CA1317706C - Particulate fabric laundering composition - Google Patents
Particulate fabric laundering compositionInfo
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- CA1317706C CA1317706C CA000609393A CA609393A CA1317706C CA 1317706 C CA1317706 C CA 1317706C CA 000609393 A CA000609393 A CA 000609393A CA 609393 A CA609393 A CA 609393A CA 1317706 C CA1317706 C CA 1317706C
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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
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
Abstract
PARTICULATE FABRIC LAUNDERING COMPOSITION
ABSTRACT
A particulate fabric laundering detergent formulation in which there is included at least one organic surfactant selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic compounds and mixtures thereof, at least one detergent builder selected from the group consisting of inorganic and organic water soluble builder salts, water insoluble builder salts and seeded builders and a mixture of a water dispersible fabric softening conditioning compound, a polydimethylsiloxane polymer and a polyoxyalkylene siloxane copolymer.
ABSTRACT
A particulate fabric laundering detergent formulation in which there is included at least one organic surfactant selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic compounds and mixtures thereof, at least one detergent builder selected from the group consisting of inorganic and organic water soluble builder salts, water insoluble builder salts and seeded builders and a mixture of a water dispersible fabric softening conditioning compound, a polydimethylsiloxane polymer and a polyoxyalkylene siloxane copolymer.
Description
1 3 ~
PARTICULATE FABRIC LAUNDERING COMPOSITION
This invention relates t:o a softening composition for use as an ingredient of a particulate detergent formulation in a fabric launderin8 operation and wherein there is provided a mixture of a fabric softening conditioning compound, a polydimethylsiloxane polymer and a polyoxyalkylene siloxane copolymer.
In some preferred embodiments of the invention, the fabric softening conditioning compound includes a cationic compound selected from the group consisting of quaternary ammonium salts and organic based compounds having C12 to Cl~
hydrocarbon chain molecules of amines, esters, acids or amine oxides. Thus, the fabric softening conditioning compound can be a quaternary ammonium salt compound of distearyl dimethyl ammonium chloride. The weight ratio of the polymer to the copolymer in the mixture is from one to three, to three to one, more preferably one to one. The softening composition contains from two percent to ten percent by weight of the polymer and the copolymer. In the polymer formula, x is an integer of about six hundred and the nominal viscosity of the polymer is about five thousand centistokes measured at 25C.
The copolymer has a nominal viscosity of about fifteen hundred centistokes measured at 25C.
The present invention is also directed to a particulate fabric laundering detergent formulation in which at least one organic surfactant is selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic compounds and mi~tures thereof, at least one detergent builder is selected from the group consisting of inorganic and organic water soluble builder salts, water insoluble builder salts and seeded builders, and a mixture of a water -2~ 7 ~ ~
dispersible fabric softening conditioning compound, a polydimethylsiloxane polymer and a polyoxyalkylene siloxane copolymer. In this formulation, there is included from about ninety to about ninety-eight percent by weight of the surfactant and the detergent builcler and from about two to about ten percent by weight of the water dispersible fabric softening conditioning compound and the polymer and copolymer.
It is, therefore, an ob~ect of the present invention to provide not only a new and novel hitherto unknown type of softening composition, but a detergent formulation including such composition. It has been found that the silicone ingredients of the compositions of the present invention are viable alternatives to the organic dispersant compounds of th~ prior art, if not in fact, superior thereto.
These and other features, objects and advantages, of the herein described present invention will become apparent when considered in con~unction with the following detailed description of the invention.
Ammonium compounds in which all of the hydrogen atoms on nitrogen have been substituted by alkyl groups are called quaternary ammonium salts. These compounds may be represented in a general sense by the formula:
Rl tR4 1+ R2]X-The nitrogen atom includes four covalently bonded substituents that provide a cationic charge. The R groups can be any organic substituent that provides for a carbon and 3 1 3 177 0~
nitrogen bond with similar and dissimilar R groups. The counterion X is typically halogen. Use of quatern~ry ammonium compounds is ba~ed on the hydrophilic portion of the molecule which bears a positive charge. Since most surfaces are negatively charged, solutions, dispersion~ and particulate mixtures, of these cationic surface active agents are readily adsorbed to the negatively charged surface, such as fabric~, clothing and ~owels.
In accordance with the present invention, the softening agent can include quaternary ammonium salts and, specifically, any of the cationic compounds de~cribed in British Patent No.
1,549,1B0 dated July, 1979, such as quaternary monoammonium compounds having either two C12-C20 alkyl chains or one ClB-~24 alkyl chain; quaternary imidazolinium textile softeners; polyammonium compounds; fabric softening polyamine salts; fully substituted polyquaternary compounds; and polyalkylene imine salts. Particular quaternary ammonium compounds suitable for use herein may include, for example, trimethyltallowammonium chloride, trimethylsoyaammonium chloride, trimethylcocoammonium chloride, dimethyldicoco-ammonium chloride, dimethyldi(hydrogenated tallow)ammonium chloride, trimethyldodecylammonium chloride, trimethylocta-decylammonium chloride, trimethylhexadecylammonium chloride, dimethylalkylbenzylammonium chloride, 1:1 mixture of trimethyltallowammonium chloride and dimethyldicocoammonium chloride, N,N,N',N',N'-pentamethyl-N-tallow-1,3-propane-diammonium dichloride, methylbis~2-hydroxyethyl)cocoammonium chloride, methylpolyoxyethylene cocoammonium chloride, methylbis(2-hydroxyethyl)oleylammonium chloride, methylpoly-oxyethylene oleyammonium chloride, methylbis(2-hydroxyethyl)-oleylammonium chloride, methylbisf2-hydroxyethyl)-ammonium chloride, methylpolyoxyethylene octadecylammonium chloride, n-dodecyl tetradecyl dimethylbenzylammonium 7 ~ ~
chloride, n-tetradecyl hexadecyl dimethylbenzylammonium chloride, n-dodecyl tetradecyl dimethyldichlorobenzylammonium chloride, n-octadecyldimethylben~ylammonium chloride, dialkylmethylbenzylammoniu~ chloride, n-dodecyl tetradecyl hexadecyl dimethylbenzylammonium chloride~ n-dodecyl tetradecyl hexadecyl dimethy1ethylbenzylammonium chloride, methyl sulfate quaternary of ethyoxylated tallow diethylene-triamine condensate, methyl sulfate quaternary of propoxylated tallow diethylenetrialmine condensate, l-(tallow amidoethylena~-2-nor (tallow alkyl)2-imidazolinium and methyl sulfate quaternary.
The silicone compositions of the present invention have been found to have no negative effect on the rewettability of fabrics treated in a laundry operation. The silicones are delivered to the fabric in the orm o~ granules or particulates. The silicone particulates including the polymer, the copolymer and the active quaternary ammonium compound can be used alone or formulated into a fabric conditioning composition, such as a particulate detergent fabric softener. The quaternary ammonium salt based type of fabric softener compound is preferre~.
While the following examples are combinations of quaternary based softener compounds with silicone polymers and copolymers, the silicone compositions will improve softening when used in combination with any organic based fabric conditioning compound such as organic conditioning compositions comprised of long hydrocarbon C12-C18 chain molecules of amines, esters, acids, amine oxides and derivatives thereof.
The polydimethylsiloxanes used herein can be high molecular weight polymers having a molecular weight in the range from about 200 to about 200,000 and have a viscosity in the range from about 20 to 2,000,000 centistokes, preferably -5- 13177~
from about S00 to 50,000 centistokes, more preferably from about 3,000 to about 30,000 centistokes meas~red at 25C.
The siloxane polymer is generally end-blocked either with trimethylsilyl or hydroxyl groups but other end-blocking groups are also suitable. The polymer can be prepared by various techniques such as the hydrolysis of dimethyldihalosilanes and subsequent condensation of the resulting hydrolysis product or by the cracking and subsequent polymerization of dimethylcyclosilo~anes.
Example I
Towels were prepared for treatment by removing the mill textile conditioners applied at the mill during manufaeture of the towels. The process was conducted at a commercial laundromat. Bundles of 86:14 cotton polyester terry towels were washed five times with an anionic detergent containing a high level of phosphorus. Deter~ent remaining in the towel3 was removed by three rinal wash and rinse cycles from which detergent was omitted. Each bundle was sub~ected to eight complete wash and rinse cycles during the -stripping process. The treatments were conducted in a "Whirlpool"Imperial Seventy model washing ~achine. The cycle setting was Heavy/14 minutes. The Cloth to Liquor Ratio was 1:20. The w~sh temperature was Warm ~32C.). The rinse temperatur~ was Cold (11C.). The detergent used was a nonionic-anionic phosphate built detergent at a level of 0~14% by weight. The dryer was a'~hirlpoo~'model with a dryer satting of Permanent Press-High Drying, at a time of 60 minutes.
The te~t used to measure softness was a panel test in which ten to twelve people were asked to rank five to six towels in order of softne~s. The towels were treated by the method described immediately above. Following treatment, the towels were placed in a constant temperature and humidity *Trade=ark ,~
-6- 13177~6 room overnight to equilibrate and tested the next day.
Dryers tend to overdry towels and provide a harsher feel than normal and, therefore, all towels tested in a given panel were conditioned at the same temperature and humidity before testing. Each test included one control towel. The control towel was a towel which had not been treated by so~tening agent. Ten to twelve people were asked to evaluate the towels by feeling the towels and choosing the harshest towel, the softest towel and placing the remaining towels in order of increasing softness. The towels were asqigned a ranking between one and five to six with the highest value corresponding to the softest towel. Before the test was conducted, each member of the panel wa5 asked to wash their hands to remove any residue which might interfere with the test. During the evaluation, the panel members rewashed their hands to remove any softener buildup. Since the softness of a towel increases with repeated handling, a new surface of each towel was exposed for each panel member and each towel was replaced after evaluation by three people.
The resulting rankings were evaluated using the 5tudent Newman Keuls statiqtical procedure.
The rewettability or water absorbency of the treated towels was determined by cutting strips of fabric from the ~owels and measuring the height of migration of a dyed water solution over a specified time. The greater the migration of dye solution up the fabric the better the rewet properties. Food coloring was used as the dye.
The hei~ht of migration was measured after the strip had been immersed for four minutes. The variability of this wickin~ method was determined by using three bundles of twelve towels each treated with a 6% quaternary ammonium salt softener. The rewettability of one ~owel from each bundle was determined by cutting five strips of fabric from the ~1 -7- ~ 3 ~
towel and co~ducting the wicking test on each strip. The variability of the test method was found to be f /- 6.9 mm.
Formulations containing varying amounts of silicone polymer and copolymer were evaluated for softening, static and rewettability. As noted above, the fabric bundle was treated and with a detergent containing the silicone polymer, copolymer and the softener active component.
In the following examples, various combinations o~
ingredients were employed in order to further illustrate the concepts of the present invention. As base detergent, there was selected a nonionic-anionic phosphate built detergent.
This base powder was a specially formulated detergent without a softener active ingredient and therefore functioned as the control. In all cases where the base powder was employed in admixture with other ingredients, it constituted 95.57 weight percent of the total amount of formulation employed. Where used as a control, the base powder was employed at a level of one hundred percent. In those instances where the silicone polymer and copolymer were added, these materials were employed at levels of 0.13 percent by weight of total formulation and in individual ratios with respect to one another varying from one to three to three to one. The level of 0.13 percent by weight was maintained even where one silicone compound was added to the e~clusion of the other.
Except for the control composition of base powder, all test runs included the remainder of 4.3 percent by weight of fabric softener active ingredient. It is noted that in the several treatments conducted in each instance, that the ratios of the silicone copolymer to silicone polymer was respectively, 75:25, 50:50 and 25:75.
Each of the formulations employed included 4.3 percent distearyl dimethylammonium chloride(DDMAC), the active ingredient of a quaternary ammonium salt commercial -8- ~ ~r~
fabric softener solid, manufactured by Sherex Chemical Company, Dublin, Ohio, as AROSURF~ TA-lOO, a trademark of that company; together with varying amounts of the silicone composition of the present invention as noted above. The silicones and the quaternary ammonium salt softener were prepared by melting the components together. The mixture was then allowed to cool. After cooling, the mixture was granulated into powder form. A series of five treatments were conducted and eval~lations were made following the irst, third and fi~th treatments. Average softness rankings are set forth below.
Example II
Into a beaker was added the silicone polymer of the present invention, the silicone copolymer and DDMAC, each individually and in the amounts and ratios indicated above.
The ingredients were mixed while heat and agitation were applied and th~ beaker was allowed to cool. The resulting fabric softening mixture was then regranulated into small particles and sieved to between twenty to one hundred mesh size.
ExamPle III
Example II was repeated except that the procedure for the addition of the various components was altered. In this example, the silicone polymer and the silicone copolymer were first each mixed together one with the other in order to form a uniform silicone blend. The silicone blend of the polymer and copolymer was then added to DDMAC in a beaker and the mixture was heated and agitated with stirring. The beaker was allowed to cool and the contents were regranulated and sieved a~ in Example II.
In panel tests as outlined above in Example I, the paneli~ts overwhelmingly chose towels treated in accordance with the procedure of Example III as being softer than those 9 ~ 3177~
treated in accordance with the procedure of Example II after one and three treatments and, therefore, the procedure of Example III was employed and repeated in collecting the data shown hereinafter.
Example IV
The procedure o~ Example III was repeated in order to prepare the softener formulations and the formulations together with the base powder were tested for softness in accordance with the steps outlined in Example I. The results are shown in Table I.
TABLE I
Ingredients tWT.%/Ratio) Treatment QUAT Silicone Silicone Base DDMAC CoPolymer* Polymer* No. I No. III No. V
95.57 4.3 75 25 ~.8 4.~ 4.9 95.57 4.3 50 50 4.6 4.6 4.3 95.57 4.3 25 75 3.9 4.1 4.3 95.57 4.3 -- 100 3.2 3.2 3.7 95.57 4.3 100 -- 2.9 2.7 2.7 100 -- -- -- 1.4 1.3 1.1 * = Ratios of copolymer to polymer at a total level of 0.13 weight percent.
Example IV was repeated and a second set of data were collected and are shown in Table II.
~lo- ~ 31 7~
TAB~E II
Ingredients (WT.%/Ratio) Treatment QUAT Silicone Silicone Base DDMAC Copolymer* Pol~mer~ No. I No. III No. V
9~.57 4.3 25 75 5.6 4.7 3.3 95.57 4.3 50 50 4.9 4.9 5.0 95.57 4.3 75 25 3.3 3.7 3.6 95.57 4.3 -- 100 2.9 2.6 3.9 95.57 4.3 100 -- 2.2 3.8 3.7 100 -- -- -- 1.9 1.1 1.4 * = See Table I
Tables I and II in particular indicate that combinations of both the polymer and copolymer provide a synergistic effect when compared to the effect obtained by the use of either individually.
Example V
Example IV was repeated except that there was also included comparative testing based on the ethoxylated tertiary amine softener composition of U.S. Patent No. 4~741,842, which is referred to in the following tables as ETA. ETA is approximately eighty-eight percent by weight quaternary ammonium compound and eight percent by weight of ethoxylated amine. In this example, rewettability as well as static control were tested in addition to softness. The results indicate that the compositions of the present invention provide equal, if not better, softness benefits than ETA, preferential static control and do not have a negative effect on fabric rewettability.
-11- 1 3~7~6 TABLE ILI
Ingredients (WT.%/Ratio) Treatment QUAT Silicone Silicone Base DDMAC Copolymer* Pol mer* No. I Mo. III No. V
95.57 4.3 Z5 75 ~.4 3.4 3.2 95.57 4.3 50 50 3.9 3.4 4.5 95.57 4.3 75 25 2.5 4.4 3.4 95.12 4.S8** -- -- 2.3 1.9 2.6 100 -~ - 1.7 1.7 1.6 * = See Table I
** = ETA substituted for DDMAC.
The procedure for Table III was repeated and a second set of data generated and set forth in Table IV.
-12- ~77~
TABLE IV
Ingredients (WT.%/Ratio) Treatment QUAT Silicone Silicone Base DDMAC CopolYmer* Polymer~' No. I No. III No. V
9~.57 4.3 2S 75 5.0 4.4 4.4 95.57 4.3 50 50 3.2 4.3 3.6 95.57 4.3 75 25 2.1 2.6 3.1 95.12 4.88** -- -- 3.1 2.5 2.7 100 -- -- -- 1.~ 1.0 ~.0 * = See Table I.
** = ETA substituted for DDMAC.
-13- ~3~7~
TABLE V
Ingredients (WT.%/Ratio)Rewettability (mm/4 min.) QUAT Silicone Silicone Base DDMAC Copol~mer* Pol~mer* No. I No. III No. V
95.57 4.3 50 50 67 79 80 95.57 4.3 25 75 67 84 84 95.57 4.3 75 25 62 80 80 95.12 4.~8** -- -- 69 84 84 100 ~ - 67 83 83 * = See Table I.
** = ETA substituted for DDMAC.
TABLE VI
In~redients (WT.%/Ra~io) Rewettability (mm/4 min.) QUAT Silicone Silicone Base DDMAC CoPolYmer* Pol~mer* No. I No. III No. V
95.57 4.3 50 50 66 81 82 95.57 4.3 25 75 70 80 85 95.57 4.3 75 25 75 81 ~
95.12 4.88** -- -- 79 83 83.5 100 -- -- -- 74 78 78.5 * = See Table I.
** = ETA sub~tituted for DDMAC.
13177~
It should be apparent from the foregoing tables that the softener ingredient containing the compositions o the present invention imparted the best softness.
Specifically, combinations of the copolymer and the polymer e~hibited a synergistic effect in comparison to the effect obtained when either was used without the other. The rewettability of each of the foregoing is set forth and it should be pointed out that the average rewettability imparted to each fabric was not negatived by the softeners including the compositions of the present invention.
Example VI
The compositions of the present invention were evaluated for their ability to reduce static electricity.
The material ETA of Example V was a~ain included for comparative purposes. The fabric bundle used to conduct this test consisted of the following garments or equivalent in yard goods:
10% 100% Nylon Tricot 10% 100% Polyester 12% 100% Acrylic 4% 100% Rayon 4% 100% Acetate 2870 65/35 Polyester/Cotton 32% 86/14 Cotton/Polyester Towels Bundles were stripped before use by washing in hot water five times with an anionic phosphate built detergent and then rinsed three times without any detergent, as noted in Example I.
After treating the bundles with the detergent and softening mi~ture in the wash, the bundles were dried in dryers wiped with isopropanol to remove any previous residue.
The bundles were dried for 60 minutes. Each piece of fabric was taken out one at a time. Different fabrics were brought ~h,,i -15- ~3~77~
together and separated to observe static and cling. Rubber Gloves were used to eliminate any dissipation of static. The entire bundle was rated according to the following scale:
1 NONE-No items affected by static; no detectable cling.
2 VERY LIGHT-Very slight attraction when swatches are brought together ~no readably observable cling), slight static.
3 LIGHT-Some static, very little cling.
4 LIGHT MODERATE-Definite cling and static (1/3 synthetics).
MODERATE-1/4 of items affected by cling and static (2/3 synthetics).
6 MODERATE HEAVY-Same as above, but more intense.
7 HEAVY-1/2 of items affected by cling and static (all synthetics).
8 VERY ~EAVY-Same as above but more intense.
9 SEVERE-3/4 or more of items affected (all synthetics and other items).
At least two people were used to rate the static out of the dryer. The average of the two was recorded as the static rating for the particular bundle.
The results of the static tests are shown below in Tables VII and VIII and it can be seen that the compositions of the present invention were at least three ~imes more effective than the prior art material ETA.
-16- ~3177~
TABLE VII
Ingredients (WT.%/Ratio) Static Rating QUAT Silicone Silicone Base DDMAC CoPolymer* Pol~mer~ No. I No. III No. V
95.57 4.3 50 50 2 2.5 2.5 95.57 4.3 25 75 2 1.5 2 95.57 4.3 75 25 2.5 2 2.5 95.12 4.88** -- -- 6 7 8 100 ~ - 7 7 6 * = See Table I.
** = ETA substituted for DDMAC.
TABLE VIII
Ingredients (WT.%/Ratio) Static Rating QUAT Silicone Silicone Base DDMAC Copolymer* PolYmer* No. I No. III No. V
95.57 4.3 50 50 1.5 1.5 1.5 95.57 4.3 25 7~ 2.5 2 2 95.57 4.3 75 25 2 2 3 95.12 4.88** -- -- 7 7.5 7 * = See T~ble I.
** = ETA substituted for DDMAC.
-17- 1~7706 Surfactants preferred in accordance with the present invention are anionic and nonionic and mixtures thereof. Specific anionic surfactants are, for example, carboxylic acids and salts; sulfonic acids and salts such as alkylbenzenesulfonates, alkylary:lsulfonates, naphthalene-sulfonates, petroleum sulfonates, sulonates with ester, ether or amide linkages and lignosulfonates; sulfuric acid esters and salts such as sulfated alcohols, ethoxylated and sulfated alcohols and alkylpheno:ls, sulfated acids, amides and esters and sulfated natural ~Eats and oils; and phosphoric and polyphosphoric acid esters and salts such as alkoxylated and phosphated alcohols and phenols. Among the category of nonionic surfactants which can be employed are, for example, ethoxylated alcohols; ethoxylated alkylphenols; ethoxylated carboxylic esters such as glycerol esters, polyethylene glycol estars, anhydrosorbitol esters, ethoxylated anhydro-sorbitol and sorbitol esters, ethoxylated natural fats and oils, ethylene and diethylene glycol esters and propanediol esters; and etho~ylated carbo~ylic amides.
Various categories of builders can be employed exemplary of which are, for example, phosphates s~ch as pentasodium phosphate, sodium tripolyphosphate, tetra30dium pyrophosphate, trisodium phosphate, sodium polymetaphosphate and potassium phosphates; sodium carbonate; silicates;
zeolites; cl~ys; nitrilotriacetic acid and alkalies. In addition, those builders as well as surfactants set forth in U.S. Patent No. 3,936,537, issued February 3, 1976, as well as in U.S. Patent No. 4,741,842, issued May 3, 1988, may be employed herein.
The silicone copolymers of the present invention and methods for their preparation are de~cribed in U.S.
Patent No. 3,402,192, issued September 17, 1968.
Generically, such materials are described as a copolymer ~i selected from the group consisting of copolymers having the average structural formulae:
(1) RaSi[~OSiMe2)n(0SiMeG)dOSiMe2G]4 a, (2) GMe2si~osiMe2)n(osiMeG)bosiMe2G~
(3) Me3Si(OSiMe2)n(0SiMeG)cOSiMe3, and (4) R Si[(OSiMe2)n(0siMeG)cosiMe3]4-a~
formulae R is a hydrocarbon radica:L free of aliphatic unsaturation and contains from 1 to 10 carbon atoms, Me is a methyl radical, G is a radical of the structure -D(OR'')mA wherein D is an alkylene radical containing from 1 to 30 carbon atoms, R'' is composed of ethylene radicals and radicals selected from the group consisting of propylene and butylene radicals, the amount of ethylene radicals relative to the other alkylene radicals being such that the ratio of carbon atoms to oxygen atoms in the total OR'' blocks ranges from 2.3:1 to 2.8:1, m has an average value from 7 to 100, A is a radical selected from the group consisting of the -OR', -OOCR' and -OCOR' radicals wherein R' is a radical free of aliphatic unsaturation selected from the group consisting of hydrocarbon and hydrocarbonoxy radicals, the A radical containing a total of less than eleven atoms, a has an average value of from O to 1, -19- ~3~ 77~
n has an average value of from 6 to 420, d has an average value of from 0 to 30, b has an average value from 1 to 30 and c has an average value from 3 to 30, said copolymers containing at least 13 percent by weight OSiMe2 units based on the weight of the copolymer.
It will be apparent from the foregoing that many other variations and modifications may be made in the structures, compounds, compositions and methods describèd herein without departing substantially from the essential features and concepts of the present invention. Accordingly, it should be clearly understood that the forms of the invention described herein are e2emplary only and are not intended as limitations on the scope of the present invention.
PARTICULATE FABRIC LAUNDERING COMPOSITION
This invention relates t:o a softening composition for use as an ingredient of a particulate detergent formulation in a fabric launderin8 operation and wherein there is provided a mixture of a fabric softening conditioning compound, a polydimethylsiloxane polymer and a polyoxyalkylene siloxane copolymer.
In some preferred embodiments of the invention, the fabric softening conditioning compound includes a cationic compound selected from the group consisting of quaternary ammonium salts and organic based compounds having C12 to Cl~
hydrocarbon chain molecules of amines, esters, acids or amine oxides. Thus, the fabric softening conditioning compound can be a quaternary ammonium salt compound of distearyl dimethyl ammonium chloride. The weight ratio of the polymer to the copolymer in the mixture is from one to three, to three to one, more preferably one to one. The softening composition contains from two percent to ten percent by weight of the polymer and the copolymer. In the polymer formula, x is an integer of about six hundred and the nominal viscosity of the polymer is about five thousand centistokes measured at 25C.
The copolymer has a nominal viscosity of about fifteen hundred centistokes measured at 25C.
The present invention is also directed to a particulate fabric laundering detergent formulation in which at least one organic surfactant is selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic compounds and mi~tures thereof, at least one detergent builder is selected from the group consisting of inorganic and organic water soluble builder salts, water insoluble builder salts and seeded builders, and a mixture of a water -2~ 7 ~ ~
dispersible fabric softening conditioning compound, a polydimethylsiloxane polymer and a polyoxyalkylene siloxane copolymer. In this formulation, there is included from about ninety to about ninety-eight percent by weight of the surfactant and the detergent builcler and from about two to about ten percent by weight of the water dispersible fabric softening conditioning compound and the polymer and copolymer.
It is, therefore, an ob~ect of the present invention to provide not only a new and novel hitherto unknown type of softening composition, but a detergent formulation including such composition. It has been found that the silicone ingredients of the compositions of the present invention are viable alternatives to the organic dispersant compounds of th~ prior art, if not in fact, superior thereto.
These and other features, objects and advantages, of the herein described present invention will become apparent when considered in con~unction with the following detailed description of the invention.
Ammonium compounds in which all of the hydrogen atoms on nitrogen have been substituted by alkyl groups are called quaternary ammonium salts. These compounds may be represented in a general sense by the formula:
Rl tR4 1+ R2]X-The nitrogen atom includes four covalently bonded substituents that provide a cationic charge. The R groups can be any organic substituent that provides for a carbon and 3 1 3 177 0~
nitrogen bond with similar and dissimilar R groups. The counterion X is typically halogen. Use of quatern~ry ammonium compounds is ba~ed on the hydrophilic portion of the molecule which bears a positive charge. Since most surfaces are negatively charged, solutions, dispersion~ and particulate mixtures, of these cationic surface active agents are readily adsorbed to the negatively charged surface, such as fabric~, clothing and ~owels.
In accordance with the present invention, the softening agent can include quaternary ammonium salts and, specifically, any of the cationic compounds de~cribed in British Patent No.
1,549,1B0 dated July, 1979, such as quaternary monoammonium compounds having either two C12-C20 alkyl chains or one ClB-~24 alkyl chain; quaternary imidazolinium textile softeners; polyammonium compounds; fabric softening polyamine salts; fully substituted polyquaternary compounds; and polyalkylene imine salts. Particular quaternary ammonium compounds suitable for use herein may include, for example, trimethyltallowammonium chloride, trimethylsoyaammonium chloride, trimethylcocoammonium chloride, dimethyldicoco-ammonium chloride, dimethyldi(hydrogenated tallow)ammonium chloride, trimethyldodecylammonium chloride, trimethylocta-decylammonium chloride, trimethylhexadecylammonium chloride, dimethylalkylbenzylammonium chloride, 1:1 mixture of trimethyltallowammonium chloride and dimethyldicocoammonium chloride, N,N,N',N',N'-pentamethyl-N-tallow-1,3-propane-diammonium dichloride, methylbis~2-hydroxyethyl)cocoammonium chloride, methylpolyoxyethylene cocoammonium chloride, methylbis(2-hydroxyethyl)oleylammonium chloride, methylpoly-oxyethylene oleyammonium chloride, methylbis(2-hydroxyethyl)-oleylammonium chloride, methylbisf2-hydroxyethyl)-ammonium chloride, methylpolyoxyethylene octadecylammonium chloride, n-dodecyl tetradecyl dimethylbenzylammonium 7 ~ ~
chloride, n-tetradecyl hexadecyl dimethylbenzylammonium chloride, n-dodecyl tetradecyl dimethyldichlorobenzylammonium chloride, n-octadecyldimethylben~ylammonium chloride, dialkylmethylbenzylammoniu~ chloride, n-dodecyl tetradecyl hexadecyl dimethylbenzylammonium chloride~ n-dodecyl tetradecyl hexadecyl dimethy1ethylbenzylammonium chloride, methyl sulfate quaternary of ethyoxylated tallow diethylene-triamine condensate, methyl sulfate quaternary of propoxylated tallow diethylenetrialmine condensate, l-(tallow amidoethylena~-2-nor (tallow alkyl)2-imidazolinium and methyl sulfate quaternary.
The silicone compositions of the present invention have been found to have no negative effect on the rewettability of fabrics treated in a laundry operation. The silicones are delivered to the fabric in the orm o~ granules or particulates. The silicone particulates including the polymer, the copolymer and the active quaternary ammonium compound can be used alone or formulated into a fabric conditioning composition, such as a particulate detergent fabric softener. The quaternary ammonium salt based type of fabric softener compound is preferre~.
While the following examples are combinations of quaternary based softener compounds with silicone polymers and copolymers, the silicone compositions will improve softening when used in combination with any organic based fabric conditioning compound such as organic conditioning compositions comprised of long hydrocarbon C12-C18 chain molecules of amines, esters, acids, amine oxides and derivatives thereof.
The polydimethylsiloxanes used herein can be high molecular weight polymers having a molecular weight in the range from about 200 to about 200,000 and have a viscosity in the range from about 20 to 2,000,000 centistokes, preferably -5- 13177~
from about S00 to 50,000 centistokes, more preferably from about 3,000 to about 30,000 centistokes meas~red at 25C.
The siloxane polymer is generally end-blocked either with trimethylsilyl or hydroxyl groups but other end-blocking groups are also suitable. The polymer can be prepared by various techniques such as the hydrolysis of dimethyldihalosilanes and subsequent condensation of the resulting hydrolysis product or by the cracking and subsequent polymerization of dimethylcyclosilo~anes.
Example I
Towels were prepared for treatment by removing the mill textile conditioners applied at the mill during manufaeture of the towels. The process was conducted at a commercial laundromat. Bundles of 86:14 cotton polyester terry towels were washed five times with an anionic detergent containing a high level of phosphorus. Deter~ent remaining in the towel3 was removed by three rinal wash and rinse cycles from which detergent was omitted. Each bundle was sub~ected to eight complete wash and rinse cycles during the -stripping process. The treatments were conducted in a "Whirlpool"Imperial Seventy model washing ~achine. The cycle setting was Heavy/14 minutes. The Cloth to Liquor Ratio was 1:20. The w~sh temperature was Warm ~32C.). The rinse temperatur~ was Cold (11C.). The detergent used was a nonionic-anionic phosphate built detergent at a level of 0~14% by weight. The dryer was a'~hirlpoo~'model with a dryer satting of Permanent Press-High Drying, at a time of 60 minutes.
The te~t used to measure softness was a panel test in which ten to twelve people were asked to rank five to six towels in order of softne~s. The towels were treated by the method described immediately above. Following treatment, the towels were placed in a constant temperature and humidity *Trade=ark ,~
-6- 13177~6 room overnight to equilibrate and tested the next day.
Dryers tend to overdry towels and provide a harsher feel than normal and, therefore, all towels tested in a given panel were conditioned at the same temperature and humidity before testing. Each test included one control towel. The control towel was a towel which had not been treated by so~tening agent. Ten to twelve people were asked to evaluate the towels by feeling the towels and choosing the harshest towel, the softest towel and placing the remaining towels in order of increasing softness. The towels were asqigned a ranking between one and five to six with the highest value corresponding to the softest towel. Before the test was conducted, each member of the panel wa5 asked to wash their hands to remove any residue which might interfere with the test. During the evaluation, the panel members rewashed their hands to remove any softener buildup. Since the softness of a towel increases with repeated handling, a new surface of each towel was exposed for each panel member and each towel was replaced after evaluation by three people.
The resulting rankings were evaluated using the 5tudent Newman Keuls statiqtical procedure.
The rewettability or water absorbency of the treated towels was determined by cutting strips of fabric from the ~owels and measuring the height of migration of a dyed water solution over a specified time. The greater the migration of dye solution up the fabric the better the rewet properties. Food coloring was used as the dye.
The hei~ht of migration was measured after the strip had been immersed for four minutes. The variability of this wickin~ method was determined by using three bundles of twelve towels each treated with a 6% quaternary ammonium salt softener. The rewettability of one ~owel from each bundle was determined by cutting five strips of fabric from the ~1 -7- ~ 3 ~
towel and co~ducting the wicking test on each strip. The variability of the test method was found to be f /- 6.9 mm.
Formulations containing varying amounts of silicone polymer and copolymer were evaluated for softening, static and rewettability. As noted above, the fabric bundle was treated and with a detergent containing the silicone polymer, copolymer and the softener active component.
In the following examples, various combinations o~
ingredients were employed in order to further illustrate the concepts of the present invention. As base detergent, there was selected a nonionic-anionic phosphate built detergent.
This base powder was a specially formulated detergent without a softener active ingredient and therefore functioned as the control. In all cases where the base powder was employed in admixture with other ingredients, it constituted 95.57 weight percent of the total amount of formulation employed. Where used as a control, the base powder was employed at a level of one hundred percent. In those instances where the silicone polymer and copolymer were added, these materials were employed at levels of 0.13 percent by weight of total formulation and in individual ratios with respect to one another varying from one to three to three to one. The level of 0.13 percent by weight was maintained even where one silicone compound was added to the e~clusion of the other.
Except for the control composition of base powder, all test runs included the remainder of 4.3 percent by weight of fabric softener active ingredient. It is noted that in the several treatments conducted in each instance, that the ratios of the silicone copolymer to silicone polymer was respectively, 75:25, 50:50 and 25:75.
Each of the formulations employed included 4.3 percent distearyl dimethylammonium chloride(DDMAC), the active ingredient of a quaternary ammonium salt commercial -8- ~ ~r~
fabric softener solid, manufactured by Sherex Chemical Company, Dublin, Ohio, as AROSURF~ TA-lOO, a trademark of that company; together with varying amounts of the silicone composition of the present invention as noted above. The silicones and the quaternary ammonium salt softener were prepared by melting the components together. The mixture was then allowed to cool. After cooling, the mixture was granulated into powder form. A series of five treatments were conducted and eval~lations were made following the irst, third and fi~th treatments. Average softness rankings are set forth below.
Example II
Into a beaker was added the silicone polymer of the present invention, the silicone copolymer and DDMAC, each individually and in the amounts and ratios indicated above.
The ingredients were mixed while heat and agitation were applied and th~ beaker was allowed to cool. The resulting fabric softening mixture was then regranulated into small particles and sieved to between twenty to one hundred mesh size.
ExamPle III
Example II was repeated except that the procedure for the addition of the various components was altered. In this example, the silicone polymer and the silicone copolymer were first each mixed together one with the other in order to form a uniform silicone blend. The silicone blend of the polymer and copolymer was then added to DDMAC in a beaker and the mixture was heated and agitated with stirring. The beaker was allowed to cool and the contents were regranulated and sieved a~ in Example II.
In panel tests as outlined above in Example I, the paneli~ts overwhelmingly chose towels treated in accordance with the procedure of Example III as being softer than those 9 ~ 3177~
treated in accordance with the procedure of Example II after one and three treatments and, therefore, the procedure of Example III was employed and repeated in collecting the data shown hereinafter.
Example IV
The procedure o~ Example III was repeated in order to prepare the softener formulations and the formulations together with the base powder were tested for softness in accordance with the steps outlined in Example I. The results are shown in Table I.
TABLE I
Ingredients tWT.%/Ratio) Treatment QUAT Silicone Silicone Base DDMAC CoPolymer* Polymer* No. I No. III No. V
95.57 4.3 75 25 ~.8 4.~ 4.9 95.57 4.3 50 50 4.6 4.6 4.3 95.57 4.3 25 75 3.9 4.1 4.3 95.57 4.3 -- 100 3.2 3.2 3.7 95.57 4.3 100 -- 2.9 2.7 2.7 100 -- -- -- 1.4 1.3 1.1 * = Ratios of copolymer to polymer at a total level of 0.13 weight percent.
Example IV was repeated and a second set of data were collected and are shown in Table II.
~lo- ~ 31 7~
TAB~E II
Ingredients (WT.%/Ratio) Treatment QUAT Silicone Silicone Base DDMAC Copolymer* Pol~mer~ No. I No. III No. V
9~.57 4.3 25 75 5.6 4.7 3.3 95.57 4.3 50 50 4.9 4.9 5.0 95.57 4.3 75 25 3.3 3.7 3.6 95.57 4.3 -- 100 2.9 2.6 3.9 95.57 4.3 100 -- 2.2 3.8 3.7 100 -- -- -- 1.9 1.1 1.4 * = See Table I
Tables I and II in particular indicate that combinations of both the polymer and copolymer provide a synergistic effect when compared to the effect obtained by the use of either individually.
Example V
Example IV was repeated except that there was also included comparative testing based on the ethoxylated tertiary amine softener composition of U.S. Patent No. 4~741,842, which is referred to in the following tables as ETA. ETA is approximately eighty-eight percent by weight quaternary ammonium compound and eight percent by weight of ethoxylated amine. In this example, rewettability as well as static control were tested in addition to softness. The results indicate that the compositions of the present invention provide equal, if not better, softness benefits than ETA, preferential static control and do not have a negative effect on fabric rewettability.
-11- 1 3~7~6 TABLE ILI
Ingredients (WT.%/Ratio) Treatment QUAT Silicone Silicone Base DDMAC Copolymer* Pol mer* No. I Mo. III No. V
95.57 4.3 Z5 75 ~.4 3.4 3.2 95.57 4.3 50 50 3.9 3.4 4.5 95.57 4.3 75 25 2.5 4.4 3.4 95.12 4.S8** -- -- 2.3 1.9 2.6 100 -~ - 1.7 1.7 1.6 * = See Table I
** = ETA substituted for DDMAC.
The procedure for Table III was repeated and a second set of data generated and set forth in Table IV.
-12- ~77~
TABLE IV
Ingredients (WT.%/Ratio) Treatment QUAT Silicone Silicone Base DDMAC CopolYmer* Polymer~' No. I No. III No. V
9~.57 4.3 2S 75 5.0 4.4 4.4 95.57 4.3 50 50 3.2 4.3 3.6 95.57 4.3 75 25 2.1 2.6 3.1 95.12 4.88** -- -- 3.1 2.5 2.7 100 -- -- -- 1.~ 1.0 ~.0 * = See Table I.
** = ETA substituted for DDMAC.
-13- ~3~7~
TABLE V
Ingredients (WT.%/Ratio)Rewettability (mm/4 min.) QUAT Silicone Silicone Base DDMAC Copol~mer* Pol~mer* No. I No. III No. V
95.57 4.3 50 50 67 79 80 95.57 4.3 25 75 67 84 84 95.57 4.3 75 25 62 80 80 95.12 4.~8** -- -- 69 84 84 100 ~ - 67 83 83 * = See Table I.
** = ETA substituted for DDMAC.
TABLE VI
In~redients (WT.%/Ra~io) Rewettability (mm/4 min.) QUAT Silicone Silicone Base DDMAC CoPolYmer* Pol~mer* No. I No. III No. V
95.57 4.3 50 50 66 81 82 95.57 4.3 25 75 70 80 85 95.57 4.3 75 25 75 81 ~
95.12 4.88** -- -- 79 83 83.5 100 -- -- -- 74 78 78.5 * = See Table I.
** = ETA sub~tituted for DDMAC.
13177~
It should be apparent from the foregoing tables that the softener ingredient containing the compositions o the present invention imparted the best softness.
Specifically, combinations of the copolymer and the polymer e~hibited a synergistic effect in comparison to the effect obtained when either was used without the other. The rewettability of each of the foregoing is set forth and it should be pointed out that the average rewettability imparted to each fabric was not negatived by the softeners including the compositions of the present invention.
Example VI
The compositions of the present invention were evaluated for their ability to reduce static electricity.
The material ETA of Example V was a~ain included for comparative purposes. The fabric bundle used to conduct this test consisted of the following garments or equivalent in yard goods:
10% 100% Nylon Tricot 10% 100% Polyester 12% 100% Acrylic 4% 100% Rayon 4% 100% Acetate 2870 65/35 Polyester/Cotton 32% 86/14 Cotton/Polyester Towels Bundles were stripped before use by washing in hot water five times with an anionic phosphate built detergent and then rinsed three times without any detergent, as noted in Example I.
After treating the bundles with the detergent and softening mi~ture in the wash, the bundles were dried in dryers wiped with isopropanol to remove any previous residue.
The bundles were dried for 60 minutes. Each piece of fabric was taken out one at a time. Different fabrics were brought ~h,,i -15- ~3~77~
together and separated to observe static and cling. Rubber Gloves were used to eliminate any dissipation of static. The entire bundle was rated according to the following scale:
1 NONE-No items affected by static; no detectable cling.
2 VERY LIGHT-Very slight attraction when swatches are brought together ~no readably observable cling), slight static.
3 LIGHT-Some static, very little cling.
4 LIGHT MODERATE-Definite cling and static (1/3 synthetics).
MODERATE-1/4 of items affected by cling and static (2/3 synthetics).
6 MODERATE HEAVY-Same as above, but more intense.
7 HEAVY-1/2 of items affected by cling and static (all synthetics).
8 VERY ~EAVY-Same as above but more intense.
9 SEVERE-3/4 or more of items affected (all synthetics and other items).
At least two people were used to rate the static out of the dryer. The average of the two was recorded as the static rating for the particular bundle.
The results of the static tests are shown below in Tables VII and VIII and it can be seen that the compositions of the present invention were at least three ~imes more effective than the prior art material ETA.
-16- ~3177~
TABLE VII
Ingredients (WT.%/Ratio) Static Rating QUAT Silicone Silicone Base DDMAC CoPolymer* Pol~mer~ No. I No. III No. V
95.57 4.3 50 50 2 2.5 2.5 95.57 4.3 25 75 2 1.5 2 95.57 4.3 75 25 2.5 2 2.5 95.12 4.88** -- -- 6 7 8 100 ~ - 7 7 6 * = See Table I.
** = ETA substituted for DDMAC.
TABLE VIII
Ingredients (WT.%/Ratio) Static Rating QUAT Silicone Silicone Base DDMAC Copolymer* PolYmer* No. I No. III No. V
95.57 4.3 50 50 1.5 1.5 1.5 95.57 4.3 25 7~ 2.5 2 2 95.57 4.3 75 25 2 2 3 95.12 4.88** -- -- 7 7.5 7 * = See T~ble I.
** = ETA substituted for DDMAC.
-17- 1~7706 Surfactants preferred in accordance with the present invention are anionic and nonionic and mixtures thereof. Specific anionic surfactants are, for example, carboxylic acids and salts; sulfonic acids and salts such as alkylbenzenesulfonates, alkylary:lsulfonates, naphthalene-sulfonates, petroleum sulfonates, sulonates with ester, ether or amide linkages and lignosulfonates; sulfuric acid esters and salts such as sulfated alcohols, ethoxylated and sulfated alcohols and alkylpheno:ls, sulfated acids, amides and esters and sulfated natural ~Eats and oils; and phosphoric and polyphosphoric acid esters and salts such as alkoxylated and phosphated alcohols and phenols. Among the category of nonionic surfactants which can be employed are, for example, ethoxylated alcohols; ethoxylated alkylphenols; ethoxylated carboxylic esters such as glycerol esters, polyethylene glycol estars, anhydrosorbitol esters, ethoxylated anhydro-sorbitol and sorbitol esters, ethoxylated natural fats and oils, ethylene and diethylene glycol esters and propanediol esters; and etho~ylated carbo~ylic amides.
Various categories of builders can be employed exemplary of which are, for example, phosphates s~ch as pentasodium phosphate, sodium tripolyphosphate, tetra30dium pyrophosphate, trisodium phosphate, sodium polymetaphosphate and potassium phosphates; sodium carbonate; silicates;
zeolites; cl~ys; nitrilotriacetic acid and alkalies. In addition, those builders as well as surfactants set forth in U.S. Patent No. 3,936,537, issued February 3, 1976, as well as in U.S. Patent No. 4,741,842, issued May 3, 1988, may be employed herein.
The silicone copolymers of the present invention and methods for their preparation are de~cribed in U.S.
Patent No. 3,402,192, issued September 17, 1968.
Generically, such materials are described as a copolymer ~i selected from the group consisting of copolymers having the average structural formulae:
(1) RaSi[~OSiMe2)n(0SiMeG)dOSiMe2G]4 a, (2) GMe2si~osiMe2)n(osiMeG)bosiMe2G~
(3) Me3Si(OSiMe2)n(0SiMeG)cOSiMe3, and (4) R Si[(OSiMe2)n(0siMeG)cosiMe3]4-a~
formulae R is a hydrocarbon radica:L free of aliphatic unsaturation and contains from 1 to 10 carbon atoms, Me is a methyl radical, G is a radical of the structure -D(OR'')mA wherein D is an alkylene radical containing from 1 to 30 carbon atoms, R'' is composed of ethylene radicals and radicals selected from the group consisting of propylene and butylene radicals, the amount of ethylene radicals relative to the other alkylene radicals being such that the ratio of carbon atoms to oxygen atoms in the total OR'' blocks ranges from 2.3:1 to 2.8:1, m has an average value from 7 to 100, A is a radical selected from the group consisting of the -OR', -OOCR' and -OCOR' radicals wherein R' is a radical free of aliphatic unsaturation selected from the group consisting of hydrocarbon and hydrocarbonoxy radicals, the A radical containing a total of less than eleven atoms, a has an average value of from O to 1, -19- ~3~ 77~
n has an average value of from 6 to 420, d has an average value of from 0 to 30, b has an average value from 1 to 30 and c has an average value from 3 to 30, said copolymers containing at least 13 percent by weight OSiMe2 units based on the weight of the copolymer.
It will be apparent from the foregoing that many other variations and modifications may be made in the structures, compounds, compositions and methods describèd herein without departing substantially from the essential features and concepts of the present invention. Accordingly, it should be clearly understood that the forms of the invention described herein are e2emplary only and are not intended as limitations on the scope of the present invention.
Claims (2)
1. A softening composition comprising a mixture of a fabric softening conditioning compound, a polydimethyl-siloxane polymer having the formula:
where x is an integer of from one to about one hundred thousand and a polyoxyalkylene siloxane copolymer, the copolymer being selected from the group consisting of copolymers having the average structural formulae:
(1) RaSi[(OSiMe2)nOSiMe2G]4, (2) GMe2Si(OSiMe2)n(OSiMeG)bOSiMe2G, (3) Me3Si(OSiMe2)n(OSiMeG)cOSiMe3, (4) RaSi[(OSiMe2)n(OSiMeG)cOsiMe3]4, (5) RaSi[(OSiMe2)n(OSiMeG)dOSiMe2G]3, (6) RaSi[(OSiMe2)n(0SiMeG)cOSiMe3]3, in which formulae R is a hydrocarbon radical free of aliphatic unsaturation and contains from 1 to 10 carbon atoms, Me is a methyl radical, G is a radical of the structure -D(OR'')mA wherein D is an alkylene radical containing from 1 to 30 carbon atoms, R'' is composed of ethylene radicals and radicals selected from the group consisting of propylene and butylene radicals, the amount of ethylene radicals relative to the other alkylene radicals being such that the ratio of carbon atoms to oxygen atoms in the total OR'' blocks ranges from 2.3:1 to
where x is an integer of from one to about one hundred thousand and a polyoxyalkylene siloxane copolymer, the copolymer being selected from the group consisting of copolymers having the average structural formulae:
(1) RaSi[(OSiMe2)nOSiMe2G]4, (2) GMe2Si(OSiMe2)n(OSiMeG)bOSiMe2G, (3) Me3Si(OSiMe2)n(OSiMeG)cOSiMe3, (4) RaSi[(OSiMe2)n(OSiMeG)cOsiMe3]4, (5) RaSi[(OSiMe2)n(OSiMeG)dOSiMe2G]3, (6) RaSi[(OSiMe2)n(0SiMeG)cOSiMe3]3, in which formulae R is a hydrocarbon radical free of aliphatic unsaturation and contains from 1 to 10 carbon atoms, Me is a methyl radical, G is a radical of the structure -D(OR'')mA wherein D is an alkylene radical containing from 1 to 30 carbon atoms, R'' is composed of ethylene radicals and radicals selected from the group consisting of propylene and butylene radicals, the amount of ethylene radicals relative to the other alkylene radicals being such that the ratio of carbon atoms to oxygen atoms in the total OR'' blocks ranges from 2.3:1 to
2.8:1, m has an average value from 7 to 100, A is a radical selected from the group consisting of the -OR', -OOCR' and o -OCCR' radicals wherein R' is a radical free of aliphatic unsaturation selected from the group consisting of hydrocarbon and hydrocarbonoxy radicals, the A radical containing a total of less than eleven atoms, a has an average value of 0 to 1, has an average value of from 6 to 420, d has an average value of from 1 to 30, b has an average value from 1 to 30 and c has an average value from 3 to 30, said copolymers containing at least 13 percent by weight OSiMe2 units based on the weight of the copolymer.
2. A particulate fabric laundering detergent formulation comprising at least one organic surfactant selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic compounds and mixtures thereof, at least one detergent builder selected from the group consisting of inorganic and organic water soluble builder salts, water insoluble builder salts and seeded builders, and a mixture of a water dispersible fabric softening conditioning compound, a polydimethylsiloxane polymer having the formula:
where x is an integer of from one to about one hundred thousand and a polyoxyalkylene siloxane copolymer, the copolymer being selected from the group consisting of copolymers having the average structural formulae:
(1, RaSi[(OSiMe2)nOSiMe2G]4, (2) GMe2si(OSiMe2)n(OSiMeG)bOSiMe2G, (3) Me3Si(OSiMe2)n(OSiMeG)cOSiMe3, (4) Rasi[(OSiMe2)n(OSiMeG)cOSiMe3]4, (5) Rasi[(OSiMe2)n(OSiMeG)dOSiMe2G]3, (6) RaSi[(OSiMe2)n(OSiMeG)cOSiMe3]3, in which formula R is a hydrocarbon radical free of aliphatic unsaturation and contains from 1 to 10 carbon atoms, Me is a methyl radical, G is a radical of the structure -D(OR'')mA wherein D is an alkylene radical containing from 1 to 30 carbon atoms, R'' is composed of ethylene radicals and radicals selected from the group consisting of propylene and butylene radicals, the amount of ethylene radicals relative to the other alkylene radicals being such that the ratio of carbon atoms to oxygen atoms in the total OR'' blocks ranges from 2.3:1 to 2.8:1, m has an average value from 7 to 100, A is a radical selected from the group consisting of the -OR', -OOCR' and -O?OR' radicals wherein R' is a radical free of aliphatic unsaturation selected from the group consisting of hydrocarbon and hydrocarbonoxy radicals, the A radical containing a total of less than eleven atoms, a has an average value of from 0 to 1, n has an average value of from 6 to 420, d has an average value of from 1 to 30, b has an average value from 1 to 30, and c has an average value from 3 to 30, said copolymers containing at least 13 percent by weight OSiMe2 units based on the weight of the copolymer.
2. A particulate fabric laundering detergent formulation comprising at least one organic surfactant selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic compounds and mixtures thereof, at least one detergent builder selected from the group consisting of inorganic and organic water soluble builder salts, water insoluble builder salts and seeded builders, and a mixture of a water dispersible fabric softening conditioning compound, a polydimethylsiloxane polymer having the formula:
where x is an integer of from one to about one hundred thousand and a polyoxyalkylene siloxane copolymer, the copolymer being selected from the group consisting of copolymers having the average structural formulae:
(1, RaSi[(OSiMe2)nOSiMe2G]4, (2) GMe2si(OSiMe2)n(OSiMeG)bOSiMe2G, (3) Me3Si(OSiMe2)n(OSiMeG)cOSiMe3, (4) Rasi[(OSiMe2)n(OSiMeG)cOSiMe3]4, (5) Rasi[(OSiMe2)n(OSiMeG)dOSiMe2G]3, (6) RaSi[(OSiMe2)n(OSiMeG)cOSiMe3]3, in which formula R is a hydrocarbon radical free of aliphatic unsaturation and contains from 1 to 10 carbon atoms, Me is a methyl radical, G is a radical of the structure -D(OR'')mA wherein D is an alkylene radical containing from 1 to 30 carbon atoms, R'' is composed of ethylene radicals and radicals selected from the group consisting of propylene and butylene radicals, the amount of ethylene radicals relative to the other alkylene radicals being such that the ratio of carbon atoms to oxygen atoms in the total OR'' blocks ranges from 2.3:1 to 2.8:1, m has an average value from 7 to 100, A is a radical selected from the group consisting of the -OR', -OOCR' and -O?OR' radicals wherein R' is a radical free of aliphatic unsaturation selected from the group consisting of hydrocarbon and hydrocarbonoxy radicals, the A radical containing a total of less than eleven atoms, a has an average value of from 0 to 1, n has an average value of from 6 to 420, d has an average value of from 1 to 30, b has an average value from 1 to 30, and c has an average value from 3 to 30, said copolymers containing at least 13 percent by weight OSiMe2 units based on the weight of the copolymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US251,285 | 1988-09-30 | ||
| US07/251,285 US4846982A (en) | 1988-09-30 | 1988-09-30 | Particulate fabric laundering composition |
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| Publication Number | Publication Date |
|---|---|
| CA1317706C true CA1317706C (en) | 1993-05-18 |
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ID=22951275
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000609393A Expired - Fee Related CA1317706C (en) | 1988-09-30 | 1989-08-25 | Particulate fabric laundering composition |
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|---|---|
| US (1) | US4846982A (en) |
| EP (1) | EP0363080B1 (en) |
| JP (1) | JP2738962B2 (en) |
| AU (1) | AU614427B2 (en) |
| CA (1) | CA1317706C (en) |
| DE (1) | DE68920532T2 (en) |
| ES (1) | ES2069592T3 (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5057240A (en) * | 1989-10-10 | 1991-10-15 | Dow Corning Corporation | Liquid detergent fabric softening laundering composition |
| US5091105A (en) * | 1989-10-10 | 1992-02-25 | Dow Corning Corporation | Liquid detergent fabric softening laundering composition |
| US5254269A (en) * | 1991-11-26 | 1993-10-19 | Lever Brothers Company, Division Of Conopco, Inc. | Fabric conditioning composition containing an emulsified silicone mixture |
| US5300667A (en) * | 1992-08-10 | 1994-04-05 | Dow Corning Corporation | Water dispersible silicone composition |
| WO1994007979A1 (en) * | 1992-09-28 | 1994-04-14 | The Procter & Gamble Company | Method for using solid particulate fabric softener in automatic dosing dispenser |
| GB9315671D0 (en) * | 1993-07-29 | 1993-09-15 | Dow Corning Sa | Foam control agents and their use |
| US5928566A (en) * | 1995-11-29 | 1999-07-27 | International Business Machines Corporation | Plasticized, antiplasticized and crystalline conducting polymers |
| US5932143A (en) * | 1995-11-29 | 1999-08-03 | International Business Machines Corporation | Polycrystalline conducting polymers and precursors thereof having adjustable morphology and physical properties |
| US5759208A (en) * | 1996-02-29 | 1998-06-02 | The Procter & Gamble Company | Laundry detergent compositions containing silicone emulsions |
| US5723426A (en) * | 1996-02-29 | 1998-03-03 | Zhen; Yueqian | Liquid laundry detergent compositions containing surfactants and silicone emulsions |
| US6995124B1 (en) | 1998-10-24 | 2006-02-07 | The Procter & Gamble Company | Methods for laundering delicate garments in a washing machine |
| US6966696B1 (en) | 1998-10-24 | 2005-11-22 | The Procter & Gamble Company | Methods for laundering delicate garments in a washing machine |
| US7185380B2 (en) * | 1998-10-24 | 2007-03-06 | The Procter & Gamble Company | Methods for laundering delicate garments in a washing machine comprising a woven acrylic coated polyester garment container |
| US6426328B2 (en) | 1998-10-27 | 2002-07-30 | Unilever Home & Personal Care, Usa Division Of Conopco Inc. | Wrinkle reduction laundry product compositions |
| US6403548B1 (en) | 1998-10-27 | 2002-06-11 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Wrinkle reduction laundry product compositions |
| US6376456B1 (en) | 1998-10-27 | 2002-04-23 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Wrinkle reduction laundry product compositions |
| EP1167617B1 (en) * | 2000-01-19 | 2006-06-14 | Kao Corporation | Softening finish composition |
| US20070118998A1 (en) * | 2000-08-25 | 2007-05-31 | The Procter & Gamble Company | Methods for laundering delicate garments in a washing machine |
| GB0228354D0 (en) * | 2002-12-05 | 2003-01-08 | Unilever Plc | Detergent compositions |
| US20060234899A1 (en) * | 2003-03-05 | 2006-10-19 | H.H. Brown Shoe Technologies Inc. D/B/A Dicon Technologies | Hydrophilic polyurethane foam articles comprising an antimicrobial compound |
| GB0518059D0 (en) * | 2005-09-06 | 2005-10-12 | Dow Corning | Delivery system for releasing active ingredients |
| US7655609B2 (en) * | 2005-12-12 | 2010-02-02 | Milliken & Company | Soil release agent |
| US20070131892A1 (en) * | 2005-12-12 | 2007-06-14 | Valenti Dominick J | Stain repellant and release fabric conditioner |
| US20070130694A1 (en) * | 2005-12-12 | 2007-06-14 | Michaels Emily W | Textile surface modification composition |
| US20070199157A1 (en) * | 2006-02-28 | 2007-08-30 | Eduardo Torres | Fabric conditioner enhancing agent and emulsion and dispersant stabilizer |
| BR112014003551B1 (en) | 2011-08-26 | 2023-12-05 | Colgate-Palmolive Company | COMPOSITION FOR REDUCING CREASES IN FABRICS AND METHOD FOR REDUCING CREASES IN FABRIC |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA695633A (en) * | 1961-07-31 | 1964-10-06 | A. Haluska Loren | Siloxane glycol branch copolymers |
| GB1034782A (en) * | 1962-01-24 | 1966-07-06 | Union Carbide Corp | Organosilicon compositions |
| US3936537A (en) * | 1974-11-01 | 1976-02-03 | The Procter & Gamble Company | Detergent-compatible fabric softening and antistatic compositions |
| GB1549180A (en) * | 1975-07-16 | 1979-08-01 | Procter & Gamble | Textile treating compositions |
| GR75649B (en) * | 1980-07-28 | 1984-08-02 | Procter & Gamble | |
| GB8413802D0 (en) * | 1984-05-30 | 1984-07-04 | Procter & Gamble | Detergent with suds control |
| US4741842A (en) * | 1986-01-27 | 1988-05-03 | Colgate-Palmolive Company | Particulate detergent softener compositions comprising a mixture of cationic softener and ethoxylated amine |
| US4767548A (en) * | 1986-08-06 | 1988-08-30 | Dow Corning Corporation | Articles for conditioning fabrics in a laundry dryer |
| GB2200365A (en) * | 1987-01-26 | 1988-08-03 | Goodjet Ltd | Detergent composition |
| GB2206902B (en) * | 1987-07-10 | 1991-07-03 | British Petroleum Co Plc | Detergent compositions |
-
1988
- 1988-09-30 US US07/251,285 patent/US4846982A/en not_active Expired - Fee Related
-
1989
- 1989-08-25 CA CA000609393A patent/CA1317706C/en not_active Expired - Fee Related
- 1989-09-28 DE DE68920532T patent/DE68920532T2/en not_active Expired - Fee Related
- 1989-09-28 ES ES89309906T patent/ES2069592T3/en not_active Expired - Lifetime
- 1989-09-28 AU AU42300/89A patent/AU614427B2/en not_active Ceased
- 1989-09-28 EP EP89309906A patent/EP0363080B1/en not_active Expired - Lifetime
- 1989-09-30 JP JP1253813A patent/JP2738962B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU4230089A (en) | 1990-04-05 |
| EP0363080B1 (en) | 1995-01-11 |
| JP2738962B2 (en) | 1998-04-08 |
| DE68920532T2 (en) | 1995-08-17 |
| AU614427B2 (en) | 1991-08-29 |
| DE68920532D1 (en) | 1995-02-23 |
| EP0363080A1 (en) | 1990-04-11 |
| US4846982A (en) | 1989-07-11 |
| ES2069592T3 (en) | 1995-05-16 |
| JPH02145862A (en) | 1990-06-05 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |