conductivity of the molded composition. Suitable conductive fillers may be fibrous, disc-shaped, spherical or amorphous and include, for example, conductive carbon black; conductive carbon fibers, including milled fibers; conductive vapor grown carbon fibers, and various mixtures thereof. Other conductive fillers which can be used are metal-coated carbon fibers; metal fibers; metal disks; metal particles; metal-coated disc-shaped fillers such as metal-coated talcs, micas and kaolins; and the like. Preferred conductive fillers include carbon fibers, especially graphitic or partially graphitic vapor grown carbon fibers having diameters of about 3.5 to about 500 nanometers. Representative carbon fibers are the vapor grown carbon fibers described in, for example, U.S. Pat. Nos. 4,565,684 and 5,024,818 to Tibbetts et al.; U.S. Pat. No. 4,572,813 to Arakawa; U.S. Pat. No. 4,663,230 and U.S. Pat. No. 5,165,909 to Tennent; U.S. Pat. No. 4,816,289 to Komatsu et al.; U.S. Pat. No. 4,876,078 to Arakawa et al.; U.S. Pat. No. 5,589,152 to Tennent et al.; and U.S. Pat. No. 5,591,382 to Nahass et al. The conductive additive can be added directly into the compatibilized blend during the melt processing step or preferably, the conductive additive can be pre-dispersed into either the poly(arylene ether) resin or the polyamide resin. It is preferable to pre-disperse the conductive additive into the polyamide phase to make a concentrate of the conductive additive in the resin that will ultimately become the continuous phase. It is preferred for the conductive material to reside primarily with the polyamide phase as greater conductivity can be achieved with a smaller amount of the conductive additive. It is also possible to use more than one conductive additive concentrate in the preparation of the resin composition. In a preferred embodiment, carbon fibers are introduced to the composition as a so-called masterbatch in polyamide. The masterbatch may comprise about 1 to about 40 weight percent carbon fibers, with the balance being polyamide. A suitable amount of conductive filler is an amount that reduces the specific volume resistivity of the molded composition to less than about 105 Ohm-centimeters, preferably less than about 104 Ohm-centimeters, more preferably about 103 to about 104 Ohm-centimeters.
The composition of the present invention may include additional components which do not interfere with the previously mentioned desirable properties but enhance other favorable properties such as antioxidants, lubricants, mold release materials, colorants, nucleating agents, and ultraviolet (UV) stabilizers.
The compositions of present invention additionally comprise an amount of a stabilizer package effective to enhance the morphological stability of the poly(arylene ether)/polyamide blend wherein the stabilizer package comprises at least one phenolic species in combination with at one thioester species, at least one one organo-phosphite species, or at least one thioester species in combination with at least one organo-phosphite species. An effective amount is an amount that affords an increase in the average PPE-phase particle size in a molded PPE/nylon blend containing a polyester ionomer of less than 300%, preferably less than about 200% and most preferably less than about 150% when the poly(arylene ether)/polyamide blend containing a polyester ionomer is subjected to 300xc2x0 C. for five minutes, wherein the particle size increase is calculated as the difference between the average PPE-phase particle size obtained after subjecting a sample to 300xc2x0 C. for five minutes and the average PPE-phase particle size before subjecting a sample of the same composition to the heat exposure and dividing this difference by the average PPE-phase particle size of the sample before the heat exposure and multiplying the result by 100.
An effective amount is usually from about 0.01 to about 5% by weight, preferably from about 0.025 to about 3% by weight, and especially from about 0.05% to about 2% by weight, wherein all weights are based on the total weight of the composition. The weight ratios of the various species can vary widely based on the actual structure of the species, its molecular weight and effectiveness. Generally, the weight ratio of the phenolic species to the thioester species, the organo-phosphite species, or combination of thiospecies and organo-phosphite species, is between about 0.1 to about 1 to about 1 to about 0.1.
The phenolic species useful in the instant compositions embrace a large family of compounds examples of which are given below.
Simple 2,6-dialkylphenol, such as, for example, 2,6-di-tert.-butyl-4-methylphenol, 2-tert.-butyl-4,6-di-methylphenol, 2,6-di-tert.-butyl-4-methoxymethylphenol 2,6-dioctadecyl-4-methylphenol and 2,6-di-tert-butylphenol. Vitamin E and derivatives of vitamin E are also useful phenolic antioxidants.
Derivatives of alkylated hydroquinones, such as for example, 2,5-di-tert.-butyl-hydroquinone, 2,5-di-tert.-amylhydroquinone, 2,6-di-tert.-butyl-hydroquinone, 2,5-di-tert.-butyl-4-hydroxy-anisole, 3,5-di-tert.-butyl-4-hydroxy-anisole, tris-(3,5-di-tert.-butyl-4-hydroxyphenyl) phosphite, 3,5-di-tert.-butyl-4-hydroxyphenyl stearate and bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
Hydroxylated thiodiphenyl ethers, such as, for example, 2,2xe2x80x2-thio-bis-(6-tert.-butyl-4-methylphenol), 2,2xe2x80x2-thio-bis-(4-octylphenol), 4,4xe2x80x2-thio-bis-(6-tert.-butyl-3-methylphenol), 4,4xe2x80x2-thio-bis-(3,6-di-sec.-amylphenol), 4,4xe2x80x2-thio-bis-(6-tert.-butyl-2-methylphenol) and 4,4xe2x80x2-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.
Alkylidene-bisphenols, such as, for example, 2,2xe2x80x2-methylene-bis-(6-tert.-butyl-4-methylphenol), 2,2xe2x80x2-methylene-bis-(6-tert.-butyl-4-ethylphenol), 4,4xe2x80x2-methylene-bis-(6-tert.-butyl-2-methylphenol), 4,4xe2x80x2-methylene-bis-(2,6-di-tert.-butylphenol), 2,6-di(3,-tert.-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 2,2xe2x80x2-methylene-bis- greater than 4-methyl-6-(alpha-methylcyclohexyl)-phenol!, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-butane, 1,1-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propane, 1,1,3-tris-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane 1,1,5,5-tetra-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-pentane and ethylene glycol bis- greater than 3,3-bis-(3-tert.-butyl-4-hydroxyphenyl)-butyrate.
Oxe2x80x94, Nxe2x80x94 and S-benzyl compounds, such as, for example, 3,5,3xe2x80x2,5xe2x80x2-tetra-tert.-butyl-4,4xe2x80x2-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-amine and bis-(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate.
Hydroxybenzylated malonates, such as for example, dioctadecyl 2,2-bis-(3,5-di-tert.-butyl-2-hydroxybenzyl)-malonate, dioctadecyl 2-(3-tert.-butyl-4-hydroxy-5-methylbenzyl)-malonate, di-dodecylmercapto-ethyl 2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonate and di- greater than 4-(1, 1 ,3,3-tetramethylbutyl)-phenyl!2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonate.
Hydroxybenzyl-aromatic compounds, such as, for example, 1,3,5-tri-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-di-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene and 2,4,6-tri(3,5-di-tert.-butyl-4-hydroxybenzyl)-phenol.
s-Triazine compounds, such as, for example, 2,4-bisoctylmercapto-6-(3,5-di-tert.-butyl-hydroxl-anilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxy anilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-s-triazine, 1,3,5-tris-(2,6-di-methyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate and 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)isocyanurate.
Amides of beta-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid, such as, for example, 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-tria zine and N,Nxe2x80x2-di(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexamethylenediamine N,Nxe2x80x2-bis-beta-(3,5-di-t-butyl-4-hydroxyphenyl)-propionylhydrazine.
Esters of beta-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols, such as, for example with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, triethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-2.2.2-octane.
Esters of beta-(5-tert.-butyl-4-hydroxyl-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, triethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-2.2.2-octane.
Esters of 3,5-di-tert.-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, such as for example, with methanol, ethanol, octadecanol, 1,6-hexandiol, 1,9-nonanediol, ethylene glycol, 1,2-propenediol, diethylene glycol, thio-diethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-2.2.2-octane, especially the tetrakis ester of pentaerythritol.
Benzylphosphonates, such as, for example, dimethyl 3,5-di-tert.-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert.-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert.-butyl-4-hydroxybenzylphosphonate and dioctadecyl-5-tert.-butyl-4-hydroxy-3-methylbenzylphosphonate.
Phenolic species of particular interest are selected from the group consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2xe2x80x2-ethylidene-bis(4,6-di-tert-butylphenol), 1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocyanurate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris greater than 2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl-isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis(3,5-di-tert-butyl-4-hyroxyhydrocinnamate), 1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, N, Nxe2x80x2-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis)3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate!, octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and N,Nxe2x80x2-bis- greater than 2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl!-oxamide.
A most preferred embodiment has as the phenolic species, neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2xe2x80x2-ethylidene-bis(4,6-di-tert-butylphenol).
When the instant compositions contains an organo-phosphite species, such species may be, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyidialkyl phosphites, tri-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, di(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphospha-5.5-undecane, and tri-(4-hydroxy-3,5-di-tert.butylphenyl) phosphite, and/or similar phosphonites.
In a preferred embodiment, the organo-phosphite species include those selected from the group consisting of tris(2,4-di-tert-butylphenyl) phosphite, 3,9-di(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphospha greater than 5.5!undecane, tris(p-nonylphenyl) phosphite, 3,9-distearyloxy-2,4,8,10-tetraoxa-3,9-diphospha greater than 5.5!undecane, dilauryl phosphite, 3,9-di greater than 2,6-di-tert-butyl-4-(2-(n-octadecyloxycarbonyl)ethyl)-phenoxy!-2,4,8,10-tetraoxa-3,9-diphospha-5.5-undecane and tetrakis(2,-4-di-tert-butylphenyl) 4,4xe2x80x2-bis(diphenylene)phosphonite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, and tetrakis(2,4-di-tert-butylphenyl)4,4xe2x80x2-biphenylene diphosphonite. Tris(2,4-di-tert-butylphenyl) phosphite, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite are especially preferred, as well as mixtures of organo-phosphites containing at least one of the foregoing organo-phosphite species.
When the instant compositions contain a thioester species, such species may be, for example, dilauryl thiodipropionate, distearyl thiodipropionate or neopentanetetrayl tetrakis(3-dodecylthiopropionate), as well as mixture comprising at least one of these.
The instant stabilizers may readily be incorporated into the polymeric resins by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom. For example, the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer.
It is often desirous to utilize a metal salt in the compositions of the present invention. Such salts are generally known in the art as exemplified in U.S. Pat. No. 4,857,575 to van der Meer et al. and may be represented by the general formula:
M+Y(Xxe2x88x92Z)n
where M represents a metal ion such as copper, nickel, tin, cerium etc. X represents a negatively charged ion, preferably a halide such as Cl, Br, F, I; or a carboxylate such as stearate or acetate; n represents an integer of 1 to about 6, y is an integer representing the positive ionic charge of the metal ion whereas z is an integer representing the negative ionic charge of X.
Among the suitable metal salts suitable for use in the present invention are CuCl2, Cul, copper acetate and cerium stearate, all of which are commercially available from a variety of sources. Of these, Cul is preferred and is often used in combination with an additional halide source, e.g., KI. Cul may be obtained commercially or may be prepared by precipitation and isolation of the salt by reaction of copper metal and HI.
The metal halide salt will be utilized in amounts necessary to provide effective stabilization. Ordinarily at least 0.001 parts by weight of the metal halide will be necessary per 100 parts by weight of the PPE-polyamide base resin. More than about 0.5 parts metal halide per 100 parts PPE-polyamide resin will not typically afford sufficient additional benefit to justify its use at such levels. It has been found that metal salts were effective at levels as low as 200 ppm for stabilization of PPE-polyamide blends of the present invention. It is also possible to provide in situ generation of a metal halide by utilizing a metal carboyxlate such as cerium stearate in the presence of a halide source such as KI.
The preparation of the compositions of the present invention is normally achieved by merely blending the ingredients under conditions for the formation of an intimate blend. Such conditions often include mixing in single or twin screw type extruders or similar mixing devices that can apply a shear to the components.
All of the ingredients may be added initially to the processing system. Alternatively, certain additives may be precompounded with one or more of the primary components, preferably the poly(arylene ether), impact modifier and the polyamide. It appears that certain physical properties are improved if the polyester ionomer is added downstream of the polyamide addition. For example, the polyester ionomer may be added in a third extruder port downstream of the first extruder port (where the poly(arylene ether), the compatibilizing agent, optionally, the impact modifier, and, optionally, a portion of the polyamide are added) and the second extruder port (where all or the remainder of the polyamide is added). Alternatively, the polyester ionomer may be added as a so-called pellet blend immediately prior to injection molding. While separate extruders may be used in the processing, the compositions are preferably prepared by using a single extruder having multiple feed ports along its length to accommodate the addition of the various components. It is often advantageous to apply a vacuum or atmospheric vent to the melt through at least one or more vent ports in the extruder to remove volatile impurities in the composition. Those of ordinary skill in the art will be able to adjust blending times and temperatures, as well as component addition, without undue additional experimentation.
The blends of this invention can be processed by various techniques including injection molding, blow molding, extrusion into sheet, film or profiles, compression molding and the like. They can also be formed into a variety of articles for use in, for example, electrical connectors, electrical devices, computers, building and construction, outdoor equipment, trucks and automobiles.

Thermoplastic blend comprising poly(arylene ether) and polyamide


A comparator compares a first input voltage and a second input voltage to generate a comparative output depending on a result of the comparison. The comparator includes a first input terminal configured to receive the first input voltage, a second input terminal configured to receive the second input voltage, a differential pair including a first input transistor whose control terminal is connected with the first input terminal and a second input transistor whose control terminal is connected with the second input terminal, a tail current source configured to supply a tail current to the differential pair, and a load circuit connected to the first input transistor and the second input transistor, and the tail current source increases the tail current, as the first input voltage approaches the second input voltage, depending on the first input voltage.

A voltage comparator (hereinafter, simply a comparator) is used to compare two voltages to determine a magnitude relationship therebetween. FIG. 1 is a circuit diagram showing a configuration of an oscillator 10 using the comparator. The oscillator 10 includes a capacitor C1, a discharging switch SW1, a comparator 100r, a logic circuit 12, a current mirror circuit CM1, and a constant current source CS1.
One end of the capacitor C1 is grounded. The constant current source CS1 generates a predetermined reference current IREF. The current mirror circuit CM1 generates a charging current ICHG by multiplying the reference current IREF by a predetermined coefficient and supplies it to the capacitor C1. The discharging switch SW1 is provided in parallel with the capacitor C1.
The comparator 100r compares a ramp voltage VRAMP generated at the capacitor C1 and a predetermined peak voltage VPEAK to generate a comparative output CMP_OUT which is asserted (low level) when VRAMP>VPEAK. The logic circuit 12 generates a discharging signal CDIS which is asserted (high level) during a predetermined discharging period TDIS after the comparative output CMP_OUT is asserted, and outputs it to a control terminal (gate) of the discharging switch SW1 which is an N-channel MOSFET (Metal Oxide Semiconductor Field Effect Transistor).
FIG. 2 shows waveform diagrams indicating operations of the oscillator 10 in FIG. 1, Prior to time t0, the discharging signal CDIS is asserted to turn on the discharging switch SW1. During this period, the ramp voltage VRAMP is 0 V. When the discharging signal CDIS is negated at time t0, the discharging switch SW1 is turned off, and the ramp voltage VRAMP increases with a constant gradient over time according to an equation (1).VRAMP=t×ICHG/C1  (1)
The discharging signal CDIS is asserted during the discharging period TDIS after the ramp voltage VRAMP reaches the peak voltage VPEAK at time t1, and negated again at time t2. The oscillator 10 repeats the operation performed during time t0 to time t2.
If the comparator 100r has an infinite response speed (i.e., zero delay), a cycle (TOSC) of the oscillator 10 is given by a sum of a slope period TSLOPE and the discharging period TDIS, as indicated in equations (2) and (3).TOSC=TSLOPE+TDIS  (2)TSLOPE=C1×VPEAK/ICHG  (3)
However, since the actual comparator 100r has a finite response speed, a delay τ occurs from when the VRAMP reaches the VPEAK until the comparative output CMP_OUT is asserted. In FIG. 2, waveforms when there is the delay τ are shown in broken lines. The delay τ is preferable to be as short as possible, since it affects the cycle of the oscillator 10.
Generally, it is necessary to increase an operating current (bias current) of the comparator 100r in order to accelerate its response speed. In particular, it is possible to reduce the delay τ by increasing a tail current of a differential amplifier provided on an initial stage or the bias current in an output stage of the comparator 100r. However, from a viewpoint of energy saving requirements for electronic apparatus in recent years, it is not preferable to conventionally increase the operating current of the comparator 100r.

Comparator, oscillator using the same, dc/dc converter, control circuit thereof, and electronic apparatus


A variable diameter wheel comprises a central hub, a peripheral band formed by a plurality of arcuate segments, each one of the arcuate segments being linked to the hub, wherein the hub comprises radial guide means for sliding retractable radial arms, each one of the retractable radial arms being secured to the distal end thereof of one of the arcuate segments, the opposing end being provided with a connection member with a mobile plate coaxial with the hub and in relative rotation with respect to the hub, the mobile plate having curved guide areas, each one of the connection members cooperating with one of the arms in order to control the linear and radial movement of the proximal end of the corresponding arm.

The present invention relates to the field of variable diameter wheels enabling to produce a tyre tread or drive belt of variable length. Such wheels have multiple applications:
Transport equipment, where the variation in wheel diameter enables the wheel to be adapted to variable ground types
Individual equipment such as wheelchairs, city bicycles, etc., where reducing the diameter enables to reduce volume outside of usage periods
Belt drive disc, where the variation in diameter of a pair of wheels enables to modify the characteristics of a transmission
Suitcase with wheels, where the variation in diameter of the wheels enables an adaptation to the ground type whereon the suitcase is moved
Children's pushchairs, also enabling one to adapt the diameter of the wheels to the ground type.
Of course, these are simple examples of applications of such variable diameter wheels.
In the state of the art GB498623, a device intended to equip a fixed section wheel that has retractable clamps is known. This device is coaxial with a fixed size wheel and enables to improve adhesion on wet ground. These clamps are formed by retractable arms, each having a distal end forming tips which sink into soft ground.
Also, patent GB251256 defining a wheel having constant radius bandage sections which are adjustable by tangential connection parts, to facilitate the replacement of the tyre tread, is known.
Also, European patent EP0665128 defining an exterior variable diameter wheel is known. This diameter wheel comprises a tube having four holes penetrating on the cylindrical wall thereof, a seal having diaphragms corresponding to the penetration holes is assembled on the tube. Sliders are pushed and moved in the radial orifices, such that the exterior diameter of the wheel is increased by injecting compressed air from a hole arranged on an axis of an axle through the membranes. When the compressed air is used up, the exterior diameter of the wheel decreases and returns to the original size.
The solutions of the prior art implement relatively complex mechanisms inside the wheel, which makes them fragile and not very suitable for achieving small sizes like suitcase wheels.
Moreover, the number of mobile parts to ensure the variation in diameter reduces the efforts and the torque which can be transmitted by the hub to the wheel rim and causes rapid wear and tear to be produced from the unit, which can damage the lifespan and the functioning of the wheel.
Finally, the solution proposed by patent GB498623 necessarily connects a tyre tread with a constant diameter to retractable clamps improving the adhesion when the ground is soft. The diameter of the wheel itself is not variable.


A device and method is provided for separating heavier and lighter fractions of a fluid sample. The device includes a plurality of constituents. The constituents include a container, a liner in the container and a composite element in the liner for separating the fractions of a fluid sample. The separator comprises a specific density at a target density range as defined by separable fluid components densities. A fluid sample is delivered to the liner and then the device is subjected to centrifugation whereby the centrifugal load causes the liner to deform and the composite element migrates into the fluid sample and stabilizes between the heavier and lighter fractions of the fluid sample. The liner will resiliently return to its initial configuration upon termination of the centrifugal load such that the liner sealingly engages the composite element and separates the heavier and lighter fractions of the fluid sample.

1. Field of the Invention
This invention relates to a device and method for separating heavier and lighter fractions of a fluid sample. More particularly, this invention relates to a device and method for collecting and transporting fluid samples whereby the device and fluid sample are subjected to centrifugation to cause separation of the heavier fraction from the lighter fraction of the fluid sample.
2. Description of Related Art
Diagnostic tests may require separation of a patient""s whole blood sample into components, such as serum or plasma, the lighter phase component, and red blood cells, the heavier phase component. Samples of whole blood are typically collected by venipuncture through a cannula or needle attached to a syringe or an evacuated collection tube. Separation of the blood into serum or plasma and red blood cells is then accomplished by rotation of the syringe or tube in a centrifuge. Such arrangements use a barrier for moving into an area adjacent the two phases of the sample being separated to maintain the components separated for subsequent examination of the individual components.
A variety of devices have been used in collection devices to divide the area between the heavier and lighter phases of a fluid sample.
The most widely used device includes thixotropic gel materials such as polyester gels in a tube. The present polyester gel serum separation tubes require special manufacturing equipment to prepare the gel and to fill the tubes. Moreover, the shelf-life of the product is limited in that overtime globules may be released from the gel mass. These globules have a specific gravity that is less than the separated serum and may float in the serum and may clog the measuring instruments, such as the instrument probes used during the clinical examination of the sample collected in the tube. Such clogging can lead to considerable downtime for the instrument to remove the clog.
No commercially available gel is completely chemically inert to all analytes. If certain drugs are present in the blood sample when it is taken, there can be an adverse chemical reaction with the gel interface.
Therefore, a need exists for a separator device that (i) is easily used to separate a blood sample; (ii) is independent of temperature during storage and shipping; (iii) is stable to radiation sterilization; (iv) employs the benefits of a thixotropic gel barrier yet avoids the many disadvantages of placing a gel in contact with the separated blood components; (v) minimizes cross contamination of the heavier and lighter phases of the sample during centrifugation; (vi) minimizes adhesion of the lower and higher density materials against the separator device; (vii) can be used with standard sampling equipment; (viii) is able to move into position to form a barrier in less time than conventional methods and devices; and (ix) is able to provide a clearer specimen with less cell contamination than conventional methods and devices.
The present invention is a method and assembly for separating a fluid sample into a higher specific gravity phase and a lower specific gravity phase. Desirably, the assembly comprises a plurality of constituents. Preferably, the assembly of the present invention comprises a container, a liner and a composite element.
Most preferably, the container is a tube that comprises an open end, a closed end and a sidewall extending between the open end and the closed end. The sidewall comprises an outer surface and an inner surface. The tube further comprises a closure disposed to fit in the open end of the tube with a resealable septum. Alternatively, both ends of the tube may be open, and both ends of the tube may be sealed by elastomeric closures. At least one of the closures of the tube may include a resealable septum.
Most preferably, the liner comprises an open end, a closed end and a sidewall extending between the open end and the closed end. The sidewall comprises an outer surface and an inner surface. The liner is most preferably a thin wall elastomeric material. The liner is positioned in the tube such that the open end of the liner is attached to the inner surface of the tube at the open end and the closed end of the liner is near the closed end of the tube. The liner, in an unbiased condition, is cross-sectionally dimensioned along most of its length to lie in spaced relationship to the tube.
Preferably, the flexible liner comprises a qualitative stiffness that may be characterized by a non-dimensional stiffness coefficient, S* and expressed as follows:       S    *    =            E                    xe2x80x83                          (                  OD          -          D                )                    a                    xe2x80x83                          ρ        w                          D        2
Where E is the modulus of elasticity, OD is the thickness defined by the outside diameter, D is the seal diameter, a is the applied acceleration and xcfx81w is the density of water. The stiffness coefficient is about 0.003 to about 190.
Preferably, the liner has a thickness of about 1.0 mm to about 2.5 mm, a modulus of elasticity of about 13.8 MPa to about 69 MPa.
Preferably, the liner deforms due to hydrostatic pressure under applied acceleration and returns to its initial state upon removal of the acceleration, thereby forming a seal by constricting on a relatively rigid floating member which is positioned in a target density region between the higher density portion and the lower density portion of a fluid sample.
Desirably, the liner may be comprised of any natural or synthetic elastomer or mixture thereof, that are inert to the fluid sample of interest.
Preferably, the composite element is a seal body. The seal body may be a single constituent or a plurality of constituents and comprises a specific density at a target density range as defined by separable fluid components densities.
Desirably, the seal body is a substantially rigid moldable thermoplastic material such as polyvinyl chloride, polystyrene, polyethylene, polypropylene, polyester, marble and mixtures thereof that are inert to the fluid sample of interest.
Preferably, the seal body has an overall density between the densities of two phases of a blood sample.
Preferably, the seal body comprises an overall specific gravity at a target specific gravity of "sgr"t. The target specific gravity is that required to separate a fluid sample into two phases.
Most preferably, the seal body comprises at least one region of a specific gravity However, it is within the purview of the present invention that the seal plug may comprise at least two regions of differing specific gravities whereby at least one of the regions is higher than the target specific gravity and at least one of the regions is lower than the target specific gravity.
Preferably, the seal body may migrate freely when under an applied acceleration to settle at a location in the fluid sample in the target density region and thereby become a barrier at a desired level between the components of the fluid sample after the acceleration is removed.
Preferably, the seal body has an aggregate specific gravity of about 1.028 to about 1.09. Most preferably, the seal body has an aggregate specific gravity so that it will rest after centrifugal force, between the heavier and lighter phases of a blood sample.
Preferably, the seal body is initially secured to the bottom area of the liner by an interference fit until the assembly is subjected to centrifugation. When the assembly is subjected to centrifugation the seal body is released from the bottom of the liner. However, it is within the purview of the invention that the seal body may start at any location in the liner.
Preferably, the assembly of the present invention will function under load created by an applied acceleration of about 300 g to about 3000 g.
In use, a fluid sample enters the assembly by a needle. The needle penetrates the closure through the elastomeric septum and the sample enters the assembly through the needle and into the body of the liner. The needle is withdrawn from the assembly and the septum of the closure reseals.
The assembly is then subjected to centrifugation. Under centrifugation, forces exerted by the centrifuge cause the liner to expand outwardly against the tube, eliminating the interference fit with the seal body and the seal body migrates axially up the liner towards the open end. Therefore, a path is developed between the inner surface of the liner and the seal body that permits the flow of the high-density component past the seal body as it migrates up the liner. The centrifuge may be stopped after the seal body reaches the position between the lower density liquid component and higher density cellular/solid components, equal to its overall density. Upon terminating centrifugation, the liner resiliently returns to its undeformed shape, whereby the seal body seals against the inner wall of the liner, thereby creating a barrier between the higher and lower density components of the fluid. As a result, the phases of the fluid sample are isolated from one another by the seal body and may be separated for subsequent analysis.
The seal body""s position at the bottom of the liner provides easy direct loading of the fluid sample into the liner. Thus, the fluid sample is easily delivered into the liner without any interference or disturbance.
When the fluid sample is blood, the higher specific gravity portion that contains the cellular components is between the seal body and the bottom of the liner after centrifugation. The lower specific gravity portion that contains the cell free serum fraction is between the seal body and the top of the liner. At the final position of the seal body, the seal body is able to substantially eliminate the presence of red blood cells on the seal body in the lower specific gravity portion and the lower specific gravity portion is substantially free of cellular contamination.
The assembly of the present invention is advantageous over existing separation products that use gel. In particular, the assembly of the present invention will not interfere with analytes as compared to gels that may interfere with analytes. Another attribute of the present invention is that the assembly of the present invention will not interfere with therapeutic drug monitoring analytes.
Most notably, is that the time to separate a fluid sample into separate densities is achieved in substantially less time with the assembly of the present invention as compared to assemblies that use gel.
Another notable advantage of the present invention is that fluid specimens are not subjected to low density gel residuals that are at times available in products that use gel.
A further attribute of the present invention is that there is no interference with instrument probes.
Another attribute of the present invention is that samples for blood banking tests are more acceptable than when a gel separator is used.
Another attribute of the present invention is that only the substantially cell-free serum or plasma fraction of a blood sample is exposed to the top surface of the seal body, thus providing practitioners with a clean sample.
Additionally, the assembly of the present invention does not require any additional steps or treatment by a medical practitioner, whereby a blood or fluid sample is drawn in the standard fashion, using standard sampling equipment.

Device for separating components of a fluid sample


A midsole of a shoe has a low elastic part 20, a high elastic part 22 and an inclined surface 24. The low elastic part 20 and the high elastic part 22 include air bubbles. An ethylene-vinyl acetate copolymer (EVA) is used as a base polymer in the low elastic part 20 and the high elastic part 22. The inclined surface 24 is inclined upward from the inside to the outside. The low elastic part 20 is located to the inside of the inclined surface 24. The high elastic part 22 is located to the outside of the inclined surface 24. An inner high elastic part 26 is located to the inside of a low elastic part 20. The thickness of the low elastic part 20 becomes gradually larger from the outside to the inside along the inclined surface 24. The thickness of the high elastic part 22 becomes gradually larger from the inside to the outside along the inclined surface 24. The width Wa of the inclined surface 24 in left and right direction is 5 mm or more and 100 mm or less.

1. Field of the Invention
The present invention relates to shoes suitable for golf, tennis, squash, field hockey, basketball, aerobic exercise or the like.
2. Description of the Related Art
A shoe comprises an outsole, midsole, insole, upper or the like. A midsole comprises a polymer form including air bubbles. As a base polymer, ethylene-vinyl acetate copolymer (EVA) is used for a normal midsole. A midsole contributes to shock absorbability. JP-U-H2-134003 discloses a shoe comprising a multilayer-structured midsole and being superior in shock absorbability and traction.
When hitting a golf ball, a golf player sets an address such that a line connecting the right and the left is almost parallel with a the hitting direction. At the address, the head of a golf club is positioned close to the golf ball. The golf player starts the take-back, pulls the golf club head backward and then swings the golf club upward. The highest position of the head swung upward is referred to as the "top position". From the top position, the down swing is started and the golf club head is swung downward so that the head impacts the golf ball. After the impact, the golf player swings the right-handed golf club leftward, then follows and finally finishes.
From the top position to the finish, the golf player turns the body by setting the left foot as a pivot. At the same time, the golf player kicks the ground with the right foot to transfer the force to the golf ball. In other words, a right-handed golf player uses the left foot as a pivoting foot and the right foot as a kicking foot. A left-handed golf player uses the right foot as a pivoting foot and the left foot as a kicking foot.
During the swing, the golf player kicks the ground while applying his or her own body weight to the inside of the kicking foot. The golf player receives his or her own body weight mainly on the inside of the pivoting foot. At this time, force is transferred to the ground via the shoe. A shoe suitable for a golf swing is desired.
Also in various sports, a movement in which a player's body weight is applied to the inside of a foot is observed. In tennis and squash, when a racket is swung, a player's body weight is applied to the inside of a foot. In field hockey, when a stick is swung, a player's body weight is applied to the inside of a foot. In basketball and aerobics exercise, a player's body weight is applied to the inside of a foot during both clockwise and anticlockwise body turns. In these sports, a shoe suitable for movement is desired.
The object of the present invention is to provide a shoe in which a wearer's body weight is easily applied to the inside of a foot.


An adjustable precision exception handling technique is providing for handling exceptions encountered during translation of subject code to target code at varying levels of precision, depending upon the particular type of exception encountered. As an exception signal is detected by the translator, the state of the subject processor is captured at a precision determined to be sufficient for the detected exception.

1. Technical Field
The subject invention relates generally to the field of computers and computer software and, more particularly, to program code conversion methods and apparatus useful, for example, in code translators, emulators and accelerators which encounter exception signals.
2. Description of Related Art
An exception is a condition that changes the normal flow of control in a program. An exception may be generated ("raised") by hardware or software. Hardware exceptions include such signals as resets, interrupts, or signals from a memory management unit. Exceptions may be generated by an arithmetic logic unit or floating-point unit for numerical errors such as divide-by-zero, for overflow or underflow, or for instruction decoding errors such as privileged, reserved, trap or undefined instructions. Software exceptions are varied respectively across various software programs and could be applied to any kind of error checking which alters the normal behavior of the program. An exception handler is special code which is called upon when an exception occurs during the execution of a program. If the program does not provide a handler for a given exception, a default system exception handler will be called, usually resulting in abortion of the program being run and an error indication being returned.
Exception signals are a common mechanism for raising exceptions on many operating systems. The POSIX standard, which is adhered to by many operating systems, particularly Unix-like systems, specifies how this mechanism should behave so that exception signals are broadly similar across many systems. The most common events that trigger exceptions are when a process implemented by a program tries to (i) access an unmapped memory region or (ii) manipulate a memory region for which it does not have the correct permissions. Other common events that trigger exception signals are (iii) the receipt of a signal sent from another process, (iv) the execution by a process of an instruction that the process does not have the privilege level to execute, or (v) an I/O event in the hardware.
Due to the interruption of the program being executed, the delivery of an exception signal by the operating system to an exception handler normally includes a captured state of the subject processor when the exception occurred. This state can be very difficult to determine and costly to generate. In order to avoid these costs, it is generally preferable to avoid intentionally issuing exceptions unless there are no better alternatives.
Some representative exception signals issued by operating systems to define certain events are described in Table 1.
TABLE 1Exception SignalsSignalDescriptionSIGHUP"Hangup"—commonly used to indicate to a process thatits configuration has changed, and that it should re-readits config file.SIGINT"Interrupt"—usually means Ctrl-C has been pressed by theuser.SIGILL"Illegal Instruction"—the processor generates this when aninvalid instruction opcode is encountered.SIGTRAP"Breakpoint"—often used by debuggers.SIGBUS"Bus Error"—usually generated by the processor to indicatean invalid memory access. This is usually an access to anunallocated or unaligned memory address.SIGSEGV"Segmentation Violation"—generated by the processorwhen a user process has tried to do something notpermissible in user mode. For example, trying to execute aprivileged instruction, or trying to write to part of the kernelmemory would both raise this signal.SIGALRM"Alarm Clock"—a process can make the alarm( ) systemcall, which requests the delivery of this signal n secondslater.SIGTERM"Terminate"—polite request for a program to think aboutexiting, if it's not too inconvenient.SIGQUIT"Quit"—Firm request for a program to exit, now please!SIGKILL"Die"—immediately terminates the process. This signalcannot be intercepted by a signal handler.
Exception signals can come from two sources: (1) directly from a subject program or (2) from the operating system or another process. Some exception signals are generated as a direct result of an instruction executed by the subject program. For example, if a subject program executes an illegal opcode, then SIGILL is raised. Similarly, if the subject program attempts an illegal memory access then SIGSEGV is raised. These are referred to as in-band signals. Exception signals can also be generated externally, either by the operating system or by another process. SIGHUP and SIGALRM are examples of these. These externally generated exception signals are called out-of-band signals.
From a subject program's point of view, an exception signal can occur at any time. When an exception signal occurs, the operating system interrupts the execution of the signaled program and invokes a signal handler function. The operating system maintains a process-specific function table which maps each signal to a particular signal handler. The operating system also defines default signal handlers for all exceptions. The default signal handlers either take predefined actions or simply ignore the signal.
For example, in Unix, a program can override a default signal handler by invoking the sigaction( ) system call. Sigaction( ) allows the program to specify what action the operating system should take when a particular exception signal is received. The action can be: (1) ignore the exception signal; (2) call the default signal handler; or (3) call a specialized signal handler function, whose address is provided by the program. Other options that can be specified when making the sigaction( ) call include which other signals are blocked during execution of a signal handler, in much the same way as a CPU can mask certain interrupts.
A Unix signal handler can be provided with one of two prototypes. The first signal handler prototype is "void sigHandler(int sigNum)." The first argument is the number of the exception signal, so that one function can be registered to handle multiple signals. A program can request that more information be provided to the signal handler by calling sigaction( ) with the SA_SIGINFO flag. In this case, the Unix signal handler prototype becomes "void sigHandler(int sigNum, siginfo_t sigInfo, void *context)."
The second parameter ("siginfo") is a structure which contains information about the signal, including some indication of what caused the signal and where it came from. For example, in the case of a SIGILL signal, the siginfo structure contains the address of the illegal instruction. This data can be essential to allow the process to handle the signal properly. The third parameter ("context") provides access to the processor state (including all subject registers) at the time the signal was raised. Again, this data can be essential to allow correct handling of a signal. The signal handler is allowed to modify this context; when execution is resumed, the subject registers are then restored to the values of the modified context.
In both embedded and non-embedded CPU's, one finds predominant Instruction Set Architectures (ISAs) for which large bodies of software exist that could be "accelerated" for performance, or "translated" to a myriad of capable processors that could present better cost/performance benefits, provided that they could transparently access the relevant software. One also finds dominant CPU architectures that are locked in time to their ISA, and cannot evolve in performance or market reach. Such architectures would benefit from "Synthetic CPU" co-architecture.
Program code conversion methods and apparatus facilitate such acceleration, translation and co-architecture capabilities and are addressed, for example, in the co-pending patent application, U.S. patent application Ser. No. 10/439,966, filed on May 16, 2003, entitled Block Translation Optimization for Program Code Conversion and assigned to the same assignee as the present application, the disclosure of which is hereby incorporated by reference into the present application. Exception handling is one attribute of many subject programs which may be encountered in the course of program code conversion.

Method and apparatus for performing adjustable precision exception handling

International Business Machines Corporation


Disclosed herein are packages for consumer goods that provide additional functionality as an interactive device for encouraging playful interaction with the package contents. In various embodiments, the package includes a lid or top comprising a hollow body defined by a flexible shell, wherein the shell is reversibly deformable or comprises regions that are reversibly deformable, the lid adapted for launching or propelling an item when the item is placed on the shell or on a reversibly deformable region of the shell, wherein when the shell is deformed and thereafter springs back to its undeformed shape, the springing action propels the item away from the lid. Kits and methods for using the interactive packages and particularly the interactive portions of the packages are also disclosed.

1. Field of the Invention
The invention relates generally to packages, and particularly to package components that function as interactive devices for encouraging playful interaction with the package contents.
2. Description of Related Art
Packages for consumer goods are generally useful for containing, transporting, and protecting the package contents. After most packages are opened, the package contents are used for their intended purposes, and the packages are discarded. Even packages that are designed to be reused are typically resealed to protect an unused portion of the package contents and the packages are discarded after all of the package contents have been used.
Some packages, however, attempt to serve functions other than merely containing, transporting, and protecting the contents. U.S. Pat. No. 5,334,079 discloses a toy having flexible shell for launching projectiles. U.S. Pat. No. 4,152,863 discloses a popper toy for launching items. US20110088292A1 discloses packaging that includes an illumination system and audio system that purports to make the contents more appealing to consumers. US20100136875A1 discloses packaged toys with selectors for "try-me" type packaged toys. U.S. Pat. No. 7,641,052 discloses display packaging for animated toys that facilitates demonstration of the toy's features. US20080289297A1 discloses an interactive toy package for toy vehicles that operates the toy when engaged by the consumer.
Such packages may adequately function for their intended purposes, which, in addition to containing, transporting and protecting the contents, include displaying the product at a point of sale such as a retail store. However, there is a need for new interactive packages that provide functionality after the sale and throughout the life of the package and its contents. There is, therefore, a need for packages that permit consumers or users to engage in playful activities using the package contents.

Reversibly deformable interactive package components


A user interface (132)—be it graphical (GUI) or telephony (TUI) to an application (120) is defined by stored interface and feature description documents (122,124) written in XML and JavaScript, so that the user interface and changes thereto can be effected without access to source code. Interface description documents define the appearance and the behavior of the user interface toward the user, while feature description documents define the interaction of the user interface with the interfaced-to application, both in conformity with a user-interface object model (310). Stored connector object plug-ins (126) define connector objects for rendering elements of feature description documents, and stored layout object plug-ins (128) define layout objects for rendering elements of interface description documents of one or more interfaces.

Mark-up languages are languages for defining the content and structure (layout) of electronic documents. Most of the markup languages in use today are versions of the Standard Generalized Mark-up Language (SGML), which is a meta-language (a language for describing languages) standardized by the International Standards Organization (ISO). Examples of mark-up languages include the Hyper-Text Mark-up Language (HTML) which is an electronic publishing language that is used to define pages of information on the World Wide Web, Virtual Reality Mark-up Language (VRML) which is used to deliver three-dimensional images through the Internet, and Extensible Mark-up Language (XML) which is an abbreviated and simplified version of SGML that is designed to make information self-describing, and thus make it easier to define document types and to write programs to handle them.
Mark-up languages are most often used to describe electronic documents to browsers, although other applications can be used as clients. Their use allows the documents to be changed without impacting the browser, and allows the same browser to be used with different Web sites irrespective of server technology. The same type of flexibility is desirable for user interfaces. The desire is to be able to create user interfaces that can be changed or extended, or integrated with user interfaces of different other systems, without changes to the underlying systems.
The Mozilla organization of Netscape Communications Corporation has attempted to do this for graphical interfaces by defining the XML-based User Interface Language (XUL). XUL is an application of XML; it is XML with specific meanings defined for a few element types, and into which HTML and JavaScript can be scattered. XUL is designed to be used to define and develop graphical user interfaces (GUIs) which will work on multiple platforms (cross-platform GUIs). An additional benefit of designing a GUI in XUL is that it may be easily modified or expanded (added-to). However, not all platforms have, or can have, a GUI. A prime example are platforms like voice messaging systems and interactive voice response systems that interact with users via telephones and therefore must utilize a telephony user interface (TUI) made up of DTMF (Touch-Tone) signals and/or spoken instructions. Since XUL is designed for GUIs only, XUL does not provide its benefits to these platforms.
Conversely, voice XML (VXML, XML combined with voice-recognition technology) is being used by a consortium of companies to provide a telephony user interface (TUI) to Web content. However, not all platforms have, or can have, a TUI. A prime example is conventional Web browsers, which are not voice-enabled. Since VXML is designed for TUI only, VXML does not provide its benefits to these platforms.

This patent is subject to a terminal disclaimer.

Mark-up language implementation of graphical or non-graphical user interfaces


Techniques are described for directing connections between clients and the closest web server. Authoritative DNS resolvers of a network are placed at edges of the network. Using anycast, the authoritative DNS resolvers advertise routes of their destination netblock to the Internet. A request from a client to connect to the network is routed, based upon BGP tables, to the closest particular authoritative DNS resolver. Once the request is received, a response is sent to the client with the IP address of the closest web server. The closest web server is determined through in-network health check measurements, with the authoritative DNS resolvers dynamically selecting IP addresses closest to themselves. Routing protocols that directed the packet to the closest authoritative DNS resolver also dictate the route of subsequent traffic to the network. Thus, the closest web server selected by the authoritative DNS resolver is also the closest web server to the client.

The approaches described in this section are approaches that could be pursued, but not necessarily approaches that have been previously conceived or pursued. Therefore, unless otherwise indicated, it should not be assumed that any of the approaches described in this section qualify as prior art merely by virtue of their inclusion in this section.
Global load balancing or "GLB," distributes client access to servers across a distributed set of servers. The set of servers across which client access is distributed may, for example, be servers on a wide area network such as the Internet. For the purpose of discussion, examples shall be given in which GLB is used to distribute client access across servers on the Internet. The types of servers for client access may vary widely, and includes, but is not limited to, HTTP web servers, FTP servers, SMTP (mail) servers, other standard Internet protocol servers, or servers with proprietary protocols. As used herein, the term "server" shall mean any type of server listed previously.
Many GLBs use a variety of active and passive monitoring techniques to generate a complex map of the Internet. Based upon this map, the GLB makes traffic routing decisions to connect a client to the "closest" server. As used herein, "close" does not necessarily mean basing the determination only on geographic proximity. As used herein, a "close" server is a server that results in the fastest connection to the client. Thus, if a server that was located 100 miles away were slower for the client to reach than a server located 200 miles away because of heavy network congestion, then the GLB would route the client to the server 200 miles away.
The most common form of global load balancing is based upon domain name service ("DNS") which is illustrated in FIG. 1. In the system illustrated in FIG. 1, two or more data centers, which may be located in geographically distinct areas, contain large numbers of servers capable of hosting web applications. A client 105 wishes to connect to a web application that is hosted by each of two data centers. For example, one data center that hosts the web application might be located in New York 103 and the other data center that hosts the web application might be located in San Francisco 101.
Internet service providers ("ISPs") may use a centralized local name resolver, also called a recursive DNS resolver, that resides within the ISP's network and communicates with the ISP's users to service their DNS requests. The client communicates with the local name resolver, and then the local name resolver determines where to find the information that the user requested. An authoritative DNS resolver of a domain receives the request from a local name resolver and sends the local name resolver the IP address of the domain. An authoritative DNS resolver of a domain is a server that resides within and maintains data for the network of a domain. GLB may be a part of the authoritative DNS resolver or may be separate from the authoritative DNS resolver. As used herein, the term "resolver" shall refer to the authoritative DNS resolver, with which a GLB may or may not be a part.
For example, in FIG. 1, client 105 sends a request 111 to local name resolver 107 comprising a domain name, such as "www.sampledomain.com." The local name resolver 107 asks 115 the authoritative DNS resolver 109 that is the owner of "www.sampledomain.com," for the IP address of "www.sampledomain.com." The authoritative DNS resolver (and GLB) for "www.sampledomain.com" 109 responds to the local name resolver 107 with an IP address of a data center based upon the information in the map generated by the GLB. If the GLB detects high traffic to the data center in San Francisco 101, then the GLB might send the connection to the "closer" data center in New York 103, even though geographically, the data center in New York 103 is much farther away from the client 105. The local name resolver 107 sends the IP address of the data center in New York 103 to the client 105. Then, and only then, the client 105 connects 119 to the data center in New York 103 and does not connect 117 to the data center located in San Francisco 101.
Upon changes in network topology or connectivity, such as fiber cuts, equipment problems, capacity issues, netblock migration, or human intervention, the Internet map needs to be rebuilt, often from ground up. Depending upon the protocols and algorithms used to create or update the map, this process could take a significant amount of time. Due to the dynamic nature of internet topology, the GLB may have difficulty maintaining a full, accurate model of the internet. The resulting inaccuracies in the map may lead to incorrect routing decisions, which may have severe implications for client to server performance. As a result, there is a need for techniques that provide the "closest" connection to a server that are not based upon generating and maintaining a map of the internet with DNS-based GLB.

Mapless global server load balancing of network traffic using anycast routing