CA1321743C - Fabric rinse composition to remove surfactant residues - Google Patents
Fabric rinse composition to remove surfactant residuesInfo
- Publication number
- CA1321743C CA1321743C CA000584678A CA584678A CA1321743C CA 1321743 C CA1321743 C CA 1321743C CA 000584678 A CA000584678 A CA 000584678A CA 584678 A CA584678 A CA 584678A CA 1321743 C CA1321743 C CA 1321743C
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- Canada
- Prior art keywords
- weight
- composition according
- fabric
- nonionic surfactant
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
Abstract
A FABRIC RINSE COMPOSITION TO REMOVE SURFACTANT RESIDUES
ABSTRACT
A fabric rinse composition that removes residual soap and surfactant particularly anionic, left in the clothes during washing, which is disliked by consumers, consisting of low levels of a nonionic surfactant, low levels of an organic acid such as citric acid/sodium citrate, and a major amount of water, in the form of a liquid or gel.
ABSTRACT
A fabric rinse composition that removes residual soap and surfactant particularly anionic, left in the clothes during washing, which is disliked by consumers, consisting of low levels of a nonionic surfactant, low levels of an organic acid such as citric acid/sodium citrate, and a major amount of water, in the form of a liquid or gel.
Description
13~7~3 FIE~D OF TH~ INVENTION
;This invention relates to an aqueo~s fabric rinse formulation for soap and surfactant residue removal consisting essentially of a minimal amount of a water soluble nonionic surfactant such as the polyethylene oxide ; condensates of higher fatty alcohols, and a polysorbate containing 20 moles o~ ethylene oxide, a minimal amount of an organic acid having a pKa of 4.5 to 6.5 and/or a monovalent cation salt of the acid, and a major amount of water in an amount of about 84-98% by weight of the liquid for~ulation ~I having a pH within the range of about 4.5-6.5. This product may be used as an ater-rinse, at the c.ompletion of the laundering procedure, i.e. after ~ the soap and/or anionic surfactant is rinsed with water from the fabrics, ! which include wool, cotton, dacron-cotton blends and any other blends which are absorbent. The present fabric rinse has the dual function of removing ¦ substantially all the residual soap and anionic surfactant residue~ and ¦I conditloning the fabric to feel good against the skin and obviate possible `, skin irritation.
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'BACKGROUND AND PRIOR ART
~I
i~Prlor work has shown that large amounts oE anionic surf~ctants and soaps are absorbed and retained by fabrics, such as wool, cotton, dacron-cotton xttre and other fabFIc mixtu s, sFin and c.heF s mllar b~tra~s Il ~
I
I
,: , .
~L 3 21 r~ l~ 3 , during the washing process. These residual surfactants and soaps are 1, difficult to rinse from wool and skin. The removal of said residues from the skin is addressed in a copending cleanse~ composition filed of even date. Consumers perceive these residues left on clothes as a negative, since thay change the way fabrics feel, and can possibly be irritating.
Accordingly, the presence of residual anionic suractant on clothes being , perceived in a negative way by the consumer, and as a potential source of skin irritation, there is clearly a need to develop a fabric rinse product addressing this problem. A unique combination of a buffered organic acid ~¦ and a nonionic surfactant has been shown to be very effective at removing residual soap from said fabrics.
~' It has been found that this fabric rinse reduced the levels of residual ,, anionic surfactant retained by wool fabric after washing, by 40 - 60%
il compared to a water rinse. The amount of surfactant rinsed out of the ¦j fabric by the prototype was significantly greater than formulas containing either ingredient alone.
A study using wool fabric and laurate soap demonstrated that Ca++ and Mg++ salts that produce water hardness increase surfactant deposition and absorption of the soap to the wool fabric, a keratin substrate. Hence, the water hardness increases the binding of the laurate soap to wool and, by analo~y to skin, decreases the ability to wash the soap off the wool or skin, which binds the soap surfactant in a manner similarly to wool. It is the removal of this soap and/or synthetic anionic surfactant residue from the washad and water rinsed fabrics such as wool that is the subject matter of present invention.
Commercial facial detergent co~positions containing soap and assorted mixtures of surfactants for use in the wash cycle of the laundering operation has addressed the problem of fabric softness in the prior art by adding softening agents to the deter~ent composition; or by separately adding the softening agent in the rinse cycle of the laundering operation.
13217~3 However, the removal of soap and/or surfactant residue after washing fabrics with soap has not been addressed in the prior ~rt.
The use of a nonionic surfactant as one of the ingredients in a liquid detergent for cleaning fabrics is well known in the prior art as disclosed in U.S. Patent Nos. 3,764,544 wherein is disclosed a spot remover for wearing apparel containing a nonionic surfactant; 3,959,163 wherein is disclosed a stain removing composition containing a bleaching compound and a nonionic surfactant; and 4,206,070 wherein is disclosed a binary surfactant system of nonionics.
U.S. Patent No. 3,915,633 discloses an aqueous prewash aerosol spray soil release composition for use with a detergent or soap in a laundering operation, consisting of 1-20% by weight of an organic acid, i.e. citric acid, 2-30% by weight of an anionic or nonionic surfactant, water and an aerosol propellant. Canadian Patent No. 1,0%o,178 discloses a liquid heavy duty laundry detergent composition containing 20-70~ by weight of a soluble ethoxylated nonionic surfactant, 0.1-1.25~ by weight of a polyacid, i.e.
citric acid, and watertorganic solvents, having a pH of 6-7.5.
Also disclosed in the prior a}t are mi~tures of a nonionic surfactant and polyacrylate thickeners in aqueous dishwashing detergent formulations as disclosed in U.S. Patent Nos. 3,950,260 and 4,226,736.
U.S. Patent No. 4,501,680 discloses acidic liquid detergent compositions for cleaning ceramic tiles without eroding grout between them, comprising a minor proportion of glutaric acid and a lesser amount of phosphoric acid to provide a pH of 3-5, a minor amount of an ethoxylatsd fatty alcohol, a minor amount of a diethylene glycol monoalkyl ether, and a major amount of water.
U.S. Patent No. 4,172,140 discloses an antimicrobial composition for inhibiting the growth of microorganisms in an aqueou3 fluid medium comprising as the active ingredients, an admixture of 1,3-dimeth~1O1-5,5 dlmethyl hydantoin and disodium ethylene dlaminetetraacetate, for use in ~1 ~3~7~
,I metal working fluids, cuttin~ oil fluids, coolants, lubricants, and the 'I like.
¦ U.S. Patent No. 4,612,137 discloses an anti-yellowing detergent composition comprising citric acid or salt and isocitric acid or salt and a surfactant, which may be anionic, nonionic, etc.
,i None of the aforesaid prior art disclose a fabric rinse to remove ¦¦ residual soap and/or synthetic anionic surfactants absorbed by the fabric during the washing process, consisting of a low level of a nonionic surfactant as the sole surfactant, a minor amount of an organic acid (or salt thereof) having a pKa from 4.5 to 6.5 to provide a pH of about 4.5 to 6.5, and a major amount o~ water, which may be thickened with polyethylene ~lycol - 150 distearate to a thick liquid or thickened with an acrylic acid polymer to for~ a gel, and preferably contains a preservative system.
ll SUMMARY OF THE INVENTION
`¦ It has been found that the soap and anionic surfactant residue retained on the fabric after washing with soap or surfactant can cause skin irritation and change the way fabrics feel. It has additionally been found that the soap residue can be effectively removed from the fabrics with the present novel rinse formulation consisting essentially of a minor amount of a water soluble nonionic surfactant, with the pH adjusted to about 4.5-6.5, using an organic acid having a pKa from 4.5 to 6.5 and a major amount of water, preferably deionized water. The novel fabric rinse is a clear product with viscosities ranging from watery solutions to thick gels, by the addition of a viscosity control agent selected from the group consisting of a diester of stearic acid and polyoxyethylene (PEG 150 distearate), and a polyacrylic acid resin (Carbopol 941~ Compositions prepared with either thickener yield soft, smooth fabricJ similar to the unthickened watery solution, without leaving a slimy or tacky feeling. The present novel composition functions as a fabric rinse which removes the absorbed soap andlor surfactant deposited thereon duriDg the washing process.
' '',` , ~ ~ ','; ~ ,,j '~ ~
~3~17~3 Accordingly, the present invention seeks to provide a liquid fabric rinse composition ~o remove soap and anionic surfactant residue from the washed fabric and thereby prevent possible irritation due to the soap or surfactant.
This invention also seeks to provide a fabric rinse~
to be used after washing with soap or surfaetant and water, which results in a soft, smooth fabrlc feel.
This invention further seeks to provide a fabric rinse containing as the major ingredients, a nonionic surfactant, an organic acid, a major amount of water, and having a pH adjusted to about 4.5-6.5.
This invention also seeks to provide a clear liquid afterwash fabric rinse or pre-fabric rin~e with viscosities ranging from watery solutions to thick gels.
This invention also seeks to provlde a thickened or gelled fabric rinse containing a diester of stearic acid and polyoxyethylene or a polyacrylic acid resin as the thickening agent.
This invention also seeks to provide a fabric rinse also containing a preservative system.
Additional advantages and novel features of the invention will be set forth in part in the descxiptlon which follows, and in part will become apparent upon examination of the following specificàtion or may be learned by practice of this invention.
To achieve the foregoing in accordance with the present invention, as embodied and broadly described herein, the novel liquid fabric rinse composition to remove soap or anionic surfactant residue from the wa~hed fabric in accordance with this invention, consists essentially of a ma~or amount of water, preferably deionized water, about 0.25-6% by weight of a 13217~3 nonionic surfactant as the sole surfa~tant, about 0.05-5% by weight of an organic acid having a pKa from 4.5 to 6.5 or a monovalent cation salt of the a~id or a mixture of said a~id and salt, said composition having a pH o~ 4.5-6.5 and pre~erabl~ 5-6, said nonionic sur~actant is a water soluble ethoxylated nonionic surfactant selected from the yroup consisting of a polyglycol ether condensate of a C8-C20 fatty alcohol or mixture of fatty alcohols with an average of 5 to 30 mQles of ethylene o~ide, and a polysorbate containing 20 moles of ethylene oxide, preservative means containing about 0.1-4 by ~eight of a thickening agent selected from ~he group consisting of a diester of stearic acid and polyoxyethylene, and polyacrylic acid resin.
More specifically, the clear liquid fabric rinse composition of the present invention, which remove~ soap and surfactant residue from the washed fabric, consists essentially of about 84-~8~ water; about 0.7-6% by weight of a water-soluble ethoxylated nonionic surfactant as the sole surfactant, selected from the group consisting of a polyethylene glycol ether condensate of a C8-C20 fatty alcohol or mixture of fatty alcohols with an average of 5 to 30 moles of eth~lene oxide, and a polysorbate having an average of 20 moles of ethylene oxide; about 0.1-2% by weight of an organic acid, and~or sodium salt of the acid to adjust the pH of the composition to about 5-6; about 0.5-4% and preferably 0.6-2% by wei~ht of a thickening agent selected from the group consisting of a diester of stearic acid and polyoxyethylene, and a polyacrylic acid resin; and a preservative system, which might comprise 1,3-dimethylol-5~5 dimeth~l h~dantoin and disodium ethylene diamine-tetraacetate in equal amounts, or ~ermaben II.
~32~3 62301-1526 The after-wash fabric rinse of the present invention is preferably thickened to increas~ consumer acceptability by using the polyacrylic acid resin to form a gel, or the diester of stearic acid and polyoxyethylene to form a thick liquid.
The preservative systems in the present novel compositions effectively preserve the product against bacteria such as B. subtilis, and mold.
The formulations in accordance with present invention can also be used to remove soap from other surfaces that contain keratins, or similar proteins, such as hair.
DETAILED DESCRIPTION OF THE INVENTION
The major essential component in the li~uid fabric rinse compositions of the present invention is about 84 to 98%
by weight water, preferably deionized water. The water component is essential in the preparation of the present stable mild fabric rinse and functions as a solvent or vehicle for 6a B
.
1321 7~3 Il the other active ingredients in the composition, which are capable of being readily rinsed from the fabric.
Another essential ingredient in the present fabric rinse is a ¦ water-soluble nonionic surfactant, as the sole surfactant, preferably an i ethoxylated nonionic surfactant selected from the group consisting of a polyethylene glycol ether condensate of a C~~C-~n fatty alcohol or mixture of fatty alcohols with an average of 5-30 moles of ethylene oxide, and a Il polysorbate containing 20 moles ethylene oxide. Suitable fatty alcohols ¦ p~eferably contain 9 to 18 carbon atoms and most preferably 11 to 15 carbon l atoms. Typical examples are lauryl, tridecyl, myristyl, cetyl, stearyl and A ! oleyl alcohols or mixtures thereof, which may be condensed with about 5 to 20 moles ethylene oxide. Typical commercial products are the Tergitols obtainable from Union Carbide. More specifically, Tergitol 15-S-9 is a ¦ polyethylene glycol ether of a mixture of synthetic Ctl_l5 fatty alcohols with an average of 9 moles of ethylene oxide. Tergitol 25-L-7 is a polyethylene glycol ether of a mixture of synthetic Cl2_l5 fatty alcohols with an average of 7 moles of ethylene oxide.
The polysorbates are condensates of polyethylene oxide with fatty acid esters or mixtures of fatty acid esters of sorbitol and sorbitol anhydride.
Fatty acid esters include laurate esters, stearate esters, palmitate esters or oleate esters. The fatty acid esters of sorbitol and sorbitol anhydride are preferably condensed with 20 moles of ethylene oxide. Typical products are Tweens obtainable from the Atlas Company, also known as Polysorbates.
More specifically, Polysorbate 20 (Tween ~0) is a mixture of laurate esters of sorbitol and sorbitol anhydrides, consisting predominately of the monoester, condensed with about 20 moles of ethylene oxide, commonly known as Polyoxyethylene (20) Sorbitan Monolaurate. Polysorbate 80 (Tween 80) is a mixture of oleate esters of sorbitol and sorbitol anhydrides, consisting predominantly of the monoester, condensed with about 20 moles of ethyl~ne oxide, commonly known as Polyoxyethylene C20) sorbitan monooleate. The ¦¦ ~ 1'RP~fi ~ftP~I<
,' 132l7~ ~
nonionic surfactant constitutes about 0.25-6%, preferably about 0.7-6%, and most preferably 0.5-2% by weight of the composition. The minimal amount oF
nonionic surfactant necessary for the aqueous rinse base to adequately remove bound soap is shown in Table I.
Wool fabric was used to quantitively compare the removal of residual soap from absorbent fabric with various rinse treatments. Wool was pretreated with a solution of radiolabelled soap, rinsed with hard water to remove loosely bound soap, and then treated with various rinse formulations. The amount of soap removed from the wool is determined by analyzing the rinse solutions and wool for radioactivity.
Rinse formulations were prepared containing 2.0~ citric acid, and nonionic surfactant (Tergitol 15-S-9) varying in concentration from 0 to 2.0~. All solutions were adjusted to pH 5Ø The results shown in Table I
indicate that in the absence of the nonionic surfactant, iess than 20~ of the residual soap is removed. The addition of even a small amount of surfactant increases the removal to almost 90~ and that a maximum in residue removal is reached at about 2.0%. These results show that nonionic surfactant is necessary for the rinse base to adequately remove bound soap, however the amount needed for almost complete removal is relatively low.
TABLE I
~ffect of Surfactant Concentration of Residual Soap Removal by a Rinse Formula Treatment* Percent Soap Remo~al 0% Tergitol 17.9 +/- 1.10 0.25Z Tergitol 87.0 +/- 2.34 0.50Z Tergitol 91.4 ~/- 0.38 0.75Z Tergitol 89.5 +/- 0.80 l.OOZ Tergitol 92.9 +/- 1.66 2.00Z Tergitol 96.4 +/- 0.31 * All treatment colutions contained 2~ ci-ric acld, djusted to pd 5.0 i' 13~17~3 Another essential ingredient in the present fabric rinse is an organic acid having a pKa value from 4.5 to 6.5, a monovalent cation salt of the acid, or a ~ixture of said acid and salt. The preferred acid is citric acid C3H4(0H)(COOH)3, or a mixturs of citric acid and a citrate salt made with a monovalent cation such as sodium or triethanolamine. The citric acid and/or citrate buffers soap and anionic detergent removal from the washed fabrics by coacting with the nonionic surfactant in removing soap and detergent residue bound to the fabric. Other sui~able acids include acetic, succinic and glutaric acids. The organic acid constitutes about 0.05 to 5%, preferably 0.1 to 2% by weight of the composition. The minimal amount of organic acid required to buffer soap removal from the fabric is shown in Table II, using the pretreated wool fabric as defined above, and the ~mount of soap removed is similarly determined.
Rinse formulations were prepared containing 0.25~ Tergitol, pH 5.0, and citric acid concentrations varying from O to 2%. The results are shown in Table II. As-can be clearly seen, citric acid is also necessary for adequate residue removal. The rinse base removes only 66% of the residual soap, while addition of the smallest amount of citric acid (0.25~) increases the performance of the product to 88~. The results show a deviation from ideal behavior, in that there is an optimum concentration of citric acid for maximum performance near O.S~, followed by a decrease in performance as the citric acid ncentratlon ~ontinues to In~rease.
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Il 132~7~3 TAEffect of Organic Acid Concentration on Residual Soap Re~oval by a Rinse ~ormula 1 Treatment* Percent Soap Removal ,¦0% Citric Acid 66.0 +/- 5.4 0.25~ Citric Acid 87.4 +/- 0.41 0.50% Citric Acid 88.6 +/- 0.27 0.75~ Citric Acid 86.8 ~/- 1.28 1.00Z Citric Acid 84.9 +¦- 1.30 2.00% Citric Acid 72.5 +¦- 6.42 ~ All treatment solutions contained 0.25Z Tergitol, adjusted Il to pH 5.0 The effectiveness of the unique combination of the buffered organic acid and a nonionic surfactant of present invention for the removal of residual surfactants from wool fabrics was determined using the followin~
procedure: 100 m.g. wool test fabrics were treated with 20 mM solutions of radiolabelled sodium dodecyl sulfate (SLS) or linear dodecylbenzene sulfonate (LAS) for 1.5 hours, followed by a water r~nse containing 100 ppm hardness (Ca:Mg 3:2) for 1.5 hours, followed by a rinse in the solutions containing either 100 ppm water; a buffered 2~ sodium citra~e to a pH of 6.0; 2.0~ Tergitol, 15-S-9 adjusted to pH 6; or 2~ sodium citrate and 2%
Tergitoll for one hour. The wool fabric is filtered from the rinse treatment solutions and analyzed for radioactive surfactants. The total surfactant present in the fabric at the beginning of the rinse treatment was the sum of the surfactant in the solution and the fabric after the treatment, and the percent removal was calculated from the before and after levels. Radioactivity was measursd with a Packard Tri-Carb 3375 liquid scintillation Spectrometer (Downers Grove, IL) using Biofluor scintillation cocktail (New ~ngland Nuclear, Boston, MAj.
:
10 ;
7 ~ 3 i~! The results in lable III show that large amounts of surfactant are 1`
retained by the fabric after the first water rinse, and only small amounts of surfactant are removed by a second water rinse. Treatment with buffered citrate solution alone rinses out small amo~nts of surfactant, and Tergitol rinses out moderate amounts of SLS. When used in combination, however, large amounts of surfactant are rinsed from the fabric, and it is anticipated that a larger volume of rinse solution would result in even higher rinsing efficacy. The combination of these two matPrials is clearly synergistic.
These results show that the use of a combination of buffered citrate and Tergitol nonionic surfactant results in large reductions in the residual surfactant left in wool fabric after washing, and rinsing with water. Prior experiments have shown that other nonionic stlrfactants, such as Tween~ are equally as effective as Tergitol at removing residual soap and surfactants from wool.
Table III
Rinsing of Residual Surfactants from Wool Fabric Residual Surfactant in Wool (UMlR)l Rinse: None Water Citr. N.I. Citr/N.I.
Treatment SLS 211 1~2 186 143 79 ~ Removal: - 9 12 32 63 L~S 171 168 166 133 96 X Removal: - 2 3 22 44 'ThQ absorption of surfactant is defined as micromoles of surfactant sorbed per ~ram of substrate (uM/g) A preferred additive in present fabric rinse is a thickening aBent selected from the group consisting of a diester of stearic acid and polyoxyethylene (P~G 150 distearate) and a polyacrylic resin ~such as Carbopol 941 or 940 or 1342). Carbopol 940 has rinsibility advantages over Carbopol 941. The Carbopol resins obtainable from the Goodrich Co., as a fluffy, dry powder are water soluble pol~mers of acrylic acid with a 7 ~ 3 poly/functional agent, also known as polyacrylic acid resins by the CTFA
name of Carbomers. Low concent~ations of polyacrylic acid resins, about 0.1-4~ and preferably about 0.1-2~ by weight, effectively thicken the fabric rinse and form a gel fabric rinse which is clear, colorless and flows slowly when poured. However, Carbopol gels lose viscosity when exposed to W light. Therefore, a W stabilizer such as benzophenone should be added, especially if the product is sold in a clear bottle. The P~G-150 distearate, in amounts of 0.1-4% and preferably 2-4Z by weight, increases the viscosity of the watery solution to a desired thickness, preferably to a thick liquid.
It has been found that the aforesaid two viscosity control agents provide viscosity control without attributing negative sensory feel to the treated fabric. It has additionally been found that said two thickening a~ents enable the formulation of this product to vary wlthin a range of viscosities, from watery solutions to thick gels, while maintaining the clarity as well as the tactile sensatioDs afforded by the unthickened formulations. Other suitable thickening`agents capable of maintaining the clarity and the tactile sensations of the unthickened formulations may be also used. However, it has been found that the use of the thickening agents guar gums and cellulose resins are unacceptable from a sensory standpoint.
ThQ product containing guar gum resulted in a slimy feel~on the fabric; and the product containing cellulose thlckener resulted in a tacky feel on the fabric. Accordingly, the preferred thickening agents are P~G-150 distearate and the polyacrylic resins.
Another optional additive in the fabric rinse is a preservative system of 1,3-dimethylol-5,5 dimethyl hydantoin (DMDM hydantoin) and disodi~
ethylene diamine tetraacetate (EDTA), preferably in equal amounts of 0.3% by weight of ea~h component. This preservative system effectively preserves the fabric r~nse of present invention against mold and bacteria such as B.
subtilis. An aqueous solution of a combination of P`~M hydantoin and EDTA
a~ ~n alltimicrobial compositiun ~o~ inllibiting ~rowth of microor~nisms is described in U.S. Patent N~o 4~172~140 ~
This patent describes the usé of a 0.25:1 to 20:1 ratio o~ DMDM hydalltoill ~o EDTA as a preservative in metal working fluids, cutting oil fluids and other coolants. Another suitable preservative is Germaben 11, a product of SuLton Laborats~ries, lnc., whic comprises propylene glycol S0%, diazolidil1yl urea 30%, mQthylparaben 11~, alll1 propy1paraboll 3~. '1`11o Cormaben 1I praservative does not reduce vlscoslty as much as Llla combillaLlon of ~DTA and DM~M llydantoln prasorvative, so lqss Carbopo1 is needad to acllleve Lhe sa~e vlscosity.
jl The fabric rinse compositions of this invention also may contain minor amounts of conventional additiollal componen~s to lmpart any desired characteristlc, which are compatible with the ~abric rinse formulation, an~
do not adversely affect its tactile properties and soap and surfactant removal properties. Suitable addltives include fragranc~s, coloring agents and the liho, in minimal amounts, not to exceed 5% by wei~ht of the co~position. These addltives will replace some of the water ln the ~or~ulatlon.
The pll of the clear liquid fabrie rinse of present lnvention, which mfly bQ ln the form of a watery solution, a thiek liquid~ or a gel, may vary wlthin the rang~ of 4.5 to 6.5 and preferably from 5 to 6. Using the prstrQ~tQd wool substrate d~serlbed in thQ prevlous experiment~ to ~scartaln tho QffQct ol surfactant conc~ntratlon on rlnss b~s~
effeetivQness, i.e. residual soap and surfactant removal, a ~tudy of the efect of changing the rinso base pl1 was conducted. The surfactant .~nsl or~anlc aeid concentrations were held constant at 0.25Z and 2% respectively.
The rQsulLs shown in Table lV lndicaLa Lhat lncroaslnK tl1e pll s)r Lllu r~nse formulatioll decreases tlla offlele1lcy of soap removal only sllgl1tly, from about 90% at pl~ 4.5 to B3% at pll 6.5. The~e ~ ht losses ln product ,':' ' '' ~ 1~217~3 ¦ perfor~ance can be made up by optimi~ation of the surfactant and organic acid concentrations.
, TABL~ IV
EEfect of pH on Residual Soap Removal by a Rinse Formula Treatment* Percent S_ p Removal 1~ pH 4.5 89,2 +/- 2.34 Il p~ 5.0 90~5 +1- 1.90 !I pH 5.5 84.2 ~/- 0.79 I! pH 6.0 82~9 +/- 0.27 j~ pH 6.5 83.1 +/- 4.41 ll * All treatment solutions contained 0.25~ Tergitol and 2.0 I citric acid , Using the pretreated wool substrate described in previous experiments, efficacy of the fabric rinse formulas in removing residual soap was evaluated. Formulas 'A' and 'C' contained 2.0% citric acid, were adjusted to pH 5.0, and had 1~ and 6% tergitol respectively. Formula '~' contained Il 300 ppm hard water only. The results of the study are shown in Table V, i compared to the appropriate controls.
TABL~ ~
Efficacy of Fabric Rinse Formulas in Removin~ Residual Soap Treatment Percent Soap Removal Product A (l~ Tergitol~* 92.2 ~/- 1.05 Product B (Hard Water) 13.7 ~/- 0.77 Product C ~6~ Tergitol)* 98.1 +/- 0.30 Control 1 ~l~ Tergitol, 2% Citric Acid) 92.9 ~/- 1.66 Control 2 (Hard Water) 14.9 +/- 0.66 * These formulas contained 2.0X citric acid, adjusted to pH
5.0 The results o~ the soap removal study agree with the formula composition, i.e. hard water ('B') removed the least amount of soap (13.7%), the 1~
Tergitol formula ('A') removed 93%, and the 6% formula ('C') removed 98% of the residual soap from the wool keratin samples.
Evaluations further show that the optimum formula ingredient levels for removing residual soap with a p~ 6.0 ~ormula were 0.54% citric acid and 0.77~ Tergitol 15-S-9, exhibiting a 99% soap removal.
13~17'13 Ths coaction of the nonionic surfactant, the citric acid and the pH
provides a fabric rinse which optimizes residual soap and surfactant removal, and provides a desirable tactile sensation feel to the fabric.
Test data has shown that compositions containing the combination of 0.5%
citric acid and 0.5% nonionic surfactant removes about 91% soap, whereas citric acid compositions remove about 10% soap, 1% Tergitol (nonionic) removes about 77% soap, and the control (water only) removes 33.9% soap.
Accordingly, the criticality of the ingredients and the specificity of each ingrediant is necessary in the formulation of the present novel fabric rinse which is used as an after-rinse in the laundering of clothes.
The fabric rinse of the present inven~ion are generally prepared by mixing the thickening agent, when used, with water until hydrated, then admixing the nonionic surfactant and the organic acid andlor the sodium salt thereof, such as the citric acid andlor sodium citrate, to form a uniform aqueous thickened solution, adding an aqueous solution of the preservative system to said aqueous solution with mixing, mixing until a homogeneous thick liquid or gel is formed, and adjusting the pH if necessary.
The fabric rinse compositions of present invention are clear, colorless, liquids which can be poured from any suitable container. The thin or watery liquids flow rapidly like water, when poured. The viscous or thlck liquids flow slowly when poured. The gel also flows slowly when poured.
This product is used after washing fabrics with soap and/or surfactant and water. After the soap and surfactant is rinsed away, the fabric rinse of present invention is applied to the fabric by any suitable means. For example, the fabric rinse is added to the washing machine as an after-rinse at the completion of the laundering procedure. The fabric rinse can also be r~ed as an a t r-rinse on hand wa~hed fabrics.
, , ' ~-~
,,," ''':
~L32~7'~3 The following examples merely illustrate the invention, but it is understood that the invention is not limited thereto. All amounts of various in~redients in the examples and elsewhere in the specification are ¦ by weight unless otherwise specified.
Examples 1 and 2 ~1 Pabric Rinse Il In~redients % %
¦¦ Tergitol 15-S-9 1 6 I Sodium citrate 2.0 2.0 Water 97.0 92.0 pH 5 5 I¦ These products are prepared by adding the Tergitol and the sodium ¦¦ citrate to the water and mixing until a uniform solution is obtained.
ll Examples l and 2 were also used as a pre-fabric rinss to prevent or ¦~ reduce the deposition of soap on the fabric during the laundering operation.
It was demonstrated that these formulations will reduce the deposition I of UR to 33% of soap on wool fabric.
¦ Example 3 Gel Fabric Rinse In~redient Sterile Deionized Water 95.9%
Tergitol 15-S-9 2.0%
Carbopol 941 1.0%
Citric Acid o.5%
DMDM Hydantoin 0.3%
Ethylene diamine tetra acetic acid (EDTA) 0.3%
100.0% .
The gel fabric rinse is a clear, colorle}s e~l~ wblch flows sIowly when poured.
:
1~.17LI3 This ~roduct is prepared by dissolving Carbopol (Carbomer 941) in deionized water then adding Tergitol (Pareth 15-9) and citric acid and I, mixing until a uniform thickened aqueous solution is obtained. DMDM
¦¦ hydantoin (Glydent-Glyco) and EDTA are added to the solution and mixed until completely dissolved. A gel is formed as the pH is adjusted to 6.0 with sodium hydroxide.
This formulation can also be used as a pre-fabric rinse to reduce the deposition of soap on the fabric (wool was used as the test fabric).
Example 4 Gel Fabric Rinse ¦ 1.0X Tergitol 15-S-9 ¦1 0.6~ Carbopol 940 (thickener) ¦ O.3% DMDM Hydantoin ¦ O.3% EDTA
0.1% Citrate 97.7% Sterilized Deionized Water pH adjusted to 6.0 with sodium hydroxide This gel is prepared in accordance with the procedure set forth in Example 3.
This product exhibits the same tactile properties of smoothness, when applied as a non-gelled fabric rinse after washing with soap.
Example 5 Fabric Rinse In~redients Ter$itol 15-S-9 2.0 Sodium Citrate 2.0 Water 96.0 pH 6.0 This product is prepared in accordance with the procedure set forth in Example 1. This product removed 63% sodiu~ lauryl sulfate surfactant from a 1~217~
wool fabric sample, and 44% linear dodecyl benzene sulfonate surfactant from 1j another sample of wool fabric.
The aforedescribed e~amples may be modified by the substitution of ! other nonionic surfactants for the Tergitol 15-S-9, such as Tween 20, Tween li 80 and Neodol 25-7 (Pareth 25-7-Shell), without adversely affecting the ¦¦ efficacy of the compositions. Likewise, PEG-distearate may be substituted ¦j for the Carbopol thickening agent to form a thick liquid. Also, the citric acid or citrate may be replaced by glutaric, succinic or acetic acid and/or l the sodium or triethanolamine salts thereof.
¦l It is understood that the foregoing detailed description is given ¦ merely by way of illustration and that variations may be made therein ~h-~ "~ t ~ n-- n
;This invention relates to an aqueo~s fabric rinse formulation for soap and surfactant residue removal consisting essentially of a minimal amount of a water soluble nonionic surfactant such as the polyethylene oxide ; condensates of higher fatty alcohols, and a polysorbate containing 20 moles o~ ethylene oxide, a minimal amount of an organic acid having a pKa of 4.5 to 6.5 and/or a monovalent cation salt of the acid, and a major amount of water in an amount of about 84-98% by weight of the liquid for~ulation ~I having a pH within the range of about 4.5-6.5. This product may be used as an ater-rinse, at the c.ompletion of the laundering procedure, i.e. after ~ the soap and/or anionic surfactant is rinsed with water from the fabrics, ! which include wool, cotton, dacron-cotton blends and any other blends which are absorbent. The present fabric rinse has the dual function of removing ¦ substantially all the residual soap and anionic surfactant residue~ and ¦I conditloning the fabric to feel good against the skin and obviate possible `, skin irritation.
`. ~
'BACKGROUND AND PRIOR ART
~I
i~Prlor work has shown that large amounts oE anionic surf~ctants and soaps are absorbed and retained by fabrics, such as wool, cotton, dacron-cotton xttre and other fabFIc mixtu s, sFin and c.heF s mllar b~tra~s Il ~
I
I
,: , .
~L 3 21 r~ l~ 3 , during the washing process. These residual surfactants and soaps are 1, difficult to rinse from wool and skin. The removal of said residues from the skin is addressed in a copending cleanse~ composition filed of even date. Consumers perceive these residues left on clothes as a negative, since thay change the way fabrics feel, and can possibly be irritating.
Accordingly, the presence of residual anionic suractant on clothes being , perceived in a negative way by the consumer, and as a potential source of skin irritation, there is clearly a need to develop a fabric rinse product addressing this problem. A unique combination of a buffered organic acid ~¦ and a nonionic surfactant has been shown to be very effective at removing residual soap from said fabrics.
~' It has been found that this fabric rinse reduced the levels of residual ,, anionic surfactant retained by wool fabric after washing, by 40 - 60%
il compared to a water rinse. The amount of surfactant rinsed out of the ¦j fabric by the prototype was significantly greater than formulas containing either ingredient alone.
A study using wool fabric and laurate soap demonstrated that Ca++ and Mg++ salts that produce water hardness increase surfactant deposition and absorption of the soap to the wool fabric, a keratin substrate. Hence, the water hardness increases the binding of the laurate soap to wool and, by analo~y to skin, decreases the ability to wash the soap off the wool or skin, which binds the soap surfactant in a manner similarly to wool. It is the removal of this soap and/or synthetic anionic surfactant residue from the washad and water rinsed fabrics such as wool that is the subject matter of present invention.
Commercial facial detergent co~positions containing soap and assorted mixtures of surfactants for use in the wash cycle of the laundering operation has addressed the problem of fabric softness in the prior art by adding softening agents to the deter~ent composition; or by separately adding the softening agent in the rinse cycle of the laundering operation.
13217~3 However, the removal of soap and/or surfactant residue after washing fabrics with soap has not been addressed in the prior ~rt.
The use of a nonionic surfactant as one of the ingredients in a liquid detergent for cleaning fabrics is well known in the prior art as disclosed in U.S. Patent Nos. 3,764,544 wherein is disclosed a spot remover for wearing apparel containing a nonionic surfactant; 3,959,163 wherein is disclosed a stain removing composition containing a bleaching compound and a nonionic surfactant; and 4,206,070 wherein is disclosed a binary surfactant system of nonionics.
U.S. Patent No. 3,915,633 discloses an aqueous prewash aerosol spray soil release composition for use with a detergent or soap in a laundering operation, consisting of 1-20% by weight of an organic acid, i.e. citric acid, 2-30% by weight of an anionic or nonionic surfactant, water and an aerosol propellant. Canadian Patent No. 1,0%o,178 discloses a liquid heavy duty laundry detergent composition containing 20-70~ by weight of a soluble ethoxylated nonionic surfactant, 0.1-1.25~ by weight of a polyacid, i.e.
citric acid, and watertorganic solvents, having a pH of 6-7.5.
Also disclosed in the prior a}t are mi~tures of a nonionic surfactant and polyacrylate thickeners in aqueous dishwashing detergent formulations as disclosed in U.S. Patent Nos. 3,950,260 and 4,226,736.
U.S. Patent No. 4,501,680 discloses acidic liquid detergent compositions for cleaning ceramic tiles without eroding grout between them, comprising a minor proportion of glutaric acid and a lesser amount of phosphoric acid to provide a pH of 3-5, a minor amount of an ethoxylatsd fatty alcohol, a minor amount of a diethylene glycol monoalkyl ether, and a major amount of water.
U.S. Patent No. 4,172,140 discloses an antimicrobial composition for inhibiting the growth of microorganisms in an aqueou3 fluid medium comprising as the active ingredients, an admixture of 1,3-dimeth~1O1-5,5 dlmethyl hydantoin and disodium ethylene dlaminetetraacetate, for use in ~1 ~3~7~
,I metal working fluids, cuttin~ oil fluids, coolants, lubricants, and the 'I like.
¦ U.S. Patent No. 4,612,137 discloses an anti-yellowing detergent composition comprising citric acid or salt and isocitric acid or salt and a surfactant, which may be anionic, nonionic, etc.
,i None of the aforesaid prior art disclose a fabric rinse to remove ¦¦ residual soap and/or synthetic anionic surfactants absorbed by the fabric during the washing process, consisting of a low level of a nonionic surfactant as the sole surfactant, a minor amount of an organic acid (or salt thereof) having a pKa from 4.5 to 6.5 to provide a pH of about 4.5 to 6.5, and a major amount o~ water, which may be thickened with polyethylene ~lycol - 150 distearate to a thick liquid or thickened with an acrylic acid polymer to for~ a gel, and preferably contains a preservative system.
ll SUMMARY OF THE INVENTION
`¦ It has been found that the soap and anionic surfactant residue retained on the fabric after washing with soap or surfactant can cause skin irritation and change the way fabrics feel. It has additionally been found that the soap residue can be effectively removed from the fabrics with the present novel rinse formulation consisting essentially of a minor amount of a water soluble nonionic surfactant, with the pH adjusted to about 4.5-6.5, using an organic acid having a pKa from 4.5 to 6.5 and a major amount of water, preferably deionized water. The novel fabric rinse is a clear product with viscosities ranging from watery solutions to thick gels, by the addition of a viscosity control agent selected from the group consisting of a diester of stearic acid and polyoxyethylene (PEG 150 distearate), and a polyacrylic acid resin (Carbopol 941~ Compositions prepared with either thickener yield soft, smooth fabricJ similar to the unthickened watery solution, without leaving a slimy or tacky feeling. The present novel composition functions as a fabric rinse which removes the absorbed soap andlor surfactant deposited thereon duriDg the washing process.
' '',` , ~ ~ ','; ~ ,,j '~ ~
~3~17~3 Accordingly, the present invention seeks to provide a liquid fabric rinse composition ~o remove soap and anionic surfactant residue from the washed fabric and thereby prevent possible irritation due to the soap or surfactant.
This invention also seeks to provide a fabric rinse~
to be used after washing with soap or surfaetant and water, which results in a soft, smooth fabrlc feel.
This invention further seeks to provide a fabric rinse containing as the major ingredients, a nonionic surfactant, an organic acid, a major amount of water, and having a pH adjusted to about 4.5-6.5.
This invention also seeks to provide a clear liquid afterwash fabric rinse or pre-fabric rin~e with viscosities ranging from watery solutions to thick gels.
This invention also seeks to provlde a thickened or gelled fabric rinse containing a diester of stearic acid and polyoxyethylene or a polyacrylic acid resin as the thickening agent.
This invention also seeks to provide a fabric rinse also containing a preservative system.
Additional advantages and novel features of the invention will be set forth in part in the descxiptlon which follows, and in part will become apparent upon examination of the following specificàtion or may be learned by practice of this invention.
To achieve the foregoing in accordance with the present invention, as embodied and broadly described herein, the novel liquid fabric rinse composition to remove soap or anionic surfactant residue from the wa~hed fabric in accordance with this invention, consists essentially of a ma~or amount of water, preferably deionized water, about 0.25-6% by weight of a 13217~3 nonionic surfactant as the sole surfa~tant, about 0.05-5% by weight of an organic acid having a pKa from 4.5 to 6.5 or a monovalent cation salt of the a~id or a mixture of said a~id and salt, said composition having a pH o~ 4.5-6.5 and pre~erabl~ 5-6, said nonionic sur~actant is a water soluble ethoxylated nonionic surfactant selected from the yroup consisting of a polyglycol ether condensate of a C8-C20 fatty alcohol or mixture of fatty alcohols with an average of 5 to 30 mQles of ethylene o~ide, and a polysorbate containing 20 moles of ethylene oxide, preservative means containing about 0.1-4 by ~eight of a thickening agent selected from ~he group consisting of a diester of stearic acid and polyoxyethylene, and polyacrylic acid resin.
More specifically, the clear liquid fabric rinse composition of the present invention, which remove~ soap and surfactant residue from the washed fabric, consists essentially of about 84-~8~ water; about 0.7-6% by weight of a water-soluble ethoxylated nonionic surfactant as the sole surfactant, selected from the group consisting of a polyethylene glycol ether condensate of a C8-C20 fatty alcohol or mixture of fatty alcohols with an average of 5 to 30 moles of eth~lene oxide, and a polysorbate having an average of 20 moles of ethylene oxide; about 0.1-2% by weight of an organic acid, and~or sodium salt of the acid to adjust the pH of the composition to about 5-6; about 0.5-4% and preferably 0.6-2% by wei~ht of a thickening agent selected from the group consisting of a diester of stearic acid and polyoxyethylene, and a polyacrylic acid resin; and a preservative system, which might comprise 1,3-dimethylol-5~5 dimeth~l h~dantoin and disodium ethylene diamine-tetraacetate in equal amounts, or ~ermaben II.
~32~3 62301-1526 The after-wash fabric rinse of the present invention is preferably thickened to increas~ consumer acceptability by using the polyacrylic acid resin to form a gel, or the diester of stearic acid and polyoxyethylene to form a thick liquid.
The preservative systems in the present novel compositions effectively preserve the product against bacteria such as B. subtilis, and mold.
The formulations in accordance with present invention can also be used to remove soap from other surfaces that contain keratins, or similar proteins, such as hair.
DETAILED DESCRIPTION OF THE INVENTION
The major essential component in the li~uid fabric rinse compositions of the present invention is about 84 to 98%
by weight water, preferably deionized water. The water component is essential in the preparation of the present stable mild fabric rinse and functions as a solvent or vehicle for 6a B
.
1321 7~3 Il the other active ingredients in the composition, which are capable of being readily rinsed from the fabric.
Another essential ingredient in the present fabric rinse is a ¦ water-soluble nonionic surfactant, as the sole surfactant, preferably an i ethoxylated nonionic surfactant selected from the group consisting of a polyethylene glycol ether condensate of a C~~C-~n fatty alcohol or mixture of fatty alcohols with an average of 5-30 moles of ethylene oxide, and a Il polysorbate containing 20 moles ethylene oxide. Suitable fatty alcohols ¦ p~eferably contain 9 to 18 carbon atoms and most preferably 11 to 15 carbon l atoms. Typical examples are lauryl, tridecyl, myristyl, cetyl, stearyl and A ! oleyl alcohols or mixtures thereof, which may be condensed with about 5 to 20 moles ethylene oxide. Typical commercial products are the Tergitols obtainable from Union Carbide. More specifically, Tergitol 15-S-9 is a ¦ polyethylene glycol ether of a mixture of synthetic Ctl_l5 fatty alcohols with an average of 9 moles of ethylene oxide. Tergitol 25-L-7 is a polyethylene glycol ether of a mixture of synthetic Cl2_l5 fatty alcohols with an average of 7 moles of ethylene oxide.
The polysorbates are condensates of polyethylene oxide with fatty acid esters or mixtures of fatty acid esters of sorbitol and sorbitol anhydride.
Fatty acid esters include laurate esters, stearate esters, palmitate esters or oleate esters. The fatty acid esters of sorbitol and sorbitol anhydride are preferably condensed with 20 moles of ethylene oxide. Typical products are Tweens obtainable from the Atlas Company, also known as Polysorbates.
More specifically, Polysorbate 20 (Tween ~0) is a mixture of laurate esters of sorbitol and sorbitol anhydrides, consisting predominately of the monoester, condensed with about 20 moles of ethylene oxide, commonly known as Polyoxyethylene (20) Sorbitan Monolaurate. Polysorbate 80 (Tween 80) is a mixture of oleate esters of sorbitol and sorbitol anhydrides, consisting predominantly of the monoester, condensed with about 20 moles of ethyl~ne oxide, commonly known as Polyoxyethylene C20) sorbitan monooleate. The ¦¦ ~ 1'RP~fi ~ftP~I<
,' 132l7~ ~
nonionic surfactant constitutes about 0.25-6%, preferably about 0.7-6%, and most preferably 0.5-2% by weight of the composition. The minimal amount oF
nonionic surfactant necessary for the aqueous rinse base to adequately remove bound soap is shown in Table I.
Wool fabric was used to quantitively compare the removal of residual soap from absorbent fabric with various rinse treatments. Wool was pretreated with a solution of radiolabelled soap, rinsed with hard water to remove loosely bound soap, and then treated with various rinse formulations. The amount of soap removed from the wool is determined by analyzing the rinse solutions and wool for radioactivity.
Rinse formulations were prepared containing 2.0~ citric acid, and nonionic surfactant (Tergitol 15-S-9) varying in concentration from 0 to 2.0~. All solutions were adjusted to pH 5Ø The results shown in Table I
indicate that in the absence of the nonionic surfactant, iess than 20~ of the residual soap is removed. The addition of even a small amount of surfactant increases the removal to almost 90~ and that a maximum in residue removal is reached at about 2.0%. These results show that nonionic surfactant is necessary for the rinse base to adequately remove bound soap, however the amount needed for almost complete removal is relatively low.
TABLE I
~ffect of Surfactant Concentration of Residual Soap Removal by a Rinse Formula Treatment* Percent Soap Remo~al 0% Tergitol 17.9 +/- 1.10 0.25Z Tergitol 87.0 +/- 2.34 0.50Z Tergitol 91.4 ~/- 0.38 0.75Z Tergitol 89.5 +/- 0.80 l.OOZ Tergitol 92.9 +/- 1.66 2.00Z Tergitol 96.4 +/- 0.31 * All treatment colutions contained 2~ ci-ric acld, djusted to pd 5.0 i' 13~17~3 Another essential ingredient in the present fabric rinse is an organic acid having a pKa value from 4.5 to 6.5, a monovalent cation salt of the acid, or a ~ixture of said acid and salt. The preferred acid is citric acid C3H4(0H)(COOH)3, or a mixturs of citric acid and a citrate salt made with a monovalent cation such as sodium or triethanolamine. The citric acid and/or citrate buffers soap and anionic detergent removal from the washed fabrics by coacting with the nonionic surfactant in removing soap and detergent residue bound to the fabric. Other sui~able acids include acetic, succinic and glutaric acids. The organic acid constitutes about 0.05 to 5%, preferably 0.1 to 2% by weight of the composition. The minimal amount of organic acid required to buffer soap removal from the fabric is shown in Table II, using the pretreated wool fabric as defined above, and the ~mount of soap removed is similarly determined.
Rinse formulations were prepared containing 0.25~ Tergitol, pH 5.0, and citric acid concentrations varying from O to 2%. The results are shown in Table II. As-can be clearly seen, citric acid is also necessary for adequate residue removal. The rinse base removes only 66% of the residual soap, while addition of the smallest amount of citric acid (0.25~) increases the performance of the product to 88~. The results show a deviation from ideal behavior, in that there is an optimum concentration of citric acid for maximum performance near O.S~, followed by a decrease in performance as the citric acid ncentratlon ~ontinues to In~rease.
,,~ "~.
Il 132~7~3 TAEffect of Organic Acid Concentration on Residual Soap Re~oval by a Rinse ~ormula 1 Treatment* Percent Soap Removal ,¦0% Citric Acid 66.0 +/- 5.4 0.25~ Citric Acid 87.4 +/- 0.41 0.50% Citric Acid 88.6 +/- 0.27 0.75~ Citric Acid 86.8 ~/- 1.28 1.00Z Citric Acid 84.9 +¦- 1.30 2.00% Citric Acid 72.5 +¦- 6.42 ~ All treatment solutions contained 0.25Z Tergitol, adjusted Il to pH 5.0 The effectiveness of the unique combination of the buffered organic acid and a nonionic surfactant of present invention for the removal of residual surfactants from wool fabrics was determined using the followin~
procedure: 100 m.g. wool test fabrics were treated with 20 mM solutions of radiolabelled sodium dodecyl sulfate (SLS) or linear dodecylbenzene sulfonate (LAS) for 1.5 hours, followed by a water r~nse containing 100 ppm hardness (Ca:Mg 3:2) for 1.5 hours, followed by a rinse in the solutions containing either 100 ppm water; a buffered 2~ sodium citra~e to a pH of 6.0; 2.0~ Tergitol, 15-S-9 adjusted to pH 6; or 2~ sodium citrate and 2%
Tergitoll for one hour. The wool fabric is filtered from the rinse treatment solutions and analyzed for radioactive surfactants. The total surfactant present in the fabric at the beginning of the rinse treatment was the sum of the surfactant in the solution and the fabric after the treatment, and the percent removal was calculated from the before and after levels. Radioactivity was measursd with a Packard Tri-Carb 3375 liquid scintillation Spectrometer (Downers Grove, IL) using Biofluor scintillation cocktail (New ~ngland Nuclear, Boston, MAj.
:
10 ;
7 ~ 3 i~! The results in lable III show that large amounts of surfactant are 1`
retained by the fabric after the first water rinse, and only small amounts of surfactant are removed by a second water rinse. Treatment with buffered citrate solution alone rinses out small amo~nts of surfactant, and Tergitol rinses out moderate amounts of SLS. When used in combination, however, large amounts of surfactant are rinsed from the fabric, and it is anticipated that a larger volume of rinse solution would result in even higher rinsing efficacy. The combination of these two matPrials is clearly synergistic.
These results show that the use of a combination of buffered citrate and Tergitol nonionic surfactant results in large reductions in the residual surfactant left in wool fabric after washing, and rinsing with water. Prior experiments have shown that other nonionic stlrfactants, such as Tween~ are equally as effective as Tergitol at removing residual soap and surfactants from wool.
Table III
Rinsing of Residual Surfactants from Wool Fabric Residual Surfactant in Wool (UMlR)l Rinse: None Water Citr. N.I. Citr/N.I.
Treatment SLS 211 1~2 186 143 79 ~ Removal: - 9 12 32 63 L~S 171 168 166 133 96 X Removal: - 2 3 22 44 'ThQ absorption of surfactant is defined as micromoles of surfactant sorbed per ~ram of substrate (uM/g) A preferred additive in present fabric rinse is a thickening aBent selected from the group consisting of a diester of stearic acid and polyoxyethylene (P~G 150 distearate) and a polyacrylic resin ~such as Carbopol 941 or 940 or 1342). Carbopol 940 has rinsibility advantages over Carbopol 941. The Carbopol resins obtainable from the Goodrich Co., as a fluffy, dry powder are water soluble pol~mers of acrylic acid with a 7 ~ 3 poly/functional agent, also known as polyacrylic acid resins by the CTFA
name of Carbomers. Low concent~ations of polyacrylic acid resins, about 0.1-4~ and preferably about 0.1-2~ by weight, effectively thicken the fabric rinse and form a gel fabric rinse which is clear, colorless and flows slowly when poured. However, Carbopol gels lose viscosity when exposed to W light. Therefore, a W stabilizer such as benzophenone should be added, especially if the product is sold in a clear bottle. The P~G-150 distearate, in amounts of 0.1-4% and preferably 2-4Z by weight, increases the viscosity of the watery solution to a desired thickness, preferably to a thick liquid.
It has been found that the aforesaid two viscosity control agents provide viscosity control without attributing negative sensory feel to the treated fabric. It has additionally been found that said two thickening a~ents enable the formulation of this product to vary wlthin a range of viscosities, from watery solutions to thick gels, while maintaining the clarity as well as the tactile sensatioDs afforded by the unthickened formulations. Other suitable thickening`agents capable of maintaining the clarity and the tactile sensations of the unthickened formulations may be also used. However, it has been found that the use of the thickening agents guar gums and cellulose resins are unacceptable from a sensory standpoint.
ThQ product containing guar gum resulted in a slimy feel~on the fabric; and the product containing cellulose thlckener resulted in a tacky feel on the fabric. Accordingly, the preferred thickening agents are P~G-150 distearate and the polyacrylic resins.
Another optional additive in the fabric rinse is a preservative system of 1,3-dimethylol-5,5 dimethyl hydantoin (DMDM hydantoin) and disodi~
ethylene diamine tetraacetate (EDTA), preferably in equal amounts of 0.3% by weight of ea~h component. This preservative system effectively preserves the fabric r~nse of present invention against mold and bacteria such as B.
subtilis. An aqueous solution of a combination of P`~M hydantoin and EDTA
a~ ~n alltimicrobial compositiun ~o~ inllibiting ~rowth of microor~nisms is described in U.S. Patent N~o 4~172~140 ~
This patent describes the usé of a 0.25:1 to 20:1 ratio o~ DMDM hydalltoill ~o EDTA as a preservative in metal working fluids, cutting oil fluids and other coolants. Another suitable preservative is Germaben 11, a product of SuLton Laborats~ries, lnc., whic comprises propylene glycol S0%, diazolidil1yl urea 30%, mQthylparaben 11~, alll1 propy1paraboll 3~. '1`11o Cormaben 1I praservative does not reduce vlscoslty as much as Llla combillaLlon of ~DTA and DM~M llydantoln prasorvative, so lqss Carbopo1 is needad to acllleve Lhe sa~e vlscosity.
jl The fabric rinse compositions of this invention also may contain minor amounts of conventional additiollal componen~s to lmpart any desired characteristlc, which are compatible with the ~abric rinse formulation, an~
do not adversely affect its tactile properties and soap and surfactant removal properties. Suitable addltives include fragranc~s, coloring agents and the liho, in minimal amounts, not to exceed 5% by wei~ht of the co~position. These addltives will replace some of the water ln the ~or~ulatlon.
The pll of the clear liquid fabrie rinse of present lnvention, which mfly bQ ln the form of a watery solution, a thiek liquid~ or a gel, may vary wlthin the rang~ of 4.5 to 6.5 and preferably from 5 to 6. Using the prstrQ~tQd wool substrate d~serlbed in thQ prevlous experiment~ to ~scartaln tho QffQct ol surfactant conc~ntratlon on rlnss b~s~
effeetivQness, i.e. residual soap and surfactant removal, a ~tudy of the efect of changing the rinso base pl1 was conducted. The surfactant .~nsl or~anlc aeid concentrations were held constant at 0.25Z and 2% respectively.
The rQsulLs shown in Table lV lndicaLa Lhat lncroaslnK tl1e pll s)r Lllu r~nse formulatioll decreases tlla offlele1lcy of soap removal only sllgl1tly, from about 90% at pl~ 4.5 to B3% at pll 6.5. The~e ~ ht losses ln product ,':' ' '' ~ 1~217~3 ¦ perfor~ance can be made up by optimi~ation of the surfactant and organic acid concentrations.
, TABL~ IV
EEfect of pH on Residual Soap Removal by a Rinse Formula Treatment* Percent S_ p Removal 1~ pH 4.5 89,2 +/- 2.34 Il p~ 5.0 90~5 +1- 1.90 !I pH 5.5 84.2 ~/- 0.79 I! pH 6.0 82~9 +/- 0.27 j~ pH 6.5 83.1 +/- 4.41 ll * All treatment solutions contained 0.25~ Tergitol and 2.0 I citric acid , Using the pretreated wool substrate described in previous experiments, efficacy of the fabric rinse formulas in removing residual soap was evaluated. Formulas 'A' and 'C' contained 2.0% citric acid, were adjusted to pH 5.0, and had 1~ and 6% tergitol respectively. Formula '~' contained Il 300 ppm hard water only. The results of the study are shown in Table V, i compared to the appropriate controls.
TABL~ ~
Efficacy of Fabric Rinse Formulas in Removin~ Residual Soap Treatment Percent Soap Removal Product A (l~ Tergitol~* 92.2 ~/- 1.05 Product B (Hard Water) 13.7 ~/- 0.77 Product C ~6~ Tergitol)* 98.1 +/- 0.30 Control 1 ~l~ Tergitol, 2% Citric Acid) 92.9 ~/- 1.66 Control 2 (Hard Water) 14.9 +/- 0.66 * These formulas contained 2.0X citric acid, adjusted to pH
5.0 The results o~ the soap removal study agree with the formula composition, i.e. hard water ('B') removed the least amount of soap (13.7%), the 1~
Tergitol formula ('A') removed 93%, and the 6% formula ('C') removed 98% of the residual soap from the wool keratin samples.
Evaluations further show that the optimum formula ingredient levels for removing residual soap with a p~ 6.0 ~ormula were 0.54% citric acid and 0.77~ Tergitol 15-S-9, exhibiting a 99% soap removal.
13~17'13 Ths coaction of the nonionic surfactant, the citric acid and the pH
provides a fabric rinse which optimizes residual soap and surfactant removal, and provides a desirable tactile sensation feel to the fabric.
Test data has shown that compositions containing the combination of 0.5%
citric acid and 0.5% nonionic surfactant removes about 91% soap, whereas citric acid compositions remove about 10% soap, 1% Tergitol (nonionic) removes about 77% soap, and the control (water only) removes 33.9% soap.
Accordingly, the criticality of the ingredients and the specificity of each ingrediant is necessary in the formulation of the present novel fabric rinse which is used as an after-rinse in the laundering of clothes.
The fabric rinse of the present inven~ion are generally prepared by mixing the thickening agent, when used, with water until hydrated, then admixing the nonionic surfactant and the organic acid andlor the sodium salt thereof, such as the citric acid andlor sodium citrate, to form a uniform aqueous thickened solution, adding an aqueous solution of the preservative system to said aqueous solution with mixing, mixing until a homogeneous thick liquid or gel is formed, and adjusting the pH if necessary.
The fabric rinse compositions of present invention are clear, colorless, liquids which can be poured from any suitable container. The thin or watery liquids flow rapidly like water, when poured. The viscous or thlck liquids flow slowly when poured. The gel also flows slowly when poured.
This product is used after washing fabrics with soap and/or surfactant and water. After the soap and surfactant is rinsed away, the fabric rinse of present invention is applied to the fabric by any suitable means. For example, the fabric rinse is added to the washing machine as an after-rinse at the completion of the laundering procedure. The fabric rinse can also be r~ed as an a t r-rinse on hand wa~hed fabrics.
, , ' ~-~
,,," ''':
~L32~7'~3 The following examples merely illustrate the invention, but it is understood that the invention is not limited thereto. All amounts of various in~redients in the examples and elsewhere in the specification are ¦ by weight unless otherwise specified.
Examples 1 and 2 ~1 Pabric Rinse Il In~redients % %
¦¦ Tergitol 15-S-9 1 6 I Sodium citrate 2.0 2.0 Water 97.0 92.0 pH 5 5 I¦ These products are prepared by adding the Tergitol and the sodium ¦¦ citrate to the water and mixing until a uniform solution is obtained.
ll Examples l and 2 were also used as a pre-fabric rinss to prevent or ¦~ reduce the deposition of soap on the fabric during the laundering operation.
It was demonstrated that these formulations will reduce the deposition I of UR to 33% of soap on wool fabric.
¦ Example 3 Gel Fabric Rinse In~redient Sterile Deionized Water 95.9%
Tergitol 15-S-9 2.0%
Carbopol 941 1.0%
Citric Acid o.5%
DMDM Hydantoin 0.3%
Ethylene diamine tetra acetic acid (EDTA) 0.3%
100.0% .
The gel fabric rinse is a clear, colorle}s e~l~ wblch flows sIowly when poured.
:
1~.17LI3 This ~roduct is prepared by dissolving Carbopol (Carbomer 941) in deionized water then adding Tergitol (Pareth 15-9) and citric acid and I, mixing until a uniform thickened aqueous solution is obtained. DMDM
¦¦ hydantoin (Glydent-Glyco) and EDTA are added to the solution and mixed until completely dissolved. A gel is formed as the pH is adjusted to 6.0 with sodium hydroxide.
This formulation can also be used as a pre-fabric rinse to reduce the deposition of soap on the fabric (wool was used as the test fabric).
Example 4 Gel Fabric Rinse ¦ 1.0X Tergitol 15-S-9 ¦1 0.6~ Carbopol 940 (thickener) ¦ O.3% DMDM Hydantoin ¦ O.3% EDTA
0.1% Citrate 97.7% Sterilized Deionized Water pH adjusted to 6.0 with sodium hydroxide This gel is prepared in accordance with the procedure set forth in Example 3.
This product exhibits the same tactile properties of smoothness, when applied as a non-gelled fabric rinse after washing with soap.
Example 5 Fabric Rinse In~redients Ter$itol 15-S-9 2.0 Sodium Citrate 2.0 Water 96.0 pH 6.0 This product is prepared in accordance with the procedure set forth in Example 1. This product removed 63% sodiu~ lauryl sulfate surfactant from a 1~217~
wool fabric sample, and 44% linear dodecyl benzene sulfonate surfactant from 1j another sample of wool fabric.
The aforedescribed e~amples may be modified by the substitution of ! other nonionic surfactants for the Tergitol 15-S-9, such as Tween 20, Tween li 80 and Neodol 25-7 (Pareth 25-7-Shell), without adversely affecting the ¦¦ efficacy of the compositions. Likewise, PEG-distearate may be substituted ¦j for the Carbopol thickening agent to form a thick liquid. Also, the citric acid or citrate may be replaced by glutaric, succinic or acetic acid and/or l the sodium or triethanolamine salts thereof.
¦l It is understood that the foregoing detailed description is given ¦ merely by way of illustration and that variations may be made therein ~h-~ "~ t ~ n-- n
Claims (18)
1. A clear liquid fabric rinse composition to remove soap and synthetic anionic surfactant residue from washed fabrics, consisting essentially of a major amount of about 84-98% by weight of water, about 0.25-6% by weight of a non-ionic surfactant as the sole surfactant, about 0.5-5% by weight of an organic acid having a pKa from 4.5-6.5, or a monovalent cation salt of the acid or a mixture of acid and salt, said composition having a pH of 4.5-6.5; said nonionic surfactant is a water soluble ethoxylated nonionic surfactant selected from the group consisting of a polyglycol ether condensate of a C8-C20 fatty alcohol or mixture of fatty alcohols with an average of 5 to 30 moles of ethylene oxide, and a polysorbate containing 20 moles of ethylene oxide, preservative means containing about 0.1-4% by weight of a thickening agent selected from the group consisting of a diester of stearic acid and polyoxyethylene, and polyacrylic acid resin.
2. The composition according to claim 1, wherein said preservative means comprises 1,3-dimethylol-5,5 dimethyl hydantoin and disodium ethylene diamine-tetraacetate, in equal amounts.
3. The composition according to claim 1, in the form of a clear gel containing about 0.1-2% by weight of a polyacrylic acid resin.
4. The composition according to claim 1, in the form of a thick liquid containing about 2-4% by weight of a diester of stearic acid and polyoxyethylene.
5. The composition according to claim 1, wherein the nonionic surfactant constitutes 0.7-6% by weight of the composition having a Ph of 5-6.
6. The composition according to claim 1, wherein the nonionic surfactant is a polyethylene glycol ether of a mixture of synthetic C11-C15 fatty alcohols with an average of 9 moles of ethylene oxide.
7. The composition according to claim 5, wherein the nonionic surfactant is a polyethylene glycol ether of a mixture of synthetic C12-C15 fatty alcohols with an average of 7 moles of ethylene oxide.
8. The composition according to claim 5, wherein the nonionic surfactant is a mixture of laurate or oleate esters of sorbitol and sorbitol anhydrides condensed with about 20 moles of ethylene oxide.
9. The composition according to claim 1, wherein the nonionic surfactant constitutes about 0.5-2.0% by weight of the composition.
10. The composition according to claim 1, wherein the organic acid and acid salt is citric acid and sodium citrate and constitutes about 0.1-2.0% by weight of the composition.
11. The composition according to claim 2, wherein each of the ingredients in the preservative system constitutes about 0.3% by weight of the composition.
12. The composition according to claim 2, consisting of 2.0% by weight of nonionic surfactant, 2.0% by weight citric acid, and having a pH of 6.
13. The composition according to claim 2, consisting of 1% nonionic surfactant, 2% sodium citrate, and having a pH
of 5.
of 5.
14. The composition according to claim 3, wherein the gel consists of 2% by weight nonionic surfactant, 1% by weight polyacrylic acid resin, 0.5% by weight citric acid, 0.3% by weight DMDM hydantoin, 0.3% by weight ethylene diamine tetra acetic acid and 95.9% by weight deionized water, having a pH
of 6.
of 6.
15. The composition according to claim 3, wherein the gel consists of 1% nonionic surfactant, 0.6% by weight polyacrylic acid resin, 0.1% by weight sodium citrate, 0.3%
by weight DMDM hydantoin, 0.3% by weight ethylene diamine tetraacetic acid and 97.7% deionized water, having a pH of 6.
by weight DMDM hydantoin, 0.3% by weight ethylene diamine tetraacetic acid and 97.7% deionized water, having a pH of 6.
16. The composition according to claim 1, in the form of a liquid fabric rinse to reduce the deposition of soap and detergent on the fabric.
17. The composition according to claim 3, in the form of a gel fabric rinse for reducing the deposition of soap and detergent on the fabric.
18. The composition according to claim 4, in the form of a thick liquid fabric rinse to reduce the deposition of soap and detergent on the fabric.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/127,735 US4828750A (en) | 1987-12-02 | 1987-12-02 | Fabric rinse composition to remove surfactant residues |
| US127,735 | 1987-12-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1321743C true CA1321743C (en) | 1993-08-31 |
Family
ID=22431670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000584678A Expired - Fee Related CA1321743C (en) | 1987-12-02 | 1988-12-01 | Fabric rinse composition to remove surfactant residues |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4828750A (en) |
| EP (1) | EP0323395A3 (en) |
| JP (1) | JPH02229900A (en) |
| AU (1) | AU629519B2 (en) |
| CA (1) | CA1321743C (en) |
| DK (1) | DK675288A (en) |
| FI (1) | FI885602A (en) |
| MX (1) | MX163644B (en) |
| NO (1) | NO173022C (en) |
| PT (1) | PT89125B (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0323798A3 (en) * | 1987-12-02 | 1991-07-03 | Colgate-Palmolive Company | Mild cleansing and conditioning composition to yield a soft, smooth skin |
| US5008030A (en) * | 1989-01-17 | 1991-04-16 | Colgate-Palmolive Co. | Acidic disinfectant all-purpose liquid cleaning composition |
| US5080825A (en) * | 1989-10-30 | 1992-01-14 | International Business Machines Corporation | Tape drive cleaning composition |
| JP3148365B2 (en) * | 1992-06-29 | 2001-03-19 | 花王株式会社 | Keratinous fiber modifier kit |
| US5254336A (en) * | 1992-09-24 | 1993-10-19 | Helene Curtis, Inc. | Method of increasing hair shine and repairing alkaline-damaged hair |
| GB2286596B (en) * | 1994-02-14 | 1998-03-11 | Boryung Pharm | A detergent composition |
| US6323172B1 (en) * | 1996-03-22 | 2001-11-27 | The Procter & Gamble Company | Concentrated, stable fabric softening composition |
| US5792739A (en) * | 1996-04-24 | 1998-08-11 | Lever Brothers Company, Division Of Conopco, Inc. | Liquid compositions comprising hydrophobically modified polyalkylene glycols as mildness actives |
| DE19923303C2 (en) * | 1999-05-21 | 2002-10-31 | Umweltanalytik Und Forschungs | Detergent for removing the detergent residues and for producing textiles that are compatible with the skin after the washing process |
| US7026278B2 (en) | 2000-06-22 | 2006-04-11 | The Procter & Gamble Company | Rinse-added fabric treatment composition, kit containing such, and method of use therefor |
| ATE297456T1 (en) * | 2001-03-07 | 2005-06-15 | Procter & Gamble | FABRIC DETERGENT COMPOSITION FOR USE IN THE PRESENCE OF DETERGENT RESIDUE |
| US6884763B2 (en) | 2001-10-30 | 2005-04-26 | Permatex, Inc. | Waterless hand cleaner containing plant derived natural essential oil |
| US6723308B2 (en) * | 2001-11-02 | 2004-04-20 | Kenra, Llc | Hair clarifying treatment |
| US6805136B2 (en) * | 2001-11-02 | 2004-10-19 | Kenra, Llc | Hair relaxer |
| KR100913557B1 (en) * | 2002-01-28 | 2009-08-21 | 미쓰비시 가가꾸 가부시키가이샤 | Liquid detergent for semiconductor device substrate and method of cleaning |
| GB2386612A (en) * | 2002-03-22 | 2003-09-24 | Reckitt Benckiser Nv | Cleaning method |
| CN1643202A (en) * | 2002-03-28 | 2005-07-20 | 美利肯公司 | Nonwoven fabric having low ion content and method for producing the same |
| GB2401604A (en) * | 2003-05-10 | 2004-11-17 | Reckitt Benckiser Nv | Water-softening product |
| US7445643B2 (en) | 2003-12-03 | 2008-11-04 | The Procter & Gamble Company | Automatic machine laundering of fabrics |
| US7135449B2 (en) | 2004-02-20 | 2006-11-14 | Milliken & Company | Composition for removal of odors and contaminants from textiles and method |
| WO2006066115A2 (en) * | 2004-12-17 | 2006-06-22 | The Procter & Gamble Company | Process for extracting liquid from a fabric |
| US20100305019A1 (en) * | 2009-06-01 | 2010-12-02 | Lapinig Daniel Victoria | Hand Fabric Laundering System |
| BR112017026647B1 (en) | 2015-06-19 | 2022-05-10 | Unilever Ip Holdings B.V. | Aqueous laundry pretreatment composition, use of the aqueous laundry pretreatment composition, and method of removing oily or sebaceous stains from stained fabrics |
| US11781093B2 (en) | 2018-11-07 | 2023-10-10 | The Procter & Gamble Company | Process for treating a fabric and related compositions |
| JP7335131B2 (en) | 2018-11-07 | 2023-08-29 | ザ プロクター アンド ギャンブル カンパニー | Low pH fabric care composition |
| WO2020123113A1 (en) | 2018-12-13 | 2020-06-18 | The Procter & Gamble Company | Method for treating fabrics with a varying ph profile during wash and rinse cycles |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU52504A1 (en) * | 1966-12-02 | 1968-08-16 | ||
| DE1617156C2 (en) * | 1967-01-02 | 1975-07-17 | Mülheims, Hans, Dr.med., 4100 Duisburg | Additive for rinse water for laundry |
| US3915633A (en) * | 1972-09-21 | 1975-10-28 | Colgate Palmolive Co | Complexing acid pre-wash composition and method |
| US4226736A (en) * | 1974-07-22 | 1980-10-07 | The Drackett Company | Dishwashing detergent gel composition |
| US4206070A (en) * | 1975-12-24 | 1980-06-03 | The Procter & Gamble Company | Detergent compositions |
| CA1086178A (en) * | 1977-04-04 | 1980-09-23 | Christian R. Barrat | Liquid detergent composition |
| US4172140A (en) * | 1977-08-19 | 1979-10-23 | Glyco Chemicals, Inc. | Antimicrobial hydantoin derivative compositions and method of use |
| US4140656A (en) * | 1977-10-07 | 1979-02-20 | Armour-Dial, Inc. | Anhydrous clear gel facial cleanser |
| LU81257A1 (en) * | 1979-05-15 | 1980-12-16 | Oreal | COSMETIC COMPOSITION FOR THE TREATMENT OF HAIR AND SKIN, CONTAINING SALSEPAREILLE EXTRACT |
| EP0070587B2 (en) * | 1981-07-17 | 1988-11-30 | THE PROCTER & GAMBLE COMPANY | Rinse aid composition |
| DE3312328A1 (en) * | 1983-04-06 | 1984-10-11 | Joh. A. Benckiser Gmbh, 6700 Ludwigshafen | Rinsing agent for the mechanical washing of laundry |
| EP0137475A2 (en) * | 1983-10-12 | 1985-04-17 | S.C. Johnson & Son, Inc. | Aqueous laundry prespotting composition |
| GB8328077D0 (en) * | 1983-10-20 | 1983-11-23 | Unilever Plc | Rinse aid |
| US4501680A (en) * | 1983-11-09 | 1985-02-26 | Colgate-Palmolive Company | Acidic liquid detergent composition for cleaning ceramic tiles without eroding grout |
| US4960533A (en) * | 1988-07-11 | 1990-10-02 | Colgate-Palmolive Company | Silicone-based hard surface cleaner |
| JPH05207711A (en) * | 1992-01-24 | 1993-08-13 | Matsushita Electric Ind Co Ltd | Molded motor |
-
1987
- 1987-12-02 US US07/127,735 patent/US4828750A/en not_active Expired - Fee Related
-
1988
- 1988-11-30 EP EP88730263A patent/EP0323395A3/en not_active Withdrawn
- 1988-11-30 PT PT89125A patent/PT89125B/en not_active IP Right Cessation
- 1988-12-01 FI FI885602A patent/FI885602A/en not_active Application Discontinuation
- 1988-12-01 NO NO885366A patent/NO173022C/en unknown
- 1988-12-01 CA CA000584678A patent/CA1321743C/en not_active Expired - Fee Related
- 1988-12-01 AU AU26460/88A patent/AU629519B2/en not_active Ceased
- 1988-12-02 MX MX14018A patent/MX163644B/en unknown
- 1988-12-02 DK DK675288A patent/DK675288A/en not_active Application Discontinuation
- 1988-12-02 JP JP63305894A patent/JPH02229900A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU2646088A (en) | 1989-06-08 |
| EP0323395A3 (en) | 1990-04-25 |
| FI885602A (en) | 1989-06-03 |
| MX163644B (en) | 1992-06-10 |
| PT89125B (en) | 1993-09-30 |
| DK675288A (en) | 1989-06-03 |
| US4828750A (en) | 1989-05-09 |
| NO885366L (en) | 1989-06-05 |
| PT89125A (en) | 1989-12-29 |
| AU629519B2 (en) | 1992-10-08 |
| EP0323395A2 (en) | 1989-07-05 |
| NO885366D0 (en) | 1988-12-01 |
| NO173022B (en) | 1993-07-05 |
| FI885602A0 (en) | 1988-12-01 |
| JPH02229900A (en) | 1990-09-12 |
| DK675288D0 (en) | 1988-12-02 |
| NO173022C (en) | 1993-10-13 |
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