CA1037209A - Detergent compositions having fabric conditioning properties - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Detergent compositions having fabric conditioning properties com-prising an organic surface-active agent and low concentrations of substantially water-insoluble particulate material; said compositions imparting anti-wrinkling, ease of ironing, softness, anti-static, and appearance improve-ments to fabrics treated therewith.

Description

:,. ..
BACKGROUND OF THE INVENTION
This invention relates to detergent compositions which comprise in j addition to conventional organic surface-active components a substantially 10 water-insoluble particulate material.
Modern detergent compositions, machinery and adjunct chemical additives, e. g., fabric softeners, washing machines and dryers, are hap-hazardly aimed at achieving benefits other than the obvious goal of rendering a clean wash. Among the benefits sought to be imposed upon the fabrics carried through an entire cycle from washing to drying are fluffiness, soft-- ness, body, reduced electrostatic charge, diminishedwrinkling, ease of ironing, and improvement in appearance. No single product or machine process is presently available which will achieve all of these benefits simultaneously .
For example, present day fabric softeners impart a softness to the fabric (actually this softness is best likened to a tactile sensation of lubricity, which is distinguishable from fabric softness occasioned by enhanced fabric bul~ciness) and control of electrostatic charge. Modern day washing machines and dryers by means of elaborate cycles and temperature control are able to markedly improve the extent of fabric wrinkling. Other products such as well-known laundry starches, if desired in combination .1 with particulate organic constituents having a melting point below ironing temperatures, impart when applied after the washing cycle, crease perma-nence and ease of ironing benefits and also imparts a body to the fabric, i. e.,30 a sizing effect.
The detergent compositions of this invention, however, impart all of these benefits simultaneously through the wash. That is, the detergent .
`' ,, ,;, . . ~ ' , . , , , . : ' , ;. : , ' ~ ' ' .: ~ .. , . . . :: : .: . : , . . .

;.
~$s~.' 10372~g compositions of this invention, by some imperfectly understood physico-chemical interaction at the fiber or yarn level, impart through the wash cycle the above enumerated benefits. These benefits are solely attributable to the presence of water-insoluble particulate material hereinafter defined in combination with organic surface-acti-ve agents.
Detergent compositions comprising various particulate materials for the purpose of a specific function are known in the art. Examples thereof are detergent scouring compositions containing water-insoluble particulate materials, which mostly have a particle diameter in the range from about 50 to 100 micrometers and a hardness of about 7 on the Mohs scale. It has , long been known that gross quantities of starch by means of its gel-forming character impart desirable physical properties to toilet soap bars. Also, the properties of starch as a binding agent, as an agglomerating agent, as a , film-forming agent, and as an inert diluent have been exploited in granulated detergent compositions. Starch and starch derivatives have also been used in gross amounts in synthetic detergent compositions to improve the efficiency of the prilling process, that i9, formation of the detergent granules from the aqueous medium in which it was either synthesized or resolubilized.
Thermoplastic particulate materials are also known in the art and have been used in connection with laundering operations, mainly for the purpose of textile finishing, ease-of-ironing and sizing agents. These materials are softened or fused during e. g. ironing thereby providing a sizing to the fabric.
It is also known that some clay materials having exchangeable calcium and magnesium ions can be deposited on fabrics to impart softening properties thereto .

,;:; .:
'; Such clay deposition is usually realized by contacting fabrics to be so treated with aqueous clay suspensions (see for example, U.S. Patents 3,033,699 and 3,594,221). Canadian Patent No. 981,141 of T.D, Storm and J,P. Nirschl, issued January 6, 1976; U.S. Patent 3,852,211 of T.H. Ohren, issued December 3, 1974; U.S. Patent 3,862,058 of J.P. Nirschl and R.A.

Gloss, issued January 21, 1975; U.S. Patent 3,915,882 of J.P. Nirschl and R.A. Gloss; U.S. Patent 3,954,632 of R.A. Gloss, issued May 4, 1976;

' - 2 _ ":
. . .
,:
.. . . .

r~.

U.S. Patent 3,993,573 of R.A. Gloss, issued November 23, 1976; and UOS.
Patent 3,886,075 of Bernardino, relate to the use of clays in detergent and softening compositions.
The prior art teachings, however, aim at achieving specific func-tions and objectives which, as regards the properties of the particulate materials, i.e., water-insolubility, shape, integrity, particle size diameter, hardness, presence of exchangeable alkaline earth metal ions and melting (softening) temperatures, are essentially different from the physical pro-perties of the water-insoluble particulate materials which qualify for use in the compositions of the instant invention.
In any event, prior art detergent compositions containing the particulate materials referred to hereinbefore do not produce the fabric conditioning benefits of the instant compositions, and in many cases, tend to impart har shne s s or stiffne s s to the fabr ic .
Accordingly, it is an object of the present invention to provide detergent compositions containing water-insoluble particulate materials which impart anti-wrinkling, ease of ironing, fabric softening, anti-static, folding ease, enhanced fabric drapability and appearance benefits to fabrics treated ther ewith.
It is an additional object of the present invention to provide detergent compositions capable of simultaneously cleaning and conditioning ` fabrics treated therewith with a view to obtaining a degree of enhanced tactile and appearance properties at least comparable to what results from the use of rinse softeners applied subsequently to conventional washing, i.e., during ; the rinsing operation.
By utilization of certain particulate materials capable of conferring desirable fabric benefits when present in combination with organic surface-active agents, these above-described objectives can now be attained and detergent compositions formulated which are capable of simultaneously cleaning the fabrics treated therewith and also imparting to these fabrics a series of desirable properties including anti-wrinkling, ease of ironing, fabric softening, anti-static, folding ease, enhanced fabric drapability, and appearance benefits.

''' ' :', ~, ,:, , , - ' ~: :

~ ! 10372~9 SUMMARY OF THE INVENTION
The instant invention provides laundry detergent compositions which are capable of concurrently cleansing and imparting desirable fabric proper-ties to the fabrics treated therewith. Such compositions comprise: -.. ~ . .
j - (a) from about 2% to about 89. 5% by weight of an organic .. . .
surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic . ~ .
detergents and mixtures thereof;
(b) from about 0O 05% to about 10% by weight of a substantially ; 10 water-insoluble particulate material having:
(i) an average particle size in the range from about 1 to about 50 micrometers;
(ii) a shape having an anisotropy of about 5:1 to 1:1;
(iii) a hardness of less than about 5. 5 on the Mohs scale;
(iv) a melting point above about 150C; and (v) substantial freedom from exchangeable calcium and and magnesium ions; and (c) from about 10% to about 60% by weight of a detergent builder salt.
In its method aspects, this invention relates to a method for treating fabrics to simultaneously cleanse and impart anti-wrinkling, ease of ironing, softening, anti-static and appearance benefits. Such a method com-: prises treating fabrics in an aqueous liquor comprising:
(a) from about 10 ppm (parts per million) to about 10,000 ppm of an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof; and (b) from about 0. 2 ppm to about 1000 ppm of a substantially water-insoluble particulate material having (i ) an average particle size in the range from about ' 1 to about 50 micrometers;
. .
~ (ii) a shape having an anisotropy of about 5:1 to 1:1;

: 10372Q~
" (iii) a hardness of less than about 5. 5 on the Mohs scale;
(iv) a melting point above about 150C; and (v) substantial freedom of exchangeable calcium and magnesium ions.
DETAILED DESCRIPTION OF THE INVENTION
. ~ .
The present invention relates to detergent compositions capable of i..
concurrently cleaning and imparting desirable textile properties to fabrics washed therewith.
These compositions comprise: (1) an organic surface-active agent 10 and (2) a substantially water-insoluble particulate material as herein defined.
~, Unless indicated to the contrary. the "%" indications stand for "% by weight".
,, The essential organic surface-active component suitable for use in the compositions of the present invention is selected from the group consisting , :
of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof, Said component is to be used in an amount from about 2% to about ~., .
89, 5%, preferably from about 4% to about 60%, more preferably from about , 6% to about 40%, by weight of the composition.
Examples of suitable surface-active compounds which can be employed in accordance with the present invention include the following:
; i Anionic Detergents Water-soluble soaps. Suitable soaps include the sodium, potassium, ammonium and aLkanolammonium (e.g., mono-, di, and triethanolammonium) salts of higher fatty acids (Clo-C22). The sodium and potassium salts of the mixturea of fatty acids derived from coconut oil and tallow, i.e. sodium and potassium tallow and coconut soaps, are particularly useful.
Anionic synthetic detergents also include water-soluble salts, particularly the alkali metal aalts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a moiety selected from the group consisting of sulfonic acid and sulfuric acid ester moieties. (Included in the term alkyl is the alkyl portion of higher acyl moieties. ) Examples of this group of ':, 0372as synthetic detergents which form a part of the preferred built detergent com-positions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating higher alcohols (Cg-Clg carbon atoms) produced by reducing glycerides of tallow or coconut oil; sodium and .. . .
potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 20 carbon atoms in straight chain or branched-chain con-figuration, e.g., those of the type described in United States Patents Numbers

2,220,099 and 2,477,383 (especially valuable are linear straight chain alkyl - ben~ene sulfonates in which the average of the alkyl groups is about 1108 10 carbon atoms and commonly abbreviated as Cll gLAS); 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; sodium and potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl groups contain from about 8 to about 12 carbon atomsO
Anionic phosphate surfactants are also useful in the present inven-; tion. These are surface active materials having substantial detergent capabil-ity in which the anionic solubilizing group connecting hydrophobic moieties ; is an oxy acid of phosphorus. The more common solubiliYing groups, of 20 course, are -SO4H and -SO3H. Alkyl phosphate esters such as (R-C~QP02H
and ROPO3H2 in which R represents an alkyl chain containing from about 8 to about 20 carbon atoms are useful herein.
These phosphate esters can be modified by including in the molecule from one to about 40 alkylene oxide units, e.g., ethylene oxide units.
Formulae for these modified phosphate anionic detergents are .
'':'' O
[R-O-tcH2cH2On]2 P-O-M or .: O

Il [R- O- (CH2cH2O)n] P- O-M
O-M
in which R represents an alkyl group containing from about 8 to 20 carbon atoms, or an alkylphenyl group in which the alkyl group contains from about ~ ~037209 ~- 8 to 20 carbo~toms, and M represents a soluble cation such as hydrogen, .
sodium, potassium, ammonium or substituted ammonium; and in which n is an integer from 1 to about 40.
Another class of suitable anionic organic detergents useful in this invention includes salts of 2-acyloxyalkane-1-sulfonic acids. These salts have the formula , . O
,::' 11 ., OCR2 Rl - CH- CH2SO3M
10 where Rl is alkyl of about 9 to about 23 carbon atoms (forrning with the two - carbon atoms an alkane group); R2 is alkyl of 1 to about 8 carbon atoms; and - M is a water-soluble cation.
The water-soluble cation, M, in the hereinbefore described structural formula can be, for example, an alkali metal cation (e.g., sodium, potassium, lithium), ammonium or substituted-ammonium cation. Specific examples of substituted ammonium cations include methyl-, dimethyl- and . trimethyl- ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures 20 thereof, and the like.
Specific examples of beta-acyloxy-alkane-1-sulfonates, or alterna-, ~., tively 2-acyloxy-alkane-1-sulfonates, useful herein include the sodium salt of 2-acetoxy-tridecane-1-sulfonic acid; the potassium salt of 2-propionyloxy-tetradecane-l-sulfonic acid; the lithium salt of 2-butanoyloxy-tetradecane-1-; sulfonic acid; the sodium salt of 2-pentanoyloxy-pentadecane-1-sulfonic acid;
the sodium salt of 2-acetoxy-hexadecane-1-sulfonic acid; the potassium salt of 2-octanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-acetoxy-heptadecane-l-sulfonic acid; the lithium salt of 2-acetoxy-octadecane-1-sulfonic acid; the potassium salt of 2-acetoxy-nonadecane-1-sulfonic acid;

30 the sodium salt of 2-acetoxy-uncosane-1-sulfonic acid; the sodium salt of 2-propionyloxy-docosane-1-sulfonic acid; the isomers thereof. -,', ~

-: 10372(~9 Preferred beta-acyloxy-alkane-l-sulfonate salts herein are the alkali metal salts of beta-acetoxy-alkane-l-sulfonic acids corresponding to the above formula wherein Rl is an alkyl of about 12 to about 16 carbon atoms, these salts being preferred from the standpoints of their excellent cleaning properties and ready availability.
Typical examples of the above described beta-acetoxy alkanesulfo-nates are described in the literature: Belgium Patent 650,323 issued July 9, 1963, disclosec the preparation of certain Z-acyloxy alkanesulfonic acids, Similarly, U.S. Patents 2,094,451 issuedSeptember 28, 1937, toGuenther, et al., and 2,086,215 issued July 6, 1937, to DeGroote disclose certain salts of beta-acetoxy alkanesulfonic acids.
~, .; .
Another class of anionic detergent compounds herein, both by virtue of superior cleaning properties and low sensitivity to water hardness (Ca++ and Mg++ ions) are the alkylated ~-sulfocarboxylates, containing about ,t,~ 10 to about 23 carbon atoms, and having the formula O
". Il R - CH - C - OR' .., ~ ;03M

wherein R is C8 to C20 alkyl, M is a water-soluble cation as hereinbefore disclo~ed, preferably sodium ion, and R' is short-chain alkyl, e.g., methyl, ethyl, propyl, and buty~. These compounds are prepared by the esterification of d-sulfonated carboxylic acids, which are commercially available, using standard techniques. Specific examples of the alkylated -sulfocarboxylates for use herein include:
ammonium methyl-~,-sulfopalmitate, triethanolammonium ethyl-~B-sulfostearate, sodium methyl-~-sulfopalmitate, s odium ethyl -~- sulfopalmitate, s odium butyl - c~- s ulfostearate, potassium methyl-o~-sulfolaurate, lithium methyl -o(- s ulfolaur ate, as well as mixtures thereof.

_ 8 -' ` ~037Z(~9 ,' Still another class of anionic organic detergents are the,~3-alkyloxy alkane sulfonates. These compounds have the following formula:
, OR2 H
;. I I .
' R 1 - f - C - S 03M
H H
, where Rl is a straight chain alkyl group having from 6 to 20 carbon atoms, R2 i~ a lower alkyl group having from 1 (preferred) to 3 carbon atoms, and ; M is a water-soluble cation as hereinbefore described.
;; Specific examples of ,B-all~yloxy alkane sulfonates, or alternatively ~ 10 2-all~yloxy-alkane-1-sulfonates, having low hardness (calcium ion) sensitivity , :
,~ useful herein to provide superior cleaning levels under household washing eonditions include:
potassium-R-methoxydecanesulfonate, sodium 2-methoxytridecanesulfonate, '~
~::
potassium 2-ethoxytetradecylsulfonate, sodium 2-isopropoxyhexadecylsulfonate, lithium 2-t-butoxytetradecylsulfonate, sodium ,~3-methoxyoctadecylsulfonate, and ammonium ~-n-propoxydodecylsulfonate.
Additional examples of anionic non-soap synthetic detergents which ` come within the terms of the present invention are the reaction product of fatty acids esterified with isethionie aeid and neutralized with sodium hydroxide 1''~
where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty aeid amides of methyl tauride in which the fatty acids,for example, are derived from eoconut oil. Other anionie synthetic detergents of this variety are set forth in United States Patents 2,486,921; 2,486,922;
and 2,396,278.
` Additional examples of anionic, non-soap, synthetic detergents, which come within the terms of the present invention, are the compounds which 30 eontain two anionic functional groups. These are referred to as di-anionic detergents. Suitable di-anionic detergents are the disulfonates, disulfates, ` or mixtures thereof which may be represented by the following formulae:

_ 9 _ ''.: :

~;

1(~37209 R(S3)2M2~ R(SO4)zM2, R(SO3) (SO4)M2, where R is an acyclic aliphatic hydrocarbyl group having 15 to 20 carbon : .: .
,; ~ atoms and M is a water-solubilizing cation, for example, the Cls to C20 ,,; .:, disodium 1,2-alkyldisulfates, Cls to C20 dipotassium-1,2-alkyldisulfonates ordisulfates, disodium 1,9-hexadecyl disulfates, Cls to C20 dipotassium-1,2-alkyldisulfonates or disulfates, disodium 1,9-hexadecyl disulfates, Cls to C20 disodium-1,2-alkyldisulfonates, disodium 1,9-stearyldisulfates and ~, 1 0-octadecyldisulfates .
The aliphatic portion of the disulfates or disulfonates is generally 10 substantially linear, thereby imparting desirable biodegradable properties to the detergent compound.
The water-solubilizing cations include the customary cations known in the detergent art, i. e., the alkali metals, and the ammonium cations, as well as other metals in group IIA, IIB, IIIA, IVA and IVB of the Periodic :: :
Table except for boron. The preferred water-solubilizing cations are : sodium or potassium. These dianionic detergents are more fully described in British Letters Patent 1,151,392.
Still other anionic synthetic detergents include the class designated ~; as succinamates. This class includes such surface active agents as disodium 20 N-octadecylsulfosuccinamate; tetrasodium N-(l ,2-dicarboxyethyl)-N-octadecyl-sulfo-succinamate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester :
; ~ of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acidO

The preferred surface-active agents for use in the compositions of the instant invention include alkyl ether sulfates and "olefin sulfonates''u The preferred alkyl ether sulfates have the formula Ro(c2H4)xso3M
`I wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30, and M is a salt forming cation such as alkali metal (sodium, lithium, potassium) ammonium, amines and substituted ammonium. Examples of 30 these latter include lower Cl_4 alkyl amines, and mono, di and tri-methanol and ethanolaminesO

, ' 103~2(~ ~
Especially preferred are those alkyl ether sulfates wherein R has from about 14 to about 18 carbon atoms and wherein x has an average value of about 1 to about 6. Specific examples of especially preferred species are:
sodium coconut alkyl ethylene glycol ether sulfate; sodium tallow alkyl tri-ethylene glycol ether sulfate; sodium tallow alkyl pentaoxyethylene sulfate;
ammonium tetradecyl pentaoxyethylene sulfate and ammonium lauryl hexaoxy-ethylene sulfate.
Especially preferred alkyl ether sulfate components have an average (arithmetic mean) carbon chain length within the range of from about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms; and an average (arithmetic mean) degree of ethoxylation of from about 1 to 4 moles of ethylene oxide, preferably from about 2 to 3 moles of ethylene oxide.
Such mixtures comprise from about 0. 05% to 5% by weight of mixture of C12_13 compounds, from about 55% to 70% by weight of mixture of C14_1s compounds, from about 25% to 40% by weight of mixture of C16_17 compounds and from about 0.1% to 5% by weight of mixture of Clg_lg com-pounds. In addition, such preferred alkyl ether sulfate mixtures comprise from about 15% to 25% by weight of mixture of compounds having a degree of ethoxylation of 0, from about 50% to 65% by weight of mixture of compounds having a degree of ethoxylation from 1 to 4, from about 12%to 22%by weight of mixture of compounds having a degree of ethoxylation from 5 to 8 and from about 0~ 5% to 10% by weight of mixture of compounds having a degree of ethoxylation greater than 8.
., . :
Examples of alkyl ether sulfate mixtures falling within the above-! ';- ~
specified ranges are set forth in Table I.

.

3 0 ,':

- 11 - :
' ' `
10372~9 .

. r~
. . ~ oo ~ o ~
E~ ~ ~ . co Ln ~ Lt ~
~i H ~ Ifl ~Y) ~ ~ J ~;
.. .`
' - _ ._ ... _._ ..
~1 , ~ ::
¢ 00 ~ Ln O~ _l h ~ ~ . ~ u~ ~ o ~
E~ ~ ~P ~D ~ ~ ~ ~ ~ Z ':
,':, U~
",: ~ _ ... _ .. ~
H ~ I . ~ ~ ~
H ~ ~ t~ ~ t~ n ~ ~;

~,` .. __ _ ~,',' " ,_1 .
~' ~ ~O ~ CO ~ ~ .' ,,, ¢ ~ _~ ~
~1 ~
:~ ~
` ~- ~o ô o V O ~ ~.

~ .... ~ ~
h.~ bq X ~ o ~ ~oC ~oC ~C
¢~ "a a a a ~ O ~

~Id ~ h h h h ~ ~ co ~) a~- (d (d t~ t~ a.~ O o ~
h ~ ~ ~ a` ~ ~o H ~ 0 t~ 00 ~ ~3 ~ 00 ~
¢ -I ~ l ¢ O ~ V~

,'~

' ~
, .
:` '` : ' ' ` . : - :

~10372~
':
The preferred "olefin sulfonates" utilizable herein have from about 12 to about 24 carbon atoms. Said ingredients can be produced by sulfonation of a(-olefins by means of uncomplexed sulfur dioxide followed by neutraliza-tion in conditions such that any sultones present are hydrolyzed to the corresponding hydroxy-all~ane sulfonates. The o~-olefin starting materials preferably have from 14 to 16 carbon atoms, Said preferred ~-olefin sulfo-; nates are described in great detail in U.S. Patent specification 3,332,880, Adriaan Kessler et al., patented July 25, 1967~
Said ~-olefin sulfonates can be represented either by individual 10 species or by mixtures containing structurally different sulfonation products.
Preferred mixtures are disclosed by Kessler et al.; one such mixture con-sists essentially of from about 30% to about 70% by weight of a Component A, , from about 20% to about 70% by weight of a Component B, and from about ~ ~
; ;.
2% to about 15% of a Component C, wherein ,. ..
1 (a) said Component A is a mixture of double-bond positional isomers,........................................................................ :~
of water-soluble salts of alkene-l-sulfonic acids containing from / ~ about 20 to about 24 carbon atoms, said mixture of positional ,, , isomers including about 10% to about 25% of an alpha-beta , unsaturated i~omer, about 30% to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25% of gamma-delta unsaturated isomer, and about 5% to about 10% of a delta-epsilon unsaturated isomer;
(b) said Component B is a mixture of water-soluble salts of bi-functionally-substituted sulfur-containing saturated aliphatic compounds containing from about 20 to about 24 carbon atoms, ` the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atoms at least 90% of the hydroxy radical substitutions being in 3, 4, and 5 positions; and ': :

..

1037ZC~9 (c) said Component C is a mixture comprising from about 3~-95~10 water-soluble salts of alkene disulfonates containing from about 20 to about 24 carbon atoms, and from about 5% to about 70%
water-soluble salts of hydroxy disulfonates containing from about 20 to about 24 carbon atoms, said alkene disulfonates : . containing a sulfonic group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal " - carbon atom, the alkene double bond being distributed between the I. 10 terminal carbon atom and about the seventh carbon atoms, said "; . ,.
: hydroxy disulfonates being saturated aliphatic compounds having . a sulfonate radical attached to a terminal carbon, a second sulfonate . group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than . . about four carbon atoms removed from the site of attachment of said second sulfonate group.
;~4~
' . Especially preferred for use in the instant compositions are 3-, 4-, and 5-hydroxy alkyl sulfonates and mixtures thereof. Specific examples of 20 9aid hydroxy-sulfonates include sodium salts of sodium 3-hydroxy-n-decyl-1-sulfonate, sodium 3-hydroxy-n-dodecyl-1-sulfonate, ;; sodium 3-hydroxy-n-tetradecyl-1-sulfonate, sodium 3-hydroxy-n-hexadecyl-1-sulfonate, sodium 3-hydroxy-n-octadecyl-1-sulfonate, sodium 3-hydroxy-n-eicosyl-1-sulfonate, sodium 3-hydroxy-n-docosyl-1-sulfonate, sodium 3-hydroxy-n-tetracosyl-1-sulfonate, : . sodium 4-hydroxy-n-decyl-1-sulfonate, : 30 sodium 4-hydroxy-n-dodecyl-1-sulfonate, sodium 4-hydroxy-n-tetradecyl-1-sulfonate, sodium 4-hydroxy-n-hexadecyl-1-sulfonate, . .

r' : 1037209 , ~ sodium 4-hydroxy-n-octadecyl-1-sulfonate, ,: . .
,r, sodium 4-hydroxy-n-eicosyl-1-sulfonate, sodium 4-hydroxy-n-docosyl-1-sulfonate, . sodium 4-hydroxy-n-tetracosyl- 1 -sulfonate, ,?. sodium 5-hydroxy-n-decyl-1-sulfonate, sodium 5-hydroxy-n-dodecyl-1-sulfonate, ~;, :- .
sodium 5-hydroxy-n-tetradecyl-1-sulfonate, s sodium 5-hydroxy-n-hexadecyl-1-sulfonate, , . . .
sodium 5 -hydroxy-n-octadecyl- 1 -sulfonate, ;; 10 sodium 5-hydroxy-n-eicosyl-1-sulfonate, sodium 5-hydroxy-n-dodosyl-1-sulfonate, and `
~; sodium 5-hydroxy-n-tetracosyl-1-sulfonate.
,; Among these preferred species the 4-hydroxy substituent is preferred, e.g.
;, -; for use in combination with 3-hydroxy- and 5-hydroxy-compounds. This ~s~ means that in a binary system of these, the 4-hydroxy is present in excess of 50~o by weight of the active detergent ingredient.
Nonionic Synthetic Deter~ents Most commonly, nonionic surfactants are compounds producedby the condensation of an alkylene oxide (hydrophilic in nature) with an organic hydrophobic compound which is usually aliphatic or alkyl aromatic in nature.
The length of the hydrophilic or polyoxyalkylene moiety which is condensed with any particular hydrophobic compound can be readily adjusted to yield ; a water-soluble compound having the desired degree of balance between hydro-philic and hydrophobic elements. Another type of nonionic surfactants are the so-called polar nonionics derived from amine oxides, phosphine oxides or sulfoxides. Examples of suitable nonionic surfactants include:
(1) The polyethylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain - 30 or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived, . ' :
: ' -; - 15 -: `

. -, : . : , : ~ . . . - -lQ3~7~9 for example, from polymeri~ed propylene, diisobutylene, octene, or noneneO
Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol, dodecyl phenol condensed with about 12 moles of ethylene oxide per mole of phenol, dinonyl ,. .
~ phenol condensed with about 15 moles of ethylene oxide per mole of phenol, :, .
di-isooctylphenol condensed with about 15 moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include "Igepal CO-610" 1 marketed by the GAF Corporation; and "Triton"2 X-45, X-114, X-100 and X-102, all marketed by the Rohm and Haas Company.
(2) The condensation products of aliphatic alcohols with ethylene oxide. The alkyl chain of the aliphatic alcohol may either be straight or branched and generally contains from about 8 to about 22 carbon atoms.
Examples of such ethoxylated alcohols include the condensation product of about 6 moles of ethylene oxide with 1 mole of tridecanol, myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of myristyl alcohol, the condensation product of ethylene oxide with coconut fatty alcohol wherein the coconut alcohol is a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms and wherein the condensate contains about 6 moles of ethylene oxide per mole of alcohol, and the condensation product of about 20 9 moles of ethylene oxide with the above-described coconut alcohol. Examples of commercially available nonionic surfactants of this type include "Tergitol 15-S-9"3 marketedby the Union Carbide Corporation, "Neodol 23-6.5"4 marketed by the Shell Chemical Company and "Kyro EoB"5 marketed by The Procter & Gamble Company.
(3) The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
- The h,vdrophobic portion of these compounds has a molecular weight of from about 1500 to 1800 and of course exhibits water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the 30 water-solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about . ,:
`- 1, 2, 3, 4 and 5 - Trademarks - 16 _ ~i 10372(~9 50% of the total weight of the condensation product. Examples of compounds - of this type include certain of the commercially available "Pluronic" 6 surfactants marketed by the Wyandotte Chemicals Corporation.
,; (4) The condensation products of ethylene oxide with the product ~, resulting from the reaction of propylene oxide and ethylene diamine. The hydrophobic base of these products consists of the react;on product of ethylene diamine and excess propylene oxide, said base having a molecular weight of from about 2500 to about 3000. This base is condensed with ethylene oxide ~, to the extent that the condensation product contains from about 40% to about 10 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available "Tetronic" 7 compounds marketed by the Wyandotte Chemicals Corporation.
(5) Surfactants having the formula RlR2R3N-o (amine oxide sur- -,. ......................................................................... .
factants) wherein Rl is an alkyl group containing from about 10 to about 28 ;
carbon atoms, from 0 to about Z hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of Rl which is an alkyl group containing from about 10 to about 18 carbon atoms and no ether linkages, and each R2 and R3 is selected from the group consisting of alkyl groups and 20 hydroxyalkyl groups containing from 1 to about 3 carbon atoms;
Specific examples of amine oxide surfactants include: dimethyl-dodecylamine oxide, dimethyltetradecylamine oxide, ethylmethyltetradecyl-amine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetyl-ethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyldodecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, ; bix-(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, (2-hydroxy-; propyl)methyltetradecylamine oxide, dimethyloleylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, and the corresponding decyl, hexadecyl and octadecyl homologs of the above compounds.
(6) Surfactants having the formula RlR2R3P-o (phosphine oxide surfactants) wherein Rl is an alkyl group containing from about 10 to about 6 and 7 - Trademarks '' , ,, ~

~^: lQ372~9 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of Rl which is an alkyl group ; containing from about 10 to about 18 carbon atoms and no ether linkages, and each R2 and R3 is selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atomsO
Specific examples of the phosphine oxide detergents include:
dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide, ethyl-, i~ methyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethyl-stearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecyl phosphine oxide, diethyltetradecylphosphine oxide, dipropyldodecylphosphine oxide, dipropyldodecylphosphine oxide, bis-(hydroxymethyl)-dodecylphosphine oxide, bis-(2-hydroxyethyl)dodecylphosphine oxide, (2-hydroxypropyl)methyl-tetradecylphosphine oxide, dimethyloleylphosphine oxide, and dimethyl-(2-hydroxydodecyl)phosphine oxide and the corresponding decyl, hexadecyl, and octadecyl homologs of the above compounds.
(7) Surfactants having the formula Rl - S - R2 (sulfoxide surfactants) wherein Rl is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 5 ether linkages and from 0 to about 2 hydroxyl substituents, at least one moiety of Rl being an alkyl group ; containing no ether linkages and containing from about 10 to about 18 carbon atoms, and wherein R2 is an alkyl group containing from 1 to 3 carbon atcms and from zero to two hydroxyl groups. Specific examples of sulfoxide sur-factants include octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetra-decyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-methoxytri-decyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, octa-decyl 2-hydroxyethyl sulfoxide, and dodecylethyl sulfoxide.
Of all the above-described types of nonionic surfactants, preferred nonionic surfactants include the condensation product of ncnyl phenol with about 9O5 moles of ethylene oxide per mole of nonyl phenol, the condensation product of coconut fatty alcohol with about 6 moles of ethylene oxide per mole ., - 18 _ ;' ':

1~)372(~9 ~ ......
of coconut fatty alcohol, the condensation product of tallow fatty alcohol with , about ll moles of ethylene oxide per mole of tallow fatty alcohol and the S - condensation product of a secondary fatty alcohol containing about 15 carbon - atoms with about 9 moles of ethylene oxide per mole of fatty alcohol. Ampholvtic Synthetic Detergents s Ampholytic synthetic detergents can be broadly described as deriva-tives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 10 8 to 18 carbon atoms and at least one contains an anionic water-solubilizing -- group, e.g., carboxy, sulfonate, sulfato. Examples of compounds falling within this definition are sodium 3-(dodecylamino)-propionate, sodium 3-(dodecylamino)propane-l-sulfonate, sodium 2-(dodecylamino)ethyl sulfate, ~; sodium 2-(dimethylamino)octadeconoate, disodium 3-(N-carboxymethyldodecyl-amino)-propane-l-sulfonate, disodium octadecyl-iminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N,N-bis(2-hydroxyethyl)-2-; sulfato-3-dodecoxypropylamine. Sodium 3-(dodecylamino)propane-1-sulfonate is preferred.
Zwitterionic Synthetic Deter~ents Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amine, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary ` phosphonium or tertiary sulfonium compounds. The cationic atom in the quaternary compound can be part of a heterocyclic ring. ~ all of these com-; ~ pounds there is at least one aliphatic group, straight chain or branched, containing from about 3 to 18 carbon atoms and at least one aliphatic sub-stituent containing an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfato, phosphato, or phosphono. Examples of various classes of i zwitterionic surfactants operable herein are described as follows:
Compounds corresponding to the general formula (R2) Rl Yl - R3 - Z
`':' , . .. . . .
": ~ ,,,, , " ,, ,:, ~ , , , "

10372(~9 wherein Rl is alkyl, alkenyl or a hydroxyalkyl containing from about 8 to about 18 carbon atoms and containing if desired up to about 10 ethylene oxide ~ moieties and/or a glyceryl moiety; Yl is nitrogen, phosphorus or sulfur, "/ - R2 is alkyl or monohydroxyalkyl containing 1 to 3 carbon atoms; x is 1 when Yl is S, 2 when Yl is N or P; R3 is alkylene or hydroxyal~ylene containing from 1 to about 5 carbon atoms; and Z is a carboxy, sulfonate, sulfate, phosphate or phosphonate group. Examples of this class of ~witterionic s urfactants include 3 - (N, N - dimethyl -N -hexadecylammonio ) -pr opane - 1 -sulfonate; 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-10 sulfonate; 2-(N,N-dimethyl-N-dodecylammonio)acetate; 3-(N,N-dimethyl-N-dodecylammonio)-propionate; 2-(N,N-dimethyl-N-octadecylammonio) ethane-l-sulfate; 3-(P,P-dimethyl-P-dodecylphosphonio)propane-l-sulfonate;
' 2 - (S -methyl -S -tert -hexadecylsulfonio )ethane - 1 - sulfonate; 3 - (S -methyl -S -dodecylsulfonio)propionate; 4-(S-methyl-S-tetradecylsulfonio)butyrate;
3-(N,N-dimethyl-N-4-dodecenylammonio)propane-1-sulfonate: 3-(N,N-dimethyl-N-2-diethoxyhexadecylammonio)propane - 1 -phosphate; and 3 - (N, N-dimethyl-N -4-glyceryldodecylammonio)propionate .
, Preferred compounds of this class from a commercial standpoint are 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate;
20 3-(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate, the alkyl group being derived from tallow fatty alcohol; 3-(N,N-dimethyl-N-hexadecyl-armmonio )pr opane - 1 - s ulfonate; 3 - (N, N - dimethyl -N -tetrade cylammonio ) -~ propane-l-sulfonate; 3-(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-i l-sulfonate, the alkyl group being derived from the middle cut of coconut :.. .
fatty alcohol; 3 - (N, N-dimethyldodecylammonio) - 2 -hydroxypr opane - 1 -sulfonate; 4-(N,N-dimethyl-tetradecylammonio)butane-l-sulfonate; 4-(N,N-dimethyl-N-hexadecylammonio)butane-l-sulfonate; 4-(N,N-dimethyl-`` hexadecylammonio)butyrate; 6-(N,N-dimethyl-N-octadecylammonio)hexa-noate; 3-(N,N-dimethyl-N-eicosylammonio)-3-methylpropane-1-sulfonate;
30 and 6-(N,N-dimethyl-N-hexadecylammonio)hexanoate.

Means for preparing many of the surfactant compounds of this class ,~ are described in U. S. Patents 2, lZ9,264, 2,774,786, 2,813,898, 2,828,332 and 3,529,521 and German Patent 1,018,421.
``"' ,, ~' 10372~
~; Compounds having the general formula: -wherein R4 is an al~yl, cycloalkyl, aryl, aralkyl or alkaryl group containing ,: . .
from 10 to 20 carbon atoms; M is a bivalent radical selected from the group `
consisting of aminocarbonyl, carbonylamino, carbonyloxy, aminocarbonyl-amino, the corresponding thio groupings and substituted amino derivatives:
Rs and R8 are ah~ylene groups containing from 1 to 12 carbon atoms; R6 is 10 alkyl or hydroxyalkyl containing from 1 to 10 carbon atoms; R7 is selected from the group consisting of R6 groups R4-M-R5-, and -RgCOOMe wherein R4, Rs, R6 and R8 are as defined above and Me is a monovalent salt-forming cation. Compounds of the type include N,N-bis(oleylamidopropyl)-n-methyl-N-carboxymethylammonium betaine; N, N-bis (stearamidopropyl)-N-methyl-N-carboxymethylammonium betaine; N-(stearamidopropyl)-N-dimethyl-N-carboxymethylammonium betaine; N, N-bis (oleylamidopropyl) -N- (2 -hydroxy-ethyl)-N-carboxymethylammonium betaine; and N-N-bis-(stearamidopropyl)-.: .
N- (2 -hydroxyethyl) -N-carboxymethylammonium betaine . Zwitterionic surfactants of this type are prepared in accordance with methodR described 20 in U. S. Patent 3, 265, 719 and DAS 1, 018, 421 .
Compounds having the general formula R9 - CH - (CH2)n - CH - S0~33 N~
:,' /1 \
Rll R12 R13 wherein Rg is an alkyl group, Rlo is a hydrogen atom or an ah7~yl group, the total number of carbon atoms in Rg and Rlo being from 8 to 16 and / IN\ represents a quaternary ammonio group in which each Rll R12 R13 30 group Rll, R12 and R13 is an alkyl or hydroxyalkyl group or the groups Rll, R12 and R13 are conjoined in a heterocyclic ring and n is 1 or 2. Examples of suitable zwitterionic surfactants of this type include the ~ and ~ hexadecyl .'.

.' ;, , . .. - . , -` ~L0372~9 pyridino sulphobetaines, the y and ~ hexadecyl l~-picolino sulphobetaines, the ~ and ,~ tetradecyl pyridino sulphobetaines and the hexadecyl trimethyl-ammonio sulphobetaines. Preparation of such zwitterionic surfactants is described i~ published South African patent application 69/5788.
- Compounds ha~ring the general formula ,.~ R16 wherein R14 is an alkarylmethylene group containing from about 8 to 24 10 carbon atoms in the alkyl chain; Rls is selected from the group consisting of R14 groups and alkyl and hydroxyalkyl groups containing from 1 to 7 carbon atoms; R16 is alkyl or hydroxyalkyl containing from 1 to 7 carbon ; -,~ atoms; R17 is alkylene or hydroxyalkylene containing from I to 7 carbon atoms and Zl is selected from the group consisting of sulfonate, carboxy and sulfate. Examples of zwitterionic surfactants of this type include 3-(N-dodecylbenzyl-N,N-dimethylammonio)propane-l-sulfonate; 4-(N-dodecyl-benzyl-N, N-dimethylammonio)butane- 1 -sulfonate; 3-(N-hexadecylbenzyl-N,N-dimethylammonio)propane-l-sulfonate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)propionate; 4-(N-hexadecylbenzyl-N,N-dimethylammonio~
20 butyrate; 3-(N-tetradecylbenzyl-N,N-dimethylammonio)propane-I-sulfate;
3-(N-dodecylbenzyl-N,N-dimethylammonio)-2-hydroxypropane- l-sulfonate;
3-[N,N-di(dodecylbenzyl)-N-methylammonio]propane-l-sulfonate; 4-[N,N-dithexadecylbenzyl)-N-methylammonio]-butyrate; and 3-[N,N-di(tetradecyl-benzyl)-N-methylammonio]-2-hydroxypropane-1-sulfonate.
Zwitterionic surfactants of this type as well as methods for their preparation are described in U. S. Patents 2,697,116; 2,697,656 and , ~ 2,669,991 and Canadian Patent 883,864.
Compounds having the general formula ,'~`` ., :

R187N/33 - ~C~ - R23 - S3(~

~ R20 R21 R22 :~ :

. ,' ,; wherein Rlg is an alkylphenyl, cycloalkylphenyl or alkenylphenyl group containing from 8 to 20 carbon atoms, in the alkyl, cycloalkyl or alkenyl moiety; Rlg and R20 are each aliphatic groups containing from 1 to 5 carbon atoms; R21 and R22 are each hydrogen atoms, hydroxyl groups or aliphatic groups containing from 1 to 3 carbon atoms and R23 is an alkylene group containing from 2 to 4 carbon atoms. ;~
Examples of zwitterionic surfactants of this type include 3-(N-dodecylphenyl-N,N-dimethylammonio)propane-l-sulfonate; 4-(N-hexadecyl-phenyl-N,N-dimethyl)butane-l-sulfonate; 3-(N-tetradecylphenyl-N,N-10 dimethylammonio)-3, 3 -dimethylpropane -1 -sulfonate and 3-(N-dodecylphenyl-N,N-dimethylammonio)-3-hydroxypropane-1-sulfonate. Compounds of this type are described more fully in British Patents 970,883 and 1,046,252.
Of all the above-described types of zwitterionic surfactants, preferred compounds include 3(N,N-dimethyl-N-alkylammonio)propane-1-sulfonate and 3(N ,N-dimethyl-N-alkylammonio)-2-hydroxypropane- l-sulfonate wherein in both compounds the alkyl group averages 14. 8 carbon atoms in length; 3(N,N-dimethyl-N-hexadecylammonio)propane-l-sulfonate; 3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane- 1 -sulfonate; 3-(N-.; dodecylbenzyl-N,N-dimethylammonio)propane-l-sulfonate; (N-dodecylbenzyl-20 N,N-dimethylammonio)acetate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)-- propionate; 6-(N-dodecylbenzyl-N,N-dimethylammonio)hexanoate; and (N, N -dimethyl-N-hexadecylammonio)acetate .
Y~-. The operable substantially water-insoluble particulate component for use in the compositions of the instant invention is identified by a series of characteristics; namely, (1) an average particle size from about 1.0 to about 50, preferably from about 5 to about 30 micrometers; (2) a shape having an anisotropy of about 5:1 to 1:1; (3) a hardness of less than about 5.5 on the Mohs scale; (4) a melting (softening) temperature above about 150C; and (5) substantial freedom from exchangeable calcium and magnesium ionsO
Said particulate component is used in the instant compositions in an ; amount from about 0. 05% to about 10%, preferably from about 0.1% to about 6%, more preferably, from about 0.2%to about 4%. Above the upper limit, .:`

. .

11~)37Z09 the previously enumerated fabric benefits can be diminished or even elimi-nated to the extent that undesirable stiffness and harshness to fabrics ' treated with the instant compositions occurs.
- The average particle size of the substantially water-insoluble - particulate compcnent is within the range from about 1 to about 50, prefer-ably from about 5 to about 30 micrometers. Although no certain explanation is available as to why the specified range of diameters is required, the particle diameter limitation seems to relate to the diameters of (commer-cially) available textile fibers which fall mostly within the range of about 10 10 to about 30 micrometers. Accordingly, the use of particulate water-insoluhle materials having an average diameter of more than about 50 micro-meters will not procure the fabric benefits enumerated hereinbefore. On the other hand, the use of particulate water-insoluble materials having an average particle size diameter of less than about 1 micrometer can, under c ertain cir cumstanc e s, pr ovide s ome of the individual advantage s r eferr e d to hereinbefore but by no means will provide the overall fabric benefits as can be obtained from the conventional use of the compositions as claimed.
The substantially water-insoluble particulate component is further characterized by an anisotropy (axial ratio) of about 5:1 to 1:1. The 20 determination of particle size can be based on the measurement of the pro-jection area of the water-insoluble particle or on the linear measures of , this projection area. Or, in other words, the loose particle resting on its surface of maximum stability, the long and intermediate axis are normally horizontal and the short axis vertical. In that context, the term "long axis"
represents the maximum overall length of the particle; "intermediate axis"
stands for the maximum dimension of a particle in a direction perpendicular to the long axis; whereas "short axis" represents the maximum dimension in a direction perpendicular to the plane containing the long and intermediate axis. The meaning of anisotropy represents the ratio of long axis to short 30 axis for a specific particulate material. Preferred for use in the composi-tions of this invention are particulate materials having an anisotropy within -the range from about 3:1 to about 1.1:1.
. ~ .

j. ~
s ~.0372~9 See also: Advances in OPTICAL and ELECTRON MICROS50PY, Vol. 3, R. Barer and V.E. Cosslett, ACADEMIC PRESS 1969, London and New York.
The essential particulate component for use herein has a hardness ~
of less than about 5.5 on the Mohs scale. The hardness as so measured is ~- -a criterion of the resistance of a particular material to crushing. It is known as being a fairly good indication of the abrasive character of a particulate ingredient. Examples of materials arranged in increasing order -of hardness according to the Mohs scale are as follows: h(hardness)-l:talc;
dried filter~press cakes, soap-stone, waxes, aggregated salt crystals;
h-2: gypsum, rock salt, crystalline salt in general, barytes, chalk, brim-stone; h-4: fluorite, soft phosphate, magnesite, limestone; h-5: apatite, hardphosphate, hardlimestone, chromite, bauxite; h-6: feldspar, ilmenite, hornblendes; h-7: quartz, granite; h-8: topaz; h-9: corrundum, emery;
and h-10: diamond.
Suitable particulate materials have a hardness of less than about 50 5 on the Mohs Acale. Although some fabric care benefits can be obtained from particulate materials having a Mohs hardness of, for example 7, as regards overall benefits, said particulate materials do not qualify for use ., ` ~ 20 in the instant compositions. Apparently, excessive particle hardness causes , fiber and yarn damage which adversely affect the fabric, particularly through ;, cumulative action resulting from multicycle laundering and washing operations.
The substantially water-insoluble particulate material has a melting point above about 150C (300F). Particulate materials having a melting point below that temperature do not provide the fabric benefits because of their tendency to melt in the course of ironing and accordingly spread through the fabric thereby giving body to the fabric which is commonly known as sizing. This is per se undesirable in the context of this invention and the particulate materials must be such as to maintain under ironing conditions, i.e., around 150C, their integrity and shape as said characteristics are essential for the attainment of the fabric care benefits derivable from the use of the compositions of the instant invention.

.

~i In addition, the particulate material must be substantially water-insoluble as its function in the context of the present invention depends upon its integrity, shape, firmness, etc. as described in detail hereinbefore.
'- It should be recognized, however, that minor parts of the particulate ingredient, for example, less than 20%, can be water dispersible and/or water soluble without markedly decreasing the performance advantages.
The water~insoluble particulate materials are substantially free of exchangeable calcium and magnesium ionsO Apparently, the presence of exchangeable alkaline earth metal ions such as calcium and magnesium in 10 the particulate materials increases their hydrophilic properties. This results in enhanced swellability characteristics, which, in turn, constitute . . .
an obstacle to the uniform and stable enmeshing of particulate material within the fiber structure. As a result, particulate materials having ex-changeable calcium and magnesium ions in their structure may contribute to the attainment of some fabric-care benefits, but detract from attaining ; overall fabric benefits as described hereinabove.
Particularly preferred for use in the instant compositions are -starch derivatives such as surface-modified starches bearing hydrophobic ' moieties which have been reacted with the starch molecule to form ester 20 and ether linkages. As a result of its chemical modification, this starch derivative is water-repellent and accordingly substantially water-insoluble.
, Such starch derivatives are commercially available under the trademark DRY-FLO from National Starch Products Co. DRY-FLO starches have an average particle size diameter of about 9-11 micrometers.
Additional substantially water-insoluble particulate materials suitable for use in the compositions of the instant invention include:

. " .' ' :

- : . . . . : . - -..
...
. .~, O
N ~
d u~ d P~ d '': o . ~ o -. ~ a a) a~ oo ooO O I ~O O I I In ~ ^
.' ~,N ~ 1~ I I d . ~" d .-. ¢ o '" V .~

, " ^ h N
, ~ ~ N .

V V ov ~ N

¦ V V N ~ o o N

--~ N ~ ~ p~ h ,~ ,~ h ... ~ , .
.. ~
; ~ ~;

^ d ~";\. _, o ~ d ~ V . ~d a E ~ z d O-' ' : ' : '' :.'' .
:.

..

: 1037Z~9 ! Average Particle Range Particle ~, In~redient Size ~m Size,~m -fine glass microballoons (EC C OSPHERES ) (4) 8 5 - 15 -glass beads PF 12-R
' (coated) (5) 17 5-45 - -glass beads PF-ll (5) 30 10-50 -glass beads (unispheres) (5) 22 15-37 -glass microballoons (ECCOSPHERES IG) (4) 30 ---glass beads PF-12 (5) 17 5-44 -glass beads PF-12S (5) 17 --; (4) Emerson & Cuming; Caton, MassO
(5) Cataphote Corp.; Jackson, Misso See also: (1) Technical Data Sheet for "Teflon" 7A; and brochure ; re "Typical Properties Common to All Granular "Teflon" FFE-Fluorocarbon ; .; .
Resins", NoO A-43044; both being issued by E.Io DuPont de Nemours &
Company; (2) Catalog of Small Glass Beads, issued by Microbeads Division, Cataphote Corporation, Jackson, Mississippi; particularly documents 20 MB-Ill-DS-5/72; MB-IV-DS-5/72; MB-V-5/72; and MB-VIII-LP-5/72; and (3) Technical Information Brochure concerning ECCOSPHERES~), hollow glass and ceramic microspheres, MICROBALLOONS *, issued by Emerson & Cuming , Inc., Canton , Massachusetts .
Another substantially water-insoluble particulate component for use in the instant compositions is a starch granule having, in addition to the essential parameters as defined in the claims, a swelling power of less than about 15 at a temperature of 65C. Modification of the starch granules in a matter such as to render it more soluble by gelatinizing, derivatizing, or degrading is to be avoided to the extent it leads to starches which can lose 30 their firm shape and also do not qualify for use in the present invention.
Soluble or gelatinizable starches having a swelling power of more than about 15 at 65C are less suitable as they tend to lose their individual shape and , consequently run into the fiber which, in turn, leads to undesirable stiffness ` of fabrics.
* Trademark.

.
-28 _ : :-,........ .. , . ., . . .- , -~.,., : . . . . - - : - .

The swelling power is determined according to the method set forth in Cereal Chem., 36, pp. 534-544 (1959) Harry W, Leach, et al. Ten grams of starch is suspended in 180 ml. of distilled water in a tared 250-ml.
centrifuge bottle. The suspension is mechanically stirred with a small stainless-steel paddle (0.75-in. wide, 105-inO high) at a rate just sufficient to keep the starch completely suspended (iOe., 200 r.p.m. ) This low speed avoids shearing the fragile swollen granules and consequent solubilization of the starchO The bottle is lowered into a thermostatted water bath main-tained at a temperature of 65C (+ 0.1C) and held for 30 minutes, slow 10 stirring being continued during this period. The bottle is then removed, wiped dry, and placed on the torsion balanceO The stirrer is removed and - rinsed into the bottle with sufficient distilled water to bring the total weight of water present to 200.0 gO (including the moisture in the original starch).
The bottle is stoppered, mixed by gentle shaking, and then centrifuged for 15 minutes at 2200 r.p.m. (iOeO, 700 times gravity). The clear supernate is carefully drawn off by suction to within 1/4 inO of the precipitated paste.
An aliquot of this supernate is evaporated to dryness on the steam bath and then dried for 4 hours in the vacuum oven at 120C. The percentage of solubles extracted from the ~tarch is calculated to dry basis. The remaining Z0 aqueous layer above the sedimented starch paste is then siphoned off as quantitatively as possible. The bottle and paste are reweighed on the torsion balance, and the swelling power calculated as the weight of sedimented paste per g. of dry-basis starch.
Starches having a swelling power of more than 15 at 65C are not suitable for use in the instant composition. Although the final choice of starch which will meet requirements of this invention depends upon the origin of the material and also upon process conditions such as bleaching, degradation, and isolation applied to a given species, suitable starches can, for example, be obtained from corn, wheat, and rice. Current potato and tapioca starches 30 have a swelling power exceeding 15 at a temperature of 65C and, therefore, .. .
are not suitable for being used in the compositions of this invention. More -- complete information concerning water-insoluble starches, the processes ., 0372(~
for their preparation and isolation from a variety of raw materials are well kno~,vn [see, for example: 1~, Knight, J.W., Pergamon Press, London (1969)]o As explained hereinafter, however, without being limited as a result thereof, it is thought that the parameters of the particulate material ;- for use in the instant compositions are essential to the extent that said characteristics directly contribute to the beneficial fabric properties.
These critical limitations as to the nature of the particulate material were determined initially by actual experimentation. While appli-lO cants will not be held by any theoretical interpretation of these criticallimitations, it appears that the particulate material interacts with the textile material at the fiber level to impart the above enumerated benefits to the `~
textile fabric as a whole. In this respect it is to be noted that textile materials consist essentially of assemblies of fine flexible fibers arranged in more or less orderly geometrical arrays. Individual fibers within the assembly are usually in a bent or twisted configuration and are in various states of contact with neighboring fibersO When the assembly is deformed ~; the fibers move relative to each other and this relative motion accounts to a large extent for the characteristic flexibility of textile materials. To what 20 extent a given textile material will recover when a deforming force is removed is largely determined by the nature of the interaction of the individual fibers making up the textile material. Textile fibers are viscoelastic and hence will exhibit delayed recovery from strain. However, the large number of interfiber contact points provide frictional restraints which further hinder the recovery process. In most textile structures the area of interfiber contact is probably less than 1% of the total fiber area. The force per contact point is generally estimated to be within the range of 1 to 10 dynes.
It is with this view of textile materials that applicants hypothesis going to explain the efficacy of particulate materials in imparting the related 30 effects of anti-wrinkling, ease of ironing, softness, anti-static benefits and `
appearance improvements can be appreciated. For purpose of conceptualiza-tion, this hypothesis will hereinafter be referred to as the "ball bearing effect".
. ~ .

: `:.
. .~ . - .. , : .. , - ~ , , :

The conceptualization is useful in interpreting the interaction of the particu-late material and the textile matrix under imposed forces of cleformation.
By means of microscopic analysis and staining techniques, it has been determined that textile fabrics treated in accordance with the present invention are characterized by having discrete particulate materials intimately dispersed, in a substantive fashion, in the interstices of the fiber matrix. It is believed that these particulate materials, so interfiberly positioned, act in the manner of ball bearings to reduce interfiber forces during deformation of the textile fabric as a whole. The gross effect is the enhancement of viscoelastic recovery (anti-wrinkling effect) and diminution of the forces operable at interfiber contact points (ease of ironing effect)O
Under this conceptualization, and as already referred to hereinbefore, the particle diameter limitation is appreciated since most commercially available textile fibers have diameters which fall within the range of about 10 to about ':
30 micrometers. Therefore, to be effective, the particulate material of the invention must preferably be comparable to the textile fiber diameters.
The above-mentioned benefits are similarly related to the presence of the particulate material at points within interstices of individual fiber yarns. Microscopic examination of textile yarns in cross section reveals that textiles treated in accordance with the present invention have greater - yarn diameters than similar textile yarns which are distinguishable by the absence of particulate materialsO Apparently, the particulate materials positioned in the interfiber spaces effectively open up the yarn (apparent -~ increase in bulk) resulting in a softer, fluffier textile fabricO The anti-static benefit appears to be related to a change in resistivity of the fabric matrix containing the particulate materials; for example, the copresence of chemically modified starch granules such as DRY-FLO starch, in the textile fabric increases the equilibrium moisture content of the matrix, thereby . .
decreasing its resistivity and diminishing static build-upo The particulate material can be admixed with a previously prepared detergent, or can be sprayed onto a previously prepared detergent formulation just prior to packaging. But in every case, the admixing step is subsequent .,' .

' ` 1037209 to any step, for example, heating, which might alter the native granular integrity of the particulate material.
Detergent builder salts can also advantageously be employed in the , compositions of the present invention. Suitable builder salts can be in-organic or organic in nature and can be selected from a wide variety of known ~` builder salts; said builders are normally used in an amount from about lO~o ~::
to about 60~1o~ preferably from about 10% to about 40%. The weight ratio of organic surface-active agent to detergent builder salt is normally from about ;
20:1to 1:20,andpreferablyfrom 10:1 to 1:10. Suitable alkaline, inorganic 10 builder salts include alkali metal carbonates, aluminates, phosphates, poly-phosphates and silicates. Specific examples of these salts are sodium or ` potassium tripolyphosphates, aluminates, carbonates, phosphates and hexamethaphosphates. Suitable organic builder salts include the alkali metal, ammonium and substituted ammonium polyphosphonates, polyacetates, and polycarboxylates.
The polyphosphonates specifically include the sodium and potassium salts of ethylene diphosphonic acid, sodium and potassium salts of ethane-l-hydroxy-l, l-diphosphonic acid and sodium and potassium salts of ethane-l, 1,2-triphosphonic acid~ Gther examples include the water-soluble [sodium, 20 potassium, ammonium and substituted ammonium (substituted ammonium, as used herein, includes mono-, di-J and triethanol ammonium cations)] salts .; . '~
of ethane-2-carboxy-1,1-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,1J3J3-tetraphosphonic acid, propane-1,1,2-3-tetraphosphonic acid. Examples of these polyphos-phonic compounds are disclosed in British Patents 1,026,366; 1J035J913;
1J129J687; 1J136J619; and 1J14OJ98O.
.
The polyacetate builder salts suitable for use herein include the sodiumJ potassium lithium, ammonium, and substituted ammonium salts of -~
30 the following acids; ethylenediaminetetraacetic acid, N-(2-hydroxyethyl)-ethylenediaminetriacetic acid N- (2 -hydroxyethyl) -nitrilodiacetic acid, diethyl-enetriaminepenta~cetic acid, 1,2-diaminocyclohexanetetraacetic acid and nitrilo-triacetic acid. The trisodium salts of the above acids are generally preferred.

". , i ..
- 32 _ . . : . . :, : .

`` 1037Z0~
` The polycarboxylate builder salts suitable for use herein consist ., of water soluble salts of polymeric aliphatic polycarboxylic acids as, for example, described in U.S. Patent 3,308,067 to F.L. Diehl, patented March 7, 1967.
- Preferred detergent builder salts for use in the compositions of the instant invention include the water-soluble salts of: (l) amino polycar-boxylates; (2) ether polycarboxylates; (3) citric acid; and (4) aromatic poly-carboxylates derived from benzene. These preferred detergent builder salts are preferably used in an amount from about 10% to about 40%.
The water-soluble amino-polycarboxylate compounds ha~e the structural formula R - IN
CHzC OOM
wherein R is selected from:
-CHzCOOM; -CH2CHzOH; and -CH2CH2N \
, . .
R~

Z0 wherein R' is -CH2CH2OH, -CH2COOM, or - CHzCH2N\

- and each M is selected from hydrogen and a salt-forming cationO
These materials include the water-soluble aminopolycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2-hydroxyethyl)nitrilodiacetates. Especially preferred are water-soluble salts of nitrilotriacetic acid.
The water-soluble "ether polycarboxylates" have the formula:

o/ 1 1~372(~9 . wherein Rl is selected from:
CH2COOM; -CH2CH2COOM; and ~:
COOM COOM COOM COOM ~ .
- C = C - ; and - CH - CH
and R2 is selected from:
-CH2COOM; -CH2CH2 COOM; - fH - CHz ; :
: ", C OOM OOM
; -~
/C OOM C OOM ,C OOM ~:
- C H ; - C = C - ; and COOM
: C OOM C OOM ~ -,,: I .: -: -CH - CH
. whereby Rl and R2 form a closed ring structure in the event said moieties : :
;. ~ : .
are selected from .
COOM COOM COOM COOM
... - C = C -; and - CH - CH ; and :: ,.
each M is selected from hydrogen and a salt-forming cation.
Specific examples of this class of carboxylate builders include the : :. ;, water-soluble salts of oxydiacetic acid having the formula .~ . :
.~ 20 CH2COOM
''' 0/ ; '' ""

oxydisuccinic acid having the formula ; -,~.. , ... ~ :
:, C OOM COOM :, bH CH2 <CH - CH2 C OOM C OOM
- carbox~r methyl oxysuccinic acid having the formula . 30 .' ~ . .
, ~ .
- 3 4 - . .

. .

~ ` :
10372C~3 ÇOOM f OOM

CH - CHz .;:` \
,~ CH2 - C OOM
furan tetracarboxylic acid of the formula COOM COOM
C -~ C
' \C-- 1 COOM COOM
- and tetrahydrofuran tetracarboxylic acid having the formula COOM Cl OOM ~;
~1H - CH ;
,', \ I ~
ÇH - CH

C OOM b OOM

- The salt-forming cation M can be represented, for example, by alkali metal cations such as potassium, lithium and sodium and also ammonium and ; ~ ammonium derivatives.
.. . .
Water-soluble polycarboxylic builder salts derived from citric acid ; constitute another class of a preferred builder for use herein. Citric acid, also known as 2-hydroxy-propane-l,Z,3-tricarboxylic acid, has the formula ^

C(OH)~ COOH
I
CHz- COOH

Citric acid while it occurs in free state in nature, large quantities ". ~., .
of it are produced, for example, as a by-product of sugar departing from .: .
sugar beets. For use in the compositions of this invention, it can be desir-able to use the acid and partially neutralized species whereby the neutralizing 30 cation is preferably selected from alkali metal ions such as sodium, potas-- sium, lithium and from ammonium and substituted ammonium such as mono-, di-, and trimethylolammonium and also mono-, di-, and triethanolammonium cations .

- _ . ; , : ~ . ., 10372~9 Water-soluble salts of mellitic acid, benzenepentacarboxylic acid and mixtures thereof constitute another class of preferred p~lycarboxylate `
builders for use in the subject compositions.
A particular aspect of the present invention encompasses a method of simultaneously cleansing and imparting beneficial characteristics to fabrics. To that end, suitable treating liquors will normally contain:

In parts per million (ppm) of treatin~ liquor Es pe c ially Preferred Preferred 10 Organic surface-active agent 10-10,00040-6,000 60-4,000 Particulate material 0.2-1,0001-600 2-400 :, The organic surface-active agent and particulate material species `~
suitable for being used in the method embodiment are identical to those which fit the requirements of the composition aspects of this invention; said species are described in great detail hereinbefore.
In a preferred method aspect, fabrics are treated in an aqueous `
, liquor comprising, in addition to the essential organic surface-active agents and particulate material referred to hereinbefore, as well as from about 50 ppm to about 6000 ppm, preferably from about 50 ppm to about 4000 ppm, 20 of a detergent builder salt.
.
The aqueous washing liquor used for carrying out the method of this invention can, for example, be prepared by adding to a substantially : aqueous medium, laundry formulations corresponding to the detergent compo-sitions encompassed in this invention~ Similar results are obtained, however, .::
by adding the individual ingredients to an aqueous mediumO As an example thereof, one can add to the aqueous medium a granular detergent composition containing all ingredients except the particulate material which is added ~ ` -separately. It is also possible to prepare a detergent composition containing actives and other usual ingredients, adding the particulate material in combina-30 tion with fillers such as sodium sulfate or with builders such as sodium carbonate.

:` :

. : . .: . . . . ,. ~ , ~03720~
In the foregoing, the essential ingredients which are contained in the detergent formulations of this invention are described in detail. Cther optional components such as detergent builder salts have been described in detail as well. In addition to said ingredients, however, in the finished detergent formulations of this invention, there can be added major amounts of other optional detergent composition ingredients which make the product more effective and more attractive. So, for example, organic and inorganic peroxy bleach compounds can be incorporated in these compositions in an amount from about 5% to about 40%.
- 10 The peroxy bleach compound can be any of the usual inorganic and organic ingredients which are known to be satisfactory for being incorporated for that purpose in detergent compositions. Examples of inorganic peroxy bleach compounds are the alkali metal salts of perborates, percarbonates, persilicates, persulfates, andperphosphates. As is wellknown, the per-:
borates can have different degrees of hydration. Although frequently the tetra hydrate form is used, it is for certain purposes desirable to incorporate -~ perborates having a lower degree of hydration water, for example, one mole, two moles, or three moles. Organic peroxy bleach agents may be used as well. The like ingredients can be incorporated as such, i.e,, they have 20 been prepared previously or they may be prepared in situ through the addition of, for example, any peroxy bleach agents suitable for being used in combina-tion with an organic peroxy bleach activator~
Specific examples of the organic peroxy bleach compounds are the water-soluble salts of mono- and di-peroxy acids such as perazelaic acid, monoperoxy phthalic acid, diperoxy terephthalic acid, 4-chlorodiperoxy-phthalic acid. Preferred aromatic peracids include the water-soluble salts of diperiosphthalic acid, m-chloroperbenzoic acid and p-nitroperbenzoic acid.
In the event the peroxy bleach compound is to be prepared in situ, then its precursors, i.e., the peroxy bleach agent and peroxygen activators - 30 are to be added separately to the detergent composition. The peroxygen bleach can be represented by all oxygen bleaching agents which are commonly used in detergent technology, i.e., organic and inorganic species, as :

lQ37Z09 mentioned hereinbefore. The activating agents can be represented by all oxygen activators known as being suitable for use in detergent technology.
Specific examples of the preferred activators include acylated glycoluriles, tetra-acetyl methylene diamine, tetra-acetyl ethylene diamine, triacetyl isocyanurate and benzoylimidazole. Acid anhydride activators which bear at least one double bond between carbon atoms in ~ ,~1 to the carbonyl group of the anhydride radical can be used as wellO Examples thereof are phthalic and male ic anhydr ide s O
In the event the peracid is prepared in situ, then the molar ratio 10 of peroxygen bleach agent to bleach activator shall preferably be in the range from about 5:1 to 1:2, especially from 2:1 to 1:102. .
'~ Other detergent composition ingredients used herein include suds regulating agents such as suds boosters and suds suppressing agents, tarnish inhibitors, soil suspending agents, buffering agents, additional enzymes, -~
brighteners, fluorescers, perfumes, dyes and mixture. The suds boosters can, e.g., berepresentedbydiethanolamidesO Silicones, hydrogenatedfatty , acid, and hydrophobic alkylene oxide condensates can be used in the like - compositions for suds suppressing purposes or, more generally, for suds ;
; regulating purposesO Benzotriazole and ethylenethiourea can be used as ;, . .. ~., 20 tarnish inhibitors. Carboxymethyl cellulose is a well-known soil suspending ,~
agent. In addition to the initial proteolytic constituents, different enzymes such as amylase can be added as wellO The above additional ingredients, when used in the instant compositions, are employed in the usual conventional concentrations O i As indicated earlier, there is no criticality as to combining the above-mentioned components in preparation of the detergent compositions of this invention other than the requirement that the particulate component ultimately be represented in discrete granular form in the environment of the laundering liquor. As mentioned earlier, if the composition is in granular 30 or flaked form, the particulate material is merely admixed in dry form or sprayed on from a non-heated aqueous dispersion. In detergent compositions of liquid form, the particulate ingredients are likewise merely added in proper proportionO

- 38 _ 103720~
In order to evaluate the detergent compositions of the present invention, it was necessary to perform certain tests upon textile fabrics -~ treated in accordance with the present invention. The manner of these tests is set forth below.
Anti-Static Test A bundle of mixed fabrics (ca. 53% all-cotton; 12% 65/35 polyester/
cotton blend; 17% nylon; 18% "Dacron"*) is washed for 10 minutes in a miniature agita~;or washer containing two gallons of aqueous washing liquor containing the test laundry compositions (as set forth below). The laundering 10 temperature is 100F; water hardness 7 grains/gallon artificial hardness~
The bundle comprises 5% by weight of the washing liquor. The bundle is - spun dry and rinsed for two minutes in two gallons of water at 100F and 7 grains/gallon hardness. The fabrics are then dried in a commercial dryer.
The static charge on each fabric is then measured by a standard electrostatic technique within a Faraday cage. The sum of the absolute values of the charges on all fabrics in the bundle, divided by the sum of the area (yards2) of the total fabric surface (2 sides of the fabric) is then com-puted. This so-called "static value" (volts/yard2) correlates with gross observations of the effects of static charges on fabric surfaces, i.e., 20 electrical shocks, sparks, fabric clinging, etc. Depending on the fabric bundle tested, no static clinging is exhibited by fabrics having a static value less than about 1.5 volts/yards2; substantial static clinging is noted in fabrics having a static value above 4~5 volts/yard ; Anti-Wrinklin Test A bundle of mixed fabrics (ca~ 53% all-cotton; 12% 65/35 polyester/
cotton blends; 17% nylon; 18% "Dacron") is washed for ten minutes in a miniature agitator washer containing two gallons of aqueous washing liquor containing the test laundry compositions (as set forth below)O The laundering temperature is 100F; water hardness 7 grains/gallon artificial hardness.
30 The bundle is spun dried and rinsed for two minutes in two gallons of water at 100F and 7 grains/gallon hardness. The fabrics are then dried in a commercial dryer.

* Trademark of DuPont for a polyethylene terephthalate fiber having high strength and low water absorption.

_ 39 _ .- :

:~0372(}9 The extent of wrinkling on a given piece of fabric is then measured by mounting the fabric on a flat, movable surface within a light-tight boxO
A fine beam of light from a source above the fabric impinges upon the fabric at an angle of 90O As the mounted fabric is moved through a predetermined distance, a miniature photocell affixed adjacent to the stationary light source responds to scattered light at an angle of 45 to the fabric surface. A plot of the light intensity measured by the photocell versus the length of the fabric path traversed gives a profile (curve) which is in all practical respects a facsimile of the surface of the test fabric. That is, a smooth, unwrinkled --fabric gives essentially a straight line of constant light intensity; whereas a wrinkled fabric gives a series of peaks and minima. The ratio of the absolute distance through which the fabric was moved to the length of the . ..
plotted curve is quantitatively related to the extent of wrinkling.

Ease of Ironin~ Test ,.. ~ ~ - , A bundle of mixed fabrics (ca. 53% all-cotton; 12% 65/35 polyester/
cotton blends; 17% nylon; 18% "Dacron") is washed for ten minutes in a miniature agitator washer containing two gallons of aqueous washing liquor containing the test laundry compositions (as set forth below)O The laundering temperature is 100F; water hardness 7 grains/gallon artificial hardness.
20 The bundle comprises 5% by weight of the washing liquorO The bundle is spun dry and rinsed for two minutes in two gallons of water at 100F and .
7 grains/gallon hardnessO The fabrics are then dried in a commercial dryer.
; The ease of ironing of each fabric is then measured by using an instrumented, but otherwise conventional, ironO In essence, the iron by means of sensors fitted in its interior measures the amount of effort ; required by a naive operator to smooth the surface of the test fabric to a subjectively smooth appearance. The total amount of work required to achieve this appearance is a function of the force exerted on the iron (measured) and the distance traversed by the iron in the plane of the fabric (measured).

30 These tests are performed against untreated controls by naive operatorsO
Othertests suchas softness (relatedtobulkiness), ease offolding, -fabric drapability, fragrance and general state of cleanliness were assessed subjectively by expert panelists against unmarked controls.

: ~037Z(:~
The laundry detergent compositions and process of the instant invention are illustrated by the following examples.
BASE C OMPOS ITION
In~redient % by Weight ' Linear C13 all~ylbenzene sodium sulfonate 17 Sodium tripolyphosphate 50 - ` ~ Sodium s ilicate s olids (ration SiO2 /Na2 O = 2 . 0) 6 Sodium sulfate 15 - Particulate material (see below) 0.1 10 Minor additives and moisture Balance to 100 ~ The base composition is prepared by admixing all ingredients except -~ the particulate material in a crutcher and spray-drying to form granules.
These granules are then uniformly mixed with the particulate material. Said composition is then used, at a 0.12% product concentration, to launder soiled fabrics in standard fashion. The fabrics are cleansed and dried and ' performance can be appreciated by testing the fabrics for anti-wrinkling and ease of ironing as described hereinbefore. The test fabrics as compared against control fabrics exhibit reduced wrinkling, easier ironing, enhanced softness, reduced static charge and improved appearance.
The following particulate materials when incorporated in the base composition set forth above in the concentration specified provide the advantages described in the preceding paragraph.
Average Particle Melting Example Particulate Material Size ~m Point ( C) Glass micro balloons 30 --(E C C OS PHERES IG ) II Poly(tetrafluorethylene) 10 __ (MOLYKOTE 522)*
III Poly(ureaformaldehyde) 6 Thermo-30 IV Poly(methylmethacrylate) 18 200 (syndiotactic ) V Glass beads PF-12S 17 --VI Glass beads PF-12T 17 --VII "DRY-FLO" Starch 10 --, ,'. ~, ~C~37209 .
Average Particle Melting Example Particulate Material Size ~m Point (C) :: VIII Poly(melamineformaldehyde- 5 Thermo- :
: ureaformaldehyde) setting I~ Glass beads (Uispheres) 2Z _ - X Glass beads PF-12R 17 --XI Poly(styrenedivinylbenzene) 6 -- ~ ~
XII Glass beads PF-ll 30 -- ::
* Trademark Substantially identical results are also obtained when 0. 3% of the following particulate materials are used: poly(melamine formaldehyde- -~
ureaformaldehyde) average particle size, 15~m; poly(styrene-divinylbenzene) average particle size, 6, 10, 16, 20, 25 and 30,~m, respectivelyO
Substantially identical fabric care benefits are also obtained when the anionic surface-active agent of the base composition is replaced with an equivalent amount of 2-acetoxytridecane-1-sulfonic acid; sodium methyl-~(-. sulfopalmitate; sodium-~-methoxyoctadecyl sulfonate; sodium coconut alkyl ethylene glycoether sulfonate and the sodium salt of the sulfuric acid ester of the reaction product of one mole of tallow fatty alcohol and three moles of 20 ethylene oxide, respectively, Substantially equivalent softening, anti-wrinkling, ease of ironing, - anti-static and appearance benefits are obtained when the anionic surfactant of the base composition is replaced with an equivalent amount of a condensa-tion product of nonylphenol with about 9. 5 moles of ethylene oxide per mole . of nonylphenol; the condensation product of coconut fatty alcohol with about : -six moles of ethylene oxide per mole of coconut fatty alcohol; the condensa-tion product of tallow fatty alcohol with about eleven moles of ethylene oxide per mole of tallow fatty alcohol; the condensation product of a secondary fatty alcohol containing about fifteen carbon atoms with about nine moles of 30 ethylene oxide per mole of fatty alcohol; 3(N,N-dimethyl-N-alkyl ammonio)-propane-l-sulfonate or 3(N,N-dimethyl-N-alkyl ammonio)-2-hydroxy-propane-l-sulfonate wherein in both compounds the alkyl group averages 14.8 carbon atoms in length; 3(N,N-dimethyl-N-hexadecyl ammonio)-..
' ``` ~L037209 propane- 1 -sulfonate; 3(N, N-dimethyl-N-hexadecyl ammonio)-2-hydroxy propane-l-sulfonate; 3(N-dodecylben7yl-N,N-dimethyl ammonio)-propane-l-sulfonate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)acetate; 3-(N-dodecylbenzyl-N, N-dimethylammonio)propionate; 6 - (dodecyl-ben~yl -N, N-"` dimethylammonio)hexanoate; 2-(N,N-dimethyl-N-hexadecylammonio)acetate;
and sodium 3-(dodecylamino)-propane-1-sulfonate, respectively.
Substantially identical results are also obtained in the event the particulate materials and mixtures thereof are used at the following concen-`~ trations: 0.2%, 0.4%, 0.6%, 0O9%J 1.2%, 104%, 2%, 2.6%, 3.5%, 4.2%, 10 6.0%, 7.5%, and 9.0%
EXAMPLE XIII
A laundry detergent product is prepared having the following compo-sition:
Components Wt. %
Sodium Soap (1) 40. 0 Pota s s ium Soap ( 1 ) 1 1 . 2 TAE3S (2) lOo 7 Cll gLAS (3) 80 8 Sodium Silicate 80 9 Sodium Sulfate llo 9 Modified cornstarch ("DRY-FLO") 1. 0 Miscellaneous including moistureBalance (1) Soap mixture comprising 90% tallow and 10% coconut soaps.

(2) Sodium salt of ethoxylated tallow aLkyl sulfate having an average ` of about 3 ethylene oxide units per moleculeO

(3) Sodium salt of a linear alkyl benzene sulfonate having an average alkyl chain length of about 12 carbon atomsO
~- The foregoing ingredients, except the "DRY-FLO" starch are mixed in a crutcher and spray dried to provide a granular, soap based compositionO

30 To this soap based composition is added 1. 0 wt. % of "DRY-FLO" starch having an average particle diameter of 10 micrometers.

,' '`~ ~'.

10372(~9 The foregoing composition is added to an aqueous laundering liquor at 100F at a concentration of about 0.12 wt. %. The composition rapidly -dissolves and the "DRY-FLO" starch granules are uniformly and indepen- -dently dispersed throughout the laundering liquor. Fabrics laundered in said liquor are concurrently cleansed, and benefited with respect to wrinkling, ease of ironing, softness, anti-static and appearance as deter-mined by, among others, the before~mentioned tests against control fabrics laundered exactly as above except in the absence of the starch componentO
Substantially identical results are obtained when the "DRY-FLO'' -starch is replaced with an equivalent amount of a particulate material selected from glass micro balloons (ECCOSPHERES IG); poly(tetrafluor-ethylene) (MOLYKOTE 522); poly(ureaformaldehyde); poly(methylmeth- ~ `
acrylate) (syndiotactic); glass beads PF~12S; glass beads PF-12T; poly-(melamineformaldehyde-ureaformaldehyde); glass beads (Unispheres);
glass beads PF-12R; poly(styrenedivinylbenzene); glass beads PF-ll;
said particulate materials having average particle size diameters and melting -point as indicated in Examples I-XII.
.
EXAMPLE XIV

A detergent composition is prepared having the following composi-; 20 tion:

Components Parts Sodium tallow alkyl trioxy ethylene sulfate 20 Poly(methylmethacrylate); Mp = 200C;
; av. particle size: 18~m 2 Sodium oxydisuccinate 20 Sodium perborate 20 ;~ Sodium sulfate 10 `; Minor ingredients and moisture 6 The above composition provides excellent cleaning and outstanding fabric 30 conditioning properties to textiles laundered therein.

-; ~ Substantially identical results are obtained when sodium tallow alkyl trioxyethylene sulfate is replaced with an equivalent quantity of sodium coconut , .
`:

:~ .
', .
.

`` 10372(~9 al~cyl ethylene glycol ether sulfate; sodium tallow alkyl glycol ether sulfate;
sodium tallow alkyl pentaoxyethylene sulfate; ammonium tetradecylpentaoxy ethylene sulfate; ammonium lauryl hexaoxyethylene sulfate; sodium tallow alkyl hexaoxyethylene sulfate; and also the Alkyl Ether Sulfate Mixtures Nos.
1, II, III, and IV from Table I.
Substantially similar results are also obtained in the event the sodium tallow alkyl trioxyethylene sulfate is substituted by an equivalent amount of an ot-olefin sulfonate having from 12 to 24 carbon atoms and which have been prepared by means of uncomplexed sulfur dioxide as described 10 in U.S. Patent 3,332,880, Adriaan Kessler, et al.
XAMPLE XV
A through-the-wash-cycle fabric conditioning additive having the following composition is prepared:
` ~ Components Parts Sodiurn bicarbonate 19. 5 "DRY-FLO" starch (average particle size lO,~m) 0. 5 Sodium sulfate 20. 0 This additive is used for treating textiles in combination with a detergent base granule having the following composition.
Components Parts Sodium linear dodecyl benzene sulfonate 6 ` Sodium silicate solids (ratio SiO2/Na2O= 2. 0) 12 Sodium carbonate 12 Sodium sulfate 28 Minor s 2 - The conditioning additive is either combined with the detergent base granule prior to dissolving said mixture in the washing liquor or is added separately to the washing liquor. In both cases, the product concentration, based on the . . -sum of both, is 0.12% by weight, representing 0. 05/0 by weight of condition- -30 ing additive and 0. 07% by weight of detergent base granule.

Fabrics treated with the laundering liquor of this invention exhibit , superior fabric properties relative to what is obtained from a similar method :~

containing equivalent concentration of a detergent composition known in the art.
,' ; ' :
. . . . . .. . . . .

Claims (16)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A laundry detergent composition having fabric conditioning properties comprising:
(a) from about 2% to about 89.5% by weight of an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof;
(b) from about 0.05% to about 10% by weight of a substantially water-insoluble particulate material having:
(i) an average particle size in the range from about 1 to about 5.0 micrometers;
(ii) a shape having an anisotropy of about 5:1 to 1:1;
(iii) a hardness of less than about 5.5 on the Mohs scale;
(iv) a melting point above about 150°C; and (v) substantial freedom from exchangeable calcium and magnesium ions, said water-insoluble particulate material being selected from the group consisting of glass beads, hollow, hole-free, low density particles of glass, ceramic beads, and mixtures thereof;
granular substantially water-insoluble starch having an average particle diameter from 1.0 to about 45 micrometers and a swelling power of less than about 15 at a temperature of 65°C;

and surface-modified starches bearing hydro-phobic moieties which have been reacted with the starch molecule to form ester and ether linkages, and (c) from about 10% to about 60% by weight of a detergent builder salt.

2. A laundry detergent composition having fabric conditioning properties comprising:
(a) from about 4% to about 60% by weight of an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof;
(b) from about 0.1% to about 6% by weight of granular substantially water-insoluble starch having an average particle diameter from 1.0 to about 45 micrometers and a swelling power of less than about 15 at a temperature of 65°C; and (c) from about 10% to about 60% by weight of a detergent builder salt.

3. A detergent composition in accordance with claim 2, wherein the component (a) surface-active agent is present to the extent of from about 6% to about 40% by weight.

4. A detergent composition in accordance with claim 3, wherein the component (b) granular starch is present to the extent of from about 0.2% to about 4% by weight.

5. A detergent composition in accordance with claim 4, wherein the component (a) organic surface-active agent is selected from the group consisting of:
(i) alkylether sulfates having the formula RO(C2H4O)xSO3M
wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30 and M is a salt-forming cation; and (ii) olefin sulfonates having from about 12 to about 24 carbon atoms.

6. A detergent composition in accordance with claim 5, wherein the weight ratio of said builder to the organic surface-active agent is in the range from about 20:1 to about 1:20.

7. A detergent composition in accordance with claim 1, wherein the component (a) organic surface-active agent is used in an amount from about 4% to about 60% by weight.

8. A detergent composition in accordance with claim 7, wherein the component (b) particulate material is used in an amount from about 0.1% to about 6% by weight.

9. A detergent composition in accordance with claim 8, wherein an anionic organic surface-active agent is used selected from the group consisting of:
(i) C9-C20 linear alkylbenzyl sulfonates;
(ii) alkylether sulfates having the formula RO(C2H4O)xSO3M
wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30 and M is a salt-forming cation; and (iii) olefin sulfonates having from about 12 to about 24 carbon atoms.

10. A detergent composition in accordance with claim 9, wherein the component (b) particulate material is a surface-modified starch bearing hydrophobic moieties which have been reacted with the starch molecule to form ester and ether linkages.

11. A detergent composition in accordance with claim 9, wherein the weight ratio of said builder salt to the organic surface-active agent is in the range from about 20:1 to about 1:20.

12. A method for treating fabrics to simultaneously cleanse and impart anti-wrinkling, ease of ironing, softening, anti-static, and appearance benefits, said method comprising treating fabrics in an aqueous liquid comprising:
(a) from about 10 ppm (parts per million) to about 10,000 ppm of an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic deter-gents and mixtures thereof;
(b) from about 0.2 ppm to about 1,000 ppm of a substantially water-insoluble particulate material having:
(i) an average particle size in the range from about 1 to about 50 micrometers;
(ii) a shape having an anisotropy of about 5:1 to 1:1;
(iii) a hardness of less than about 5.5 on the Mohs scale;
(iv) a melting point above about 150°C; and (v) substantial freedom from exchangeable calcium and magnesium ions, said water-insoluble particulate material being selected from the group consisting of glass beads, hollow, hole-free, low density particles of glass, ceramic beads, and mixtures thereof; granular substantially water-insoluble starch having an average particle diameter from 1.0 to about 45 micrometers and a swelling power of less than about 15 at a temperature of 65°C; and surface-modified starches bearing hydrophobic moieties which have been reacted with the starch molecule to form ester and ether linkages; and (c) from about 50 ppm to about 6,000 ppm of a detergent builder salt.

13. A method in accordance with claim 12, wherein the component (a) organic surface-active agent is used in an amount from about 40 ppm to about 6,000 ppm; and the component (b) substantially water-insoluble particulate material is used in an amount from about 1 ppm to about 600 ppm.

14. A method in accordance with claim 13, wherein the component (a) organic surface-active agent is selected from the group consisting of (i) C2-C20 linear alkylbenzyl sulfonates;
(ii) alkylether sulfates having the formula RO(C2H4O)xSO3M
wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30 and M is a salt-forming cation; and (iii) olefin sulfonates having from about 12 to about 24 carbon atoms.

15. A method for treating fabrics to simultaneous-ly cleanse and impart anti-wrinkling, ease of ironing, soften-ing and anti-static properties, said method comprising treat-ing fabrics in an aqueous liquor comprising:
(a) from about 10 ppm to about 5,000 ppm of an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitter-ionic and ampholytic detergents and mixtures thereof;
(b) from about 0.1 ppm to about 900 ppm of a granu-lar substantially water-insoluble starch having an average particle diameter from 1.0 to about 45 micrometers and a swelling power of less than about 15 at a temperature of 65°C;
and (c) from about 50 ppm to about 6,000 ppm of a detergent builder salt.

16. A method in accordance with claim 15, wherein the component (a) organic surface-active agent is present to the extent of from about 100 ppm to about 3,000 ppm; and the component (b) starch is used to the extent of from about 2 ppm to about 200 ppm.