A light duty liquid detergent with desirable cleansing properties and mildness to the human skin comprising at least two surfactants, an improved preservative system, and water.

This invention relates to a light duty liquid cleaning composition having an improved preservative system and the composition imparts mildness to the skin and is designed in particular for cleaning hard surfaces as well as being effective in removing grease soil and/or bath soil and in leaving unrinsed surfaces with a shiny appearance.
In recent years all-purpose liquid detergents have become widely accepted for cleaning hard surfaces, e.g., painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or tile floors, washable wall paper, etc. Such all-purpose liquids comprise clear and opaque aqueous mixtures of water-soluble organic detergents and water-soluble detergent builder salts. In order to achieve comparable cleaning efficiency with granular or powdered all-purpose cleaning compositions, use of water-soluble inorganic phosphate builder salts was favored in the prior art all-purpose liquids. For example, such early phosphate-containing compositions are described in U.S. Pat. Nos. 2,560,839; 3,234,138; 3,350,319; and British Patent No. 1,223,739.
In view of the environmentalist""s efforts to reduce phosphate levels in ground water, improved all-purpose liquids containing reduced concentrations of inorganic phosphate builder salts or non-phosphate builder salts have appeared. A particularly useful self-opacified liquid of the latter type is described in U.S. Pat. No. 4,244,840.
However, these prior art all-purpose liquid detergents containing detergent builder salts or other equivalent tend to leave films, spots or streaks on cleaned unrinsed surfaces, particularly shiny surfaces. Thus, such liquids require thorough rinsing of the cleaned surfaces which is a time-consuming chore for the user.
In order to overcome the foregoing disadvantage of the prior art all-purpose liquid, U.S. Pat. No. 4,017,409 teaches that a mixture of paraffin sulfonate and a reduced concentration of inorganic phosphate builder salt should be employed. However, such compositions are not completely acceptable from an environmental point of view based upon the phosphate content. On the other hand, another alternative to achieving phosphate-free all-purpose liquids has been to use a major proportion of a mixture of anionic and nonionic detergents with minor amounts of glycol ether solvent and organic amine as shown in U.S. Pat. No. 3,935,130. Again, this approach has not been completely satisfactory and the high levels of organic detergents necessary to achieve cleaning cause foaming which, in turn, leads to the need for thorough rinsing which has been found to be undesirable to today""s consumers.
Another approach to formulating hard surface or all-purpose liquid detergent composition where product homogeneity and clarity are important considerations involves the formation of oil-in-water (o/w) microemulsions which contain one or more surface-active detergent compounds, a water-immiscible solvent (typically a hydrocarbon solvent), water and a xe2x80x9ccosurfactantxe2x80x9d compound which provides product stability. By definition, an o/w microemulsion is a spontaneously forming colloidal dispersion of xe2x80x9coilxe2x80x9d phase particles having a particle size in the range of about 25 to about 800 xc3x85 in a continuous aqueous phase.
In view of the extremely fine particle size of the dispersed oil phase particles, microemulsions are transparent to light and are clear and usually highly stable against phase separation.
Patent disclosures relating to use of grease-removal solvents in o/w microemulsions include, for example, European Patent Applications EP 0137615 and EP 0137616xe2x80x94Herbots et al; European Patent Application EP 0160762xe2x80x94Johnston et al; and U.S. Pat. No. 4,561,991xe2x80x94Herbots et al. Each of these patent disclosures also teaches using at least 5% by weight of grease-removal solvent.
It also is known from British Patent Application GB 2144763A to Herbots et al, published Mar. 13, 1985, that magnesium salts enhance grease-removal performance of organic grease-removal solvents, such as the terpenes, in o/w microemulsion liquid detergent compositions. The compositions of this invention described by Herbots et al. require at least 5% of the mixture of grease-removal solvent and magnesium salt and preferably at least 5% of solvent (which may be a mixture of water-immiscible non-polar solvent with a sparingly soluble slightly polar solvent) and at least 0.1% magnesium salt.
However, since the amount of water immiscible and sparingly soluble components which can be present in an o/w microemulsion, with low total active ingredients without impairing the stability of the microemulsion is rather limited (for example, up to about 18% by weight of the aqueous phase), the presence of such high quantities of grease-removal solvent tend to reduce the total amount of greasy or oily soils which can be taken up by and into the microemulsion without causing phase separation.
The following representative prior art patents also relate to liquid detergent cleaning compositions in the form of o/w microemulsions: U.S. Pat. No. 4,472,291xe2x80x94Rosario; U.S. Pat. No. 4,540,448xe2x80x94Gauteer et al; U.S. Pat. No. 3,723,330xe2x80x94Sheflin; etc.
Liquid detergent compositions which include terpenes, such as d-limonene, or other grease-removal solvent, although not disclosed to be in the form of o/w microemulsions, are the subject matter of the following representative patent documents: European Patent Application 0080749; British Patent Specification 1,603,047; U.S. Pat. Nos. 4,414,128; and 4,540,505. For example, U.S. Pat. No. 4,414,128 broadly discloses an aqueous liquid detergent composition characterized by, by weight:
(a) from about 1% to about 20% of a synthetic anionic, nonionic, amphoteric or zwitterionic surfactant or mixture thereof;
(b) from about 0.5% to about 10% of a mono- or sesquiterpene or mixture thereof, at a weight ratio of (a):(b) lying in the range of 5:1 to 1:3; and
(c) from about 0.5% about 10% of a polar solvent having a solubility in water at 15xc2x0 C. in the range of from about 0.2% to about 10%. Other ingredients present in the formulations disclosed in this patent include from about 0.05% to about 2% by weight of an alkali metal, ammonium or alkanolammonium soap of a C13-C24 fatty acid; a calcium sequestrant from about 0.5% to about 13% by weight; non-aqueous solvent, e.g., alcohols and glycol ethers, up to about 10% by weight; and hydrotropes, e.g., urea, ethanolamines, salts of lower alkylaryl sulfonates, up to about 10% by weight. All of the formulations shown in the Examples of this patent include relatively large amounts of detergent builder salts which are detrimental to surface shine.
U.S. Pat. No. 5,082,584 discloses a microemulsion composition having an anionic surfactant, a cosurfactant, nonionic surfactant, perfume and water; however, these compositions are not light duty liquid compositions.
The present invention relates to a light duty liquid detergent compositions with high foaming properties, containing a nonionic surfactant, a sulfonate or sulfate surfactant, an ethoxylated alkyl ether sulfate surfactant, an inorganic magnesium salt, polyethylene glycol, an improved preservative system and water. The compositions may also optionally contain from 0 to 10% of an alkyl monoalkanol amide, an alkyl dialkanol amide, an amine oxide, a zwitterionic surfactant and/or alkyl polyglucoside surfactant.
Nonionic surfactants are in general chemically inert and stable toward pH change and are therefore well suited for mixing and formulation with other materials. The superior performance of nonionic surfactants on the removal of oily soil is well recognized. Nonionic surfactants are also known to be mild to human skin. However, as a class, nonionic surfactants are known to be low or moderate foamers. Consequently, for detergents which require copious and stable foam, the application of nonionic surfactants is limited. There have been substantial interest and efforts to develop a high foaming detergent with nonionic surfactants as the major active ingredient. Yet, little has been achieved.
The prior art is replete with light duty liquid detergent compositions containing nonionic surfactants in combination with anionic and/or betaine surfactants wherein the nonionic detergent is not the major active surfactant, as shown in U.S. Pat. No. 3,658,985 wherein an anionic based shampoo contains a minor amount of a fatty acid alkanolamide. U.S. Pat. No. 3,769,398 discloses a betaine-based shampoo containing minor amounts of nonionic surfactants. This patent states that the low foaming properties of nonionic detergents renders its use in shampoo compositions non-preferred. U.S. Pat. No. 4,329,335 also discloses a shampoo containing a betaine surfactant as the major ingredient and minor amounts of a nonionic surfactant and of a fatty acid mono- or di-ethanolamide. U.S. Pat. No. 4,259,204 discloses a shampoo comprising 0.8-20% by weight of an anionic phosphoric acid ester and one additional surfactant which may be either anionic, amphoteric, or nonionic. U.S. Pat. No. 4,329,334 discloses an anionic-amphoteric based shampoo containing a major amount of anionic surfactant and lesser amounts of a betaine and nonionic surfactants.
U.S. Pat. No. 3,935,129 discloses a liquid cleaning composition based on the alkali metal silicate content and containing five basic ingredients, namely, urea, glycerin, triethanolamine, an anionic detergent and a nonionic detergent. The silicate content determines the amount of anionic and/or nonionic detergent in the liquid cleaning composition. However, the foaming property of these detergent compositions is not discussed therein.
U.S. Pat. No. 4,129,515 discloses a heavy duty liquid detergent for laundering fabrics comprising a mixture of substantially equal amounts of anionic and nonionic surfactants, alkanolamines and magnesium salts, and, optionally, zwitterionic surfactants as suds modifiers.
U.S. Pat. No. 4,224,195 discloses an aqueous detergent composition for laundering socks or stockings comprising a specific group of nonionic detergents, namely, an ethylene oxide of a secondary alcohol, a specific group of anionic detergents, namely, a sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol, and an amphoteric surfactant which may be a betaine, wherein either the anionic or nonionic surfactant may be the major ingredient.
The prior art also discloses detergent compositions containing all nonionic surfactants as shown in U.S. Pat. Nos. 4,154,706 and 4,329,336 wherein the shampoo compositions contain a plurality of particular nonionic surfactants in order to effect desirable foaming and detersive properties despite the fact that nonionic surfactants are usually deficient in such properties.
U.S. Pat. No. 4,013,787 discloses a piperazine based polymer in conditioning and shampoo compositions which may contain all nonionic surfactant or all anionic surfactant.
U.S. Pat. No. 4,671,895 teaches a liquid detergent composition containing an alcohol sulfate surfactant, a nonionic surfactant, a paraffin sulfonate surfactant, an alkyl ether sulfate surfactant and water but fails to disclose an alkyl polysaccharide surfactant.
U.S. Pat. No. 4,450,091 discloses high viscosity shampoo compositions containing a blend of an amphoteric betaine surfactant, a polyoxybutylene polyoxyethylene nonionic detergent, an anionic surfactant, a fatty acid alkanolamide and a polyoxyalkylene glycol fatty ester. But, none of the exemplified compositions contains an active ingredient mixture wherein the nonionic detergent is present in major proportion, probably due to the low foaming properties of the polyoxybutylene polyoxyethylene nonionic detergent.
U.S. Pat. No. 4,595,526 describes a composition comprising a nonionic surfactant, a betaine surfactant, an anionic surfactant and a C12-C14 fatty acid monethanolamide foam stabilizer.
However, none of the above-cited patents discloses a liquid detergent composition containing a nonionic surfactant, an anionic or sulfate sulfonate surfactant, an ethoxylated alkyl ether sulfate surfactant, an improved preservative system, an inorganic magnesium salt, polyethylene glycol and water and optionally an alkyl monoalkanol amide such as an alkanol monoethanol amide (LMMEA), a zwitterionic surfactant, an amine oxide and/or an alkyl polyglucoside surfactant, and the composition does not contain gluconic acid, ethylene diaminetetraacetate sodium salt, 5-bromo-5-nitro-1,3dioxane, any abrasives, silicas, alkaline earth metal carbonates, alkyl glycine surfactant, cyclic imidinium surfactant, alkali metal carbonates or more than 3 wt. % of a fatty acid or its salt thereof, a nitrogenous buffer selected from the group consisting of ammonium or alkaline carbonates, quanidine derivatives, alkoxyl alkylamines, and alkyleneamines, and a grease release agent which is an ethoxylated maleic anhydride-alpha-olefin copolymer having a comblike structure with both hydrophobic and hydrophilic chains and the copolymer is characterized by the formula:
wherein n is about 5 to about 14, x is about 7 to 19, and y is of such a value as to provide a molecular weight about 10,000 to about 30,000.
This invention relates to a light duty liquid detergent composition containing at least a paraffin or a linear alkyl benzene sulfonate surfactant and at least one other surfactant selected from the group consisting of nonionic surfactants, an alkyl sulfate surfactant, an ethoxylated alkyl ether sulfate surfactants, alkyl polyglucoside surfactants, zwitterionic surfactants, amine oxide surfactants, and alkyl monoalkanol or dialkanol amide surfactants and mixtures thereof, an improved preservative system, and optionally, polyethylene glycol, a solubilising agent, a proton donating agent and/or an inorganic magnesium salt and water, wherein the composition does not contain gluconic acid, ethylene diamine tetraacetate sodium salt, 5-bromo-5-nitro-1,3dioxane, any silicas, abrasives, alkali metal carbonates, alkaline earth metal carbonates, alkyl glycine surfactant, cyclic imidinium surfactant, or more than 3 wt. % of a fatty acid or salt thereof, wherein the improved preservative system comprises a mixture of 2-bromo-2-nitropropane-1,3diol and tetrasodium iminodisuccinate and optionally some isothiazolones or 1,3-dimethylol-5,5-dimethylhydantoin.
An object of this invention is to provide a novel light duty liquid detergent with desirable high foaming and cleaning properties which is mild to the human skin and has an improved preservative system.
Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
To achieve the foregoing and other objects and in accordance with the purpose of the present invention, as embodied and broadly described herein the novel, high foaming light duty liquid detergent of this invention comprises a paraffin or a linear alkyl benzene sulfonate surfactant and at least one other surfactant, polyethylene glycol, an improved preservative system, a proton donating agent, an inorganic magnesium salt and water, wherein the composition does not contain gluconic acid, ethylene diamine tetraacetate sodium salt, 5-bromo-5-nitro-1,3dioxane, any silicas, abrasives, alkali metal carbonates, alkaline earth metal carbonates, alkyl glycine surfactant, cyclic imidinium surfactant or more than 3 wt. % of a fatty acid or salt thereof, a nitrogenous buffer selected from the group consisting of ammonium or alkaline carbonates, quanidine derivatives, alkoxyl alkylamines, and alkyleneamines, and a grease release agent which is an ethoxylated maleic anhydride-alpha-olefin copolymer having a comblike structure with both hydrophobic and hydrophilic chains and the copolymer is characterized by the formula:
wherein n is about 5 to about 14, x is about 7 to 19, and y is of such a value as to provide a molecular weight about 10,000 to about 30,000.
The light duty liquid compositions of the instant invention comprise approximately by weight:
(a) 5% to 30% of a paraffin or a linear alkyl benzene sulfonate surfactant;
(b) 0.5% to 15% of at least one other surfactant selected from the group consisting of alpha olefin sulfonate, alkyl sulfate, ethoxylated alkyl ether sulfate, alkyl polyglucoside, amine oxide, ethoxylated nonionic, ethoxylated/propoxylated nonionic, C12-C14 alkyl monoalkanol and dialkanol amide and zwitterionic surfactant and mixtures thereof;
(c) 0.001% to 0.4% of a preservative which is 2-bromo-2-nitropropane-1,3diol (Bronopol) or a mixture of bronopol with some isothiazolones or some 1,3-dimethylol-5,5-dimethylhydantoin;
(d) 0.01% to 0.3% of a preservative potentiator which is preferably a tetra sodium iminodisuccinate (IDSNa); and
(e) the balance being water.
The instant compositions do not contain any grease release agents such as choline chloride or buffering system which is a nitrogenous buffer which is ammonium or alkaline earth carbonate, guanidine derivates, alkoxylalkyl amines and alkyleneamines and the composition is pourable and not a gel and the compositions exhibit a viscosity in the range of 100 to 1000 milli Pascal.second (m Pas) as measured at 25xc2x0 C. with a Brookfield RVT viscometer.
The water soluble nonionic surfactants utilized in this invention are commercially well known and include the primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates and ethylene-oxide-propylene oxide condensates on primary alkanols, such a Plurafacs (BASF) and condensates of ethylene oxide with sorbitan fatty acid esters such as the Tweens (ICI). The nonionic synthetic organic detergents generally are the condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen or the oxygen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a water-soluble nonionic detergent. Further, the length of the polyethenoxy chain can be adjusted to achieve the desired balance between the hydrophobic and hydrophilic elements.
The nonionic detergent class includes the condensation products of a higher alcohol (e.g., an alkanol containing about 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with about 5 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide (EO), tridecanol condensed with about 6 to moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.
A preferred group of the foregoing nonionic surfactants are the Neodol ethoxylates (Shell Co.), which are higher aliphatic, primary alcohol containing about 9-15 carbon atoms, such as C9-C11 alkanol condensed with 7 to 10 moles of ethylene oxide (Neodol 91-8), C12-13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12-15 alkanol condensed with 12 moles ethylene oxide (Neodol 25-12), C14-15 alkanol condensed with 13 moles ethylene oxide (Neodol 45-13), and the like. Such ethoxamers have an HLB (hydrophobic lipophilic balance) value of about 8 to 15 and give good O/W emulsification, whereas ethoxamers with HLB values below 8 contain less than 5 ethyleneoxide groups and tend to be poor emulsifiers and poor detergents.
Additional satisfactory water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide. Examples of commercially available nonionic detergents of the foregoing type are C11-C15 secondary alkanol condensed with either 9 EO (Tergitol 15-S-9) or 12 EO (Tergitol 15-S-12) marketed by Union Carbide.
Other suitable nonionic detergents include the polyethylene oxide condensates of one mole of alkyl phenol containing from about 8 to 18 carbon atoms in a straight- or branched chain alkyl group with about 5 to 30 moles of ethylene oxide. Specific examples of alkyl phenol ethoxylates include nonyl phenol condensed with about 9.5 moles of EO per mole of nonyl phenol, dinonyl phenol condensed with about 12 moles of EO per mole of phenol, dinonyl phenol condensed with about 15 moles of EO per mole of phenol and di-isoctylphenol condensed with about 15 moles of EO per mole of phenol. Commercially available nonionic surfactants of this type include Igepal CO-630 (nonyl phenol ethoxylate) marketed by GAF Corporation.
Also among the satisfactory nonionic detergents are the water-soluble condensation products of a C8-C20 alkanol with a heteric mixture of ethylene oxide and propylene oxide wherein the weight ratio of ethylene oxide to propylene oxide is from 2.5:1 to 4:1, preferably 2.8:1 to 3.3:1, with the total of the ethylene oxide and propylene oxide (including the terminal ethanol or propanol group) being from 60-85%, preferably 70-80%, by weight. Such detergents are commercially available from BASF-Wyandotte and a particularly preferred detergent is a C10-C16 alkanol condensate with ethylene oxide and propylene oxide, the weight ratio of ethylene oxide to propylene oxide being 3:1 and the total alkoxy content being about 75% by weight.
Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-C10-C20 alkanoic acid esters having a HLB of 8 to 15 also may be employed as the nonionic detergent ingredient in the described composition. These surfactants are well known and are available from Imperial Chemical Industries under the Tween trade name. Suitable surfactants include polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate.
Other suitable water-soluble nonionic detergents are marketed under the trade name xe2x80x9cPluronics.xe2x80x9d The compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion of the molecule is of the order of 950 to 4000 and preferably 200 to 2,500. The addition of polyoxyethylene radicals to the hydrophobic portion tends to increase the solubility of the molecule as a whole so as to make the surfactant water-soluble. The molecular weight of the block polymers varies from 1,000 to 15,000 and the polyethylene oxide content may comprise 20% to 80% by weight. Preferably, these surfactants will be in liquid form and satisfactory surfactants are available as grades L 62 and L 64.
The anionic sulfonate surfactants which may be used in the detergent of this invention are water soluble and include the sodium, potassium, ammonium and ethanolammonium salts of linear C8-C16 alkyl benzene sulfonates; C10-C20 paraffin sulfonates, alpha olefin sulfonates containing about 10-24 carbon atoms and C8-C18 alkyl sulfates and mixtures thereof. The preferred anionic sulfonate surfactant is a C12-18 paraffin sulfonate.
The paraffin sulfonates may be monosulfonates or di-sulfonates and usually are mixtures thereof, obtained by sulfonating paraffins of 10 to 20 carbon atoms. Preferred paraffin sulfonates are those of C12-18 carbon atoms chains, and more preferably they are of C14-17 chains. Paraffin sulfonates that have the sulfonate group(s) distributed along the paraffin chain are described in U.S. Pat. Nos. 2,503,280; 2,507,088; 3,260,744; and 3,372,188; and also in German Patent 735,096. Such compounds may be made to specifications and desirably the content of paraffin sulfonates outside the C14-17 range will be minor and will be minimized, as will be any contents of di- or poly-sulfonates.
Examples of suitable other sulfonated anionic detergents are the well known higher alkyl mononuclear aromatic sulfonates, such as the higher alkylbenzene sulfonates containing 9 to 18 or preferably 9 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, or C8-15 alkyl toluene sulfonates. A preferred alkylbenzene sulfonate is a linear alkylbenzene sulfonate having a higher content of 3-phenyl (or higher) isomers and a correspondingly lower content (well below 50%) of 2-phenyl (or lower) isomers, such as those sulfonates wherein the benzene ring is attached mostly at the 3 or higher (for example 4, 5, 6 or 7) position of the alkyl group and the content of the isomers in which the benzene ring is attached in the 2 or 1 position is correspondingly low. Preferred materials are set forth in U.S. Pat. No. 3,320,174, especially those in which the alkyls are of 10 to 13 carbon atoms.
The C8-18 ethoxylated alkyl ether sulfate surfactants have the structure
Rxe2x80x94(OCH2CH2)nOSOxe2x88x923M+
wherein n is about 1 to about 22 more preferably 1 to 3 and R is an alkyl group having about 8 to about 18 carbon atoms, more preferably 12 to 15 and natural cuts, for example, C12-14 or C12-16 and M is an ammonium cation or a metal cation, most preferably sodium. The ethoxylated alkyl ether sulfate is present in the composition at a concentration of about 2.0 to about 5.0 wt. %, more preferably about 2.5% to 4.5 wt. %.
The ethoxylated alkyl ether sulfate may be made by sulfating the condensation product of ethylene oxide and C8-10 alkanol, and neutralizing the resultant product. The ethoxylated alkyl ether sulfates differ from one another in the number of carbon atoms in the alcohols and in the number of moles of ethylene oxide reacted with one mole of such alcohol. Preferred ethoxylated alkyl ether polyethenoxy sulfates contain 12 to 15 carbon atoms in the alcohols and in the alkyl groups thereof, e.g., sodium myristyl (3 EO) sulfate.
The alpha olefin sulfonates, include long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. These alpha olefin sulfonate surfactants may be prepared in a known manner by the reaction of sulfur trioxide (SO3) with long-chain olefins containing 8 to 25, preferably 12 to 21 carbon atoms and having the formula RCHxe2x95x90CHR1 where R is a higher alkyl group of 6 to 23 carbons and R1 is an alkyl group of 1 to 17 carbons or hydrogen to form a mixture of sultones and alkene sulfonic acids which is then treated to convert the sultones to sulfonates. Preferred alpha olefin sulfonates contain from 14 to 16 carbon atoms in the R alkyl group and are obtained by sulfonating an a-olefin.
The alkyl polysaccharides surfactants have a hydrophobic group containing from about 8 to about 20 carbon atoms, preferably from about 10 to about 16 carbon atoms, most preferably from about 12 to about 14 carbon atoms, and polysaccharide hydrophilic group containing from about 1.5 to about 10, preferably from about 1.5 to about 4, most preferably from about 1.6 to about 2.7 saccharide units (e.g., galactoside, glucoside, fructoside, glucosyl, fructosyl; and/or galactosyl units). Mixtures of saccharide moieties may be used in the alkyl polysaccharide surfactants. The number x indicates the number of saccharide units in a particular alkyl polysaccharide surfactant. For a particular alkyl polysaccharide molecule x can only assume integral values. In any physical sample of alkyl polysaccharide surfactants there will be in general molecules having different x values. The physical sample can be characterized by the average value of x and this average value can assume non-integral values. In this specification the values of x are to be understood to be average values. The hydrophobic group (R) can be attached at the 2-, 3-, or 4-positions rather than at the 1-position, (thus giving e.g. a glucosyl or galactosyl as opposed to a glucoside or galactoside). However, attachment through the 1-position, i.e., glucosides, galactoside, fructosides, etc., is preferred. In the preferred product the additional saccharide units are predominately attached to the previous saccharide unit""s 2-position. Attachment through the 3-, 4-, and 6-positions can also occur. Optionally and less desirably there can be a polyalkoxide chain joining the hydrophobic moiety (R) and the polysaccharide chain. The preferred alkoxide moiety is ethoxide.
Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 20, preferably from about 10 to about 18 carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to 3 hydroxy groups and/or the polyalkoxide chain can contain up to about 30, preferably less than about 10, alkoxide moieties.
Suitable alkyl polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls and/or galactosyls and mixtures thereof.
The alkyl monosaccharides are relatively less soluble in water than the higher alkyl polysaccharides. When used in admixture with alkyl polysaccharides, the alkyl monosaccharides are solubilized to some extent. The use of alkyl monosaccharides in admixture with alkyl polysaccharides is a preferred mode of carrying out the invention. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
The preferred alkyl polysaccharides are alkyl polyglucosides having the formula
R2O(CnH2nO)r(Z)x
wherein Z is derived from glucose, R is a hydrophobic group selected from the group consisting of alkyl, alkylphenyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3 preferably 2, r is from 0 to 10, preferable 0; and x is from 1.5 to 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7. To prepare these compounds a long chain alcohol (R2OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkyl polyglucosides can be prepared by a two step procedure in which a short chain alcohol (R1OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkyl polyglucosides can be prepared by a two step procedure in which a short chain alcohol (C1-6) is reacted with glucose or a polyglucoside (x=2 to 4) to yield a short chain alkyl glucoside (x=1 to 4) which can in turn be reacted with a longer chain alcohol (R2OH) to displace the short chain alcohol and obtain the desired alkyl polyglucoside. If this two step procedure is used, the short chain alkylglucoside content of the final alkyl polyglucoside material should be less than 50%, preferably less than 10%, more preferably less than about 5%, most preferably 0% of the alkyl polyglucoside.
The amount of unreacted alcohol (the free fatty alcohol content) in the desired alkyl polysaccharide surfactant is preferably less than about 2%, more preferably less than about 0.5% by weight of the total of the alkyl polysaccharide. For some uses it is desirable to have the alkyl monosaccharide content less than about 10%.
The used herein, xe2x80x9calkyl polysaccharide surfactantxe2x80x9d is intended to represent both the preferred glucose and galactose derived surfactants and the less preferred alkyl polysaccharide surfactants. Throughout this specification, xe2x80x9calkyl polyglucosidexe2x80x9d is used to include alkyl polyglycosides because the stereochemistry of the saccharide moiety is changed during the preparation reaction.
An especially preferred APG glycoside surfactant is APG 625 glycoside manufactured by the Henkel Corporation of Ambler, Pa. APG25 is a nonionic alkyl polyglycoside characterized by the formula:
CnH2n+1O(C6H10O5)xH
wherein n=10 (2%); n=122 (65%); n=14 (21-28%); n=16 (4-8%) and n=18 (0.5%) and x (degree of polymerization)=1.6. APG 625 has: a pH of 6 to 10 (10% of APG 625 in distilled water); a specific gravity at 25xc2x0 C. of 1.1 g/ml; a density at 25xc2x0 C. of 9.1 lbs/gallon; a calculated HLB of 12.1 and a Brookfield viscosity at 35xc2x0 C., 21 spindle, 5-10 RPM of 3,000 to 7,000 cps.
The water-soluble zwitterionic surfactant, which can also be used provides good foaming properties and mildness to the present nonionic based liquid detergent. The zwitterionic surfactant is a water soluble betaine having the general formula:
wherein R1 is an alkyl group having 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, or the amido radical:
wherein R is an alkyl group having 9 to 19 carbon atoms and a is the integer 1 to 4; R2 and R3 are each alkyl groups having 1 to 3 carbons and preferably 1 carbon; R4 is an alkylene or hydroxyalkylene group having from 1 to 4 carbon atoms and, optionally, one hydroxyl group. Typical alkyldimethyl betaines include decyl dimethyl betaine or 2-(N-decyl-N,N-dimethyl-ammonia)acetate, coco dimethyl betaine or 2-(N-coco N,N-dimethylammonio)acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, lauryl diemethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine, etc. The amidobetaines similarly include cocoamidoethylbetaine, cocoamidopropyl betaine and the like. A preferred betaine is coco(C8-C18)amidopropyl dimethyl betaine.
Amine oxide semi-polar nonionic surfactants comprise compounds and mixtures of compounds having the formula:
wherein R1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms, R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl, and n is from 0 to 10. Particularly preferred are amine oxides of the formula:
wherein R1 is a C12-16 alkyl and R2 and R3 are methyl or ethyl. The above ethylene oxide condensates, amides, and amine oxides are more fully described in U.S. Pat. No. 4,316,824 which is hereby incorporated herein by reference.
The instant composition can contain a mixture of a C12-14 alkyl monoalkanol amide such as lauryl monoalkanol amide and a C12-14 alkyl dialkanol amide such as lauryl diethanol amide or coco diethanol amide.
The composition also optionally contains at a concentration of 0 to 5 wt. %, more preferably 0.1 wt. % to 5 wt. % of an inorganic or organic salt of oxide of a multivalent metal cation, particularly Mg++. The metal salt or oxide provides several benefits including improved cleaning performance in dilute usage, particularly in soft water. Magnesium sulfate, either anhydrous or hydrated (e.g., heptahydrate), is especially preferred as the magnesium salt. Good results also have been obtained with magnesium oxide, magnesium chloride, magnesium acetate, magnesium propionate and magnesium hydroxide. These magnesium salts can be used with formulations at neutral or acidic pH since magnesium hydroxide will not precipitate at these pH levels.
Although magnesium is the preferred multivalent metal from which the salts (inclusive of the oxide and hydroxide) are formed, other polyvalent metal ions also can be used provided that their salts are nontoxic and are soluble in the aqueous phase of the system at the desired pH level.
Polyethylene glycol which can be optionally used at a concentration of 0 to 6 wt. %, more preferably 0.1 wt. % to 6 wt. % in the instant composition has a molecular weight of 200 to 1,000 wherein the polyethylene glycol has the structure
xe2x80x83HO(CH2CH2O)nH
wherein n is 4 to 52. The concentration of the polyethylene glycol in the instant composition is 0.1% to 6 wt. %, more preferably 0.1 wt. % to 5 wt. %.
The instant compositions can contain about 0 to about 10 wt. %, more preferably about 0.1 wt. % to about 8 wt. %, of at least one solubilizing agent which is sodium xylene sulfonate, sodium amine sulfonate, a C2-5 mono, dihydroxy or polyhydroxy alkanols such as ethanol, isopropanol, glycerol ethylene glycol, diethylene glycol and propylene glycol and mixtures thereof. The solubilizing agents are included in order to control low temperature cloud clear properties. Urea can be optionally employed in the instant composition as a supplemental solubilizing agent at a concentration of 0 to about 10 wt. %, more preferably about 0.5 wt. % to about 8 wt. %.
The instant formulas explicitly exclude alkali metal silicates and alkali metal builders such as alkali metal polyphosphates, alkali metal carbonates and alkali metal phosphonates because these materials, if used in the instant composition, would cause the composition to have a high pH as well as leaving residue on the surface being cleaned.
The final essential ingredient in the inventive compositions having improved interfacial tension properties is water. The proportion of water in the compositions generally is in the range of 35% to 70%, preferably 40% to 60% by weight of the composition.
The proton donating agent which is optionally used at a concentration of 0 to 5 wt. %, more preferably 0.1 wt. % to 4 wt. % is selected from the group consisting of inorganic acids such as sulfuric acid and hydrochloric acid and hydroxy containing organic acid, preferably a hydroxy aliphatic acid, which are selected from the group consisting of lactic acid or citric acid, orthohydroxy benzoic acid or citric acid or glycolic and mixtures thereof.
In final form, the instant compositions exhibit stability at reduced and increased temperatures. More specifically, such compositions remain clear and stable in the range of 5xc2x0 C. to 50xc2x0 C., especially 10xc2x0 C. to 43xc2x0 C. Such compositions exhibit a pH of 5 to 8. The compositions are readily pourable and exhibit a viscosity in the range of 100 to 1000 milliPascal.second (mPas.) as measured at 25xc2x0 C. with a Brookfield RVT Viscometer. Preferably, the viscosity is maintained in the range of 150 to 600 mPas.

Light duty liquid cleaning compositions having improved preservative system


A joint assembly for coupling a ceramic member to a metal member is comprised of a ceramic shaft portion attached to the ceramic member; a slotted shrink fitter formed of a first metal and disposed around and in torque transmitting contact with the ceramic shaft portion to define a first interface surface therebetween; and a sleeve formed of a second metal disposed around and in torque transmitting contact with the shrink fitter to define a second interface surface therebetween. Either the shrink fitter or the sleeve attached to the metal member. The coefficient of thermal expansion of the second metal is relatively low compared to that of the first metal and the diameters of the first interface, (d1), and the second interface, (d2), are determined from the equation, d1/d2=(xcex1cxe2x88x92xcex11)/(xcex12xe2x88x92xcex11) where xcex1c, xcex11 and xcex12 are the coefficients of thermal expansion of the ceramic, the first metal and the second metal respectively. A compliant sleeve is disposed the ceramic shaft portion and the slotted shrink fitter.

This invention relates generally to gas turbine engines and in particular to a joint assembly for coupling a ceramic member to a metal member.
It has long been recognized that the efficiency and performance of gas turbine engines could be improved by increasing the temperature of the gas through the turbine section. Historically, these temperatures have been limited by the materials, usually high temperature steel or nickel alloy, used in forming the turbine rotor. To permit higher gas temperatures it has been proposed to form the turbine rotor from a high density, high strength, silicon nitride, or silicon carbide ceramic which can withstand higher temperatures than steels or nickel alloys.
The ceramic turbine rotor extracts energy from the hot gas in the engine and converts it into torque. To transmit this torque to other components of the engine and thereby cause them to rotate, the ceramic turbine rotor needs to be coupled to a superalloy or metal component of the engine such as the compressor rotor. Because monolithic ceramic has a higher compressive strength in comparison to its tensile strength, it is advantageous to use an interference fit type joint to couple the turbine rotor to the compressor rotor. Typically, this joint is comprised of a metal sleeve pressed on to a shaft portion of the ceramic turbine rotor with the metal sleeve applying a compressive load to the ceramic shaft portion. A disadvantage to this type of joint is that due to the thermal expansion mismatch between the metal and ceramic, a conventional interference fit loses its torque transmitting capability at temperatures in the range of 400 to 500xc2x0C. depending on the specific metal and ceramic chosen and the magnitude of the interference fit.
Accordingly, there is a need for a joint assembly for coupling a ceramic member to a metal member that is capable of transmitting torque at temperatures greater than 500xc2x0 C.
An object of the present invention is to provide a joint assembly for coupling a ceramic member to a metal member that is capable of transmitting torque at temperatures greater than 500xc2x0 C.
The present invention achieves this objective by providing a joint assembly for coupling a ceramic member to a metal member that is comprised of a ceramic shaft portion attached to the ceramic member; a slotted shrink fitter formed of a first metal and disposed around and in torque transmitting contact with the ceramic shaft portion to define a first interface surface therebetween; and a sleeve formed of a second metal disposed around and in torque transmitting contact with the shrink fitter to define a second interface surface therebetween. Either the shrink fitter or the sleeve is attached to the metal member. The coefficient of thermal expansion of the second metal is relatively low compared to that of the first metal and the diameters of the first interface, (d1), and the second interface, (d2), are determined from the equation, d1!d2=(xcex1cxe2x88x92xcex11)/(xcex12xe2x88x92xcex11) where xcex1c, xcex11 and xcex12 are the coefficients of thermal expansion of the ceramic, the first metal and the second metal, respectively.
A solid lubricant is introduced at the interface between the shrink fitter and the ceramic member to provide a shear limiting layer to prevent cracking of the ceramic member due to the axial thermal expansion mismatch between the ceramic member and the shrink fitter. Without this solid lubricant, and depending on the coefficient of friction at this interface, the magnitude of the thermal mismatch, the magnitude of the interference fit, and the service temperature, very high shear stresses can be transmitted as tensile stresses to the interface of the ceramic member once the joint assembly is heating up to its operating temperature, which will ultimately result in cracking of the ceramic. The solid lubricant will allow the ceramic to slide axially with respect to the shrink fitter once the sheer stress exceed the yield strength of the solid lubricant, thereby limiting the shear stresses to an acceptable order of magnitude for the ceramic.
By selecting the appropriate metals and interface diameters, the contact pressure, which is directly related to torque transmitting capability, between the ceramic to metal interface will remain essentially constant even at temperature above 500xc2x0 C.
These and other objects, features and advantages of the present invention, are specifically set forth in, or will become apparent from, the following detailed description of a preferred embodiment of the invention when read in conjunction with the accompanying drawings.


A power management system controls power and energy drawn by a load monitoring total drawn power and energy and modifying load usage. A power meter monitors power drawn by a load and provides a control circuit with an indication of power draw. The control circuit controls the power delivered to the load based on predetermined criteria, such a power threshold. Other sensors and controls such as environment status detectors or emergency commands are used by the control circuit to adjust the power provided to the load, or even to shut off power to the load. The control circuit can be a microprocessor based controller, or can be a remotely located personal computer which interacts with load drivers through a communication link. The control circuit can also have a profile for operation under various criteria, with profile parameters adjustable depending upon conditions. The profile parameters can be adjusted automatically by a control program, or by a user remotely. The control circuit can also drive the load at a known value and compare the power drawn with a stored reference value for the load. The system can thus be evaluated for failed or degraded components based on changes in the expected power draw.

1. Field of the Invention
The present invention relates generally to a power and/or energy management system and, more particularly, to a system capable of monitoring the power and/or energy being consumed by a load and reducing the power and/or energy being consumed in order to stay below a predetermined value.
2. Related Art
Energy management systems capable of turning connected loads on and off to maintain the total connected power consumption below a predetermined maximum value are well known.
U.S. Pat. No. 5,196,982 to Landsberg et al. and assigned to The Fleming Group discloses a method and system incorporating an integral power consumption monitor-circuit breaker panel for industrial or commercial buildings and facilities. The power consumption monitor-circuit breaker panel not only protects each end use within the building against harmful overloads, but also monitors peak power demands of each end use. Electrical current, voltage and phase information is provided by each monitor-breaker. This information is then fed to a processing circuit that provides a power consumption value. The power consumption value is then fed to a recording device to provide a power consumption history for each end use. Each monitor-breaker is identified by its end use, as for example, by color coding. The monitor device of each circuit breaker is designed to provide a voltage that is proportional to the circuit load. Two methods may be used to provide such a voltage signal: a) the voltage signal can be developed across a built-in shunt in each circuit breaker; and b) a proportional voltage can be obtained by use of a circuit breaker with a built-in Hall effect device, wherein the product of the instantaneous current and voltage, along with the phase angle between them, provides the power measurement. The current and/or instantaneous power information can be sent to the recording device via a power line carrier, radio link, or optical fiber. The information can be integrated to provide either kW or kWxc2x7hr readings.
U.S. Pat. No. 4,819,180 to Heldman et al. and assigned to Dencor Energy Cost Control, Inc. discloses a method and system for regulating power delivered to different commercial or residential users in which each user has variable demands for power consumption, there being a power source from which power is transmitted by a utility to each user and a utility control signal which is transmitted from the utility to each user in order to modify the power consumed by each user, the method and system of the Heldman et al. reference being characterized by measuring the power consumption of each user over a selected real time interval, and modifying the power consumption by each user by an amount directly related to the power consumption measurement of each user over that time interval.
U.S. Pat. No. 4,977,515 to Rudden et al. discloses a plug in device, furnished by an electric power utility to a customer, which is installed by the customer between a wall outlet and an appliance, particularly a room air conditioner. The device contains a microprocessor that is programmable and controllable by the utility to determine the ON-OFF cycling of the appliance. The microprocessor, with the aid of sensors, records date and time of each instance that a programmed OFF interval is overridden through a manual input, and each instance of disconnection of the appliance from the device after the first connection. Also, the device is arranged on command to record the power being drawn by the attached appliance, either on a one time basis or on a scheduled interval over a predetermined time span. A remote transmitter is also provided as a source of customer I.D. and control signals for utility control of selected devices in use. Certain embodiments have a component that is installed by qualified personnel, hard wired into a control circuit, having a removable component removable either by service personnel or the customer for return to the utility to read out the contents of its memory as to its history of use. Similarly, the customer installed unit is returned or has a component returned for utility readout.
U.S. Pat. No. 4,075,699 to Schneider et al. and assigned to Lockheed Electronics Co., Inc. discloses an electrical power controlling/load shedding system that includes power consumption metering and meter interfacing circuitry for entering overall power consumption into a central processing unit (CPU). The CPU memory includes a data storage table characterizing each system electrical load under each of a hierarchy of operational levels, and circuitry is provided for turning local and remote loads on/off, responsive to CPU-issued commands. The digital computing apparatus operates on the meter supplied information and projects energy consumption over the monitoring interval. If power must be shed to obviate an excessive projected demand, loads are examined seriatim and selectively shed on a priority basis as required, depending upon the operational parameters and status characterizing each load for the then prevailing load level condition.
U.S. Pat. No. 5,572,438 to Elhers et al. and assigned to TECO Energy Management Services discloses an energy management and building automation system including a local area network or home automation data bus such as the CEBus. Each load is connected to the bus via a control module which may contain a circuit breaker to disconnect the load from the mains upon command or upon occurrence of a power outage. Current monitoring control modules measure load current and power monitor modules monitor power consumed by selected loads, both modules transmitting bus messages indicating load status and status changes. A first microcomputer preferably is external to the customer premises, adjacent the electric utility power meter. A second microcomputer preferably is inside the customer premises. The two microcomputers communicate with each other and with the various modules via the network/data bus. The first microcomputer communicates with the utility company via any appropriate communications link. The second microcomputer serves, in part, as an input/output terminal for the system, allowing the customer to set parameters and query the system as to power usage, displaying reports requested by the customer and messages transmitted by the utility company and by either microcomputer. The first microcomputer acts as a master controller and/or network server, communicating with the world outside the premises, as a communications gateway between voice, video and data services, and as the primary data collector and operator of the load control modules; the second microcomputer provides certain backup functions. The utility company can access selected utilization data and control at least some loads via messages to the first microcomputer.
Unfortunately, the preceding patents disclose systems which completely disconnect one or more selected loads (reduce output power to zero) when the power usage exceeds a predetermined maximum. None of these systems have the ability to reduce the power/energy to the load without completely disconnecting the load. Accordingly there is a need in the art for a new power/energy management system capable of monitoring output power/energy draw and varying available output power/energy to maintain desirable output power/energy draw.
In order to overcome the disadvantages of the prior art, a circuit for controlling power drawn from a source of utility power and delivered to a load according to the present invention includes:
a power monitoring circuit operable to produce a sense signal indicative of an amount of output power drawn by the load;
a control circuit operable to receive the sense signal from the power monitoring circuit and produce a control signal indicative of whether the amount of power drawn from the source by the load has exceeded a threshold; and
an output circuit operable to receive input power from the source and deliver the output power to the load, the output circuit reducing the output power when the control signal indicates that the threshold has been exceeded.


Embodiments of the present invention disclose a method, computer program product, and system for generating a schedule for promotions using promotional windows. A set of product data associated with a plurality of products is received. Promotion data is received, and a plurality of intensity scores are calculated for the associated promotional data. A set of target product data associated with a target product is determined. A set of target promotional attributes is determined and a plurality of promotion windows are generated for display. A confidence value is determined for each generated promotion window of the plurality of promotion windows. An order list is generated for display. In response to receiving a second set of promotion data, the determined confidence value is modified for each generated promotion window of the plurality of promotion windows.

The present invention relates generally to the field of computer data modeling, and more particularly to model generation of the effects of external events on consumer-packaged goods.
Perishable items are often put on clearance sale when it nears expiry date in order to clear inventory, maximize profits, or minimize loss of product. Typically, products are discarded if not sold by the expiration date. Promotions, such as putting items on "sale" or "clearance," are used to avoid having to discard the expired items. It may be advantageous to determine an optimal promotion time frame or window to maximize profits and minimize waste.

Mitigation of perishable product waste through promotion recommendation

International Business Machines Corporation


The invention is a laminate structure made by coating at least one side of a substrate with a laminating adhesive, bringing a coated side of said substrate into contact with a second substrate to form a multi-layer film, and treating said multi-layer film with a free radical initiator, wherein said laminating adhesive is the reaction product of a multifunctional acrylate, an aminofunctional silane, and an ethylenically unsaturated acid, optionally dissolved in a solvent, wherein the multifunctional acrylate has a molecular weight of from 100 to 3000.

The invention relates to silicone containing laminates having barrier properties which are useful in packaging applications.
It is well known that coatings containing silane compounds and itaconic acid improve the gas, oil, and flavor barrier performance of organic polymer film substrates. Moreover, the adhesion of the coating to the film surface, as well as the improved barrier characteristics provided by the silane coating, are greatly enhanced by exposing the coated film to electron beam radiation.
A particularly useful barrier composition is described in U.S. Pat. No. 5,215,822, which teaches a methanol solution of a vinyl benzyl amine silane (Dow Corning Corp. Z-6032), itaconic acid, and water; coating this solution on a corona treated low density polyethylene film, drying, and then subjecting the coated film to electron beam radiation to graft the coating to the film surface and further improve the barrier properties of the silane coating. However, while this coating gives excellent gas barrier properties at low to moderate relative humidity values, the gas permeability increases drastically at very high relative humidity values. The present inventors have surprisingly discovered that the combination of an aminofunctional silane, a multifunctional acrylate and an ethylenically unsaturated acid gives excellent gas barrier properties at low to moderate relative humidity values, as well as excellent gas barrier properties at very high relative humidity values.
While other patents teach the combination of a mono or multifunctional acrylate with an aminofunctional silane, none teaches the addition of the ethylenically unsaturated acid with an acrylate. For example, U.S. Pat. No. 5,368,941 teaches a deformable, abrasion-resistant coating formulated from at least one multi-functional acrylate monomer, at least one aminofunctional silane, colloidal silica and at least one acrylate-terminated polyalkylene oxide, but does not teach the addition of an ethylenically unsaturated acid. The acrylate-terminated polyalkylene oxide helps prevent gelling of the coating composition during stripping and also imparts the composition with deformability, without sacrificing abrasion resistance. Also, U.S. Pat. No. 5,434,007 teaches a silane resin coated on a plastic film, where the silane resin is composed of a monofunctional acrylate and an aminofunctional silane. The composition does not utilize a free radical cure, nor does it incorporate the ethylenically unsaturated acid.
U.S. Pat. Nos. 5,260,350 and 5,374,483 relate to a silicone coating composition which, when cured on a solid substrate either by ultraviolet or electron beam radiation, provides a transparent abrasion resistant coating firmly adhered thereon. The silicone coating is prepared by reacting at least one multifunctional acrylate monomer with an amino-organofunctional silane, mixing the modified silane with at least one acrylic monomer and thereafter adding colloidal silica. Again however, neither of these compositions teach the addition of an ethylenically unsaturated acid to achieve barrier properties.
JP (Kokai) publication 7-18221 published on Jan. 20, 1995 teaches a surface treatment composition for gas barrier comprising an aminosilane and a compound having an aromatic ring or hydrogenated ring. The present invention is distinguishable, however, because it does not require the addition of cyclic compounds having an aromatic ring.
The present invention is distinguishable from the prior art because none teach the addition of a polymerizable additive to achieve gas barrier properties, nor do they teach a composition having both barrier and adhesive characteristics.
The invention comprises a laminate structure made by the following method:
coating at least one side of a substrate with a laminating adhesive,
bringing a coated side of said substrate into contact with a second substrate to form a multi-layer film,
and curing said multi-layer film by initiating a free-radical reaction after the second substrate is contacted with the first substrate, wherein said laminating adhesive is the reaction product of a multifunctional acrylate, an amninofunctional silane, and an ethylenically unsaturated acid,
optionally dissolved in a solvent, wherein the multifunctional acrylate has a molecular weight of from 100 to 3000, and the aminofunctional silane has at least one molecule of the formula
wherein
0xe2x89xa6axe2x89xa64
R1 is independently hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, arylalkyl, acryl, methacryl, alkylaryl, R2xe2x80x94SiRm(OR)3xe2x88x92m, or an alkylene linking group having 2 to 12 carbon atoms connected to one or two nitrogen atoms, with the proviso that at least one R1 is a hydrogen atom and at least one R1 is an R2xe2x80x94SiRm(OR)3xe2x88x92m group, where m is 0, 1 or 2, and R is independently a hydrogen or an all group having from 1 to 6 carbon atoms;
R2 is independently selected from the group consisting of:
linear or branched alkylene groups having from 1 to 12 carbon atoms;
arylene groups having from 6 to 12 carbon atoms; and
linear or branched hydrocarbon groups having from 1 to 16 carbon atoms and at least one alcohol, alcohol ether, ester, amide, urea, thiourea or polyether group.
The invention is a laminate, which can be made from a variety of substrates. The laminate can then be used alone or with other substrates to give structural or barrier properties to packaging containers. The laminate adhesive can be further cured by drying in the presence of water prior to exposure to electron beam irradiation.
A composition according to the present invention may be employed to provide a barrier layer which improves resistance of the material to transmission of gases and aromas therethrough. For example, a 30 xcexcm uncoated biaxilly oriented, corona treated polypropylene film is generally found to have a permeability to oxygen of 1500 ml/m2/day as measured at ASTM D3985-81 measured at 80% relative humidity. With the present coatings, the oxygen transmission rate of the same film can be reduced to less than 250 ml/m2/day as measured at 80% relative humidity. As used herein, the terminology xe2x80x9cimproved barrierxe2x80x9d refers to a coating which can reduce oxygen transmission rate of the aforementioned uncoated polypropylene film from 1500 ml/m2/day to 250 ml/m2/day as measured at ASTM D3985-81 measured at 80% relative humidity.
While the invention is susceptible of embodiment in many different forms there is described herein in detail preferred and alternate embodiments of the invention.
The aminofunctional silanes are described generally by the formula:
wherein
0xe2x89xa6axe2x89xa64
R1 is independently hydrogen, alkyl substituted alkyl, aryl, substituted aryl, arylalkyl, acryl, methacryl, alkylaryl, R2xe2x80x94SiRm(OR)3xe2x88x92m, or an alkylene linking group having 2 to 12 carbon atoms connected to one or two nitrogen atoms, with the proviso that at least one R1 is a hydrogen atom and at least one R1 is an R2xe2x80x94SiRm(OR)3xe2x88x92m group, where m is 0, 1 or 2, and R is independently a hydrogen or an alkyl group having from 1 to 6 carbon atoms;
R2 is independently selected from the group consisting of:
linear or branched alkylene groups having from 1 to 12 carbon atoms;
arylene groups having from 6 to 12 carbon atoms; and
linear or branched hydrocarbon groups having from 1 to 16 carbon atoms and at least one alcohol, alcohol ether, ester, amide, urea, thiourea or polyether group.
The most preferred aminofunctional silanes useful for the present invention are N-(2-aminoethyl)-3-aminopropyltrimethoxy silane. and aminopropyltriethoxysilane, and blends thereof.
For the purpose of the present invention, the above mentioned amine functional silane has the general formula
In the above formula, R1 is a monovalent radical independently selected from the group consisting of hydrogen; acryl, methacryl, alkyl groups having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, isobutyl, hexyl, octyl, decyl, dodecyl, and octadecyl; substituted alkyl having 1 to 18 carbon atoms, such as 3-chloropropyl and 3,3,3-trifluoropropyl; aryl having 6 to 16 carbon atoms, such as phenyl and naphthyl; substituted aryl having 6 to 30 carbon atoms, such as chlorophenyl, chlorotolyl and dichloroxylyl; arylalkyl having 7 to 9 carbon atoms, such as benzyl, phenethyl and 3-phenylpropyl; and alkylaryl having 7 to 16 carbon atoms, such as tolyl, xylyl, ethylphenyl and propyltolyl. According to the invention, at least one R1 group is hydrogen. Further, at least one R1 is an R2xe2x80x94SiRm(OR)3xe2x88x92m group, where R is an alkyl group having from 1 to 6 carbon atoms, m is 0, 1, or 2 and R2 is defined below. The remaining R1 groups on the aminosilane are preferably hydrogen or methyl, R1 can also be an alkylene linking group which links two different nitrogen atoms on the same molecule together, thus forming a cyclic aminosilane. The alkylene linking group can also be an arylene group which is connected to two different bonding sites on the same nitrogen atom. The alkylene linking group will have at least 2 carbon atoms and as many as 12 carbon atoms.
R2 is an organic connecting group which provides a separation of at least one carbon atom between the nitrogen atoms or the nitrogen and silicon atoms. Thus, R2 can be an alkylene group having at least 1 carbon atom or an arylene group having at least 6 carbon atoms. Preferably, R2 is selected from the group consisting of ethylene, propylene, butylene, isobutylene, trimethylene, trimethylene, and hexaethylene.
In addition, R2 can contain polar groups such as, linear or branched hydrocarbon groups having from 1 to 16 carbon atoms and at least one alcohol, alcohol ether, ester, amide, urea, thiourea or polyether group. Specific examples of such groups include, those having the general formula xe2x80x94CH2CH(OH)(CH2)xxe2x80x94, xe2x80x94CH2CH(OH)(CH2)xxe2x80x94Oxe2x80x94(CH2)yxe2x80x94, xe2x80x94CH2CH(CH3)C(xe2x95x90O)xe2x80x94Oxe2x80x94(CH2)yxe2x80x94, xe2x80x94CH2CH2C(xe2x95x90O)xe2x80x94Oxe2x80x94(CH2)yxe2x80x94, xe2x80x94CH2CH2C(xe2x95x90O)xe2x80x94N(R)xe2x80x94(CH2)yxe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94N(R)xe2x80x94(CH2)yxe2x80x94, xe2x80x94C(xe2x95x90S)xe2x80x94N(R)xe2x80x94(CH2)yxe2x80x94, or where x and y are each integers from 1 to 12. The hydroxyl and ester groups are highly polar, and it is believed the polar nature of the groups improve barrier properties.
Examples of specific amine-containing groups include such structures as xe2x80x94CH2CH2CH2NH2, xe2x80x94CH2CH2CH2N(H)CH2CH2NH2, xe2x80x94CH2CH2CH2N(H)CH2CH2N(H)CH2CH2NH2, xe2x80x94CH2CH2CH2CH2NH2, xe2x80x94CH2CH2CH2CH2CH2NH2, xe2x80x94CH2CH2CH2N(H)Me, xe2x80x94CH2CH2CH2N(H)CH2CH2NMe2, xe2x80x94CH2CH2CH2N(H)Et, xe2x80x94CH2CH2CH2N(Et)H, xe2x80x94CH2CH(CH3)CH2N(H)CH2CH2NH2 and xe2x80x94CH2CH(CH3)CH2NH2, inter alia, wherein Me and Et denote methyl and ethyl, respectively. A specific example of an amine containing cyclic group is piperazine.
As used herein the term xe2x80x9caminofunctional silanexe2x80x9d can mean a single species of the formula described above, such as N-(2-aminoethyl-3-aminopropyltrimethoxy silane, or it can mean mixtures or one or more species of aminofunctional silanes, such as N-(2-aminoethyl)-3-aminopropyltrimethoxy silane and aminopropyltriethoxysilane.
The above described amninofunctional silanes can be prepared by methods known to those skilled in the art, and which are amply described in the chemical literature.
The multifunctional acrylates of the present invention are defined as acrylates having, on average, greater than two functional acrylate groups per molecule and a molecular weight of from about 100 to about 3000. Multifunctional acrylates are preferred over monofunctional acrylates because monofunctional acrylates do not form flexible, crack free coatings as do the multifunctional acrylates. The majority of multifunctional acrylates commercially available can be used, but it is the smaller, more compact, i.e., proportionally more reactive acrylates that give the best results. The multifunctional acrylates are preferably selected from the group consisting of acrylated polyols with molecular weights of from about 150 to about 600; polyester urethane acrylates with molecular weights of from about 1000 to about 2000; polyether acrylates with molecular weights from 200 to 1500; polyurethane acrylates with molecular weights of from about 400 to about 2000; polyurea acrylates with molecular weights of from about 400 to about 2000; epoxy acrylates with molecular weights of from about 300 to about 1000; and mixtures of multifunctional acrylates thereof.
Most preferred acrylates are pentaerythritol tetracrylate; an acid functional acrylate; polyester tetra acrylate; polyether tetra acrylate; an aliphatic urethane acrylate, Ebecryl 1290; ditrimethylolpropane tetra acrylate; an ethoxylated trimethylol propane triacrylate, Ebecryl 160. Other preferred acrylate include glycerol triacrylate, triacrylate ester of tris-[z-hydroxy-ethyl] isocyanurate, hexane dioldiacrylate, and dipentaerythritol hexacrylate. Ethoxylated and propoxylated versions of these acrylates may be used in this invention. These acrylates and methods of their production are well know in the art, and available commercially from such companies as UCB Radcure, (Brussels, Belgium) and Sartomer Corp. (Philadelphia, Pa.) As used herein, the term xe2x80x9cmixtures of multifunctional acrylatesxe2x80x9d means mixtures of different acrylates of the same species, such as two different epoxy acrylates, or mixtures of different species of acrylates, such as epoxy acrylates and urethane acrylates.
In addition to the aminosilane and the multifunctional acrylate, a quantity of an ethylenically unsaturated acid is added to the composition. By xe2x80x9cethylenically unsaturated acidxe2x80x9d it is meant any acid which has vinyl unsaturation. It is believed that the ethylenically unsaturated acid substantially improves the oxygen barrier performance of the compositon because the carboxylic group forms an amine salt with amino groups of the aminosilane, which contributes significantly to the coating""s barrier properties. The ethylenically unsaturated acid is likely to be added in the amount of at least 5 to about 60 parts by weight of the composition, with about 30 to about 50 parts by weight being most preferred. The most preferred ethylenically unsaturated acids used in the present invention are dicarboxylic (i.e. have two carboxylic acid groups) and the most preferred is itaconic acid: however, other acids such as fumaric, maleic, citraconic, methacrylic, cinnamic, vinyl sulfonic acid, mesaconic acid, and itaconic acid monomethylester may also be used. The term xe2x80x9cethylenically unsaturated acidxe2x80x9d as used herein includes mixtures of one or more of the aforementioned acids.
The components of the present invention can optionally be reacted together in a solvent. In general, water, alcohols and blends thereof will serve as suitable solvents because the multifunctional acrylate and the ethylenically unsaturated acid are soluble therein. Typically, the solvent is a water/alcohol mixture where the alcohol is present in an amount of about 1-99%. In addition, the selected solvent must wet the substrate. Preferably, the solvent will be nontoxic, and will not extend the drying time of the coating beyond what is commercially acceptable. The amount of solvent can range from about 20 to about 99 parts by weight and is preferably from about 60 to about 95 parts by weight of the total composition. Preferred solvents are methanol, ethanol, n-propanol, isopropanol, butanol, and 1-methoxy-2-propanol (available as xe2x80x9cDowanol PMxe2x80x9d from the Dow Chemical Co., Midland, Mich.).
During the reaction of aminosilanes with multifunctional acrylates, it is possible to utilize an excess of multifunctional acrylate over and above that required to react with the amino nitrogen atoms. In multifunctional acrylates, such as pentaerythritol tetraacrylate, the amine chains attached to the trimethoxysilyl groups may also have pendent acrylate groups which will undergo further polymerization under the influence of ionizing radiation. It is believed that the acrylate groups of the multifunctional acrylate and the amino groups of the aminofunctional silane undergo an addition reaction (Michael Addition) readily upon mixing of these two components. In addition, hydroxyl groups and solvents present may interact with alkoxy groups attached to the silicone atoms of the aminofunctional silane and cause a thickening of the composition at certain concentrations of the components in the solvent. For example, one may employ an xe2x80x9camine richxe2x80x9d system, in which the total number of amine functional sites in the composition due to the aminofunctional silane can be up to about six (6) times greater than the total number of acrylate sites in the composition due to the multifunctional acrylate, i.e., the ratio of amine functionality to the acrylate functionality can be from about 6:1 to about 1:1, with a ratio of about 4:1 to about 1:1 being preferred, and with a ratio of 2:1 being most preferred. In the case where the aminofunctional silane is N-(2-aminoethyl)-3-aminopropyltrimethoxy silane or aminopropyltriethoxy silane, and the multifunctional acrylate is pentaerythritol tetraacrylate, the ratios in the amine rich system can be expressed in terms of molar ratios, with the preferred molar ratio of aminosilane to multifunctional acrylate being from about 6:1 to about 1:1 with a molar ratio of about 4:1 being most preferred.
Excellent results can also be achieved using an xe2x80x9cacrylate richxe2x80x9d system, where the total number of reactive nitrogen sites in the composition from the aminofunctional silane is up to about six (6) times less than the total number of reactive acrylate sites in the composition due to the multifunctional acrylate, i.e., the ratio of amine functionality to acrylate functionality, can be from about 1:1 to about 1:6. with a range of about 1:3 being preferred. In the case where the aminofunctional silane is N-(2-aminoethyl)-3-aminopropyltrimethoxy silane or aminopropyltriethoxysilane, and multifunctional acrylate is pentaerythritol tetraacrylate, the ratios of the acrylate rich system can be expressed in terms of molar ratios, with the preferred molar ratio of aminosilane to multifunctional acrylate being from about 1:1 to about 1:3, with a molar ratio of about 1:1.5 being most preferred.
Although the order of addition of the components to provide a composition according to the present invention is not critical, certain methods are preferable. For example, the aminofunctional silane and the acrylate component can be added together to form a Michael Adduct, before the addition of the ethylenically unsaturated acid. Also, the ethylenically unsaturated acid may be added at some point after the Michael Addition reaction begins, but before the aminosilane and/or the acrylate are completely consumed. xe2x80x9cQuenchingxe2x80x9d the reaction by adding the ethylenically unsaturated acid can occur at any point in the reaction process, i.e., the acid may be added to the aminosilane before any acrylate is added, or after most of the acrylate is added. Practically, the reaction may be quenched at a predetermined point by simply adding part of the acrylate to the aminosilane, then adding the rest of the acrylate and the acid to this mixture. It is preferred that the quenching technique be used with the amine rich formulations of the invention.
The key factor in determining whether a particular formulation is acceptable as a laminate adhesive is whether the composition exhibits a minimum degree of tackiness. If the laminate adhesive is at least minimally tacky, then it will fall within the scope of the invention. The tackiness can be achieve by optimizing the ratios of the components as described above, or by adding a tackifier, such as multifunctional acyrlates.
The coating can be applied in any desired amount, however, it is preferred that the coating be applied in an amount of from about 0.05 to about 20 g/m2, the preferred coating weight being from about 0.5 to about 10 g/m2. Coating weight can be determined by gravimetric comparison. The coating can be applied to the substrate by any conventional method, such as spray coating, roll coating, slot coating, meniscus coating, immersion coating, and direct, offset, and reverse gravure coating.
The coating can be disposed on a wide variety of substrates, including, but not limited to polyolefins, such as oriented polypropylene (OPP), cast polypropylene, polyethylene and polyethylene copolymers, polystyrene, polyesters, such as polyester terephthalate (PET), or polyethylene naphthalate (PEN), polyolefin copolymers, such as ethylene vinyl acetate, ethylene acrylic acid and ethylene vinyl alcohol (EVOH), polyvinylalcohol and copolymers thereof, polyamides, such as nylon, and MXD6, polyimides, polyacrylonitrile, polyvinylchloride, polyvinyl dichloride, polyvinylidene chloride, and polyacrylates, ionomers, polysaccharides, such as regenerated cellulose, and silicone, such as rubbers or sealants, other natural or synthetic rubbers, glassine or clay coated paper, paper board or craft paper, and metallized polymer films and vapor deposited metal oxide coated polymer films, such as AlOx, SiOx, or TiOx.
The aforesaid substrates are likely to be in the form of a film or sheet, though this is not obligatory. The substrate may be a copolymer, a laminate, a coextruded, a blend, a coating or a combination of any of the substrates listed above according to the compatibility of the materials with each other. In addition, the substrate may be in the form of a rigid container made from materials such as polyethylene, polypropylene, polystyrene, polyamides, PET, EVOH, or laminates containing such materials.
The aforesaid substrates may also be pretreated prior to coating by corona treatment, plasma treatment, acid treatments and flame treatments, all of which are known in the art.
In addition, the compositions of the present invention can be used in a wide variety of packaging containers, such as pouches, tubes, bottles, vials, bag-in-boxes, stand-up pouches, gable top cartons, thermoformed trays, brick-packs, boxes, cigarette packs and the like. Of course, the present invention is not limited to just packaging applications, and may be used in any application wherein gas, or aroma barrier properties are desired, such as tires, buoyancy aides, inflatable devices generally, etc.
Any of the foregoing substrates may have primers applied thereon. The primers are applied to the substrates by methods known in the art such as spray coating, roll coating, slot coating, meniscus coating, immersion coating, and direct, offset and reverse gravure coating. Suitable primers include, but are not limited to carbodiimide, polyethylenimine, and silanes, such as N-(2-aminoethyl)-3-aminopropyltrimethoxy silane and aminopropyltriethoxysilane.
The most preferred laminate structures are (where Si represents the coating composition of this invention), OPP/Si/OPP, OPP/Si/PE, metOPP/Si/OPP, metOPP/Si/PET, metal oxide coated PET/Si/PE, metal oxide coated OPP/Si/PE, metal oxide coated PET/Si/PP, metal oxide coated OPP/Si/PP, and PE/Si/PE.
While the compositions of the present invention will form films at ambient conditions, optimum results are achieved by heating and/or free radical cures of the laminate structure. For example, the first substrate may be exposed to heat and/or moisture prior to lamination of the second substrate. Generally, the higher the temperature, the faster the coating will dry. The upper limit to the heating temperature is the temperature at which the substrate will undergo unacceptable distortion. Also, temperature will accelerate the rate of hydrolysis of silicon/alkoxy groups and also the rate of condensation of the silicon/alkoxy groups with silicon/hydroxy groups to form silicon-oxygen-silicon groups. The composition may be heated at room temperature or in an oven at temperatures up to about 140xc2x0 C., with temperatures of from about 60xc2x0 C. to about 120xc2x0 C. being preferred and temperatures of about 90xc2x0 C. to about 110xc2x0 C. being most preferred. Heating time is temperature dependent and the coating will reach tack free time in one to 10 seconds. The heating step serves to evaporate the solvent and accelerate the condensation reaction between Sixe2x80x94OH groups and SiOH/SiOH groups. The compositions may be further cured by initiating a free radical reaction after the second substrate is contacted with the first substrate. The most preferred method of initiating the free radical reaction is through the use of electron beam radiation, although ultraviolet or free radical generators such as azo compounds and peroxides may also be used.
The compositions are preferably cured by a free radical generator, such as ultraviolet, electron beam, or gamma radiation or chemical free radical generators such as azo compounds and peroxides. Low energy electron beam is the preferred method of curing because it is cheaper than gamma sources like Cobalt M-60. Its advantage over ultraviolet radiation as a cure system lies in its ability to generate free radicals without photoinitiators. It also imparts higher yields of crosslink density and chemical grafting of the coating to the substrate. Electron beam accelerators of various types such as van de Graaf-type, resonance transformer-type, linear-type, dynamatron-type and high frequency-type can be used as a source of electron beam. Electron beam having energy of from about 5 to about 2000 KeV, preferably from about 50 to about 300 KeV discharged therefrom may be irradiated in a dose of from about 0.1 to about 10 Mrads (MR). Low electron beam voltages Tess than 20 KeV) may be used if the substrate is treated in a vacuum. Commercially available sources of electron beam are Electro Curtain CB-150 available from Energy Sciences, Inc. (Wilmington, Mass.). The compositions may also be ultraviolet light cured if one or more photoinitiators is added prior to curing. There are no special restrictions on the photoinitiators as long as they can generate radicals by the absorption of optical energy. Ultraviolet light sensitive photoinitiators or blends of initiators used in the UV cure of the present composition include 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173), sold by EM Chemicals, and 2,2 Dimethoxy-2-phenyl-acetol-phenone (Urgacure 651), sold by Ciba-Geigy Corporation, Hawthorne, N.Y. For purposes of this invention, it has been found that from about 0.05 to about 5 weight percent based on the total solids in the composition, of the photoinitiators described therein will cause the composition to cure.
In addition to radical polymerization and grafting to crosslink the coating after it has been applied to the film substrate, it is possible to further crosslink the amine silane materials utilizing acid catalyzed condensation reactions. In this reaction, a methoxylated active hydrogen compound, such as trimethylol phenol, or a mixture of formaldehyde with aldehydes, ketones, and other active hydrogen compounds react with amine salts, such as the itaconate salts of the amine silanes or derivatives to form alkylated amines.
To prepare the preferred embodiment of the invention, the acrylate component, preferably PETA, is dissolved in a solvent such as Dowanol PM. Itaconic acid, in an amount of 10.4 moles is then added to the equilibrated solution. The silane, preferably N-(2-amino ethyl) gamma aminopropyl trimethoxysilane is added to the above solution so the molar ratio of aminosilane to acrylate is about 4:1. This mixture is allowed to equilibrate for one hour at ambient conditions. The coating solution is applied to corona treated 30 xcexcm thick xe2x80x9cRayoppxe2x80x9d oriented polypropylene film available from UCB Films Corporation. The coated film is placed immediately in an oven maintained at about 80-1000xc2x0 C. and held there for 1-10 seconds. The oven is maintained at a relative humidity of about 50%. A second substrate, such as metalized oriented polypropylene film is place on the laminate adhesive, then the laminate structure is xe2x80x9ccuredxe2x80x9d by an electron beam dose of 10 Megarads at 170 kV.
Various optional additives can be added to the composition to improve various properties. These additives may be added as desired and in any amount as long as they do not degrade the performance of the barrier coatings as illustrated herein. Examples of additives include additional additives as earlier described, antiblock and slip aides such as stearamide oleamide or polar additives, such as epoxides, polyols, glycidols or polyamines, such as polyethylenimine, and other silanes such as N-(2-aminoethyl)-3-aminopropyltrimethoxy silane and aminopropyltriethoxysilane may also be added. Specifically excluded from the scope of the present invention are colloidal silicas and silanes or other molecules having four alkoxy or other hydrolyzable groups disposed on a single silicone or other organometalic atom, such as tetra ethoxy silane, and the like. Wetting agents, such as a polyethoxylated alkyl phenyol may also be added.


An ablation catheter system and method of use is provided to endoscopically access portions of the human esophagus experiencing undesired growth of columnar epithelium. The ablation catheter system and method includes controlled depth of ablation features and use of either radio frequency spectrum, non-ionizing ultraviolet radiation, warm fluid or microwave radiation, which may also be accompanied by improved sensitizer agents.

A system and method for treating abnormal epithelium in an esophagus.
Two of the major functions of the human esophagus are the transport of food from intake to the stomach and the prevention of retrograde flow of gastrointestinal contents. The retrograde flow is, in part, prevented by two esophageal sphincters which normally remain closed and which are functional rather than distinct entities. In particular, a lower esophageal sphincter normally remains closed until parasympathetic activation causes its relaxation, allowing food to pass into the stomach from the esophagus. Various types of food and other activity may cause relaxation of the sphincter, such as fatty meals, smoking and beverages having xanthine content. Certain drugs or pharmaceuticals also may cause relaxation of this lower esophageal sphincter, as well as localized trauma or other problems such as neuromuscular disorders.
Regardless, patients having such difficulties may present with clinical indications including dysphagia, or difficulty in swallowing, as well as more classic symptoms of heartburn and other similar complaints. Recurrent problems of this nature often lead to a disorder known as reflux esophagitis, consisting of esophageal mucosa damage due to the interaction of the gastric or intestinal contents with portions of the esophagus having tissue not designed to experience such interaction. As suggested above, the causative agent for such problems may vary.
The treatment for the underlying cause of such inflammatory mechanisms is not the subject of this patent application, but rather the invention is focused on treatment of secondary damage to tissue in the effected region of the esophagus.
An ablation catheter and method of use is provided to endoscopically access portions of the human esophagus experiencing undesired growth of columnar epithelium. The ablation catheter system and method includes controlled depth of ablation features and use of either radio frequency spectrum, non-ionizing ultraviolet radiation, warm fluid or microwave radiation, which may also be accompanied by improved sensitizer agents.

System and method of treating abnormal tissue in the human esophagus


The straw includes an output end that is inventively constructed to provide added benefits for the user. An output shield is attached to the output opening. The output shield has an upper portion, a first projection and an interior angle. The upper portion of the output shield extends outward from the output end. The angular placement of the first projection allows the first projection to project in front of the output opening. When fluid exits the output opening and strikes the output shield and the first projection, the fluid is directed downward towards the tongue rather than striking the roof of the mouth.

Conventional straws typically cause a hot fluid or liquid that is drawn through the straw to strike the roof of the mouth. When the liquid first strikes the roof of the mouth and mixes with air the taste of the liquid can be noticeably altered. The original taste of the liquid is thus changed prior to striking the taste buds on the tongue. The taste buds are predominately located on the tongue, thus of all the parts of the mouth, the tongue is the most capable of fully appreciating the subtle and distinctive tastes of a liquid being drank.
Additionally, another undesirable effect occurs when conventional straws cause the hot liquid to strike the roof of the mouth. The roof of the mouth is the most perceptive part of the mouth with regard to heat sensitivity. The hot liquid drawn through the conventional straw is extremely hot when it immediately contacts the roof of the mouth, leading to discomfort or even immediate burning of the skin tissue.
Therefore, there is a need for a straw that will allow the liquid to contact the taste buds of the tongue first, so that the taste of the liquid is fully enjoyed.
Additionally there is a second desire that the straw direct the hot liquid away from the roof of the mouth, which has the greatest heat sensitivity.
The present invention of a new and useful straw fulfills the aforementioned needs, by achieving the objectives of first allowing the liquid to contact the taste buds of the tongue immediately, and secondly the present invention directs the hot liquid away from the roof of the mouth, which avoids discomfort or pain caused by the heat sensitivity of the roof of the mouth.
The new straw can substantially take the shape and form of a typical straw through out much of the straw""s length. The shape can be a hollow cylindrical body having a diameter, an input end with an input opening, an output end with an output opening, an upper surface and a lower surface. Commonly used straws take this symmetrical form with the input opening and the output opening having the same shape. Alternately, the straw can be other than a cylindrical shape, such as, a square, octagonal or oval shape.
In the present invention the output end is inventively constructed to provide added benefits for the user. An output shield is attached to the output opening. The upper surface is extended to form the output shield. The output shield has an upper portion, a first projection, and an interior angle.
In a preferred embodiment, the upper portion of the output shield extends outward from the output end. The upper portion is substantially parallel to the surface of the hollow cylindrical body. The first projection attaches to the upper portion at an angle, thus forming an interior angle between the upper portion and the first projection. The angular placement of the first projection allows the first projection to project in front of the output opening. The straw is typically positioned in the mouth with the upper portion of the output shield near the roof of the mouth and the lower surface closer to the tongue. Fluid exits the output opening striking the output shield and the first projection, which direct the fluid downward toward the tongue.
The output end can have a lower edge, with the lower edge having a curvature, which indents the lower surface in the direction of the input end. The curvature thus reduces the length of the lower surface in relation to the upper surface. The curvature can conform to the shape of a person""slip. Thus, when the output end and output shield are placed firmly against the person""s lip or tongue, the output opening is sealed and the flow of the fluid halted. In this manner the initiating of the fluid flow and stopping of the fluid flow can be controlled. Either the tongue or the lower lip can be used to control the flow. Both are supple enough to conform to the shape of the output opening, particularly when the lower edge has a curvature that conforms to the shape of a person""s lip. Alternately the lower edge of the output opening can be straight with no indentation curvature, so that the length of the lower surface is equal to that of the upper surface, when you exclude the output shield.
A second projection can be attached to the first projection. An exterior angle is formed by the first projection and the second projection, the exterior angle being between 45 degrees and 170 degrees. A preferred embodiment has an exterior angle of about 90 degrees.
The second projection can be positioned to touch the roof of the mouth, providing stimulation to the sensitive skin area. Alternately the second projection can be positioned downward so that any fluid that splashes past the first projection toward the back of the mouth will be directed by the second projection toward the tongue and taste buds.
The first projection has a first length and the second projection has a second length. In one embodiment the first projection has a length of about between 5 and 6 milimeters and the second projection has a length of about between 5 and 6 milimeters. The length of the projections can vary to create different paths and directions of fluid flow. A longer first projection tends to substantially deflect the fluid or liquid towards the tongue, so that minimal amount of the fluid actually deflected from the second projection. When the first projection is very short then a partial deflection of the liquid is performed by the first projection and the liquid strikes the second projection with a substantial force. The second projection when properly angled can then fully deflect the remainder of the liquid towards the tongue.
The first projection or the second projection can take various shapes including substantially; a square, rectangle, triangle or a half circle. When the second projection is included in the design embodiment then the first projection should be a rectangle, square or other shape that provides a sufficient end edge, to which, the second projection can be attached.
The diameter of the hollow cylindrical body can vary. A preferred embodiment has a diameter of about 7 milimeter. In one embodiment, the first projection and the second projection can have a length about equal to the diameter of the straw. This relationship provides a form that sufficiently deflect the fluid towards the tongue.
The upper portion can have edges that are straight or the edges may have an angular curvature. The upper portion may be deminimis, such that, first projection begins about immediately from the output end and output opening.
In a preferred embodiment the straw is formed from a plastic material. The straw can be clear, a single color, multi-colored or other color variations and designs.
One version of the straw includes a hollow body having an input end, an input opening, an output end, an output opening, a lower edge, an upper surface, and a lower surface. An output shield is formed by the upper surface extending beyond the output end and beyond the lower surface. The output shield is attached to the output opening. The output shield has an upper portion, a first projection and an interior angle formed by the upper portion and the first projection. The interior angle is less than 160 degrees. In a preferred version the interior angle is about 60 degrees. A fluid drawn through the straw will strike the output shield, and the fluid is directed toward a tongue of a mouth.
The straw can be formed so the hollow body is cylindrical. The lower edge can include a curvature that conforms to the shape of a person""s lip. When the output end and the output shield are placed firmly against the person""s lip or tongue, the output opening is sealed by the lip or tongue to stop the flow of the fluid.
A second projection can be attached to the first projection having an exterior angle that is between 45 degrees and 170 degrees. In a preferred version the exterior angle is about 90 degrees. The distance between the first projection and the output end can be between about 7 and 15 milimeters. The distance between the upper portion and the second projection can be between about 7 and 15 milimeters. The invention is illustrated with additional detail in the appended drawings and description.