A method for inhibiting loss of gel strength in an acidic aqueous based solid antiperspirant composition gelled with one or more polysaccharides comprising adding to said composition an effective amount of a gel degradation inhibitor and an acidic aqueous based solid antiperspirant composition containing at least one phase gelled with one or more polysaccharide gelling agents, wherein the improvement comprises including in the polysaccharide gelled phase at least one gel degradation inhibitor.

The invention is in the field of antiperspirant compositions.
Antiperspirant stick compositions are usually anhydrous. They are typically solidified with waxes or various other types of gelling agents such as fatty alcohols, amino acid amides, and the like. One problem with such sticks is that they may be greasy and leave an undesirable residue on underarms and clothing.
The traditional drawbacks with wax-based antiperspirant sticks are remedied with aqueous based antiperspirant sticks gelled with polysaccharide gellants as taught in U.S. Pat. Nos. 6,033,651 and 6,171,581. Such formulas are unique to the antiperspirant market. They provide superior wetness protection and provide a sheer, cool-feeling application on the skin with little or no residue. One problem with such sticks is that the polysaccharide gellants that contribute to the desirable tactile properties tend to lose gel strength over time, which in turn contributes to stick breakage. Gel strength is a measure of the strength of a gelled solid. In antiperspirant solid sticks the gel strength must be carefully monitored to provide a commercially acceptable product. If gel strength is too hard the stick does not have adequate payoff. If the gel strength is not adequate the stick will break too easily. To further complicate the situation, the gel strength of a stick immediately after manufacture may be adequate, but due to the interaction between the various ingredients found within the stick the gel strength decreases over time.
The need gap in the antiperspirant solid stick market is to produce a solid stick that exhibits superior efficacy, sheer application, and minimal residue. In order to be commercially acceptable such sticks must exhibit stability and long term gel strength.
It is an object of the invention to provide solid antiperspirant stick compositions having a long term gel strength.
It is a further object of the invention to provide a method for improving gel strength and inhibiting loss of gel strength in an aqueous acidic composition gelled with polysaccharide gellants comprising adding a gel strengthening effective amount of a gel degradation inhibitor.
The invention is directed to a method for inhibiting loss of gel strength in an acidic aqueous based solid antiperspirant composition gelled with one or more polysaccharides comprising adding to said composition an effective amount of a gel degradation inhibitor.
The invention is also directed to a method for preparing an aqueous based antiperspirant composition having improved gel strength comprising the steps of:
a) preparing a water phase by combining antiperspirant salts, one or more polysaccharide gellants, a gel degradation inhibitor, and water and heating to a temperature sufficient to form a homogeneous mixture;
b) preparing an oil phase by combining at least one oil with one or more compatible ingredients,
c) emulsifying the water phase into the oil phase.
The invention is also directed to a method for preparing an aqueous based solid antiperspirant composition having improved gel strength comprising the steps of:
a) preparing a first aqueous phase comprised of antiperspirant salts, water, and a gel degradation inhibitor and mixing well to form a homogeneous solution,
b) preparing a second aqueous phase comprising water and at least one polysaccharide gellant,
c) preparing an oil phase comprising at least one oil in combination with one or more oil compatible ingredients,
d) emulsifying the second aqueous phase (b) into the oil phase (c) to form an emulsion; and
e) emulsifying the first aqueous phase (a) into the mixture of (d) to form a water and oil emulsion solid antiperspirant composition.
one or more polysaccharide gellants, and a gel degradation inhibitor and heating to a temperature sufficient to form a homogeneous mixture,
The invention is also directed to acidic aqueous based solid antiperspirant composition gelled with one or more water soluble polysaccharide gelling agents, wherein the improvement comprises including in the water phase an effective amount of a gel degradation inhibitor in the form of a water soluble metal salt.
All percentages mentioned herein are percentages by weight unless otherwise indicated.
The pH values of the solutions are measured at 15% w/w @25xc2x0 C.
The term xe2x80x9cgel strengthxe2x80x9d means the strength of a gel composition measured in grams per centimeter squared (gm/cm2). Preferably, the gel strength is measured using a TA.XT2i analyzer with a cylindrical probe having a diameter of 2 inches. A circle about 1 cm. in diameter and 1 cm. in height is cut from a gel and placed on a glass slide beneath the elevated probe. The machine is activated and the probe falls on gel. The gel strength of the sample is the maximum force in grams/cm2 required to fracture the gel sample.
I. The Method of the Invention
Typically aqueous based solid antiperspirant sticks contain efficacious levels of astringent antiperspirant salts which are acidic in nature. The acidity contributes to the effectiveness of such salts in inhibiting perspiration. However, antiperspirant salts are very difficult to formulate because their inherent acidity reduces the pH of the stick which in turn may have a negative impact on other ingredients in the stick which may be pH labile. Increasing the pH of the antiperspirant stick by including other neutralizing ingredients in the stick, or reacting the antiperspirant salts themselves with a neutralizing agent, may reduce the incompatibility between the low pH salts and other ingredients in the stick but the effectiveness of the antiperspirant salts on inhibiting perspiration is then compromised. It has been discovered that antiperspirant salts that are too neutralized are not as effective in inhibiting perspiration. Thus, a certain balance must be maintained between formula stability and efficacy.
It has been found that aqueous based antiperspirant stick compositions gelled with polysaccharides are particularly susceptible to stick degradation, e.g. the sticks lose a significant amount of gel strength within one week (especially at elevated temperature) after they are poured because polysaccharide gellants readily hydrolyze in acidic media. Certain tests on such sticks show that the aqueous-based antiperspirant sticks gelled with polysaccharides lose as much as 33% of their original gel strength when stored at 40xc2x0 C. for one week, and as much as 65% of their original gel strength when stored at 40xc2x0 C. for five weeks. Typically the pH of these antiperspirant sticks is in the range of 3.2 to 3.5.
In the method of the invention, the loss in gel strength over time can be minimized by including at least one gel degradation inhibitor in the aqueous based antiperspirant compositions gelled with polysaccharides, preferably in the aqueous phase. Most suitable gel degradation inhibitors are those materials which are capable of increasing the pH of the antiperspirant composition to a range of about 4.2 to 4.5. Examples of suitable gel degradation inhibitors include water soluble inorganic or organic bases that are stable (i.e. do not precipitate the antiperspirant salts), and are capable of increasing the pH of the compositions at least xc2xd unit. The following materials may be suitable gel degradation inhibitors: salts of alkali and alkaline earth metals, urea, imidazole, tris buffers, N,N-tetrakis-2-hydroxypropyl-ethylenediamine, EDTA, alkali and alkaline earth metals reacted with amino acids, and so on. Further examples of such gel degradation inhibitors include sodium hydroxide, potassium hydroxide, zinc glycinate, and the like. Particularly preferred is zinc glycinate.
In a more preferred embodiment of the claimed method, the gel degradation inhibitor is added at certain times during manufacture of the compositions. In the case where the compositions are a single phase gel, the antiperspirant salts, agarose, water, and gel degradation inhibitor are combined and heated to 80xc2x0 C. with stirring to dissolve all components until a clear solution is formed. The composition is poured into molds and allowed to cool. In preparing the single aqueous phase composition, it may be desirable to prepare the composition by combining all ingredients together and mixing well, preferably with elevated temperature.
It may also be desired to prepare separate phases of the single aqueous phase composition as a pre-mix, and then combine the separate pre-mixes together. For example, it is believed that the final composition exhibits improved stability when the single aqueous phase is prepared as two pre-mixes. The first pre-mix is an aqueous solution of antiperspirant salt and the gel degradation inhibitor. The second pre-mix comprises water, the polysaccharide gellant, and any other desired water soluble ingredients. The second pre-mix is then emulsified into the oil phase, which comprises at least one liquid oil and any other desired oil soluble ingredients. The first pre-mix is then emulsified into the emulsion. The resulting mixture is in the form of an emulsion with the water phase ingredients dispersed in the oil phase, or in the alternative where the oil phase is dispersed in the continuous water phase. The composition is poured into molds and allowed to cool.
While the preferred compositions made according to the claimed method are in the emulsion form, it may be desired to make single phase aqueous antiperspirant compositions. Such compositions are made by combining all of the aqueous phase ingredients and mixing well with heat to form a single homogeneous solution. The compositions are poured into molds to solidify. Alternatively, it may be desired to make two pre-mixes and then combine them to form the compositions. A first pre-mix is prepared by combining water, the antiperspirant salts, and the gel degradation inhibitor, and mixing well until a homogeneous solution is formed. A second pre-mix is prepared by combining water, the polysaccharide gellant, and any other desired water soluble ingredients and mixing with heat to form a homogeneous solution. Then the two pre-mixes are combined and mixed well and poured into appropriate containers.
In either case, the inclusion of the gel degradation inhibitor in the same water phase as the antiperspirant salts greatly enhances the stability of the product and causes significant inhibition in loss of gel strength. In a more preferable embodiment, the inhibitor is added during the manufacture of the antiperspirant active.
II. The Compositions
The invention is also directed to acidic aqueous based solid compositions gelled with one or more polysaccharides, wherein the improvement comprises inclusion of an effective amount of a gel degradation inhibitor.
A. Polysaccharide Gellants
The polysaccharide gellants used in the claimed compositions are present at about 0.05-50%, preferably about 0.1-40%, more preferably about 0.5-35% by weight of the total gel composition. The term xe2x80x9cpolysaccharide gellantxe2x80x9d means a water soluble compound or composition (i) containing at least one saccharide moiety; and (ii) which, upon mixing with water in a ratio of about 1 to 1 at room temperature (25xc2x0 C.) is capable of forming either a soft gel having a gel having a viscosity of about 1,000 to 800,000 centipoise at 25xc2x0 C., and/or a gel strength of about 10 to 5,000 grams/cm2 at 25xc2x0 C. as measured using a TA.XT2i texture analyzer with a xc2xd inch diameter cylindrical probe. The term xe2x80x9csaccharide moietyxe2x80x9d means a polyhydroxy aldehyde or ketone, or acid hydrolysis product thereof, which, preferably, has the general formula Cx(H2O)y. Examples of saccharide moieties include the D and L forms of glucose, fructose, xylose, arabinose, fucose, galactose, pyruvic acid, succinic acid, acetic acid, galactose, 3,6-anhydro-galactose sulfate, galactose-4-sulfate, galactose-2-sulfate, galactose-2,6-disulfate, mannose, glucuronic acid, mannuronic acid, guluronic acid, galactouronic acid, rhamnose, and so on. Preferably the polysaccharide gellants have a molecular weight ranging from about 500 to 15,000,000 daltons, preferably 5,000 to 1,000,000, more preferably 25,000 to 500,000 daltons. Polysaccharide gellants which fulfill the above criteria include polysaccharides such as galactans, galactomannans, glucomannans, polyuronic acids, and the like. Suitable galactans are agar, agarose, and kappa carageenan, iota carageenan, lambda carageenan. Examples of suitable galactomannans are locust bean gum and guar; examples of glucans are cellulose and derivatives thereof, starch and derivatives, dextrans, pullulan, beta 1,3-glucans, chitin, xanthan, tamarind and the like; examples of glucomannans are konjac; examples of polyuronic acids are algin, alginates, pectins; examples of heteropolysaccharides are gellan, welan, gum arabic, karaya gum, okra gum, aloe gum, gum tragacanth, gum ghatti quinceseed gum, psyllium, starch arabinogalactan and so on.
Preferred are galactans, in particular agarose, which is a polysaccharide comprised of basic repeating units of 1,3-linked beta-D-galactopyranose and 1,4-linked 3,6-anhydro-alpha-L-galactopyranose saccharide moieties. The agarose may be substituted by hydrophobic or hydrophilic groups. Examples of hydrophobic groups are alkoxy, in particular, methoxy. Examples of hydrophilic or polar groups are sulfate, pyruvate and the like. Examples of such substitutions are taught in Aoki, T. T.; Araki and M. Kitamikado; 1990, Vibrio sp. AP-2. Eur. J. Biochem, 187, 461-465, which is hereby incorporated by reference. The average molecular weight of agarose ranges between 35,700 and 144,000 daltons. The agarose suitable for use in the compositions of the invention may be from any suitable source or locale. For example an article authored by M. Lahaye and C. Rochas, Hydrobiologia, 221, 137-148, 1991, which is hereby incorporated by reference, discusses the numerous different types of agarose from different origins of seaweed species, all of which are suitable for use in the compositions of the invention. Also suitable for use in the compositions of the invention are chemically modified agaroses, such as those taught in an article authored by K. B. Guiseley in Industrial Polysaccharides:Genetic Engineering, Structure/Property Relations and Applications, Edited by M. Yalpani, 1987, Elsevier Science Publishers, which is hereby incorporated by reference. The Guiseley article teaches methods for the chemical modification of agaroses to obtain optimum gelling properties. One example of modified agarose is a hydroethylated agarose which is sold under the brand names SeaPlaque and SeaPrep from FMC, Inc. In general, any modification of agarose which does not affect the helical conformation (i.e. which is obtained via linkage of the O6 and O4 of galactose to the O2 of 3,6-anhydrogalactose) will preserve the gelling capability.
In the most preferred embodiment of the invention, the composition contains at least two polysaccharide gellants, preferably a galactan and one gellant which is a galactomannan, glucan, glucomannan, polyuronic acid, or heteropolysaccharide. Agarose suitable for use in the compositions can be purchased from FMC Inc, under the tradenames Seakem LE and Seakem CLE.
B. Antiperspirant Active
The compositions of the invention contain 1-30%, preferably 5-25%, more preferably 10-22% by weight of the total composition of antiperspirant active salt.
The term xe2x80x9cantiperspirant active saltxe2x80x9d or xe2x80x9cantiperspirant saltxe2x80x9d means any compound or composition having antiperspirant activity, preferably astringent metallic salts such as the inorganic and organic salts of aluminum, zirconium, and zinc, and mixtures thereof. Particularly preferred are the aluminum and zirconium salts such as aluminum halides, aluminum hydroxide halides, zirconyl oxide halides, zirconyl hydroxy halides, and mixtures thereof. Aluminum salts include those of the formula:
Al2(OH)aClb.xH2O
wherein a is from about 2 to 5; a+b=6; x is from about 1 to about 6; and wherein a, b, and x may have non-integer values. Zirconium salts include those of the formula:
ZrO(OH)2-aCla.xH2O
wherein a is from about 1.5 to about 1.87; x is from about 1 to about 7; and wherein a and n may have non-integer values.
Examples of aluminum and zirconium salts include aluminum chloride, aluminum chlorohydrate, aluminum chlorohydrex PEG, aluminum chlorohydrex PG, aluminum dichlorohydrate, aluminum dichlorohydrex PEG, aluminum dichlorohydrex PG, aluminum sesquichlorohydrate, aluminum sesquichlorohydrex PEG, aluminum sesquichlorohydrex PG, aluminum zirconium octachlorohdrate, aluminum zirconium octachloroydrex GLY, aluminum zirconium pentachlorohydrate, aluminum zirconium pentachlorohydrex GLY, aluminum zirconium tetrachlorohydrate, aluminum zirconium tetrachlorohydrex GLY, aluminum zirconium trichlorohydrate, aluminum zirconium trichlorohydrex GLY, and mixtures thereof.
Particularly preferred zirconium salts are those complexes also containing aluminum and glycine, in particular, aluminum zirconium tetrachlorohydrex GLY. The antiperspirant salts used in the composition of the invention are solubilized in the water. While preferably the antiperspirant salts are completely dissolved in the water, in some cases small amounts of salts may not be dissolved, i.e. may remain in the crystalline or suspensoid form.
C. Water
The compositions of the invention contain water in amounts ranging from about 1-90%, more preferably about 3-80%, most preferably about 5-60% water.
In one preferred embodiment of the invention the composition is clear or translucent, which means that the composition has a refractive index ranging from about 1.0 to 1.6, preferably 1.2 to 1.5 at 21xc2x0 C. and an optical clarity of less than about 50 Nephelometric turbidity units (NTU) when measured with an Orbeco-Hellige #965 direct reading turbidometer, and a gel strength of 500 to 5000 grams/cm2.
D. Gel Degradation Inhibitor
The compositions contain about 0.01-15%, preferably about 0.05-12%, more preferably about 0.1-10% by weight of the total composition of a gel degradation inhibitor. Suitable gel degradation inhibitors include water soluble organic or inorganic salts water soluble inorganic or organic bases that are stable (i.e. do not precipitate the antiperspirant salts), and are capable of increasing the pH of the compositions at least xc2xd unit. The following materials may be suitable gel degradation inhibitors: water soluble salts of alkali and alkaline earth metals, alkali and alkaline earth metal oxides, hydroxides, carbonates, bicarbonates, and trivalent metallic hydroxides, urea, imidazole, tris buffers, N,N-tetrakis-2-hydroxypropyl-ethylenediamine, ethylene diamine tetraacetic acid, and metal salts of amino acids, and so on. Particularly preferred is where the metal is salt is a metal salt of an amino acid glycine and the metal zinc.
E. Other Ingredients
The composition may also contain a variety of other ingredients that may improve the aesthetic or other features of the compositions, such as gel structure modifiers, humectants, preservatives, emollients and so on.
1. Gel Structure Modifiers
Preferably, the composition contains 1-50%, preferably 2-40%, more preferably 5-35% of at least on gel structure modifier. The term xe2x80x9cgel structure modifierxe2x80x9d means an ingredient which is capable of modifying the gel structure in some fashion; for example by plasticizing the gel structure, improving texture or moisturizing properties, which provide the end result of improving payoff when applied to the skin. For example, antiperspirant stick or gel compositions, when applied to the skin, must deposit a certain amount of product onto the skin. The amount of material deposited onto the skin as the gel is rubbed across the skin surface is called xe2x80x9cpay offxe2x80x9d. If a gel does not have adequate pay off, when the gel is rubbed across the underarm skin, a sufficient amount of the gel composition will not rub off onto the skin. On the other hand, if the gel has too much pay off, when it is rubbed across the underarm skin too much of the gel deposits on the skin. Thus, it is important to regulate the gel structure and consistency so that pay off is optimal. Generally, suitable gel structure modifiers include polyols, aliphatic short chain mono-, di, and polyhydric alcohols, ethoxylated and/or propoxylated fatty alcohols or glycols, monomer and polymeric ethers and block copolymers, and the like.
a). Polyols
Suitable polyols are defined as compounds which contain three or more hydroxyl groups per molecule. Examples of suitable polyols include fructose, glucamine, glucose, glucose glutamate, glucuronic acid, glycerin, 1,2,6-hexanetriol, hydroxystearyl methylglucamine, inositol, lactose, malitol, mannitol, methyl gluceth-10, methyl gluceth-20, methyl glucose dioleate, methyl glucose sesquicaprylate/sesquicaprate, methyl glucose sesquicocoate, methyl glucose sesquiisostearate, methyl glucose sesquilaurate, methyl glucose sesquistearate, phytantriol, riboflavin, sorbeth-6, sorbeth-20, sorbeth-30, sorbeth-40, sorbitol, sucrose, thioglycerin, xylitol, and mixtures thereof.
b). Ethers
Also suitable as gel structure modifiers are homopolymeric or block copolymeric liquid ethers. Polymeric ethers are preferably formed by polymerization of monomeric alkylene oxides, generally ethylene or propylene oxides. Preferred monomeric ethers are those exhibiting the structure below were n=1. Preferred polymeric ethers are comprised of moieties having the general structure below wherein n=2 to 100:
where R and Rxe2x80x2 are each independently H, or C1-30 straight or branched chain alkyl, and n is 1 to 20. Examples of such polymeric ethers include PEG, PPG, PEG/PPG copolymers, and derivatives thereof as well as alkoxylated alcohols such as steareth 2-100, ceteth 2-100, and the like.
Other examples of suitable polymeric ethers include polyoxypropylene polyoxyethylene block copolymers having the general formula:
wherein x is 1-200, y is 1-200 and z is 1-200. Such compounds are sold under the CTFA name Meroxapol 105, 108, 171, 172, 174, 178, 251, 252, 254, 255, 258, 311, 312, and 314.
3. Alcohols
Mono- and dihydric alcohols are also suitable for use as gel structure modifiers. Generally, these mono- and dihydric alcohols have the general formula R(OH)N where n is 1 or 2 and R is a substituted or unsubstituted saturated C2-10, preferably C1-8 alkyl, or a substituted or unsubstituted alicyclic, bicyclic, or aromatic ring, with the substituents selected from halogen, alkoxy, hydroxy, and so on. Examples of suitable alcohols include monohydric alcohols such as ethanol, isopropanol, hexyldecanol, benzyl alcohol, propyl alcohol, and isopropyl alcohol, as well as dihydric alcohols such as hexylene glycol, diethylene glycol, ethylene glycol, propylene glycol, 1,2-butylene glycol, triethylene glycol, dipropylene glycol, methyl propanediol, and mixtures thereof
4. Sorbitan Derivatives
Sorbitan derivatives, which are defined as ethers or esters of sorbitan, are also suitable gel structure modifiers. Examples of suitable sorbitan derivatives are the Polysorbates, which are defined as stearate esters of sorbitol and sorbitan anhydrides, such as Polysorbate 20, 21, 40, 60, 61, 65, 80, 81, and 85. Also suitable are fatty esters of hexitol anhydrides derived from sorbitol, such as sorbitan trioleate, sorbitan tristearate, sorbitan sesquistearate, sorbitan stearate, sorbitan palmitate, sorbitan oleate, and mixtures thereof
5. Organosiloxane Emulsifiers
Also suitable as gel structure modifiers are organosiloxane emulsifiers, provided they are at least partially soluble in the aqueous single phase composition. Suitable organosiloxane emulsifiers generally contain at least one lipophilic radical or portion and at least one hydrophilic radical or portion so that a portion of the molecule is soluble in the aqueous phase composition and a portion of the molecule is dispersible in the aqueous phase composition. The polymeric organosiloxane used in the invention is preferably a liquid or semi-solid at 25xc2x0 C. The polymeric organosiloxane is generally a water-in-oil or oil-in-water type surfactant which is preferably nonionic, having an Hydrophile/Lipophile Balance (HLB) of 2 to 18. Preferably the organosiloxane is a nonionic surfactant having an HLB of 2 to 12, preferably 2 to 10, most preferably 4 to 6. The HLB of a nonionic surfactant is the balance between the hydrophilic and lipophilic portions of the surfactant and is calculated according to the following formula:
HLB=7+11.7xc3x97log Mw/Mo
where Mw is the molecular weight of the hydrophilic group portion and Mo is the molecular weight of the lipophilic group portion.
The term xe2x80x9corganosiloxane polymerxe2x80x9d means a polymer containing a polymeric backbone including repeating siloxy units that may have cylic, linear or branched repeating units, e.g. di(lower)alkylsiloxy units, preferably dimethylsiloxy units. The hydrophilic portion of the organosiloxane is generally achieved by substitution onto the polymeric backbone of a radical that confers hydrophilic properties to a portion of the molecule. The hydrophilic radical may be substituted on a terminus of the polymeric organosiloxane, or on any one or more repeating units of the polymer. In general, the repeating dimethylsiloxy units of modified polydimethylsiloxane emulsifiers are lipophilic in nature due to the methyl groups, and confer lipophilicity to the molecule. In addition, longer chain alkyl radicals, hydroxy-polypropyleneoxy radicals, or other types of lipophilic radicals may be substituted onto the siloxy backbone to confer further lipophilicity and organocompatibility. If the lipophilic portion of the molecule is due in whole or part to a specific radical, this lipophilic radical may be substituted on a terminus of the organosilicone polymer, or on any one or more repeating units of the polymer. It should also be understood that the organosiloxane polymer in accordance with the invention should have at least one hydrophilic portion and one lipophilic portion.
The term xe2x80x9chydrophilic radicalxe2x80x9d means a radical that, when substituted onto the organosiloxane polymer backbone, confers hydrophilic properties to the substituted portion of the polymer. Examples of radicals that will confer hydrophilicity are hydroxy-polyethyleneoxy, hydroxyl, carboxylates, sulfonates, sulfates, phosphates, or amines.
The term xe2x80x9clipophilic radicalxe2x80x9d means an organic radical that, when substituted onto the organosiloxane polymer backbone, confers lipophilic properties to the substituted portion of the polymer. Examples of organic radicals which will confer lipophilicity are C1-40 straight or branched chain alkyl, fluoro, aryl, aryloxy, C1-40 hydrocarbyl acyl, hydroxy-polypropyleneoxy, or mixtures thereof The C1-40 alkyl may be non-interrupted, or interruped by one or more oxygen atoms, a benzene ring, amides, esters, or other functional groups.
The polymeric organosiloxane emulsifier used in the invention may have any of the following general formulas:
MxQy, or
MxTy, or
MDxDxe2x80x2yDxe2x80x3zM
wherein each M is independently a substituted or unsubstituted trimethylsiloxy endcap unit, If substituted, one or more of the hydrogens on the endcap methyl groups are substituted, or one or more methyl groups are substituted with a substituent that is a lipophilic radical, a hydrophilic radical, or mixtures thereof. T is a trifunctional siloxy unit having the empirical formula RRxe2x80x2SiO1.5 or RRSiO1.5. Q is a quadrifunctional siloxy unit having the empirical formula SiO2, and D, Dxe2x80x2, Dxe2x80x3, x, y, and z are as set forth below, with the proviso that the compound contains at least one hydrophilic radical and at least one lipophilic radical. Examples of emulsifiers used in the compositions of the invention are of the general formula:
MDxDxe2x80x2yDxe2x80x3zM
wherein the trimethylsiloxy endcap unit is unsubstituted or mono-substituted, wherein one methyl group is substituted with a lipophilic radical or a hydrophilic radical. Examples of such substituted trimethylsiloxy endcap units include (CH3)2HPSiO, (CH3)2LPSiO, (CH3)2CH2HPSiO, (CH3)2CH2LPSiO, wherein HP is a hydrophilic radical and LP is a lipophilic radical. D, Dxe2x80x2, and Dxe2x80x3 are difunctional siloxy units substituted with methyl, hydrogen, a lipophilic radical, a hydrophilic radical or mixtures thereof In this general formula:
x=0-5000, preferably 1-1000
y=0-5000, preferably 1-1000, and
z=0-5000, preferably 0-1000,
with the proviso that the compound contains at least one lipophilic radical and at least one hydrophilic radical. Examples of these polymers are disclosed in U.S. Pat. No. 4,698,178, which is hereby incorporated by reference.
Particularly preferred is a linear silicone of the formula:
MDxDxe2x80x2yDxe2x80x3zM
wherein M=RRRSiO1/2
D and Dxe2x80x2=RRxe2x80x2SiO2/2
Dxe2x80x3=RRSiO2/2
x, y, and z are each independently 0-1000,
where R is methyl or hydrogen, and Rxe2x80x2 is a hydrophilic radical or a lipophilic radical, with the proviso that the compound contains at least one hydrophilic radical and at least one lipophilic radical.
Most preferred is wherein
M=trimethylsiloxy
D=Si[(CH3)][(CH2)nCH3]O2/2 where n=1-40,
Dxe2x80x2=Si[(CH3)][(CH2)nxe2x80x94Oxe2x80x94PE)]O2/2 where PE is (xe2x80x94C2HO)a(xe2x80x94C3H6O)bH, o=0-40,
a=1-100 and b=1-100, and
Dxe2x80x3=Si(CH3)2O2/2
Organosiloxane polymers useful in the compositions of the invention are commercially available from Goldschmidt Corporation under the ABIL tradename including ABIL WE 09 or ABIL WS 08 which is cetyl dimethicone copolyol.
Another type of preferred organosiloxane emulsifier suitable for use in the compositions of the invention are emulsifiers sold by Union Carbide under the Silwet(trademark) trademark. These emulsifiers are represented by the following generic formulas:
(Me3Si)y-2[(OSiMe2)x/yOxe2x80x94PE]y
wherein PE=xe2x80x94(EO)m(PO)nR
R=lower alkyl or hydrogen
Me=methyl
EO is polyethyleneoxy
PO is polypropyleneoxy
m and n are each independently 1-5000
x and y are each independently 0-5000, and
wherein PE=xe2x80x94CH2CH2CH2O(EO)m(PO)nZ
Z=lower alkyl or hydrogen, and
Me, m, n, x, y, EO and PO are as described above,
with the proviso that the molecule contains a lipophilic portion and a hydrophilic portion. Again, the lipophilic portion can be supplied by a sufficient number of methyl groups on the polymer backbone.
Particularly preferred is a Silwet(trademark) polymer of the following general formula:
Wherein n is 1-10, preferably 8.
Another preferred organosiloxane emulsifier for use in the compositions of the invention is dimethicone copolyol.
Examples of other polymeric organosiloxane surfactants or emulsifiers include amino/polyoxyalkyleneated polydiorganosiloxanes disclosed in U.S. Pat. No. 5,147,578. Also suitable are organosiloxanes sold by Goldschmidt under the ABIL trademark including ABIL B-9806, as well as those sold by Rhone-Poulenc under the Alkasil tradename. Also, organosiloxane emulsifiers sold by Amerchol under the Amersil tradename, including Amersil ME-358, Amersil DMC-287 and Amersil DMC-357 are suitable. Dow Corning surfactants such as Dow Corning 3225C Formulation Aid, Dow Corning 190 Surfactant, Dow Corning 193 Surfactant, Dow Corning Q2-5200, and the like are also suitable. In addition, surfactants sold under the tradename Silwet by Union Carbide, and surfactants sold by Troy Corporation under the Troysol tradename, those sold by Taiwan Surfactant Co. under the tradename Ablusoft, those sold by Hoechst under the tradename Arkophob, are also suitable for use in the invention.
Preferred is where the gel structure modifier is selected from a monomeric ether, polymeric ether, monohydric alcohol, dihydric alcohol, organosiloxane emulsifier, polymeric ether, or mixtures thereof. Particularly preferred is wherein the monohydric alcohol is a C2-10 alkanol, preferably ethanol, and the dihydric alcohols are of the formula RORxe2x80x2 wherein each R and Rxe2x80x2 are independently H or a C2-10 unsubstituted or substituted alkyl, where the substituent is hydroxyl or methyl; such compounds being preferably propylene glycol, dipropylene glycol, and methyl propandiol.
6. Deodorant Actives
It may be desired to incorporate into the cosmetic gel composition one or more deodorant actives. If so, a range of about 0.1-30% of deodorant active is suggested. The deodorant actives should be soluble in the aqueous single phase composition, or water dispersible carrier, such as triclosan encapsulated in cyclodextrin, which may be purchased from Lipo, Inc. Examples of suitable deodorant actives include fragrances, ammonium phenolsulfonate, benzalkonium chloride, benzethonium chloride, bromochlorophene, cetylpyridinium chloride, chlorophyllin-copper complex, chlorothymol, chloroxylenol, cloflucarban, dequalinium chloride, dichlorophene, dichloro-m-xylenol, disodium dihydroxyethyl sulfosuccinylundecylenate, domiphen bromide, hexachlorophene, lauryl pyridinium chloride, methylbenzethonium chloride, phenol, sodium bicarbonate, sodium phenolsulfonate, triclocarbone, triclosan, zinc phenolsulfonate, zinc ricinoleate, and mixtures thereof. The preferred deodorant active is triclosan, fragrance and the like.
The composition of the invention may contain other ingredients, providing such ingredients are soluble in the aqueous single phase composition, or water dispersible/miscible via emulsification or a delivery system. Such ingredients may possibly include humectants, detackifiers such as dimethyl isosorbide, preservatives, surfactants, and so on.
As noted, the single phase aqueous gel composition of the invention may be used alone, or it may be used to form an emulsion. In the latter case, the gel composition may either be dispersed into an oily phase, or the gel composition may form the continuous phase and the oily phase may be dispersed into the gel composition. The oily phase should be insoluble or immiscible with the aqueous gel phase. If the gel composition is used to form an emulsion, generally the emulsion composition will contain about 1-85%, preferably 5-70%, more preferably 7-60% by weight of the total emulsion composition of the aqueous single phase gel composition, and about 0.1-75%, preferably 0.5-65%, more preferably 1-50% by weight of the total emulsion composition of oil. Preferably, the emulsions are oil in water emulsions.
7. Oils
The oils used may be volatile or nonvolatile. The term xe2x80x9cvolatilexe2x80x9d means that the oil has a measureable vapor pressure, or a vapor pressure of at least 2 mm. of mercury at 20xc2x0 C. The term xe2x80x9cnonvolatilexe2x80x9d means that the oil has a vapor pressure of less than 2 mm. of mercury at 20xc2x0 C. Suitable volatile solvents generally have a viscosity of 0.5 to 10 centistokes at 25xc2x0 C. Suitable volatile oils include linear silicones, cyclic silicones, paraffinic hydrocarbons, or mixtures thereof.
Cyclic silicones (or cyclomethicones) are of the general formula:
where n=3-7.
Linear volatile silicones in accordance with the invention have the general formula:
(CH3)3Sixe2x80x94Oxe2x80x94[Si(CH3)2xe2x80x94O]nxe2x80x94Si(CH3)3
where n=0-7, preferably 0-5.
Linear and cyclic volatile silicones are available from various commercial sources including Dow Corning Corporation and General Electric. The Dow Corning volatile silicones are sold under the tradenames Dow Corning 244, 245, 344, and 200 fluids. These fluids comprise octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, and mixtures thereof.
Also suitable as the volatile oils are various straight or branched chain paraffinic hydrocarbons having 5 to 40 carbon atoms, more preferably 8-20 carbon atoms. Suitable hydrocarbons include pentane, hexane, heptane, decane, dodecane, tetradecane, tridecane, and C8-20 isoparaffins as disclosed in U.S. Pat. Nos. 3,439,088 and 3,818,105, both of which are hereby incorporated by reference. Preferred volatile paraffinic hydrocarbons have a molecular weight of 70-225, preferably 160 to 190 and a boiling point range of 30 to 320, preferably
60-260 degrees C., and a viscosity of less than 10 cs. at 25 degrees C. Such paraffinic ydrocarbons are available from EXXON under the ISOPARS trademark, and from the Permethyl Corporation. Suitable C12 isoparaffins are manufactured by Permethyl Corporation under the tradename Permethyl 99A. Another C12 isoparaffin (isododecane) is distributed by Presperse under the tradename Permethyl 99A. Various C16 isoparaffins commercially available, such as isohexadecane (having the tradename Permethyl R), are also suitable. Transfer resistant cosmetic sticks of the invention will generally comprise a mixture of volatile silicones and volatile paraffinic hydrocarbons.
A wide variety of nonvolatile oils are also suitable for use in the cosmetic compositions of the invention. The nonvolatile oils generally have a viscosity of greater than 10 centipoise at 25xc2x0 C., and may range in viscosity up to 1,000,000 centipoise at 25xc2x0 C. Examples of nonvolatile oils suitable for use in the cosmetic sticks of the invention include esters of the formula RCOxe2x80x94ORxe2x80x2 wherein R and Rxe2x80x2 are each independently a C1-25, preferably a C4-20 straight or branched chain alkyl, alkenyl or alkoxycarbonylalkyl or alkylcarbonyloxyalkyl. Examples of such esters include isotridecyl isononanoate, PEG-4 diheptanoate, isostearyl neopentanoate, tridecyl neopentanoate, cetyl octanoate, cetyl palmitate, cetyl ricinoleate, cetyl stearate, cetyl myristate, coco-dicaprylate/caprate, decyl isostearate, isodecyl oleate, isodecyl neopentanoate, isohexyl neopentanoate, octyl palmitate, dioctyl malate, tridecyl octanoate, myristyl myristate, octododecanol, and fatty alcohols such as oleyl alcohol, isocetyl alcohol, and the like, as well as the esters disclosed on pages 24-26 of the C.T.F.A. Cosmetic Ingredient Handbook, First Edition, 1988, which is hereby incorporated by reference.
The oil may also comprise naturally occuring glyceryl esters of fatty acids, or triglycerides. Both vegetable and animal sources may be used. Examples of such oils include castor oil, lanolin oil, triisocetyl citrate, C10-18 triglycerides, caprylic/capric/triglycerides, coconut oil, corn oil, cottonseed oil, linseed oil, mink oil, olive oil, palm oil, illipe butter, rapeseed oil, soybean oil, sunflower seed oil, walnut oil, and the like.
Also suitable as the oil are synthetic or semi-synthetic glyceryl esters, e.g. fatty acid mono-, di-, and triglycerides which are natural fats or oils that have been modified, for example, acetylated castor oil, glyceryl stearate, glyceryl dioleate, glyceryl distearate, glyceryl trioctanoate, glyceryl distearate, glyceryl linoleate, glyceryl myristate, glyceryl isostearate, PEG castor oils, PEG glyceryl oleates, PEG glyceryl stearates, PEG glyceryl tallowates, and so on.
Also suitable as the oil are nonvolatile hydrocarbons such as isoparaffins, hydrogenated polyisobutene, mineral oil, squalene, petrolatum, and so on.
Also suitable as the oil are various lanolin derivatives such as acetylated lanolin, acetylated lanolin alcohol, and so on.
Nonvolatile silicones, both water soluble and water insoluble, are also suitable as the oil component. Such silicones preferably have a viscosity of 10 to 600,000 centistokes, preferably 20 to 100,000 centistokes at 25xc2x0 C. Suitable water insoluble silicones include amodimethicone, bisphenylhexamethicone, dimethicone, hexadecyl methicone, methicone, phenyl trimethicone, simethicone, dimethylhydrogensiloxane, stearoxytrimethylsilane, vinyldimethicone, and mixtures thereof.
Also suitable as the nonvolatile oil are various fluorinated oils such as fluorinated silicones, fluorinated esters, or perfluropolyethers. Particularly suitable are fluorosilicones such as trimethylsilyl endcapped fluorosilicone oil, polytrifluoropropylmethylsiloxanes, and similar silicones such as those disclosed in U.S. Pat. No. 5,118,496 which is hereby incorporated by reference. Perfluoropolyethers like those disclosed in U.S. Pat. Nos. 5,183,589, 4,803,067, 5,183,588 all of which are hereby incorporated by reference, which are commercially available from Montefluos under the trademark Fomblin, are also suitable shine enhancers.
Guerbet esters are also suitable oils. The term xe2x80x9cguerbet esterxe2x80x9d means an ester which is formed by the reaction of a guerbet alcohol having the general formula:
with a carboxylic acid having the general formula:
R3COOH, or
HOOCxe2x80x94R3xe2x80x94COOH
wherein R1 and R2 are each independently a C4-20 alkyl and R3 is a substituted or unsubstituted fatty radical such as a C1-50 straight or branched chain saturated or unsaturated alkyl or alkylene, or phenyl, wherein the substituents are halogen, hydroxyl, carboxyl, and alkylcarbonylhydroxy. Particularly preferred is a carboxylic acid wherein the R group is such to provide an ingredient known as meadowfoam seed oil.
Preferably, the guerbet ester is a fluoro-guerbet ester which is formed by the reaction of a guerbet alcohol and carboxylic acid (as defined above), and a fluoroalcohol having the following general formula:
CF3xe2x80x94(CF2)nxe2x80x94CH2xe2x80x94CH2xe2x80x94OH
wherein n is from 3 to 40.
Examples of suitable fluoro guerbet esters are set forth in U.S. Pat. No. 5,488,121 which is hereby incorporated by reference. Suitable fluoro-guerbet esters are also set forth in U.S. Pat. No. 5,312,968 which is hereby incorporated by reference. Most preferred is a guerbet ester having the tentative CTFA name fluoro-octyldodecyl meadowfoamate. This ester is sold by Siltech, Norcross Ga. as Developmental Ester L61125A, under the tradename Silube GME-F.
Preferably, the compositions of the invention contain a mixture of volatile and nonvolatile silicone oils, so that the amount of volatile oil is about 1-10%, by weight of the total composition and the amount of nonvolatile oil is about 1-10% by weight of the total emulsion composition. In the preferred embodiment of the invention, the preferred volatile oil is cyclomethicone and the preferred nonvolatile oil is a low viscosity dimethicone i.e dimethicone having a viscosity of about 5-25 centipoise at 25xc2x0 C.
8. Waxes
The oily phase of the emulsion may contain one or more materials that are solid at room temperature such as fatty acids, fatty alcohols, and the like. These materials act as gel structure modifiers for the oily phase. Suggested ranges of oily phase gel structure modifiers are 0.1-30%, preferably 0.5-25%, more preferably 1-20% by weight of the total emulsion composition. Suitable oily phase gel structure modifiers include straight or branched chain fatty alcohols having the formula Rxe2x80x94OH wherein R is a straight or branched chain saturated or unsaturated alkyl having 6-30 carbon atoms. Such fatty alcohols include cetyl alcohol, stearyl alcohol, cetearyl alcohol, and the like. Also suitable are fatty acids having the formula Rxe2x80x94COOH wherein R is a straight or branched chain saturated or unsaturated alkyl having 6-30 carbon atoms, which may be substituted with one or more hydroxyl groups. Preferred are fatty acids wherein R is straight or branched chain alkyl have 12-22 carbon atoms, which may be substituted with one or more hydroxyl groups. Particularly preferred is 12-hydroxystearic acid.
If the aqueous gel composition is combined with an oil phase to form an emulsion, the compositions prepared may be opaque, or clear or translucent. If clear, translucent compositions are desired, the oils selected should not be hazy or cloudy in appearance. Clarity is then achieved by matching the refractive indices of both phases such that they match within about 0.0001 to 0.0006.
The invention will be further described in connection with the following examples which are set forth for the purposes of illustration only.

Stabilized aqueous acidic antiperspirant compositions and related methods


Packaging for receiving liquid, pasty, powdery, granular or solid material having tear-open means and sealed edges and made of a foil-shaped composite material. The foil-shaped composite material has multiple layers. At least one layer of the composite material does not have weakened areas. At least one layer of the composite material has weakened areas located in the packaging at least partly in the area of the filling space. The weakened areas are preferably a series of cuts or a plurality of parallel individual cuts.

1. Field of the Invention
The present invention concerns a packing with a tear aid and sealed edges, made from a film-like laminate material, a process for production of the packing, means for production of the packing and use of the packing.
2. Background Art
Sealed edge bags are known, for example, which are used for packing powdery or solid fillings. Typical fillings can come from the area of foodstuffs and luxuries such as powdered instant coffee or chocolate bars, dairy produce such as yoghurt and the like. The packing must protect the filling against mechanical, chemical and physical influences. Therefore, in many cases such packings are made from multilayer materials where individual material layers or a material layer combination can have a specific protective function. The packing material must, for example, be tear-resistant. This requires very extendible or stretchable materials of high structural strength. Opening packings made from such materials is difficult and cannot be achieved without the aid of scissors or a knife. To facilitate opening without a tool, therefore, tear aids are regularly fitted to the packing. A tear aid can, for example, be a notch on the outer edge of a sealing seam. The material of the packing equipped in this way can be torn open very easily, on further tearing through the bag wall the direction of tear can no longer be controlled and the resulting opening is often incomplete or leads to the center through a side wall. The tear aid must be applied in the packing machine. This reduces the operating speed of the packing machine. In many cases attempts are made to eliminate the disadvantages by placing a tear strip between two material layers, and by pulling of the tear strip the packing material is split. The resulting opening is clearly defined but the production of this tear aid is complex and leads to inflexible production processes.
The task of the present invention is to propose a packing which offers optimum protection to the filling but nonetheless is easy to open, can be produced in a simple manner and minimizes the use of machines while retaining maximum freedom with regard to packing design.
According to the invention this is achieved by the film-like laminate material being multilayer and at least one material layer of the laminate has no weakened zones and at least one material layer of the laminate has weakened zones and the weakened zones on the packing lie at least partly in the area of the filling cavity.
Examples of packings according to the present inventions are sachets, such as, flat sachets, sealed edge sachets, cavity sachets, self-supporting cavity sachets or hose sachets, or bags such as welded flat or folded bags. Similarly the packing can have at least one sealing seam on a side edge, e.g., a sealing seam such as a hot or cold sealing seam, weld seam or glue seam. Depending on the method of production, flat sachets can, for example, have three or four sealing seams on three or four side edges, a hose sachet can have an upper and a lower transverse seam or an upper and a lower and a back seam such as an overlapping or folded back seam.
The weakened zones on the packing according to the invention preferably lie in the area of the sealed edges and/or in areas in which by folding and/or sealing, the laminate material forms two or more layers. The weakened zones can for example extend from an outer border of a sealed edge, through this to over the filling cavity of a packing. One or more of the weakened zones can for example extend from an outer edge of a packing over the filling cavity of a packing. One or more of the weakened zones can for example also extend only over the cavity of a packing. Several weakened zones are advantageously located in a substantially straight line. Weakened zones are advantageously placed in the area of an edge closure or sealed edge closure of a packing. For example, the area, measured from an edge closure or sealed edge closure, can extend up to 50 mm, suitably up to 20 mm, over the filling cavity. The area can also extend at a distance of 2 to 20 mm parallel to an edge closure or sealed edge closure over the filling cavity in a width of for example 5 to 50 mm, suitably 5 to 20 mm.
The film-like laminate material is multilayer, for example, two, three, four layer, etc. The individual material layers can be lacquer applications, metal films, metallised coatings or films of plastics, in particular thermoplastics, or laminates of metal films and plastic films. One or more material layers can be extruded and in particular melt-extruded layers or films of thermoplastics, where applicable laminated with metal or plastic films. At least one material layer can be a lacquer application, such as, a clear lacquer, a color lacquer, a hot melt coating, etc. At least one material layer can be a metallized coating or a ceramic thin coating deposited from a vacuum. Between the individual coatings can be adhesives, extrusion adhesives, adhesion promotion agents and/or primers. To increase the mutual adhesion of the coatings, the surfaces of the films, coatings or material layers can for example be subjected to corona, flame, ozone or plasma treatment.
Material layers of thermoplastics can be transparent, translucent or opaque. For example the material layer, film or coating on the outside of the packing can be printed. In the case of a transparent or translucent outer material layer, film or coating, counter-printing or external printing and counter-printing can be applied.
For metal films, for example, steel foils and preferably aluminum foils are used. The thickness of the foil can for example be 5 to 100 mm, preferably 8 to 30 mm.
Suitable plastic films are suitably made of thermoplastics, such as, polyesters, polyolefins such as polypropylenes or polyethylenes, polyamides, polyvinyl chloride, polycarbonate, etc., or cellulose-containing materials such as cellophane. Plastic films can be monofilms or film laminates. The thickness of the plastic films can, for example, be 8 to 100 mm, preferably 12 to 30 mm and in particular 12 to 23 mm.
Extruded or melt-extruded layers can for example be made of polyolefins, such as, polypropylenes or polyethylenes. The thickness of the extrudates can, for example, be 8 to 100 mm, preferably 12 to 30 mm, and in particular 12 to 23 mm.
The side of the laminate material facing the inside of the packing can advantageously be sealed. Where applicable the side of the laminate material facing the outside can also be sealed.
Examples of multilayer laminates are laminates containing a first material layer and a second material layer. The first material layer can be a film such as a monofilm or laminate of thermoplastics such as polyesters, polyolefins such as polypropylenes or polyethylenes, polyamides, polyvinyl chloride, polycarbonate, etc., or cellulose-containing materials such as cellophane or papers. The film can be printed and/or counter-printed on the side of the finished packing facing the outside. The second material layer can, for example, be a metal foil or metal film with a sealing coating applied to the side of the finished packing facing the inside, or a sealable film. The second material layer can in another embodiment be a sealable film of thermoplastic or an extrusion layer of a thermoplastic which is preferably sealable. Where applicable, papers can be used, e.g., coated papers as a second material layer. Where applicable as the second material layer lacquer coatings or paint applications can be used. The lacquers can be clear, opaque or colorless or colored. Depending on the product to be packed, the laminate material can have barrier properties against the penetration of fluids, gases, vapors, water vapor, aromas or flavorings, etc. To achieve barrier properties one can use metal foils, metallized coatings, e.g., of aluminum, ceramic thin coatings, e.g., from silicon oxides and/or aluminum oxide applied by sputtering or deposition under vacuum, or plastic films, e.g., materials from the range of styrene copolymers, ethyl vinyl alcohol polymers or polyvinylidene chloride. Examples of sealable materials for the films or extrudates are polyolefins such as polyethylene, polypropylene or co- and terpolymers of ethylene with acrylic acid. The sealability of the laminate can also be achieved by application of a sealing lacquer.
From said material layers the following laminate materials can, for example, be made, where the material layers can be connected together where applicable by adhesives, adhesion promotion agents and/or primers, or the second material layer can be applied to the first material layer by extrusion such as melt extrusion:
a) first material layer of a1) where applicable printed,
a2) film of polyesters, polyolefins, such as, polypropylenes or polyethylenes, polyamides, polyvinyl chloride, polycarbonate, etc.;
a3) where applicable counter-printing;
b) connected by means of an adhesion promotion agent, adhesive coating or extrusion coating with
c) second material layer of c1) metal film,
c2) adhesion promotion agent, adhesive layer,
c3) sealing film or sealable extrusion coating or sealing lacquer; or in a further embodiment a
a) first material layer of a1) where applicable printed,
a2) film of polyesters, polyolefins, such as, polypropylenes or polyethylenes, polyamides, polyvinyl chloride, polycarbonate, etc.
a3) where applicable counter-printing;
b) connected by means of an adhesion promotion agent, adhesive coating or extrusion coating with
c) second material layer of sealing film or sealable extrusion layer.
Further embodiments are
a) first material layer of a,) where applicable with printing on
a2) paper,
b) connected by means of an adhesion promotion agent, adhesive coating or extrusion coating with
c) second material layer of a polyolefin coating and in particular a polypropylene coating, e.g., in a thickness of up to 100 mm, preferably 50 to 80 mm; or
a) first material layer of a,) where applicable with printing,
a2) film of polyesters, such as, polyethylene, polyethylene terephthalate,
a3) where applicable counter-printing
b) connected where applicable by means of an adhesion promotion agent, adhesive coating or extrusion coating with
c) a metal film or applied metallized coating, and
d) connected by means of an adhesion promotion agent, adhesive coating or extrusion coating with
e) second material layer of a film of polyolefins such as polyethylene; or
a) a first material layer of a1) where applicable printed,
a2) film of polyesters, polyolefins, such as, polypropylenes or polyethylenes, polyamides, polyvinyl chloride, polycarbonate, etc.,
a3) where applicable counter-printing, and
b) a second material layer of a lacquer coating or sealable extrusion coating.
In the latter case the counter-printing a3) can simultaneously constitute the second material layer.
The laminate material has weakened zones in at least one material layer of the laminate material. Preferably the weakened zones are provided on the first material layer of the laminate material. It is also possible to provide the weakened zones on the second material layer or on the first and second layers of the laminate material. In the last case it is advantageous for the weakened zones of the first material layer and the second material layer of a laminate material not to be arranged above each other but offset from each other. Weakened zones can, for example, be material weaknesses, such as, thinner material, material removed or notches in the material, or cuts in the form of individual cuts or a sequence of cuts, in particular arranged in parallel, or in the form of perforations, etc. Particularly preferred as weakened zones are cut sequences or a multiplicity of individual cuts arranged in parallel. The cut direction advantageously runs in the tear direction. For example, the space between the cuts is for example 0.1 to 1 mm, the length of the cuts 1 to 50 mm and the number of cuts per weakened zone can be 2 to 50. The weakened zones can be located only over the filling cavity of a packing, or over the filling cavity and extend to within a sealed edge or side seam. The material layer or layers with weakened zones on a packing advantageously constitute an external layer or layer facing the outside of the laminate material.
The present invention also concerns a process for application of the weakened zones to the laminate material. The laminate material is produced by provision of the first material layer, where applicable printing of the first material layer on one or both sides and simultaneous application of the weakened zones in the register. Suitable printing processes are, for example, book, offset, flexo, screen and rotogravure printing. The first material layer can be weakened in the area of the printing machine, before, between two color applications, or after the printing ink application. The weakened zones can be generated by the application of weaknesses or perforations. This can be achieved mechanically, for example, by blades such as oscillating blades, rotating blades fitted to a cylinder, punch blades or needles, etc. Other devices for application of the weakened zones are energy-rich radiation such as laser beams or electron beams. Such processes normally lead to micro perforations. The weaknesses are applied to the first material layer in the register, i.e., in synchrony with the printing. This allows precise alignment of the weakening at the same time as precise alignment of the printing on the packing material. It is also possible to perform the weakening at the start or during the printing ink application or before any proposed lacquer or protective lacquer application. The weakening is then covered by the printing inks and/or lacquer or protective lacquer. Thus a barrier effect is achieved against the exchange of substances from moisture, gases etc., for example, through the openings of a perforation or a cut. At the same time the weakened zones can be stabilized with regard to tear strength without making it difficult to achieve the desired tear-opening. Preferably, the printing and weakening processes are performed continuously on endless or rolled goods, the processing of films or leaves is however also possible.
According to the process steps described, the first material layer and the provided second material layer are joined and connected together preferably continuously. The first material layer and second material layer as endless goods can for example be connected together inseparably by lamination or adhesion of the two material layers by means of an extrusion laminator or adhesive. For example, lacquer lamination adhesives, adhesion promotion agents and/or primers can be used. Examples of adhesives are also waxes, watery glues, plastic dispersions and high pressure polyethylene layers.
The second material layer can be applied to the first material layer also by coating or by extrusion, where under pressure and heat a thermoplastic, for example high pressure polyethylene, is melted and pressed as a thin film onto the one surface of the first material layer. If the second material layer is a lacquer application, the lacquer can be applied as a second material layer in quantities of for example 0.5 to 50 g/m2, preferably 1.0 to 25 g/m2, e.g., by pouring, spraying, spreading, smooth roller application etc. onto a first material layer already containing weakened zones. The lacquers can be solvent-based and dried or hardened by vaporization of the solvent or the lacquers can be hardened by energy-rich radiation. Suitable lacquers are, for example, acrylate- or methacrylate-based, or lacquers from the range containing polyester, epoxides, cellulose nitrate, polyvinyl chloride, polyvinyl butyral or mixtures thereof.
The laminate material produced in this way can be introduced into a packing machine for example in endless or roll form and used for packing goods. Due to the production process according to the invention, the printing and the weakened zones on the laminate lie in unchanging position to each other. High quality packing units are characterized in that the printing always corresponds to the pack size and is always positioned identically in relation to the filling. Thus with the use of the present laminate material the weakened zones corresponding to the printing always lie at the same point on every packing unit. Typical packing units are for example polygonal and in particular rectangular in top view. In cross section the packing units can be round or polygonal and in particular rectangular. The weakened zones are, for example, in the area of the side edges and in longitudinal packing units in the area of one of the two long ends. In relation to the cross section of the packing unit the weakened zones suitably lie on one or both side edges. Where a packing unit has points at which the packing material forms several material layers due to folding or gluing, preferably in this area there is a weakened zone on at least one material layer. For packing units with a back seam, there is at least one weakened zone in the area of this back seam. On packing units with a back seam, for example, several weakened zones can be placed in a line in the area of one of the two long sides on one or both side edges and in the area of the back seam.

Packaging comprised of a foil-shaped composite material and method for producing said packaging


Disclosed are aqueous liquid cleaning compositions, the compositions being free of anionic surfactants and comprising: (a) linear alcohol ethoxylate; (b) amine oxide or betaine; and other, optional components, such as a cationic ammonium compound.

1. Field of the Invention
This invention relates to formulations for manually washing dishes, hand soaps, and for high foaming cleaning compositions.
2. Description of the Related Art
Light-duty liquid detergent formulations for kitchen surfaces are well known. Kitchen surfaces include counter tops, stove tops, dishes and any other hard surface commonly found in kitchen environments. The term xe2x80x9cdishesxe2x80x9d includes any utensils involved in food preparation or consumption. Kitchen surfaces, particularly dishes, must be washed free of food residues, greases, proteins, starches, gums, dyes, oils and burnt organic residues.
Most of the consumer accepted formulations in use include anionic synthetic surfactants with or without a nonionic surfactant. Many of such formulations contain a sulfonate-type anionic surfactant, for example, an alkylbenzene sulfonate or an alkane sulfonate, in conjunction with a sulfate or alkyl ether sulfate, or a nonionic surfactant, for example, an alcohol ethoxylate, an alkyl phenol ethoxylate, a mono- or diethanolamide or an amine oxide. The sulfonate material generally predominates.
It is the anionic surfactant that provides the typical high foaming (suds) characteristics generally associated with dish washing formulations. Foam (suds) is the cleaning efficacy signal relied on by consumers. Nonionic surfactants generally do not provide good foaming characteristics.
U.S. Pat. No. 2,746,928 discloses that it is not possible to mix anionic surface-active agents with quaternary ammonium germicides. The cationic quaternary ammonium germicide reacts with the anionic surface-active agent resulting in a reduction in germicidal and detergent activity.
Thus, anionic surfactants are incompatible with cationic quaternary antimicrobial surfactants and nonionic surfactants do not normally provide significant foaming capability to liquid formulations. Therefore, dish washing liquids combining good foaming and antimicrobial activities are not available to the consumer.
Solutions to the problems posed by the incompatibility of cationic and anionic surfactants have focused on various non-ionic surfactant systems. While having the potential to overcome the known compatibility problems, such systems are not capable of the cleaning efficacy and foam volume demanded by consumers. Hence, there remains a critical need for cleaning compositions based on non-ionic surfactant systems that provide excellent cleaning with high foam volume.
In general, anionic surfactant systems such as those found in the current light duty liquids are classified as high foamers. Conversely, nonionic surfactant systems are classified as low foamers.
By careful selection and extensive experimentation, we have identified nonionic and nonionic/amphoteric surfactant mixtures that produce consumer acceptable foam comparable to commercial dish washing liquids that use anionic detergents. The useful nonionic surfactants include ethoxylates that have various chain lengths not exceeding 12 carbon atoms and degrees of ethoxylation that allow the dish washing liquid to be effective on a wide range of food soils while providing excellent flash foam volume and foam stability. This system provides the consumer with effective cleaning on, but not limited to, greasy food soils, fatty food soils, and oily food soils.
The invention provides surfactant compositions based on nonionic surfactant components that function as cleaning compositions. Further included in the invention are disinfectant hand soaps, body washes, disinfectant or antibacterial dishwashing liquids, and conditioning shampoos. Each of these latter cleaning compositions includes at least one cationic ammonium salt. The specific cationic salts are selected depending on the ultimate use or function of the cleaning composition.
Certain formulations of this invention will control the presence and spread of bacteria on hard surfaces in the kitchen environment, especially dishes. In this context, the invention is a microbiological active quaternary ammonium salt ingredient homogeneously incorporated into a nonionic aqueous surfactant system. Unexpectedly, the formulations of the invention have excellent flash foaming and residual foaming capability although no anionic surfactants are included.
The invention also provides personal care compositions including a quaternary ammonium compound which is a conditioning compound.
Thus, the invention provides hand soap compositions comprising a nonionic surfactant base in combination with at least one cationic ammonium compound. The ammonium compound may be an antibacterial compound or a conditioning agent, or both. Certain hand soap formulations will include a conditioning agent and an antimicrobial compound. Similar formulations may be formulated to function as conditioning shampoos.
The unexpected foaming properties of the formulations of the invention are illustrated in the examples. The foaming properties are due to the carefully balanced mix of nonionic surfactants. The formulations tested in these examples contain preferred concentrations of ingredients.
Thus, the invention provides aqueous liquid cleaning compositions, the compositions being free of anionic surfactants and consisting essentially of a nonionic surfactant system and a cationic ammonium compound.
Significantly, the invention also provides high foaming nonionic or nonionic/amphoteric systems that are excellent grease cutters.
The nonionic surfactant system may comprise (1) from about 0.1-50% by weight based on the weight of the composition of a linear alcohol ethoxylate having an average carbon chain length of no more than 12 carbon atoms; and (2) a surfactant member selected from the group consisting of amine oxides and betaines. In these compositions, the total concentration of active components in the composition based on the weight of the composition is at least about 5%. Optional non-ionic surfactants include alkanolamides, alkyl polysaccharides, betaines,and polyhydroxy fatty acid amides. In various embodiments of the invention, these optional components may replace a portion of the alcohol ethoxylate.
The nonionic surfactant systems of the invention may be combined with a variety of cationic ammonium compounds, such as for example, quaternary ammonium compounds or cationic conditioning agents, to produce a cleaning composition that functions as dishwashing cleaner such as a an antimicrobial dishwashing liquid or handsoap or as a conditioning cleaner such as a conditioning shampoo.
As used herein, the term disinfecting or disinfectant refers to antimicrobial and/or antibacterial activity. Disinfectant, antimicrobial and antibacterial formulations of the invention are capable of reducing the rate of microbial, i.e., bacterial, reproduction, and/or killing microbial organisms.
The invention encompasses detergent compositions containing various combinations of linear alcohol ethoxylates and nonionic surfactants selected from amine oxides and betaines. Typical compositions also include at least one cationic ammonium compound. In preferred embodiments, the detergent or cleaning compositions comprise a linear alcohol ethoxylate, an amine oxide, an alkyl mono- or dialkanolamide, and a cationic ammonium compound. In such compositions, the balance of the material is water. In particularly preferred embodiments, the weight ratio of linear alcohol ethoxylate to amine oxide is from about 3:1 to 1:3.
A particularly preferred detergent composition according to the invention is the following:
a detergent formulation free from anionic surfactants consisting essentially of:
(a) from about 2-23%, preferably 8-18%, by weight of a linear alcohol ethoxylate having 6-12 carbon atoms and 3-12, preferably 3 to 7 moles of ethoxylation per mole of alcohol;
(b) from about 2-23%, more preferably 4-23%, by weight of an amine oxide selected from the group consisting of (C8-16) alkyl amido (C1-4) alkyl di(C1-4) alkyl amine oxides and (C10-16) alkyl amine oxides; and optionally
(c) from about 1-10%, more preferably 3-7%, by weight of (C10-16) alkyl mono- or dialkanolamides, where each alkanol portion independently has from 1-6 carbon atoms; and
(d) from about 0.5 to 20% of a cationic ammonium compound.
In such compositions, the weight ratio of component (a) to component (b) is most preferably from about 1:3 to 3:1. Most referred linear alcohol ethoxylates have about 4.5 moles of ethoxylation per mole of alcohol. Most preferred alkanolamides are present at about 4-6% by weight of the composition.
Another particularly preferred composition of the invention is a liquid cleaning composition consisting essentially of, by weight of the composition, from about 4-7% of a C8-10 alcohol ethoxylate having an average of about 9 moles of ethylene oxide, from about 12-20% of a C8-10 alcohol ethoxylate having an average of about 12 moles of ethylene oxide, from about 7-13% of a fatty acid amidopropylamine oxide having an average of about 10-18 fatty acid carbon atoms, from about 1-4% of a fatty acid diethanolamide having an average of about 10-18 fatty acid carbon atoms, from about 1-4% of a fatty acid monoethanolamide having an average of about 10-18 fatty acid carbon atoms; and an antibacterial effective amount of an antibacterial quaternary ammonium compound. A preferred antibacterial quaternary ammonium compound is an alkyl dimethyl benzyl ammonium chloride. The balance of the composition is water. Such a composition may also contain an emulsifier or thickener such as xanthan gum, as well as fragrances, etc.
Still another particularly preferred formulation according to the invention is an aqueous liquid cleaning composition, the compositions being free of anionic surfactants and consisting essentially of:
(a) from about 13-19% by weight based on the weight of the composition of a linear alcohol ethoxylate having an average carbon chain length of no more than 12 carbon atoms; and;
(b) from about 3-7% by weight of the composition of a mono- or dialkanolamide; and
(d) from about 5-10% by weight of the composition of an alkylpolyglycoside.
Yet another composition consists essentially of:
(a) from about 13-19% by weight based on the weight of the composition of a sulfobetaine;
(b) from about 5-20% by weight of the composition of an amine oxide, a betaine, or mixture thereof;
(c) from about 3-7% by weight of the composition of a mono- or dialkanolamide; and
(d) from about 3-7% by weight of the composition of an alkylpolyglycoside, the total concentration of surfactants in the composition being from about 30-35% by weight of the composition.
Optional, non-essential ingredients include fragrances, dyes, stabilizers, thickeners, etc.
Nonionic Surfactants
The surfactants suitable for use in the inventive compositions include the following nonionic surfactants.
Alcohol Ethoxylates
In the condensation products of aliphatic alcohols with ethylene oxide, i.e., alcohol ethoxylates, the alkyl chain of the aliphatic alcohol can either be straight or branched and generally contains from about 5 to about 22 carbon atoms. The chain of ethylene oxide can contain from 2 to 30 ethylene oxide moieties per molecule of surfactant. Examples of such ethoxylated alcohols include the condensation product of about 6 moles of ethylene oxide with 1 mole of tridecanol, myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of myristyl alcohol, the condensation product of ethylene oxide with coconut fatty alcohol wherein the coconut alcohol is a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms and wherein the condensate contains about 6 moles of ethylene oxide per mole of alcohol, and the condensation product of about 9 moles of ethylene oxide with the above-described coconut alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol 15-S-9 marketed by the Union Carbide Corporation, Neodol 23-7 marketed by the Shell Chemical Company and Kyro EOB marketed by the Procter and Gamble Company.
Amide Surfactant
The amide type of nonionic surface active agents includes the ammonia, monoethanol and diethanolamides of fatty acids having an acyl moiety of from about 7 to about 18 carbon atoms. These acyl moieties are normally derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum, or by the Fischer-Tropsch process.
The amide surfactants useful herein may be selected from those aliphatic amides of the general formula:
wherein R4 is hydrogen, alkyl, or alkylol and R5 and R6 are each hydrogen, C2-C4 alkyl, C2-C4 alkylol, or C2-C4 alkylenes joined through an oxygen atom, the total number of carbon atoms in R4, R5 and R6 being from about 9 to about 25. A further description and detailed examples of these amide nonionic surfactants are contained in U.S. Pat. No. 4,070,309, issued to Jacobsen on Jan. 24, 1978. That patent is hereby incorporated herein by reference.
Amine Oxide
Amine oxides useful in the present invention include long-chain alkyl amine oxides, ie., those compounds having the formula
wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 16 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof; x is from 0 to 3, preferably 0; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, preferably from 1 to 2 carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferably 1, ethylene oxide groups. The R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include C10-C18 alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxyethyl amine oxides. Examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, dodecylamidopropyl dimethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide. Preferred are C10-C18 alkyl dimethylamine oxide, and C10-C18 acylamido alkyl dimethylamine oxide.
Betaine
The betaines useful in the present invention are those compounds having the formula R(R1)2N+R2COOxe2x88x92 wherein R is a C6-C18 hydrocarbyl group, preferably C10-C16 alkyl group, each R1 is typically C1-C3, alkyl, preferably methyl, and R2 is a C1-C5 hydrocarbyl group, preferably a C1-C5 alkylene group, more preferably a C1-C2 alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C12-C14 acylamidopropylbetaine; Cxe2x80x94C acylamidohexyldiethyl betaine; 4-[C14-C16 acylmethylamidodiethylammonio]-1-carboxybutane; C16-C18 acylamidodimethylbetaine; C12-C16 acylamidopentanediethyl-betaine; C12-C16 acylmethyl-amidodimethylbetaine. Preferred betaines are C12-C18 dimethylamoniohexanoate and the C10-C18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Also included are sulfobetaines (sultaines) of formula R(R1)2N+R2SO3xe2x80x94, wherein R is a C6-C18 Hydrocarbyl group, preferably a C10-C16 alkyl group, more preferably a C12-C13 alkyl group; each R1 is typically C1-C3 alkyl, preferably methyl and R2 is a C1-C6 hydrocarbyl group, preferably a C1-C3 alkylene or, preferably, hydroxyalkylene group. Examples of suitable sultaines are C12-C14 dihydroxyethylammonio propane sulfonate, and C16-C18 dimethylammonio hexane sulfonate, with C12-C14 amido propyl ammonio-2-hydroxypropyl sultaine being preferred.
Polyhydroxy Fatty Acid Amide
The polyhydroxy fatty acid amides useful in the inventive detergent compositions have the formula:
wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C7-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C11-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycidyl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of of xe2x80x94CH2xe2x80x94(CHOH)nxe2x80x94CH2OH, xe2x80x94CH(CH2OH)xe2x80x94(CHOH)nxe2x88x921CH2OH, xe2x80x94CH2xe2x80x94(CHOH)2(CHOR1)xe2x80x94CH2OH, where n is an integer from 3 to 5, inclusive, and R1 is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly xe2x80x94CH2xe2x80x94(CHOH)4xe2x80x94CH2OH.
R1 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
R2xe2x80x94COxe2x80x94N less than  can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc. Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
Alkylpolysaccharides
Alkylpolysaccharides such as those disclosed in U.S. Pat. No. 4,565,647 are nonionic surfactants useful in the present invention. Suitable alkylpolysaccharides include those having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglucoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4, and/or 6-positions on the preceding saccharide units.
As noted above, the inventive formulatIons include a first nonionic surfactant member selected from the group consisting of linear alcohol ethoxylates, alkyl polysaccharides, betaines, and polyhydroxy fatty acid amides.
In preferred compositions, the first nonionic surfaccant member is preferably a linear alcohol ethoxylate having 6-10 carbon atoms and 3 to 12 moles, more preferably 5-7 moles, of ethoxylation per mole of alcohol. Other preferred alcohol ethoxylates are condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
Ethoxylated alcohols having no more than 12 carbon atoms in the alkyl position are commercially avaiable and include Neodol(trademark) 1-4; Neodol(trademark) 1-7; Neodol(trademark) 91-8, each of which is marketed by Shell Chemical Company.
The compositions of the invention optionally include a second nonionic surfactant member. In preferred compositions, the second member is an amine oxide in an amount of from about 1-11, more preferably 5-11, % by weight of the composition.
The preferred amine oxides for use as the second surfactant member may be represented by the general formula: R1R2R3Nxe2x86x92O wherein R1 is a higher alkyl radical having from 8 to 18 carbon atoms, such as lauryl, decyl, cetyl, oleyl, stearyl, hexadecyl or an amide substituted group, such as RCONH(CH3)n, wherein RCO is a long chain alkanoyl radical and n is a small whole number; R2 and R3 are each lower alkyl radicals such a methyl, ethyl, propyl or a substituted lower alkyl radical such a hydroxyethyl, hydroxyethoxyethyl, hydroxy polyethoxyethyl, etc. Examples of suitable tertiary amine oxides include lauryl dimethyl amide oxide, coconut dimethylamine oxide, dodecyl dimethyl amine oxide,
and the like.
The preferred amides are C8-C20 alkanol amides, monoethanolamides, diethanolamides, and isopropanolamides. A particularly preferred amide is a mixture of myristic monoethanolamide and lauric monoethanolamide. This preferred amide is sold by Stepan Company, Northfield, Ill. as Ninol LMP.
Cationic Ammonium Compound
The cationic compound is selected according to the desired end use for the formulationxe2x80x94typically, the cationic compound is present in amounts ranging from about 0.5 to 20% by weight of the formulation. The cationic ammonium compound is normally selected from the group consisting of quaternary ammonium salts and amine salts (salts of primary, secondary and tertiary amines).
1. Disinfectant formulations
In the antimicrobial or disinfectant formulations, the purpose of the quaternary ammonium disinfectants is to reduce the rate of reproduction of or kill on contact gram positive and gram negative organisms the organisms encountered in kitchen environments. Useful such disinfectants include BTC 8358 which is N-alkyl (50% C14, 40% C12, and 10% C16) dimethyl benzyl ammonium chloride. Other quarternary ammonium salts may be any of the well-known class of quaternary ammonium germicides characterized by the formula:
wherein at least one of the radicals, R1, R2, R3 and R4 (xe2x80x9cthe xe2x80x98Rxe2x80x99 groupsxe2x80x9d) is a hydrophobic, aliphatic, aryl aliphatic, or aliphatic aryl radical of from 6 to 26 carbon atoms, the entire cation portion of the molecule has a molecular weight of at least 165, and the remaining R groups are hydrophobic, aliphatic, aryl aliphatic, or aliphatic aryl radical of from 6 to 26 carbon atoms. The hydrophobic radicals may be long-chain alkyl, long-chain alkoxy aryl, long-chain alkyl aryl, halogen-substituted long-chain alkyl aryl, long-chain alkyl phenoxy alkyl, aryl alkyl, and so forth, in nature. The remaining radicals on the nitrogen atom other than the hydrophobic radicals are substituents of hydrocarbon structure usually containing a total of no more than 12 carbon atoms. The radical X in the above formula is any salt-forming anionic radical.
Suitable quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like. Other suitable types of quaternary ammonium salts include those in which the molecule contains either, amide or ester linkages such a octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride. N-(laurylcocoaminoformylmethyl)-pyridinium chloride, and so forth. Other very effective types of quaternary ammonium germicides are those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as in the case of lauryloxyphenyltrimethyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium methosulfate, dodecylbenzltrimethyl ammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like.
Preferred quaternary ammonium germicides of the above general types are the long-chain alkyl dimethylbenzyl quaternary ammonium salts, the alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium salts, the N-(acylcocoaminoformylmethyl)pyridinium halides, the long-chain alkyl trimethyl ammonium halides, the long-chain alkyl benzyl dimethyl benzyl ammonium halides, and the long-chain alkyl benzyl diethyl ethanol ammonium halides in which the alkyl radical contains from 8-18 carbon atoms.
The quaternary ammonium salts useful in the invention have the general formula:
wherein R1 and R2 are straight or branched chain lower alkyl groups having from one to seven carbon atoms; R3 is a straight or branched chain higher alkyl group having from about six to sixteen carbon atoms, or a benzyl group; R4 is a straight or branched chain higher alkyl group having from about six to sixteen carbon atoms; and X is a halogen or a methosulfate or saccharinate ion.
In preferred quaternary ammonium salts, R1 and R2 are methyl groups; R3 is benzyl or straight or branched chain alkyl having from about eight to sixteen carbon atoms; and R4 is straight or branched chain alkyl having from about eight to sixteen carbon atoms provided that not both R3 and R4 have sixteen carbon atoms simultaneously. A preferred halogen is chlorine, or a methosulfate or a saccharinate ion.
Illustrative of suitable quaternary ammonium germicides are: dioctyl dimethyl ammonium chloride, octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, (C12-C18) n-alkyl dimethyl benzyl ammonium chloride, (C12-C18) n-alkyl dimethyl ethylbenzyl ammonium chloride, (C12-C18) n-alkyl dimethyl benzyl ammonium saccharinate, di(C1-C7) alkyl (C6-C26) alkyl aryl ammonium salts, di(C1-C7)alkyl di(C6-C14) alkyl ammonium salts, tri(C1-C7) alkyl (C6-C26) alkyl ammonium salts, (C14-C26)alkyl di(C1-C7)alkyl aryl ammonium salts, and (C14-C16) alkyl tri (C-C7) alkyl aryl ammonium salts. This is not an exhaustive list and other quaternary ammonium salts having germicidal activity will suffice. The quaternary ammonium salt in the present invention need not be a single entity, but may be a blend of two or more quaternary ammonium salts. The amount, in weight-percent, of the quaternary ammonium salt, either as a single entity or blended, is typically from about 0.1%-10.0% and preferably about 1-3%. The preferred quaternary ammonium germicide is a mixture of about 34% by weight C12 and 16% by weight C14 n-alkyl dimethyl ethylbenzyl ammonium chloride and about 30% by weight C14, 15% by weight C16, 2.5% by weight C12 and 2.5% by weight C18 n-alkyl dimethyl benzyl ammonium chloride.
The quaternary ammonium compounds can also function as cationic surfactants to produce antistatic and conditioning effects when deposited on the substrate.
2. Conditioning formulations
The invention also encompasses cleaning compositions capable of imparting a conditioning effect on a substrate such as skin or hair. Such formulations include hand soaps and conditioning shampoos. A variety of cationic surfactants useful as detersive surfactants and as conditioning agents are well known in the art. These materials contain amino or quaternary ammonium hydrophilic moieties which are positively charged when dissolved in the aqueous composition of the present invention. Whether the cationic surfactant functions as a detersive surfactant or a conditioning agent, or both, will depend upon the particular compound as is well understood by those skilled in the art. In general, compounds with longer chain length moieties attached to the cationic nitgogen tehd to exhibit greater conditioning benefits. Cationic surfactants among those useful herein are disclosed in the following documents, all incorporated by reference herein: M. C. Publishing Co., McCutcheon""s, Detergents and Emulsifiers, (North American edition 1993); Schwartz et al., Surface Active Agents, Their Chemistry and Technology, New York; Interscience Publishers, 1949; U.S. Pat. No. 3,155,591, Hilfer, issued Nov. 3, 1964; U.S. Pat. No. 3,929,678, Laughlin et al., issued Dec. 30, 1975; U.S. Pat. No. 3,959,461, Bailey et al., issued May 25, 1976; and U.S. Pat. No. 4,387,090, Bolich, Jr., issued Jun. 7, 1983.
Quaternary ammonium salts include dialkldimethyl-ammonium chlorides and trialkyl methyl ammonium chlorides, wherein the alkyl groups have from about 12 to about 22 carbon atoms and are derived from long-chain fatty acids. These types of cationic surfactants are useful as hair conditioning agents. Examples of quaternary ammonium salts useful herein include di(coconutalkyl) dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride. Stearyl dimethyl benzyl ammonium chloride and cetyl trimethyl ammonium chloride are preferred quaternary ammonium salts useful herein. (Hydrogenated tallow) trimethyl ammonium chloride is a preferred quaternary ammonium salt. Preferred of the conventional cationic conditioning agents are cetyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, stearyldimethyl benzyl ammonium chloride, and (partially hydrogenated tallow)trimethylammonium chloride; these materials may also provide anti-static benefits to the present shampoo compositions.
Salts of primary, secondary and tertiary fatty amines are also suitable cationic surfactant materials. The alkyl groups of such amines preferably have from about 12 to about 22 carbon atoms, and may be substituted or unsubstituted. Secondary and tertiary amines are preferred, tertiary amines are particularly preferred. Such amines, useful herein, include stearamido propyl dimethyl amine, diethyl amino ethyl stearamide, dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine ethyl stearylamine, N-tallowpropane diamine, ethoxylated (5 moles E.O.) stearylamine, dihydroxy ethyl stearylamine, and arachidylbehenylamine. Suitable amine salts include the halogen, acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate salts. Such salts include stearylamine hydrochloride, soyamine chloride, stearylamine formate, N-tallowpropane diamine dichloride and stearamidopropyl dimethylamine citrate. Cationic amine surfactants included among those useful in the present invention are disclosed in U.S. Pat. No. 4,275,055, Nachtigal, et al., issued Jun. 23, 1981, incorporated by reference herein.
Cationic conditioning surfactants especially useful in shampoo formulations are quaternary ammonium or amino compounds having at least one N-radical containing one or more nonionic hydrophilic moieties selected from alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, and alkylester moieties, and combinations thereof. The surfactant contains at least one hydrophilic moiety within 4, preferably within 3, carbon atoms (inclusive) of the quaternary nitrogen or cationic amino nitrogen. Additionally, carbon atoms that are part of a hydrophilic moiety, e.g., carbon atoms in a hydrophilic polyoxyalkylene (e.g., xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94), that are adjacent to other hydrophilic moieties are not counted when determining the number of hydrophilic moieties within 4, or preferably 3, carbon atoms of the cationic nitrogen. In general, the alkyl portion of any hydrophilic moiety is preferably a C1-C3 alkyl. Suitable hydrophile-containing radicals include, for example, ethoxy, propoxy, polyoxyethylene, polyoxypropylene, ethylamido, propylamido, hydroxymethyl, hydroxyethyl, hydroxypropyl, methylester, ethylester, propylester, or mixtures thereof, as nonionic hydrophile moieties. The amino surfactants must be positively charged at the pH of the shampoo compositions. Generally, the pH of the shampoo compositions will be less than about 10, typically from about 3 to about 9.
Other cationic compounds suitable for use in the invention include NH4+, and mono-, di-, and tri-short chain alkyl ammonium salts.
Adjuvant Materials
Various adjuvant materials may be added to these foaming aqueous detergent compositions such as small amounts of viscosity builders and conditioning agents inclusive of gums and hydroxypropyl methyl cellulose. Such ingredients can be added in an amount that does not adversely effect the foaming and cleaning characteristics of the compositions. Other ingredients may include alkaline or acid buffers to aid in the adjustment and maintenance of the desired pH of the finished product such a borax, various inorganic water-soluble phosphates, sodium hydroxide, citric acid, etc. Other additions include optical brighteners, bleaches, germicides, fungicides, bactericides, colorants, perfumes, etc. in minor amounts which do not interfere with the cleaning, foaming, conditioning, or sanitizing properties of the composition.
Other ingredients include ethylenediamine tetraacetate (EDTA) and polyethylene glycol (PEG) fatty acid esters. EDTA is especically useful in antibacterial cleaning compositions, particularly handsoaps, since it increases the effectiveness of the antibacterial quaternary ammonium compound, in particular against Pseudomonas Aeruginosa, a pathogenic gram-negative organism. A representative PEG ester is PEG 600 distearate. This ester provides excellent viscosity enhancement in the inventive surfactant systems by association with other components without causing a loss of clarity or an increase in color.
All documents, e.g., patents and journal articles, cited above or below are hereby incorporated by reference in their entirety.
In the examples, all amounts are stated in percent by weight of active material unless indicated otherwise.
One skilled in the art will recognize that modifications may be made in the present invention without deviating from the spirit or scope of the invention. The invention is illustrated further by the following examples which are not to be construed as limiting the invention or scope of the specific procedures or compositions described herein.
The detergent compositions of the invention are prepared by combining water with the alcohol ethoxylate and amine oxide surfactant members, mixing until uniform and then adding the any optional components, such as, for example, amide or cationic ammonium compound, and again mixing until uniform. Heating may be employed as needed to enhance dissolution of the components.
Various antimicrobial cleaning formulations described herein were analyzed for detergency and foam height. Detergency and foam longevity was evaluated using the miniplate assay described below. Foam height was evaluated according to the Ross Miles Foam Height test as described by J. Ross and J. D. Miles in Oil and Soap, 18; 99 (1941) at 0.032% active concentration using water of 140 ppm hardness at 25xc2x0 C. Ross-Miles test results are displayed in cm.
The capability of various formulations for cleaning and degreasing was determined by the Mini-Plate Test, as follows:
Preparaton of Soil Materal
1. Melt shortening (Crisco, approx. 100 g) in a beaker at 160xc2x0 F.
2. Add a small amount (not much needed for deep color) of red dye to melted Crisco and stir until dissolved.
3. Calibrate syringe to deliver 0.36 g of Crisco soil on each plate.
4. Apply 0.36 g of Crisco oil to each of the watchglasses (One large watchglass is equivalent to three mini-plates).
5. When all of the larger watchglasses have been soiled, recalibrate syringe to deliver 0.12 g of Crisco soil to each plate.
6. Apply 0.12 g of Crisco soil to each of the smaller watchglasses.
7. Allow soiled watchglasses to harden at room temperature overnight before using.
8. Soiled watchglasses should always be stored at room temperature [(can be stored indefinitely)].
Procedure for Analyzing Test Formulations
1. A test solution may be made by diluting sufficient product with [tap] water (140 ppm hardness) to a concentration of 0.048% active material. 400 ml of such a solution is employed; heating to about 130-135xc2x0 F. may be necessary to achieve dissolution of the product.
3. The solution in placed in a Pyrex dish and then agitated with a paintbrush to generate foam, and the temperature of the solution adjusted to 120xc2x0 F.
4. At this point, large watchglasses (which represent three plates each) are washed, one every 45 seconds, by removing a thin layer of soil at a time from the surface of the plate with the paintbrush, then agitating the paintbrush in the solution to remove the adhering soil (which consequently breaks down the foam). The endpoint of the test is the number of mini-plates washed when further agitation of the solution fails to produce new/additional foam on the solution surface. In certain tests, small watchglasses representing 1/3 the surface area of a large watchglass may be used as the endpoint is neared.

High foaming detergent composition having a non-ionic surfactant base