CA1157339A - Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soap - Google Patents
Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soapInfo
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- CA1157339A CA1157339A CA000375554A CA375554A CA1157339A CA 1157339 A CA1157339 A CA 1157339A CA 000375554 A CA000375554 A CA 000375554A CA 375554 A CA375554 A CA 375554A CA 1157339 A CA1157339 A CA 1157339A
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Classifications
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
Abstract
DETERGENT COMPOSITIONS CONTAINING AN
ALUMINOSILICATE DETERGENCY BUILDER
AND AN UNSATURATED FATTY ACID SOAP
Abstract Detergent compositions comprising water-insoluble aluminosilicate detergency builder; a synthetic detergent surfactant; and an unsaturated, water-soluble or dispersible soap of an unsaturated fatty acid containing from about 16 to about 22 carbon atoms. The soap improves the detergency, especially of particulate and body soils.
ALUMINOSILICATE DETERGENCY BUILDER
AND AN UNSATURATED FATTY ACID SOAP
Abstract Detergent compositions comprising water-insoluble aluminosilicate detergency builder; a synthetic detergent surfactant; and an unsaturated, water-soluble or dispersible soap of an unsaturated fatty acid containing from about 16 to about 22 carbon atoms. The soap improves the detergency, especially of particulate and body soils.
Description
- 1 157~'~39 DETERGENT COMPOSITIONS CONTAINING
AN ALUMINOSILICATE DETERGENCY BUILDER
AND AN UNSATURATED FATTY ACID SOAP
. .
Stanton Lane Boyer and Denzel Allan Nicholson - Technical Field This invention relates to detergent compositions for use in washing textiles. The detergent compositions can be in any convenient form, including granules, pastes, solid shapes and liquids. In a preferred variation, the detergent compositions of this invention are substan~ially free of phosphate- and nitrogen-containing detergency builders.
Back~round Art Aluminosilicate detergency builders have been disclosed in the prior art in combination with a variety of surfactant systems, including soaps. Soaps have been used as detergent surfactants for centuries. How~er, their use has been declining and the soaps utilized in the mo~ern times are soaps of saturated fatty acids.
Summa~y_of the Invention The present in~ention relates to detergent compositions consisting essentially of:
(a) from about l~ to about 20% of synthetic detergent surfactant selected from the group consisting of:
(1) water-soluble nonionic detergent surfactants;
AN ALUMINOSILICATE DETERGENCY BUILDER
AND AN UNSATURATED FATTY ACID SOAP
. .
Stanton Lane Boyer and Denzel Allan Nicholson - Technical Field This invention relates to detergent compositions for use in washing textiles. The detergent compositions can be in any convenient form, including granules, pastes, solid shapes and liquids. In a preferred variation, the detergent compositions of this invention are substan~ially free of phosphate- and nitrogen-containing detergency builders.
Back~round Art Aluminosilicate detergency builders have been disclosed in the prior art in combination with a variety of surfactant systems, including soaps. Soaps have been used as detergent surfactants for centuries. How~er, their use has been declining and the soaps utilized in the mo~ern times are soaps of saturated fatty acids.
Summa~y_of the Invention The present in~ention relates to detergent compositions consisting essentially of:
(a) from about l~ to about 20% of synthetic detergent surfactant selected from the group consisting of:
(1) water-soluble nonionic detergent surfactants;
(2) water-soluble synthetic anionic detergent surfactants;
(3) water-soluble zwitterionic detergent sur-factants;
(4) water-soluble amphoteric detergent sur-factants;
(5~ water-soluble semi-pol~r nonionic detergent surfactants; and (6) mixtures thereof;
.. . . . . .
l 157339 - 2 - .. .
b) from about 5~ to about 60~ of a water-soluble or dispersible soap of unsaturated fatty acids con-taining from about 16 to 22 carbQn atoms; and.
c) from-a~out 5% to about 50% of a water-insoluble inorganic detergency builder selected from the group consisting of;
(1) zeolite A;
- (2) zeolite X;
(3) zeoIite P (B);
(4) amorphous hydrated aluminosilicate material of the empirical.formula MZ(ZAlO2'YSiO2) wherein M is sodium, potassium or .
ammonium; z is from about 0.5 to about 2; and y is 1, said zeolites A, X and P
having a particle size diameter of from about 0.01 microns to about 25 microns and containing at least 10~ water of hydration and said amorphous material having a particle size diameter of less than about 25 microns, and magnesium ion exchange.capacity of at least about S0 milligram equivalents of calcium car-bonate hardness per gram of anhydrous aluminosilicate, and a magnesium ion exchange rate of at.least about 1 grain/gallon/minute/gram/gallon; and
(5~ water-soluble semi-pol~r nonionic detergent surfactants; and (6) mixtures thereof;
.. . . . . .
l 157339 - 2 - .. .
b) from about 5~ to about 60~ of a water-soluble or dispersible soap of unsaturated fatty acids con-taining from about 16 to 22 carbQn atoms; and.
c) from-a~out 5% to about 50% of a water-insoluble inorganic detergency builder selected from the group consisting of;
(1) zeolite A;
- (2) zeolite X;
(3) zeoIite P (B);
(4) amorphous hydrated aluminosilicate material of the empirical.formula MZ(ZAlO2'YSiO2) wherein M is sodium, potassium or .
ammonium; z is from about 0.5 to about 2; and y is 1, said zeolites A, X and P
having a particle size diameter of from about 0.01 microns to about 25 microns and containing at least 10~ water of hydration and said amorphous material having a particle size diameter of less than about 25 microns, and magnesium ion exchange.capacity of at least about S0 milligram equivalents of calcium car-bonate hardness per gram of anhydrous aluminosilicate, and a magnesium ion exchange rate of at.least about 1 grain/gallon/minute/gram/gallon; and
5.) . mixtures thereof;
d~ the balance preferably being selected from the group consisting of water, sodium sulfate, Cl_4 alcohols, sodium silicates, sodium carbonate, and mixtures thereof.
~isclosùre of the Invention This invention compri5es the discovery that certain unsaturated fatty acid soaps are surprisingly effective : surfactants for detergent compositions.containing . . .
.. . .. . . .. .. . . .. .. . . . . . . .................... .
.
aluminosilicate detergency builders, especially hydratedzeolites A and X and most especially zeolite A. The presence of the unsaturated soap provides benefits in the area of particulate soil removal, body soil removal, and cool water detergency, especially when used with another detergent surfactant, preferably one which is an effective curd dispersant while minimizing and/or eliminating the formation of soap curd. A special advantage of this invention is that it provides ~ood detergency either in the absence or presence of conventional phosphate and poly-carboxylate detergency builders. In the presence of phos-phate builders the addition of soap provides only partic-ulate soil removal benefits over the same composition without the soap.
'~he essential elements in the detergent compositions of this invention are the aluminosilicate detergency builder and the combination of unsaturated fatty acid soap and synthetic detergent.
The Aluminosilicate Detergency Builder The crystalline aluminosilicate materials for use herein are those commonly known as hydrated zeolites A, X
and P~B) preferably A and X, most preferably A. These crystalline materials should contain at least about 10~
water of hydration, preferably at least about 18~ water of hydration and should have a particle size of from about 0.01 micron to about 25 microns, preferably from about 0.1 micron to about 10 microns, more preferably from about 0.5 micron to about 5 microns. Preferably the crystal size should be from about 0.1 to about 1.5 microns. These aluminosilicate materials are more fully described in U.S. Patent 4,096,081, Phenicie et al, issued June 20, 1978. Zeolite A is the preferred aluminosilicatç material having the largest capacity for controlling hardness and having been exhaus-tively tested for its overall characteristics.
Further disclosure of the above zeolite aluminosilicate materials and of the amorphous aluminosilicate materials useful herein can be found in U.S. Patent 4,180,485, Llenado, issued December 25, 1979.
.
1 15'~39 .. - 4--The above aluminosilicate detergent builders should preferably be free-of any substantial amount of particles having a diameter above about 10 microns. Also, in the case of the zeolite materials, they should have a calcium ion exchange capacity of at least about 100 milligram equiva-lents of calcium carbonate.per gram, pre~erably at least 200 milligram equivalents of calcium carbonate per gram, and most preferably at least 250 milligram equivalents of calcium carbonate per gram on an anhydrous basis. The-initial ion exchange rate of these zeolites should be atleast 2 grains/gallon~minute/gramfgallon as measured at room temperature in the presence of 7 grains of mixed 2:1 .
Ca++:Mg + and a.level of detergency builder sufficient to control that level of hardness. This initial rate can be approximated by drawing a line from the initial point to the level of hardness after 1/2 minute as determined by a calcium ion specific electrode.
The amorphous materials useful herein should have a magnesium ion.exchange.capacity-of at least about 50 milli-gram equivalents of calcium carbonate, preferably at least .about 75 milligram equivalents of calcium carbonate hardness per gram of anhydrous aluminosilicate and a magnesium ion exchange rate of at least about 1 grain/gallon/minute/gram/
gallon.
- The amount of aluminosilicate detergency builder in the compositions is from about 5% to about 50~, preferably from about 15% to about 40~,.most.preferably from about 20% to . about 30%. The aluminosilicate detergency builder is preferably present at a level to control from about.65% to 30 about 80% of the hardness. - ~ -The_Unsaturated Soa~
. - . The unsaturated fatty acid soap of this invention . .
contains from about 16 to about 22 carbon atoms, preferably - in a straight chain configuration. Preferably the number of carbon atoms in the unsaturated fatty acid soap is-from about 16 to about 18.
This unsaturated soap, in common with other anionic detergents and ather anionic materials in the detergent compositions o this invention, has a cation which renders the soap water-soluble and/or dispersible. Suitable cations include sodium, potassium, ammonium, monethanolammonium, diethanolammonium, triethanolammonium, tetramethylammonium, etc. cations. Sodium ions are preferred although in liquid formulations potassium, monoethanolammonium, diethanol-ammonium, and triethanolammonium cations are useful.
A level of at least about 5% of the unsaturated fatty acid soap is desirable to provide a noticeable improvement in performance. Preferred levels of unsaturated fatty acid soap are from about 5% to about 60%, preferably from about 10% to about 40%, most preferably from about 10% to about 20%. The unsaturated fatty acid soap is pre~erably present at a level that will provide a level of from about 150 ppm to about 600 ppm, preferably from about 150 ppm to abou~ 300 ppm in the wash solution at recommended U.S. usage levels and from about 150 ppm to about 2400 ppm, preferably from about 600 ppm to about 1500 ppm for European usage levels.
Surprisingly, the aluminosilicate assists in keeping the unsaturated soap from forming an insoluble curd.
Mono-, di-, and triunsaturated fatty acids are all essentially equivalent so it is preferred to use mostly monounsaturated soaps to minimize the risk of rancidity.
Suitable sources of unsaturated fatty acids are well known.
For example, see Baileyls Industrial Oil and Fat Products, Third Edition, Swern, published by Interscience Publisher (1964).
Preferably, the level of saturated soaps is kept as low as possible, preferably less than about 50% of the unsatura-ted soap. However, low levels of saturated soaps can be added and will provide some performance for-clay removal if they contain at least 16 carbon atoms. Preferably the level of saturated soap does not exceed the level of unsaturated soap. Tallow and palm oil soaps can be used if cost consid-erations are important, but will not give as good results as .,.
1157~39 can be obtained with all unsaturated soap. Coconut soap does not provide a benefit and should not be added in significant amounts.
The Synthetic Surfactant In addition to the unsaturated fatty acid soap there is a synthetic surfactant present, especially one which is an efficient soap curd dispersant. The synthetic detergent surfactant is selected from the group consisting of water-soluble nonionic, anionic, zwitterioni~, amphoteric, and semi-polar nonionic detergent surfactants and mixtures thereof. Especially preferred surfactants and mixtures of surfactants are those which are relatively hardness insen-sitive.
Suitable synthetic detergent surfactants include:
(1) Nonionic Detergent Surfactants.
Nonionic surfactants can be prepared by a variety of methods well known in the art. In general terms, such nonionic surfactants are typically prepared by condensing ethylene oxide with a compound containing an active hydrogen under conditions of acidic or basic catalysis. Nonionic surfactants for use herein comprise those typical nonionic surface active agents well known in the detergency arts.
Useful nonionic surfactants include those described in U.S.
Patent 4,075,118, issued to Gault et al on February 21, 1978; U.S. Patent 4,079,078 issued to Collins on March 14, 1978; and U.S. Patent 3,963,649 issued to Spadini et al on June 15, 1976.
The more conventional nonionic surfactants useful herein are those having the formula:
R(z)(C2H4O)xO-~
wherein R is an-alkyl, hydroxy aikyl, alkylene, hydroxy alkylene, acyl, or hydroxy acyl group containing from about 8 to about 22 carbon atoms or an alkylbenzene group wherein the alkyl group contains from about 6 to about 15 carbon atoms or mixtures thereof; Z is selected from the group consisting of 1 157~39 -o-, -N=, -N ~
and mixtures thereof; X is a number from 0 to about 30; and R' is selected from the group consisting of H, alkyl groups containing from 1 to about.4 carbon atoms, acyl groups 5 containing .from.2 to about 4 carbon atoms and mixtures thereof. The HLB of these.nonionic surfactants is pref-erably from about 5 to about.20, most preferably from about 8 to about 14.
(2) Anionic Detergent Suractants.
This class of detergents includes the water-soluble - salts of organic sulfuric reaction products having in their molecular structure an alkyl.group containing from about ~0 to about 20 carbon atoms and a sulfonic.acid or sulfuric acid ester group. .(Included in..the term "alkyl" is the alkyl portion of acyl groups.) A formula for representative anionic surfactants is:
R(O)y(R20)XSO3M
wherein R ha the meaning.given her~inbefore; ~ is 0 or one, but is always one when x is more than 0; R2 is selected from the group consisting of -C2H4-, -C~2CHOH-CH2-, -CH2C~(CH3)-, and mixtures thereof; x can.vary from 0 to about 30; and M
is selected from the group consisting of Na, K, N(C2H4H)0-3(H)l-4~ Ca, Mg, or mixtures thereof.
Examples of this group of synthetic detergents which form a part of the.detergent compositions of the present invention are the sodium, potassium, ammonium, monoethanol-ammonium, diethanolammonium, and triethanolammonium salts of: alkyl.sulfates, especially those obtained by sulfating the higher alcohols ~C8-C18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; and alkyl polyethoxy sulfates in which the alkyl.group contains from about .8 to 22 carbon atoms and the number of ethoxy ether .
. .groups is from about l to-about.10; olefin sulfonates containing from about 8 to about 22 carbon atoms; parafin sulfonates containing from.about 8 to about 22 carbon atoms;
a~kyl be~zene s~lfonates in which the alkyl group contains from about 9 to about 15 carbon atoms in straight chain or l 157~39 branched chain configuration, e.g., those of the type described in U.S. Patent Nos. 2,22~,099 and 2,477,383.
Other anionic detergent compounds herein include the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkyl phenol-ethylene oxide ether sulfate containing about 1 to about 1 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.
The cations of the above anionic surfactants are the same as for the unsaturated soaps.
(3) Zwitterionic Detergent Surfactants.
Zwitterionic detergents include derivatives of ali-phatic quaternary ammonium, phosphonium, and sulphoniumcompounds in which the aliphatic moieties can be straight chain or branched, preferably s~.aight chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubil-izing group. The general formula is RL~ R32 3 where R hasthe meaning given hereinbefore, R3 is an alkyl group con-taining from 1 to about 22 carbon atoms; R or one of the R3 groups being substituted with T; the portion of R or R3 between L and T preferably being interrupted by one to about 10 groups seIected from the group consisting of ether, ester, and amide groups and mixtures thereof; wherein L is-N, P or S; and T is -SO4e, -cooe, or -SO3e, there being no more than one hyd~ophobic group. -(4) Amphoteric Detergent Surfactants.
Amphoteric detergents include derivatives of aliphatic, or derivatives of heterocyclic, secondary and tertiary amines in which there is an aliphatic moiety which can be straight chain or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group. -The formula for these amphoteric detergent surfactantsis essentially the same as for the zwitterionic detergent .. . . .. . . . . . . .
1 15 ~339 _ g _ surfactants, but with one less R3 group.
~5) Semi-Polar Nonionic Detergent Surfactant.
Suitable semi-poIar nonionic detergent surfactants include tertiary amine oxides containing a straight or branched chain saturated or.unsaturated aliphatic hydro-carbon, hydroxy hydrocarbon or halohydrocarbon radical in which the alkyl portion contains~from 8 to 24 carbon atoms . and two short chain methyl, ethyl, hydroxymethyl or-hydro-xyethyl radicals. Other suitable semi-polar nonionic .
detergent surfactants include.the corresponding tertiary phosphine oxides and the sulfoxides.
The formula for representative surfactants is - O
R~C2H4O)xL(R )1-2 where R and L and x are as stated hereinbefore and each R4' '' is selected from the gro.up consisting of Cl 4 alkyl and hydroxy alkyl groups. and polyethoxyiat~ groups-containing -----from 1 to about 10 ether linkages,. said.R4 groups optionally being connected through an oxygen or a nitrogen atom.
Mixtures of all of the above synthetic detergent surfactants can be used and are usually preferred. The most preferred detergent surfactants.are anionic, amphoteric, zwitterionic and semipolar nonionic. detergent surfactants with nonionic detergent surfactants being used only as part (preferably minor) of.a surfactant mixture. Sucrose esters and amides have been demonstrated to be ineffective and should only be used as minor components in the detergent sur~actant.mixture.' Preferably sucrose esters are used in amounts less than about.2%! preferabLy less..than about 1~ -and are preferably not present.
-Preferred synthetic detergent surfactants for use hérein include Cll_15 alkyl polyethoxylate (1-5) sulfates;
C}1 15 alcohol polyethoxylates (1-10); C10 16 a1kyl di-Cl 4' -.
alkyl amine oxides; and.mixtures thereof..- -. . . .
Preferably the synthetic detergent surfactant is .
35 present in'from.about 2% to about 15%.
Miscellaneous rngredients In addition to the above named ingredients,.the comp-ositions of this invention can contain all of the usual .. .. .. ... . .. . .. . .. . . ... ....... . . . . . . ... ..
components of detergent compositions including the ingred-ients set forth in U.S. Patent 3,936,537, Baskerville et al. Such components include color speckles, bleaching agents, bleach activators, suds boosters, suds suppres-sors, antitarnish and/or anticorrosion agent, soil-suspending agents, soil-release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, perfumes, etc.
The optional components include bleaching agents such as sodium perborate (as the monohydrate or tetrahydrate), sodium percarbonate and other perhydrates, at levels from about 5% to 35% by weight of the composition, and activa-tors therefor, such as tetraacetyl ethylene diamine, tetraacetyl glycouril and other known in the art, and stabilizers therefor, such as magnesium silicate, and ethylene diamine tetraacetate.
Preferred optional ingredients include suds modifiers particularly those of suds suppressing types, exemplified by silicones, and silica-silicone mixtures.
U.S. Patents 3,933,672 issued January 20, 1976, to Bartollota et al, and 4,136,045, issued January 23, 1979 to Gault et al, disclose silicone suds controlling agents.
The silicone material can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types. The silicone material can be described as siloxane having the formula:
~ S i 0 R' x wherein x is from about 20 to about 2,000 and R and R' are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl. The polydimethylsiloxanes (R
and R' are methyl) having a molecular weight within the range of from about 200 to about 2,000,000, and higher, are all useful as suds controlling agents. Additional suitable silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl or aryl hydrocarbyl groups exhibit useful suds controlling properties. Examples of the like ingredients include diethyl-, dipropyl-, dibutyl-, methyl-, ethyl-, phenylmethylpoly-siloxanes and the like. Additional useful silicone suds controlling agents can be represented by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica~
A preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethylsila-na~ed) silica having a particle si~e in the range from about 10 millimicrons to 20 millimicrons and a specific surface area above about 50 m2/gm. intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of si icone to silanated silica of from about l:l to about 1:2. The sili-cone suds suppressing agent is advantageously releasably in-corporated in a water-soluble or water-dispersible, substan-tially non-surface-active detergent-impermeable carrier.
Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in U.S.
Patent 4,073,118, Gault et al, issued February 21, 1978.
An example of such a compound is DB-544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
Suds modifiers as described above are used at levels of up to approximately 2%, preferably from about .1 to about 1-1/2% by weight of the surfactant.
Low levels of water-soluble detergency buiiders, e.g., from about 1~ to about 35~, preferably from about 5~ to about 20% can also be used.
Nonlimiting examples of suitable water-soluble inor-ganic alkaline detergent builder salts include the alkalimetal carbonates, borates, phosphates, polyphosphates, tripolyphosphates, bicarbonates, and silicates. Specific examples of such salts include the sodil~m and potassium Pb. .
tetraborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, pentapol~phosphates and hexametaphosphates.
Sulfates are usually present also.
Organic chelating agents that can be incorporated include citric acid, nitrilotriacetic and ethylene diamine tetraacetic acids and their salts, organic phosphonate derivatives such as those disclosed in Diehl U.S. Patent 3,213,030, issued October 19, 1965; by Roy U.S. Patent 3,433,021, issued January 14, 1968; Gedge, U.S. Patent 3,292,121., issued January 9, 1968; Bersworth U.S. Patent 2,599,807, issued ~une 10, 1952; and carboxylic acid build-ers such as those disclosed.in Diehl U.S. Patent 3,308,067, issued March 7, 1967.
Other organic chelating agents include the aminotri-alkylidene phosphonates whose acids have.the general formula r R5 1 ¦
N - C - P - OH
wherein R5 and R6 represent hydrogen or Cl-C4 alkyl radi-cals. Examples of compounds within this general class are aminotri(methylenephosphonic acid), aminotri-(ethylidene-phosphonic acid), aminotri-(isopropylidenephosphonic acid), aminodi-(methylenephosphoniç acid)-mono-(ethylidenephosphon-.ic acid) and aminomono-(methylenephosphonic acid) di-(iso-propylidenephosphonic acid).
A very highly preferred class of polyphosphonates is that derived from the alkylene-polyaminopolyalkylene phos-phonic acids. Especially useful examples of these materials include ethylene diamine tetramethylene.phosphonic acid, diethylenetriamine pentamethylene phosphonic acid and hexamethylene diamine tetramethylene phosphonic acid. This 30 class of materials has been found to be outstandingly good at overcoming the fabric yellowing tendencies of compositions based predominantly on nonionic surfactants and cationic softeners. Preferred salts of this class are the alkali l l57339 metal, especially sodium, salts. The tri- or tetra- or pentasodium salts of diethylene triaminè pentamethylene phosphonates are generally thbse present in the composi-tions~ A mixture of the salts may be employed.
Preferred chelating agents include citric acid, nitrilo-triacetic acid (NTA), nitrilotrimethylene phosphonic acid (NTMP), ethylene diamine tetra methylene phosphonic acid (EDTMP), and diethylene triamine penta methylene phosphonic acid (DETPMP).
Preferably from 0.2 to 2% of the phosphonate salt is present by weight of the composition.
Preferred soil suspending and anti-redeposition agents include methyl cellulose derivatives and the copolymers of maleic anhydride and either me ~ yL vinyl ether or ethylene, lS e.g., Gantre ~ANll9 or Gantrez~595 (trade ~ark of GAF).
As used herein, all percentages, parts and ratios are by weight unless otherwise specifie~.
The following compositions were tested by washing swatches of polyester stained with clay and swatches of polyester and cotton soiled with body soil in mini-washers at a detergent composition concentration of about 0.15% and 100F in 4 grains hardness (5, 6, 7 and 8 were run at 6 grains hardness which is a more stressed condition.) The clay swatches were measured to obtain the difference in Hunter Whiteness Units (HWU) from th~ control with a dif-ference of 5 HWU-~being significant and the body soil swatch-es were graded by expert panelists with a grade of 0 being comparable to the control and a grade of 3 being a very large difference. These grades are referred to as panel score units (PSU). A difference of 1 PSU is significant.
The values given are not all based on the same number of cycles or tests and some were obtained at different times.
However, the data are fairly representative. Compositions l and 7 were the high and low controls respectively. Composi-tions 1-4 are provided for comparison to demonstrate the criticality of the ingredients.
l 15~39 EXAMPLE I
% by weight Component 1 2 3 4 5 6 Sodium zeolite A, 3-4~ average particle size (~1 ~ crystals~ O . 25 - ~ -Na2C3 20 10 -~
Sodium linoleate O O 0 15 0 10 10 Sodium stearate O O 15 0 ~o~yethoxylate(7) 0 -~ -Sodium alkyl*
benzene sulfonate 14. 7.0 0 0 0 0 15 Sodium C alcohol polyetho~y~ate (2.25) sulfate 6 5.5 10 0 10 10 Sodium tallow alkyl sulfate 0 5.5 0 0 0 0 20 Sodium silicate (2~Or) 4 ~
Sodium sulfate ~ Balance ~
4rwu Control 15 15 4 15 24 ~PSU Control 0.5 Q.6 0 -0.2 1.2 ~ 15 EXAMPLE I tContinued) ~ bY weiqht Component 7 8 9 1011 12 Sodium zeolite A, 3-4~ average particle size (~1 ~ crystals) ---~- --- - -~~~-- -Na2GQ3 1~ --------'--- .-.--- , - - ~ -.
Sodium linoleate 15 . 50 15 15 15 15 10 Sodium stearate O O O O O O
~o~ethoxylate (7) ~ 10 Sodium Cl alkyl benzene sulfonate 0 0 0 0 10 0 -15 Sodium C 4 alkyl polyethoxy~ate ~2.25) sulfate . 10 10 3 6 0 0 Sodium tallow alkyl sulfate O O O O O O
20 Sodium silicate-(2.Or) Sodium sulfate. -~ -- Balance - --- ---~-~HWU 27 33 12 ~ 20 ~PSU - - 1.5 2.2 0.6 1.5 0.8 1.2 *C13 for,composition 1 and approximately C12 for 2 and 11.
, .
l 15~3~9 EXAMPLE II
% by wei~ht Components 1 2 3 4 5 6 Zeolite A of Ex. 1 0 10 25 50 0 O
5 Na zeolite P
(5.6~ average particle size) O O O 0 25 0 Na zeolite X (2.7~
average particle size a O 25 Sodium linoleate 15 ~-Sodium C
alkyl po~ye~hoxy-late (2.25) 15 sulfate 10 - ~-Sodium silicate ~2.Or) 4 ~-Na2S04 -~ Balance ~
~HWU Control 5 15 30 6 13 As can be seen from the above, a level of greater than about 10% zeolite is required at this level of product usage and zeolite P is not acceptable at this product usage level and particle size.
EXAMPLE III
In this Example the compositions 25% of the zeolite of Example I~ 15% sodium linoleate, 10% sodium ~4 15 alkyl polyethoxylate (2.25) sulfate,. 4% sodium silicate,.and the balance Na2S04 was adjusted to the indicated pH's with the 30 indicated results. .~~ -~ 7 8 9 - 10 11 .
~WU . control 9. 21 23 12 ~SU - control 1.5 2.2 - -Surprisingly, there is a maximum p~ for optimum per-formance as shown above. Preferably the pH of the composi-tions of this invention at a 0.15% concentration in water is from about 8 to about 11, most preferably from about 9.5 to about 10.5.
- . .. .
1 15~339 - EXAMPLES IV-VIII
IV V VI VII VIII
% by weight Zeolite of Example I 20 0 35 10 0 5 Amorphous Na zeolite, Al:Si-2, <l~a~.
particle diameter 12 0 0 0 0 Na zeolite X, ~2~ av.
particle diameter 0 25 0 10 15 10 Na C olefin sul~ona~e 5 Na oleate 0 10 0 0 0 X linoleate 15 0 0 0 10 Na C~4_1 paraffin sul n ~e 0 7 0 0 Na tallowate ~I.V. 40) 0 0 30 0 0 Na palmate (I.V. 45) 0 0 0 40 0 Na a-sulfonated coconut methyl ester 0 0 0 3 0 Coconut alkyl dimethyl amine oxide 0 0 6 0 5 , C 5 alkyl polyethoxy-~ate (7) o 0 0 0 4 Na2 CO3 20 16 10 15 0 Na2 SO4 15 0 0 15 0 Na percarbonate 0 25 0 0 0 Na perborate monohydrate 0 0 15 0 0 2 C3 0 o 0 0 7 Ethyl alcohol 0 0 0 0 3.5 Dimethyl polysiloxane ~M.W.-200,000) - 2 0 0 0 0 Ethylene diamine tetra-methylene phosphonic acid 2 0 0 0 0 Diethylene triamine penta-methylene phosphonic acid 0 1.5 0 0 0 H20 and miscellaneous ~ Balance - ~-.~ . .
l l573~9 EXAMPLE IX
Zeolite of Example I 20 Na2 C3 10 `~
Na3 nitrilotriacetate 15 15 0 0 Sodium tripolyphosphate O 0 25 25 Sodium C alXyl benzene sulfona~e 4 0 6 0 Sodium C 4 alkyl polyeth~xy~te (2.25) sulfate 6 10 6 10 Sodium tallow alkyl sulfate - 6 0 6 0 Sodium linoleate . 0 15 0 15 15 Sodium silicate (2.Or) 4 Sodium sulfate ~ -- Balance ~--Control 20 Control 10 ~HWU - . . - ~8 gpg)- (8 gpg) (10 gpg~: (10 sP
~PSU.(at 8 gpg) Control 1.3 Control -0.6 The addition of the unsaturated soap, even with a reduction in synthetic surfactant and in the presence of an effective water soluble detergency builder, provides improved performance at higher hardness levels without the formation of undesirable soap scum.
.
EXAMPLE X
% by weight Na zeolite X, ~2~.
~particle diameter 15 ~ K linoleate 10 Coconut alkyl dimethyl amine oxide 5 C14_15 alkyl polyetho~yylate (7) 4 Ethyl alcohol . 3.5 35 Sodium citrate - 10 H20 and miscellaneous -~ Dalance ~--
d~ the balance preferably being selected from the group consisting of water, sodium sulfate, Cl_4 alcohols, sodium silicates, sodium carbonate, and mixtures thereof.
~isclosùre of the Invention This invention compri5es the discovery that certain unsaturated fatty acid soaps are surprisingly effective : surfactants for detergent compositions.containing . . .
.. . .. . . .. .. . . .. .. . . . . . . .................... .
.
aluminosilicate detergency builders, especially hydratedzeolites A and X and most especially zeolite A. The presence of the unsaturated soap provides benefits in the area of particulate soil removal, body soil removal, and cool water detergency, especially when used with another detergent surfactant, preferably one which is an effective curd dispersant while minimizing and/or eliminating the formation of soap curd. A special advantage of this invention is that it provides ~ood detergency either in the absence or presence of conventional phosphate and poly-carboxylate detergency builders. In the presence of phos-phate builders the addition of soap provides only partic-ulate soil removal benefits over the same composition without the soap.
'~he essential elements in the detergent compositions of this invention are the aluminosilicate detergency builder and the combination of unsaturated fatty acid soap and synthetic detergent.
The Aluminosilicate Detergency Builder The crystalline aluminosilicate materials for use herein are those commonly known as hydrated zeolites A, X
and P~B) preferably A and X, most preferably A. These crystalline materials should contain at least about 10~
water of hydration, preferably at least about 18~ water of hydration and should have a particle size of from about 0.01 micron to about 25 microns, preferably from about 0.1 micron to about 10 microns, more preferably from about 0.5 micron to about 5 microns. Preferably the crystal size should be from about 0.1 to about 1.5 microns. These aluminosilicate materials are more fully described in U.S. Patent 4,096,081, Phenicie et al, issued June 20, 1978. Zeolite A is the preferred aluminosilicatç material having the largest capacity for controlling hardness and having been exhaus-tively tested for its overall characteristics.
Further disclosure of the above zeolite aluminosilicate materials and of the amorphous aluminosilicate materials useful herein can be found in U.S. Patent 4,180,485, Llenado, issued December 25, 1979.
.
1 15'~39 .. - 4--The above aluminosilicate detergent builders should preferably be free-of any substantial amount of particles having a diameter above about 10 microns. Also, in the case of the zeolite materials, they should have a calcium ion exchange capacity of at least about 100 milligram equiva-lents of calcium carbonate.per gram, pre~erably at least 200 milligram equivalents of calcium carbonate per gram, and most preferably at least 250 milligram equivalents of calcium carbonate per gram on an anhydrous basis. The-initial ion exchange rate of these zeolites should be atleast 2 grains/gallon~minute/gramfgallon as measured at room temperature in the presence of 7 grains of mixed 2:1 .
Ca++:Mg + and a.level of detergency builder sufficient to control that level of hardness. This initial rate can be approximated by drawing a line from the initial point to the level of hardness after 1/2 minute as determined by a calcium ion specific electrode.
The amorphous materials useful herein should have a magnesium ion.exchange.capacity-of at least about 50 milli-gram equivalents of calcium carbonate, preferably at least .about 75 milligram equivalents of calcium carbonate hardness per gram of anhydrous aluminosilicate and a magnesium ion exchange rate of at least about 1 grain/gallon/minute/gram/
gallon.
- The amount of aluminosilicate detergency builder in the compositions is from about 5% to about 50~, preferably from about 15% to about 40~,.most.preferably from about 20% to . about 30%. The aluminosilicate detergency builder is preferably present at a level to control from about.65% to 30 about 80% of the hardness. - ~ -The_Unsaturated Soa~
. - . The unsaturated fatty acid soap of this invention . .
contains from about 16 to about 22 carbon atoms, preferably - in a straight chain configuration. Preferably the number of carbon atoms in the unsaturated fatty acid soap is-from about 16 to about 18.
This unsaturated soap, in common with other anionic detergents and ather anionic materials in the detergent compositions o this invention, has a cation which renders the soap water-soluble and/or dispersible. Suitable cations include sodium, potassium, ammonium, monethanolammonium, diethanolammonium, triethanolammonium, tetramethylammonium, etc. cations. Sodium ions are preferred although in liquid formulations potassium, monoethanolammonium, diethanol-ammonium, and triethanolammonium cations are useful.
A level of at least about 5% of the unsaturated fatty acid soap is desirable to provide a noticeable improvement in performance. Preferred levels of unsaturated fatty acid soap are from about 5% to about 60%, preferably from about 10% to about 40%, most preferably from about 10% to about 20%. The unsaturated fatty acid soap is pre~erably present at a level that will provide a level of from about 150 ppm to about 600 ppm, preferably from about 150 ppm to abou~ 300 ppm in the wash solution at recommended U.S. usage levels and from about 150 ppm to about 2400 ppm, preferably from about 600 ppm to about 1500 ppm for European usage levels.
Surprisingly, the aluminosilicate assists in keeping the unsaturated soap from forming an insoluble curd.
Mono-, di-, and triunsaturated fatty acids are all essentially equivalent so it is preferred to use mostly monounsaturated soaps to minimize the risk of rancidity.
Suitable sources of unsaturated fatty acids are well known.
For example, see Baileyls Industrial Oil and Fat Products, Third Edition, Swern, published by Interscience Publisher (1964).
Preferably, the level of saturated soaps is kept as low as possible, preferably less than about 50% of the unsatura-ted soap. However, low levels of saturated soaps can be added and will provide some performance for-clay removal if they contain at least 16 carbon atoms. Preferably the level of saturated soap does not exceed the level of unsaturated soap. Tallow and palm oil soaps can be used if cost consid-erations are important, but will not give as good results as .,.
1157~39 can be obtained with all unsaturated soap. Coconut soap does not provide a benefit and should not be added in significant amounts.
The Synthetic Surfactant In addition to the unsaturated fatty acid soap there is a synthetic surfactant present, especially one which is an efficient soap curd dispersant. The synthetic detergent surfactant is selected from the group consisting of water-soluble nonionic, anionic, zwitterioni~, amphoteric, and semi-polar nonionic detergent surfactants and mixtures thereof. Especially preferred surfactants and mixtures of surfactants are those which are relatively hardness insen-sitive.
Suitable synthetic detergent surfactants include:
(1) Nonionic Detergent Surfactants.
Nonionic surfactants can be prepared by a variety of methods well known in the art. In general terms, such nonionic surfactants are typically prepared by condensing ethylene oxide with a compound containing an active hydrogen under conditions of acidic or basic catalysis. Nonionic surfactants for use herein comprise those typical nonionic surface active agents well known in the detergency arts.
Useful nonionic surfactants include those described in U.S.
Patent 4,075,118, issued to Gault et al on February 21, 1978; U.S. Patent 4,079,078 issued to Collins on March 14, 1978; and U.S. Patent 3,963,649 issued to Spadini et al on June 15, 1976.
The more conventional nonionic surfactants useful herein are those having the formula:
R(z)(C2H4O)xO-~
wherein R is an-alkyl, hydroxy aikyl, alkylene, hydroxy alkylene, acyl, or hydroxy acyl group containing from about 8 to about 22 carbon atoms or an alkylbenzene group wherein the alkyl group contains from about 6 to about 15 carbon atoms or mixtures thereof; Z is selected from the group consisting of 1 157~39 -o-, -N=, -N ~
and mixtures thereof; X is a number from 0 to about 30; and R' is selected from the group consisting of H, alkyl groups containing from 1 to about.4 carbon atoms, acyl groups 5 containing .from.2 to about 4 carbon atoms and mixtures thereof. The HLB of these.nonionic surfactants is pref-erably from about 5 to about.20, most preferably from about 8 to about 14.
(2) Anionic Detergent Suractants.
This class of detergents includes the water-soluble - salts of organic sulfuric reaction products having in their molecular structure an alkyl.group containing from about ~0 to about 20 carbon atoms and a sulfonic.acid or sulfuric acid ester group. .(Included in..the term "alkyl" is the alkyl portion of acyl groups.) A formula for representative anionic surfactants is:
R(O)y(R20)XSO3M
wherein R ha the meaning.given her~inbefore; ~ is 0 or one, but is always one when x is more than 0; R2 is selected from the group consisting of -C2H4-, -C~2CHOH-CH2-, -CH2C~(CH3)-, and mixtures thereof; x can.vary from 0 to about 30; and M
is selected from the group consisting of Na, K, N(C2H4H)0-3(H)l-4~ Ca, Mg, or mixtures thereof.
Examples of this group of synthetic detergents which form a part of the.detergent compositions of the present invention are the sodium, potassium, ammonium, monoethanol-ammonium, diethanolammonium, and triethanolammonium salts of: alkyl.sulfates, especially those obtained by sulfating the higher alcohols ~C8-C18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; and alkyl polyethoxy sulfates in which the alkyl.group contains from about .8 to 22 carbon atoms and the number of ethoxy ether .
. .groups is from about l to-about.10; olefin sulfonates containing from about 8 to about 22 carbon atoms; parafin sulfonates containing from.about 8 to about 22 carbon atoms;
a~kyl be~zene s~lfonates in which the alkyl group contains from about 9 to about 15 carbon atoms in straight chain or l 157~39 branched chain configuration, e.g., those of the type described in U.S. Patent Nos. 2,22~,099 and 2,477,383.
Other anionic detergent compounds herein include the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkyl phenol-ethylene oxide ether sulfate containing about 1 to about 1 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.
The cations of the above anionic surfactants are the same as for the unsaturated soaps.
(3) Zwitterionic Detergent Surfactants.
Zwitterionic detergents include derivatives of ali-phatic quaternary ammonium, phosphonium, and sulphoniumcompounds in which the aliphatic moieties can be straight chain or branched, preferably s~.aight chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubil-izing group. The general formula is RL~ R32 3 where R hasthe meaning given hereinbefore, R3 is an alkyl group con-taining from 1 to about 22 carbon atoms; R or one of the R3 groups being substituted with T; the portion of R or R3 between L and T preferably being interrupted by one to about 10 groups seIected from the group consisting of ether, ester, and amide groups and mixtures thereof; wherein L is-N, P or S; and T is -SO4e, -cooe, or -SO3e, there being no more than one hyd~ophobic group. -(4) Amphoteric Detergent Surfactants.
Amphoteric detergents include derivatives of aliphatic, or derivatives of heterocyclic, secondary and tertiary amines in which there is an aliphatic moiety which can be straight chain or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group. -The formula for these amphoteric detergent surfactantsis essentially the same as for the zwitterionic detergent .. . . .. . . . . . . .
1 15 ~339 _ g _ surfactants, but with one less R3 group.
~5) Semi-Polar Nonionic Detergent Surfactant.
Suitable semi-poIar nonionic detergent surfactants include tertiary amine oxides containing a straight or branched chain saturated or.unsaturated aliphatic hydro-carbon, hydroxy hydrocarbon or halohydrocarbon radical in which the alkyl portion contains~from 8 to 24 carbon atoms . and two short chain methyl, ethyl, hydroxymethyl or-hydro-xyethyl radicals. Other suitable semi-polar nonionic .
detergent surfactants include.the corresponding tertiary phosphine oxides and the sulfoxides.
The formula for representative surfactants is - O
R~C2H4O)xL(R )1-2 where R and L and x are as stated hereinbefore and each R4' '' is selected from the gro.up consisting of Cl 4 alkyl and hydroxy alkyl groups. and polyethoxyiat~ groups-containing -----from 1 to about 10 ether linkages,. said.R4 groups optionally being connected through an oxygen or a nitrogen atom.
Mixtures of all of the above synthetic detergent surfactants can be used and are usually preferred. The most preferred detergent surfactants.are anionic, amphoteric, zwitterionic and semipolar nonionic. detergent surfactants with nonionic detergent surfactants being used only as part (preferably minor) of.a surfactant mixture. Sucrose esters and amides have been demonstrated to be ineffective and should only be used as minor components in the detergent sur~actant.mixture.' Preferably sucrose esters are used in amounts less than about.2%! preferabLy less..than about 1~ -and are preferably not present.
-Preferred synthetic detergent surfactants for use hérein include Cll_15 alkyl polyethoxylate (1-5) sulfates;
C}1 15 alcohol polyethoxylates (1-10); C10 16 a1kyl di-Cl 4' -.
alkyl amine oxides; and.mixtures thereof..- -. . . .
Preferably the synthetic detergent surfactant is .
35 present in'from.about 2% to about 15%.
Miscellaneous rngredients In addition to the above named ingredients,.the comp-ositions of this invention can contain all of the usual .. .. .. ... . .. . .. . .. . . ... ....... . . . . . . ... ..
components of detergent compositions including the ingred-ients set forth in U.S. Patent 3,936,537, Baskerville et al. Such components include color speckles, bleaching agents, bleach activators, suds boosters, suds suppres-sors, antitarnish and/or anticorrosion agent, soil-suspending agents, soil-release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, perfumes, etc.
The optional components include bleaching agents such as sodium perborate (as the monohydrate or tetrahydrate), sodium percarbonate and other perhydrates, at levels from about 5% to 35% by weight of the composition, and activa-tors therefor, such as tetraacetyl ethylene diamine, tetraacetyl glycouril and other known in the art, and stabilizers therefor, such as magnesium silicate, and ethylene diamine tetraacetate.
Preferred optional ingredients include suds modifiers particularly those of suds suppressing types, exemplified by silicones, and silica-silicone mixtures.
U.S. Patents 3,933,672 issued January 20, 1976, to Bartollota et al, and 4,136,045, issued January 23, 1979 to Gault et al, disclose silicone suds controlling agents.
The silicone material can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types. The silicone material can be described as siloxane having the formula:
~ S i 0 R' x wherein x is from about 20 to about 2,000 and R and R' are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl. The polydimethylsiloxanes (R
and R' are methyl) having a molecular weight within the range of from about 200 to about 2,000,000, and higher, are all useful as suds controlling agents. Additional suitable silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl or aryl hydrocarbyl groups exhibit useful suds controlling properties. Examples of the like ingredients include diethyl-, dipropyl-, dibutyl-, methyl-, ethyl-, phenylmethylpoly-siloxanes and the like. Additional useful silicone suds controlling agents can be represented by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica~
A preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethylsila-na~ed) silica having a particle si~e in the range from about 10 millimicrons to 20 millimicrons and a specific surface area above about 50 m2/gm. intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of si icone to silanated silica of from about l:l to about 1:2. The sili-cone suds suppressing agent is advantageously releasably in-corporated in a water-soluble or water-dispersible, substan-tially non-surface-active detergent-impermeable carrier.
Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in U.S.
Patent 4,073,118, Gault et al, issued February 21, 1978.
An example of such a compound is DB-544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
Suds modifiers as described above are used at levels of up to approximately 2%, preferably from about .1 to about 1-1/2% by weight of the surfactant.
Low levels of water-soluble detergency buiiders, e.g., from about 1~ to about 35~, preferably from about 5~ to about 20% can also be used.
Nonlimiting examples of suitable water-soluble inor-ganic alkaline detergent builder salts include the alkalimetal carbonates, borates, phosphates, polyphosphates, tripolyphosphates, bicarbonates, and silicates. Specific examples of such salts include the sodil~m and potassium Pb. .
tetraborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, pentapol~phosphates and hexametaphosphates.
Sulfates are usually present also.
Organic chelating agents that can be incorporated include citric acid, nitrilotriacetic and ethylene diamine tetraacetic acids and their salts, organic phosphonate derivatives such as those disclosed in Diehl U.S. Patent 3,213,030, issued October 19, 1965; by Roy U.S. Patent 3,433,021, issued January 14, 1968; Gedge, U.S. Patent 3,292,121., issued January 9, 1968; Bersworth U.S. Patent 2,599,807, issued ~une 10, 1952; and carboxylic acid build-ers such as those disclosed.in Diehl U.S. Patent 3,308,067, issued March 7, 1967.
Other organic chelating agents include the aminotri-alkylidene phosphonates whose acids have.the general formula r R5 1 ¦
N - C - P - OH
wherein R5 and R6 represent hydrogen or Cl-C4 alkyl radi-cals. Examples of compounds within this general class are aminotri(methylenephosphonic acid), aminotri-(ethylidene-phosphonic acid), aminotri-(isopropylidenephosphonic acid), aminodi-(methylenephosphoniç acid)-mono-(ethylidenephosphon-.ic acid) and aminomono-(methylenephosphonic acid) di-(iso-propylidenephosphonic acid).
A very highly preferred class of polyphosphonates is that derived from the alkylene-polyaminopolyalkylene phos-phonic acids. Especially useful examples of these materials include ethylene diamine tetramethylene.phosphonic acid, diethylenetriamine pentamethylene phosphonic acid and hexamethylene diamine tetramethylene phosphonic acid. This 30 class of materials has been found to be outstandingly good at overcoming the fabric yellowing tendencies of compositions based predominantly on nonionic surfactants and cationic softeners. Preferred salts of this class are the alkali l l57339 metal, especially sodium, salts. The tri- or tetra- or pentasodium salts of diethylene triaminè pentamethylene phosphonates are generally thbse present in the composi-tions~ A mixture of the salts may be employed.
Preferred chelating agents include citric acid, nitrilo-triacetic acid (NTA), nitrilotrimethylene phosphonic acid (NTMP), ethylene diamine tetra methylene phosphonic acid (EDTMP), and diethylene triamine penta methylene phosphonic acid (DETPMP).
Preferably from 0.2 to 2% of the phosphonate salt is present by weight of the composition.
Preferred soil suspending and anti-redeposition agents include methyl cellulose derivatives and the copolymers of maleic anhydride and either me ~ yL vinyl ether or ethylene, lS e.g., Gantre ~ANll9 or Gantrez~595 (trade ~ark of GAF).
As used herein, all percentages, parts and ratios are by weight unless otherwise specifie~.
The following compositions were tested by washing swatches of polyester stained with clay and swatches of polyester and cotton soiled with body soil in mini-washers at a detergent composition concentration of about 0.15% and 100F in 4 grains hardness (5, 6, 7 and 8 were run at 6 grains hardness which is a more stressed condition.) The clay swatches were measured to obtain the difference in Hunter Whiteness Units (HWU) from th~ control with a dif-ference of 5 HWU-~being significant and the body soil swatch-es were graded by expert panelists with a grade of 0 being comparable to the control and a grade of 3 being a very large difference. These grades are referred to as panel score units (PSU). A difference of 1 PSU is significant.
The values given are not all based on the same number of cycles or tests and some were obtained at different times.
However, the data are fairly representative. Compositions l and 7 were the high and low controls respectively. Composi-tions 1-4 are provided for comparison to demonstrate the criticality of the ingredients.
l 15~39 EXAMPLE I
% by weight Component 1 2 3 4 5 6 Sodium zeolite A, 3-4~ average particle size (~1 ~ crystals~ O . 25 - ~ -Na2C3 20 10 -~
Sodium linoleate O O 0 15 0 10 10 Sodium stearate O O 15 0 ~o~yethoxylate(7) 0 -~ -Sodium alkyl*
benzene sulfonate 14. 7.0 0 0 0 0 15 Sodium C alcohol polyetho~y~ate (2.25) sulfate 6 5.5 10 0 10 10 Sodium tallow alkyl sulfate 0 5.5 0 0 0 0 20 Sodium silicate (2~Or) 4 ~
Sodium sulfate ~ Balance ~
4rwu Control 15 15 4 15 24 ~PSU Control 0.5 Q.6 0 -0.2 1.2 ~ 15 EXAMPLE I tContinued) ~ bY weiqht Component 7 8 9 1011 12 Sodium zeolite A, 3-4~ average particle size (~1 ~ crystals) ---~- --- - -~~~-- -Na2GQ3 1~ --------'--- .-.--- , - - ~ -.
Sodium linoleate 15 . 50 15 15 15 15 10 Sodium stearate O O O O O O
~o~ethoxylate (7) ~ 10 Sodium Cl alkyl benzene sulfonate 0 0 0 0 10 0 -15 Sodium C 4 alkyl polyethoxy~ate ~2.25) sulfate . 10 10 3 6 0 0 Sodium tallow alkyl sulfate O O O O O O
20 Sodium silicate-(2.Or) Sodium sulfate. -~ -- Balance - --- ---~-~HWU 27 33 12 ~ 20 ~PSU - - 1.5 2.2 0.6 1.5 0.8 1.2 *C13 for,composition 1 and approximately C12 for 2 and 11.
, .
l 15~3~9 EXAMPLE II
% by wei~ht Components 1 2 3 4 5 6 Zeolite A of Ex. 1 0 10 25 50 0 O
5 Na zeolite P
(5.6~ average particle size) O O O 0 25 0 Na zeolite X (2.7~
average particle size a O 25 Sodium linoleate 15 ~-Sodium C
alkyl po~ye~hoxy-late (2.25) 15 sulfate 10 - ~-Sodium silicate ~2.Or) 4 ~-Na2S04 -~ Balance ~
~HWU Control 5 15 30 6 13 As can be seen from the above, a level of greater than about 10% zeolite is required at this level of product usage and zeolite P is not acceptable at this product usage level and particle size.
EXAMPLE III
In this Example the compositions 25% of the zeolite of Example I~ 15% sodium linoleate, 10% sodium ~4 15 alkyl polyethoxylate (2.25) sulfate,. 4% sodium silicate,.and the balance Na2S04 was adjusted to the indicated pH's with the 30 indicated results. .~~ -~ 7 8 9 - 10 11 .
~WU . control 9. 21 23 12 ~SU - control 1.5 2.2 - -Surprisingly, there is a maximum p~ for optimum per-formance as shown above. Preferably the pH of the composi-tions of this invention at a 0.15% concentration in water is from about 8 to about 11, most preferably from about 9.5 to about 10.5.
- . .. .
1 15~339 - EXAMPLES IV-VIII
IV V VI VII VIII
% by weight Zeolite of Example I 20 0 35 10 0 5 Amorphous Na zeolite, Al:Si-2, <l~a~.
particle diameter 12 0 0 0 0 Na zeolite X, ~2~ av.
particle diameter 0 25 0 10 15 10 Na C olefin sul~ona~e 5 Na oleate 0 10 0 0 0 X linoleate 15 0 0 0 10 Na C~4_1 paraffin sul n ~e 0 7 0 0 Na tallowate ~I.V. 40) 0 0 30 0 0 Na palmate (I.V. 45) 0 0 0 40 0 Na a-sulfonated coconut methyl ester 0 0 0 3 0 Coconut alkyl dimethyl amine oxide 0 0 6 0 5 , C 5 alkyl polyethoxy-~ate (7) o 0 0 0 4 Na2 CO3 20 16 10 15 0 Na2 SO4 15 0 0 15 0 Na percarbonate 0 25 0 0 0 Na perborate monohydrate 0 0 15 0 0 2 C3 0 o 0 0 7 Ethyl alcohol 0 0 0 0 3.5 Dimethyl polysiloxane ~M.W.-200,000) - 2 0 0 0 0 Ethylene diamine tetra-methylene phosphonic acid 2 0 0 0 0 Diethylene triamine penta-methylene phosphonic acid 0 1.5 0 0 0 H20 and miscellaneous ~ Balance - ~-.~ . .
l l573~9 EXAMPLE IX
Zeolite of Example I 20 Na2 C3 10 `~
Na3 nitrilotriacetate 15 15 0 0 Sodium tripolyphosphate O 0 25 25 Sodium C alXyl benzene sulfona~e 4 0 6 0 Sodium C 4 alkyl polyeth~xy~te (2.25) sulfate 6 10 6 10 Sodium tallow alkyl sulfate - 6 0 6 0 Sodium linoleate . 0 15 0 15 15 Sodium silicate (2.Or) 4 Sodium sulfate ~ -- Balance ~--Control 20 Control 10 ~HWU - . . - ~8 gpg)- (8 gpg) (10 gpg~: (10 sP
~PSU.(at 8 gpg) Control 1.3 Control -0.6 The addition of the unsaturated soap, even with a reduction in synthetic surfactant and in the presence of an effective water soluble detergency builder, provides improved performance at higher hardness levels without the formation of undesirable soap scum.
.
EXAMPLE X
% by weight Na zeolite X, ~2~.
~particle diameter 15 ~ K linoleate 10 Coconut alkyl dimethyl amine oxide 5 C14_15 alkyl polyetho~yylate (7) 4 Ethyl alcohol . 3.5 35 Sodium citrate - 10 H20 and miscellaneous -~ Dalance ~--
Claims (15)
1. A detergent composition consisting essentially of:
a) from about 1% to about 20% of synthetic detergent surfactant selected from the group consisting of:
1) water-soluble nonionic detergent surfactants;
2) water-soluble synthetic anionic detergent surfactants;
3) water-soluble zwitterionic detergent sur-factants;
4) water-soluble amphoteric detergent surfac-tants;
5) water-soluble semi-polar nonionic detergent surfactants; and 6) mixtures thereof;
b) from about 5% to about 60% of water-soluble soap of unsaturated fatty acids containing from about 16 to about 22 carbon atoms; and c) from about 5% to about 50% of a water-insoluble inorganic detergency builder selected from the group consisting of:
(1) zeolite A;
(2) zeolite X;
(3) zeolite P;
(4) amorphous hydrated aluminosilicate material of the empirical formula Mz(zAlO2ySiO2) wherein M is sodium, potassium or ammonium; z is from about 0.5 to about 2; and y is 1, said zeolites A, X and P having a particle size diameter of from about 0.01 microns to about 25 microns. and containing at least 10%
water of hydration and said amorphous material having a particle size diameter of less than about 25 microns, and magnesium ion exchange capacity of at least about 50 milligram equivalents of calcium carbonate hardness per gram of anhydrous aluminosilicate, and a magnesium ion exchange rate of at least about 1 grain/gallon/minute/gram/gallon; and (5) mixtures thereof;
d) the balance being selected from the group con-sisting of water, sodium sulfate, C1-4 alcohols, sodium silicates, sodium carbonate, and mixtures thereof, and the level of any saturated soap present being limited so that it does not exceed the level of said unsaturated soap.
a) from about 1% to about 20% of synthetic detergent surfactant selected from the group consisting of:
1) water-soluble nonionic detergent surfactants;
2) water-soluble synthetic anionic detergent surfactants;
3) water-soluble zwitterionic detergent sur-factants;
4) water-soluble amphoteric detergent surfac-tants;
5) water-soluble semi-polar nonionic detergent surfactants; and 6) mixtures thereof;
b) from about 5% to about 60% of water-soluble soap of unsaturated fatty acids containing from about 16 to about 22 carbon atoms; and c) from about 5% to about 50% of a water-insoluble inorganic detergency builder selected from the group consisting of:
(1) zeolite A;
(2) zeolite X;
(3) zeolite P;
(4) amorphous hydrated aluminosilicate material of the empirical formula Mz(zAlO2ySiO2) wherein M is sodium, potassium or ammonium; z is from about 0.5 to about 2; and y is 1, said zeolites A, X and P having a particle size diameter of from about 0.01 microns to about 25 microns. and containing at least 10%
water of hydration and said amorphous material having a particle size diameter of less than about 25 microns, and magnesium ion exchange capacity of at least about 50 milligram equivalents of calcium carbonate hardness per gram of anhydrous aluminosilicate, and a magnesium ion exchange rate of at least about 1 grain/gallon/minute/gram/gallon; and (5) mixtures thereof;
d) the balance being selected from the group con-sisting of water, sodium sulfate, C1-4 alcohols, sodium silicates, sodium carbonate, and mixtures thereof, and the level of any saturated soap present being limited so that it does not exceed the level of said unsaturated soap.
2. The composition of Claim 1 wherein the water-insoluble inorganic detergency builder is selected from the group consisting of zeolite A, zeolite X, and mixtures thereof containing at least about 10% water of hydration and having a particle size of from about 0.1 micron to about 10 microns in an amount from about 15% to about 40% by weight of the composition.
3. The detergent composition of Claim 2 wherein the water-insoluble inorganic detergency builder contains at least about 18% water of hydration and has a crystal size from about 0.1 to about 1.5 microns.
4. The detergent composition of Claim 2 wherein the water-insoluble inorganic detergency builder is zeolite A.
5. The detergent composition of Claim 4 wherein the water-insoluble inorganic detergency builder contains at least about 18% water of hydration and has a crystal size from about 0.1 to about 1.5 microns.
6. The detergent composition of Claim 2 wherein the synthetic detergent surfactant is selected from the group consisting of:
a) nonionic surfactants having the formula:
R(Z)(C2H4)XO-Rl wherein R is an alkyl, hydroxy alkyl, alkylene, hydroxy alkylene, acyl, or hydroxy acyl group containing from about 8 to about 22 carbon atoms or an alkylbenzene group wherein the alkyl group contains from about 6 to about 15 carbon atoms and mixtures thereof; Z is selected from the group consisting of , and mixtures thereof; X
is a number from O to about 30; and R' is selected from the group consisting of H, alkyl groups containing from 1 to about 4 carbon atoms, acyl groups containing from 2 to about 4 carbon atoms and mixtures thereof;
b) anionic surfactants having the formula:
R(O)y(R2O)xSO3M
wherein R has the meaning given hereinbefore; Y is O or one, but is always one when x is more than O;
R2 is selected from the group consisting of -C2H4-, -CH2CHOH-CH2-, -CH2CH(CH3)-, and mixtures thereof;
x can vary from O to about 30; and M is selected from the group consisting of Na, K, -N(C2H4OH)O-3 (H)1-4, Ca, Mg, and mixtures thereof;
c) zwitterionic detergent surfactants having the formula RL.THETA.R32 2-3 wherein R has the meaning given hereinbefore; R3 is an alkyl group containing from 1 to about 22 carbon atoms; R or one of the R3 groups is substituted with T; the portion of R or R3 between L and T is interrupted by one to about ten groups selected from the group consisting of ether, ester, and amide groups and mixtures thereof; L is N, P or S; and T is -SO4.THETA., -COO.THETA., or -SO3.THETA., there being no more than one hydrophobic group;
d) amphoteric detergent surfactants having the formula:
wherein R, L and R3 have the meanings given hereinbefore;
e) semi-polar nonionic detergent surfactants having the formula:
wherein R, L and x are as stated hereinbefore and each R4 is selected from the group consisting of C1-4 alkyl and hydroxy alkyl groups and poly-ethoxylate groups containing from 1 to about 10 ether linkages; and said R3 groups can be con-nected through an oxygen or a nitrogen atom; and f) mixtures thereof.
a) nonionic surfactants having the formula:
R(Z)(C2H4)XO-Rl wherein R is an alkyl, hydroxy alkyl, alkylene, hydroxy alkylene, acyl, or hydroxy acyl group containing from about 8 to about 22 carbon atoms or an alkylbenzene group wherein the alkyl group contains from about 6 to about 15 carbon atoms and mixtures thereof; Z is selected from the group consisting of , and mixtures thereof; X
is a number from O to about 30; and R' is selected from the group consisting of H, alkyl groups containing from 1 to about 4 carbon atoms, acyl groups containing from 2 to about 4 carbon atoms and mixtures thereof;
b) anionic surfactants having the formula:
R(O)y(R2O)xSO3M
wherein R has the meaning given hereinbefore; Y is O or one, but is always one when x is more than O;
R2 is selected from the group consisting of -C2H4-, -CH2CHOH-CH2-, -CH2CH(CH3)-, and mixtures thereof;
x can vary from O to about 30; and M is selected from the group consisting of Na, K, -N(C2H4OH)O-3 (H)1-4, Ca, Mg, and mixtures thereof;
c) zwitterionic detergent surfactants having the formula RL.THETA.R32 2-3 wherein R has the meaning given hereinbefore; R3 is an alkyl group containing from 1 to about 22 carbon atoms; R or one of the R3 groups is substituted with T; the portion of R or R3 between L and T is interrupted by one to about ten groups selected from the group consisting of ether, ester, and amide groups and mixtures thereof; L is N, P or S; and T is -SO4.THETA., -COO.THETA., or -SO3.THETA., there being no more than one hydrophobic group;
d) amphoteric detergent surfactants having the formula:
wherein R, L and R3 have the meanings given hereinbefore;
e) semi-polar nonionic detergent surfactants having the formula:
wherein R, L and x are as stated hereinbefore and each R4 is selected from the group consisting of C1-4 alkyl and hydroxy alkyl groups and poly-ethoxylate groups containing from 1 to about 10 ether linkages; and said R3 groups can be con-nected through an oxygen or a nitrogen atom; and f) mixtures thereof.
7. The composition of Claim 6 wherein the synthetic detergent surfactant is a nonionic surfactant.
8. The composition of Claim 6 wherein the synthetic detergent surfactant is an anionic detergent surfactant.
9. The composition of Claim 8 wherein in the synthetic detergent surfactant R is an alkyl group and X is greater than 0.
10. The composition of Claim 6 wherein the synthetic detergent surfactant is a zwitterionic detergent surfactant.
11. The detergent composition of Claim 6 wherein the synthetic detergent surfactant is an amphoteric detergent surfactant.
12. The detergent composition of Claim 6 wherein the synthetic detergent surfactant is a semi-polar nonionic detergent surfactant.
13. The detergent composition of Claim 6 wherein the synthetic detergent is from about 2% to about 20% of the composition.
14. A detergent composition according to Claim 2, Claim 4 or Claim 6, wherein the fatty acid of the soap contains from about 16 to about 18 carbon atoms, and the cation of the soap is selected from the group consisting of sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, tetramethylammonium, and mixtures thereof.
15. A detergent composition according to Claim 2, Claim 4, or Claim 6, wherein the unsaturated fatty acid soap is from about 10% to about 40% by weight of the composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/141,222 US4265777A (en) | 1980-04-17 | 1980-04-17 | Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soap |
| US141,222 | 1980-04-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1157339A true CA1157339A (en) | 1983-11-22 |
Family
ID=22494725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000375554A Expired CA1157339A (en) | 1980-04-17 | 1981-04-15 | Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soap |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4265777A (en) |
| EP (1) | EP0038591B1 (en) |
| JP (1) | JPS5736198A (en) |
| AT (1) | ATE11564T1 (en) |
| CA (1) | CA1157339A (en) |
| DE (1) | DE3168577D1 (en) |
| GR (1) | GR74458B (en) |
| IE (1) | IE51137B1 (en) |
| PH (1) | PH15715A (en) |
Families Citing this family (45)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4404128A (en) * | 1981-05-29 | 1983-09-13 | The Procter & Gamble Company | Enzyme detergent composition |
| NZ201212A (en) * | 1981-07-15 | 1985-08-16 | Unilever Plc | Detergent additives and compositions |
| DE3264287D1 (en) * | 1981-09-14 | 1985-07-25 | Procter & Gamble | Alkaline aqueous liquid detergent compositions containing normally unstable ester perfumes |
| US4440663A (en) * | 1981-09-14 | 1984-04-03 | The Procter & Gamble Company | Alkaline aqueous liquid detergent compositions containing normally unstable ester perfumes |
| US4405483A (en) * | 1982-04-27 | 1983-09-20 | The Procter & Gamble Company | Stable liquid detergents containing aluminosilicate ion exchange material |
| FR2528722A1 (en) * | 1982-06-18 | 1983-12-23 | Rhone Poulenc Chim Base | ZEOLITE AS AUXILIARY OF DETERGENCE |
| US4545919A (en) * | 1982-08-31 | 1985-10-08 | Ciba-Geigy Corporation | Detergent composition for washing off dyeings obtained with fibre-reactive dyes and washing process comprising the use thereof |
| FI73734C (en) * | 1983-01-20 | 1987-11-09 | Unilever Nv | Particulate detergent composition and its solution. |
| GB8327271D0 (en) * | 1983-10-12 | 1983-11-16 | Unilever Plc | Built liquid detergent compositions |
| US4560492A (en) * | 1984-11-02 | 1985-12-24 | The Procter & Gamble Company | Laundry detergent composition with enhanced stain removal |
| JPH0633399B2 (en) * | 1986-07-16 | 1994-05-02 | 花王株式会社 | Cleaning composition |
| JPH0633400B2 (en) * | 1986-07-16 | 1994-05-02 | 花王株式会社 | Cleaning composition |
| DE3717227A1 (en) * | 1987-05-21 | 1988-12-01 | Henkel Kgaa | PHOSPHATE-FREE DETERGENT WITH REDUCED INCRUSTING TENDENCY |
| JP2510135B2 (en) * | 1987-05-25 | 1996-06-26 | ライオン株式会社 | Liquid detergent composition for clothing |
| SE463211B (en) * | 1987-10-26 | 1990-10-22 | Berol Nobel Ab | DETAILS COMPOSITION CONTAINING A COMBINATION OF AMPOTAIR LINING AND ZEOLITE |
| DE3829847A1 (en) * | 1988-09-02 | 1990-03-15 | Basf Ag | WASHING AND CLEANING AGENT |
| GB8825783D0 (en) * | 1988-11-03 | 1988-12-07 | Unilever Plc | Novel aluminosilicates & detergent compositions containing them |
| DE3929591A1 (en) * | 1989-09-06 | 1991-03-07 | Henkel Kgaa | LIQUID DETERGENT WITH ZEOLITE |
| US5102572A (en) * | 1990-06-22 | 1992-04-07 | Ethyl Corporation | Lime soap dispersant comprising sodium cocoyl glyceryl sulfonate and N-alkyl-N,N-dimethylamine oxide |
| GB9012612D0 (en) * | 1990-06-06 | 1990-07-25 | Unilever Plc | Detergents compositions |
| GB9113675D0 (en) * | 1991-06-25 | 1991-08-14 | Unilever Plc | Particulate detergent composition or component |
| GB9119958D0 (en) * | 1991-09-18 | 1991-10-30 | Unilever Plc | Detergent compositions |
| GB9216386D0 (en) * | 1992-07-31 | 1992-09-16 | Unilever Plc | Use of aluminosilicates of the zeolite p type as low temperature calcium binders |
| LT3962B (en) | 1993-12-21 | 1996-05-27 | Albright & Wilson | Funcional fluids |
| US6489278B1 (en) * | 1993-12-30 | 2002-12-03 | Ecolab Inc. | Combination of a nonionic silicone surfactant and a nonionic surfactant in a solid block detergent |
| US5562866A (en) * | 1995-06-20 | 1996-10-08 | Albemarle Corporation | Formulated branched chain alcohol ether sulfate compounds |
| US5690539A (en) * | 1995-08-07 | 1997-11-25 | Cal-West Equipment Company Inc. | Method of abarding using surface abrasion compositions |
| GB9605534D0 (en) * | 1996-03-15 | 1996-05-15 | Unilever Plc | Detergent compositions |
| GB9605533D0 (en) * | 1996-03-15 | 1996-05-15 | Unilever Plc | Modified aluminosilicate |
| US6235704B1 (en) | 1997-07-30 | 2001-05-22 | Basf Aktiengesellschaft | Solid textile detergent formulation based on glycin-N and N-Diacetic acid derivatives |
| US6964945B1 (en) * | 1998-09-25 | 2005-11-15 | The Procter & Gamble Company | Solid detergent compositions |
| US6369021B1 (en) * | 1999-05-07 | 2002-04-09 | Ecolab Inc. | Detergent composition and method for removing soil |
| GB9913547D0 (en) | 1999-06-10 | 1999-08-11 | Unilever Plc | Particulate detergent composition containing zeolite |
| GB9913546D0 (en) | 1999-06-10 | 1999-08-11 | Unilever Plc | Granular detergent component containing zeolite map and laundry detergent compositions containing it |
| GB0031823D0 (en) | 2000-12-29 | 2001-02-14 | Unilever Plc | Detergent compositions |
| GB0031827D0 (en) | 2000-12-29 | 2001-02-14 | Unilever Plc | Detergent compositions |
| US6660713B2 (en) * | 2001-01-30 | 2003-12-09 | The Procter & Gamble Company | Hydrophobic nanozeolites for malodor control |
| GB0319367D0 (en) * | 2003-08-18 | 2003-09-17 | Unilever Plc | Detergent composition |
| EP1697476A2 (en) * | 2003-12-03 | 2006-09-06 | Cal-West Specialty Coatings, Inc. | Silica-free surface abrasion compositions and their uses |
| TW201031743A (en) | 2008-12-18 | 2010-09-01 | Basf Se | Surfactant mixture comprising branched short-chain and branched long-chain components |
| WO2011003904A1 (en) | 2009-07-10 | 2011-01-13 | Basf Se | Surfactant mixture having short- and long-chained components |
| BR112012023991A2 (en) | 2010-03-25 | 2016-08-02 | Basf Se | washing machine, fiber cleaning process, laundry detergent, method for using a washing machine, fiber, parts kit, and electro-bleach ball |
| US20110237484A1 (en) | 2010-03-25 | 2011-09-29 | Basf Se | Electrochemical textile-washing process |
| JP6607686B2 (en) * | 2015-03-26 | 2019-11-20 | ライオン株式会社 | Liquid detergent for textile products |
| CN111479913B (en) | 2017-12-15 | 2021-12-21 | 罗地亚经营管理公司 | Compositions containing lanthanide metal complexes |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB569178A (en) | 1943-11-03 | 1945-05-10 | Edwin Taylor Chemicals Ltd | Improvements in or relating to the cutting of magnesium and its alloys |
| NL75847C (en) * | 1949-07-19 | |||
| US4605509A (en) * | 1973-05-11 | 1986-08-12 | The Procter & Gamble Company | Detergent compositions containing sodium aluminosilicate builders |
| US4083793A (en) * | 1973-05-23 | 1978-04-11 | Henkel Kommanditgesellschaft Auf Aktien | Washing compositions containing aluminosilicates and nonionics and method of washing textiles |
| US4136051A (en) * | 1974-02-25 | 1979-01-23 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Pourable washing compositions containing a luminosilicates and non-ionics and method for their preparation |
| AT335590B (en) * | 1974-08-29 | 1977-03-25 | Henkel & Cie Gmbh | LIQUID TO PASTE DETERGENT AND CLEANING AGENT CONCENTRATE AND METHOD OF MANUFACTURING |
| AT375395B (en) * | 1974-10-04 | 1984-07-25 | Henkel Kgaa | METHOD FOR WASHING OR BLEACHING TEXTILES AND MEANS THEREOF |
| US4148603A (en) * | 1974-10-04 | 1979-04-10 | Henkel Kommanditgesellschaft Auf Aktien | Method of washing textiles and composition containing inorganic silicates and polycarboxylates and/or polyphosphonates |
| AT338948B (en) * | 1974-10-10 | 1977-09-26 | Henkel & Cie Gmbh | POWDERED DETERGENTS AND CLEANING AGENTS AND METHOD FOR THEIR PRODUCTION |
| DE2517218B2 (en) * | 1975-04-18 | 1977-05-05 | Henkel & Cie GmbH, 4000 Düsseldorf; Deutsche Gold- und Silber-Scheideanstalt vormals Roessler, 6000 Frankfurt | TYPE A CRYSTALLINE ZEOLITE POWDER |
| ZA767017B (en) * | 1975-12-15 | 1978-06-28 | Colgate Palmolive Co | Method for reconditioning detergent powders |
| GB2040981B (en) * | 1977-06-21 | 1982-08-25 | Procter & Gamble | Low-phosphate detergent composition for fabric washing |
| DE2729995A1 (en) * | 1977-07-02 | 1979-01-18 | Henkel Kgaa | Washing textiles using low phosphate detergent compsn. - contg. soap and nonionic surfactant and aluminium silicate cation exchanger as water softener |
| US4180485A (en) * | 1977-11-02 | 1979-12-25 | The Procter & Gamble Company | Spray-dried detergent compositions |
| JPS5638399A (en) * | 1979-09-07 | 1981-04-13 | Asahi Denka Kogyo Kk | Powder detergent for garments |
-
1980
- 1980-04-17 US US06/141,222 patent/US4265777A/en not_active Expired - Lifetime
-
1981
- 1981-04-06 EP EP81200388A patent/EP0038591B1/en not_active Expired
- 1981-04-06 AT AT81200388T patent/ATE11564T1/en not_active IP Right Cessation
- 1981-04-06 DE DE8181200388T patent/DE3168577D1/en not_active Expired
- 1981-04-08 GR GR64622A patent/GR74458B/el unknown
- 1981-04-14 PH PH25502A patent/PH15715A/en unknown
- 1981-04-15 CA CA000375554A patent/CA1157339A/en not_active Expired
- 1981-04-16 IE IE866/81A patent/IE51137B1/en not_active IP Right Cessation
- 1981-04-17 JP JP5836681A patent/JPS5736198A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| PH15715A (en) | 1983-03-14 |
| IE810866L (en) | 1981-10-17 |
| EP0038591A1 (en) | 1981-10-28 |
| JPS5736198A (en) | 1982-02-26 |
| ATE11564T1 (en) | 1985-02-15 |
| US4265777A (en) | 1981-05-05 |
| GR74458B (en) | 1984-06-28 |
| IE51137B1 (en) | 1986-10-15 |
| DE3168577D1 (en) | 1985-03-14 |
| EP0038591B1 (en) | 1985-01-30 |
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