CA1266154A - Textile treating compositions and methods - Google Patents
Textile treating compositions and methodsInfo
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- CA1266154A CA1266154A CA000528987A CA528987A CA1266154A CA 1266154 A CA1266154 A CA 1266154A CA 000528987 A CA000528987 A CA 000528987A CA 528987 A CA528987 A CA 528987A CA 1266154 A CA1266154 A CA 1266154A
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- phosphoglyceride
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Detergent Compositions (AREA)
- Semiconductor Memories (AREA)
- Basic Packing Technique (AREA)
- Medicinal Preparation (AREA)
Abstract
TEXTILE TREATING COMPOSITIONS AND METHODS
ABSTRACT OF THE DISCLOSURE
The present invention relates to textile treating compositions which are especially useful for treating textiles in the rinse cycle of a textile laundering operation to provide improved fabric softening and conditioning benefits. The textile treatment com-positions comprise a substantially water-insoluble cationic fabric softening agent in combination with a substantially saturated lipid component containing one or more phosphoglycerides. The pres-ent invention further relates to a method for softening and con-ditioning textiles by treating the textiles, preferably during the rinse cycle of a textile laundering operation, with a combination of the softening agent and substantially saturated lipid component.
ABSTRACT OF THE DISCLOSURE
The present invention relates to textile treating compositions which are especially useful for treating textiles in the rinse cycle of a textile laundering operation to provide improved fabric softening and conditioning benefits. The textile treatment com-positions comprise a substantially water-insoluble cationic fabric softening agent in combination with a substantially saturated lipid component containing one or more phosphoglycerides. The pres-ent invention further relates to a method for softening and con-ditioning textiles by treating the textiles, preferably during the rinse cycle of a textile laundering operation, with a combination of the softening agent and substantially saturated lipid component.
Description
TEXTILE TREATING COMPOSITIONS AND METHODS
Yi-Chang Fu BACKGROUND OF THE_INVENTI~)N
The present invention relates to textile treating cornposi-tions. In particular, the invention relates to concentrated textile treating compositions which provide improved fabric softening and conditioning benefits, especially when used in the rinse cycle of a textile laundering operation.
Textile treating compositions suitable for providing fabric softening and static ~ontrol benefits during laundering are well-known in the art, and have found wide-scale commercial applica-~ion. Conventionally, rins~addecl fabric softening compositions contain, as the active softening component, substantially water-insoluble cationic materials having two long alkyl chains. Typical of such materials are ditallow dimethyl ammonium chloride and imidazolinium compounds substituted with two tallow groups.
Other types of materials are also known as fabric treating and conditioning agents. One such type of fabric conditioning agent is lecithin. Thus, for example, Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Vol. 14, pages 250-269 (Grayson et al Editors; Wiley-lnterscience, New York, N.Y.;
1981 ), generally discloses the use of lecithin for emulsifying, wetting, softening and conciitioning textiles, specifically in the industrial sizing and finishing of textiles. Furthermore, U~S.
Patent 2,622,045, to Ester, Issued December 16, 1952, discloses compositions useful for lubricating and conditioning textile yarns, particularly cellulose derivatives, during industrial processing of these yarns. Some examples in this patent disclose "lecithin" as a component of yarn-treating compositions.
Textile treating compositions comprising quaternary ammonium salts in combination with other agents to provide addltional soft-ening and/or storage stability and/or static control are also known in the art. For example, U . S. Patent 2 ,372 ,985, to Roth, Issued April 3, 1945, discloses compositions containing a 35 "cation-active material" and a phosphatide. The cation-active materials preferred an~ specifically disclosed are water-soiuble amine salts. Specifically disclosed as the phosphatide component is egg-yolk lecithin and soybean lecithin, both which have unsat-urated fatty acid chains. This patent discloses that these com-5 positions have utility during industrial processing as softeningagents for wool and other textile fabrics. Furthermore, U.S, Patent 4,30~,151, to Cambre, Issued December 29, 1981, discloses detergent compositions which have fabric softening and anti-static properties. Disclosed in this patent is the use of soya-~erived 1n hydrogenated triglycerides as dispersion inhibitors in detergent compositions which also contain softening agents.
Notwithstanding the foregoing prior art developments, there remains a continuing need to identify additional textile treating compositions of these same types which are especially effective for 15 delivering fabric softening anci conditioning benefits to textiles treated therewith. it is accordingly an object of the present invention to provide improved textile treating compositions con-taining both conventional fabric softening agents and particular types of phospholipid materials. It is a further object of the 20 present invention to provide an improved textile treating method which employs such compositions to impart fabric softening and conditioning benefits.
SUMMARY OF THE INVENTION
The present invention relates to textile treating compositions 25 which provide improved textile softening and conditioning bene-fits. Such compositions comprise from about 0.1% to about 99. 9%
by weight of a substantially water-insoluble cationic fabric sof-tening agent and from about 0 .1 g6 to about 99 . 9% by weight of a substantially saturated, phosphoglyceride-containing lipid compo-30 nent. This substantially saturated lipid component comprises atleast about 50% by weight of an acetone-insoluble lipid material.
This acetone~insoluble lipid material itself comprises at least about 50% by weight of one or more acetone-insoluble phosphoglycerides.
The weight ratio of the acetone-lnsoluble lipid material in the lipid 35 component to the fabric softening agent component is in the range of from about 0.01:1 to about 5:1.
The present inventlon further reiates to a method for treat-ing textiles to impart fabric softening or conditioning benefits to textiies so treated. This method comprises contacting the textiles with a textile softenlng amount of a combination of a substantially 5 water-insoluble cationic fabric soFtening agent and a substantially saturated, phosphoglyceride-containing lipid component. The lipid component comprises at least 50~ by weight of acetone-insoluble lipid material, and the acetone-insoluble lipid material itself comprises at least about 50% by weight of one or 10 more acetone-insoluble phosphoglycerides. The weight ratio of the acetone-insoluble lipid material to fabric softening agent in the combination ranges from about 0.01:1 to about 5:1.
DETAILED DESCRIPTION OF THE INVENTION
-Substantially Water-inso!uble Gati~nic Fabric Softening Agent One essential component of the textile treating compositions useful in the present invention comprises a substantially water-insoluble, eationic fabric softening agent. Conventlonal fabric softening agents of this type are those which are known in the art to provide fabric softening and/or static eontrol benefits when ~0 used in textile laundering operations, especially, for example, during use in the rinse cycle of laundering with home laundry washing machines. A wide variety of such materials has been disclosed, for example, in such patents as Morton; U . S . Patent 3,686,025; Issued August 22, 1972; )iery et al; U.S. Patent 3,849,435; Issued November 19, 1974; Morton; U.S. Patent 3,843,395; Issued October 22, 1974: and Zaki; U.S. Patent 4,022,938; Issued May 10, 1977, Nonlimiting, general examples of classes of compounds which have been disclosed to have fabric softening properties are pri-mary, secondary, and tertiary amines, Imidazoles, imldazolines, oxazoles, pyrimidines, imidoethers, substituted pyridines, substituted ammonias, substituted ureas, substltuted thioureas, substituted guanidines, substttuted betaines, the phosphorus analogs of the foregoing types of materials, and the quaternary salts of the foregoing materlals. Conventional fabric softening agents from these classes of compounds generally possess a straight or branched, saturated or unsaturatecl, carbon chain of at least 8 carbon atoms, or an alipha~ic-aromatic group of at least 8 carbon atoms. Such compounds will furthermore frequently S have an amine nitrogen occurring either in a straigh~ chain as a primary, secondary, tertiary or quaternary nitrogen atom, or in a heterocyclic ring of 5 to 7 atoms as an imino group, tertiary nitrogen, or quaternary nitrogen~
For use in the compositions and methods of the present invention, ~he amines and amine derivatives are cationic and are substantially water-insoluble. Preferably the cationic amines and amine derivatives are used in the form of substantially water-insoluble salts, and most preferably are used as the tetraalkyl qua~ernary ammonium salts or alkyl imidazolinium salts. Gener-ally, therefore, the cationic amine and amine derivatives which have only one alkyl chain longer than about 8 carbon atoms are not useful as the substantially water-insoluble cationic fabric softening agents in the present invention.
Substantially water-insoluble cationic fabric softening agents include the softener materials which are di-C8-C30, preferably di-C12-C24, alkyl or alkenyl 'onium salts, especially mono- and poly-ammonium salts, and imidazolinium salts. Optionally, the alkyl or alkenyi groups may be substituted or interrupted by functional groups such as -OH, -()-, -CONH-, -COO-, ethylene-oxy, propyleneoxy, phenyl, benzyl, etc. The number of certain optional functional groups (e.g., -OH, -CONH-) present in the cationic fabric softening agent is limited such that the softening agent is substantially water-insoluble.
One preferred type of these cationic softeners includes the substantially water-insoluble, mono-ammonium compounds which are the quaternary ammonium and amine salt compounds having the forrnula:
rR1 R3- I ~
\ N/ X
R2/ \ R4 l whe ein R1 and R2 represent, independently, alkyl or alkenyl ~3Lr~
groups of from about 8 to about 30, preferahly from about 12 to about 24, carbon atoms, and optionally substituted or int~rrupted by groups such as -OH, -O-, -CONU-, -COO-, ethyleneoxy, propyleneoxy, phenyl, benzyl, etc.; R3 and R4 represent, inde-5 pendently, hydrogen, or alkyl, alkenyl or hydroxyalkyl groupscontaining from 1 to about 1~ carbon atoms, and optionally sub-stituted or interrupted by groups such as -O-, -CONH-, -COO-, ethyleneoxy, propyleneoxy, etc.; and X is the salt counteranion, preferably selected from halide, methylsulfate, ethylsulfate, and 10 organic anions. The number of certain optional functional groups ~e.g., -OH, -CONH-3 present in the cationic fabric softening agent is limited such that the softening agent is substantially water-insoluble .
Represen~ative examples of these quaternary softeners in-15 clude: ditallow dimethyl ammonium chloride ditallow dimethylammonium methyl sulfate; dihexadecyl dimethyl ammonium chloride:
di(hydrogenated tallow alkyl) dimethyl ammonium chloride; di-octadecyl dimethyl ammonium chloride; dieicosyl dimethyl ammonium chloride; didocosyl dimethyl ammonium chloride; di(hydrogenated 20 tallow) dimethyl ammonium methyl sulfate; dihexadecyl diethyl ammonium chloride; di(coconut alkyl) dimethyl ammonium chloride di(coconut alkyl) dimethyl ammonium methylsulfate; di(tallowyl amido ethyl) dimethyl ammonium chloride; di(tallowyl amido ethyl) dimethyl ammonium methylsulfate; cli(tallowyl amido propyl) di 25 methyl ammonium chloride; and di(tallowyl amido propyl) dimethyl ammonium methylsulfate.
Another preferred type of substantially water-insoluble cationic fabric softening agent includes compounds frorn the class of tri-C8-C30, preferably tri-C1 2~C24 ~ quaternary ammonium 30 salts. These compounds have structures similar to the di-C8-C30 alkyl or alkenyl quaternary ammonium salts immediately hereinbefore described, except that either the R3 or R4 group is a C8-C30, preferably a C1 2-C24, group selected from the same groups as can be used for the R and R groups. Representa-35 tive examples are tri(hardened tallowalkyl)methylammonium salts,trioleylmethylammonium salts, and tripalmitylmethylammonium salts.
f~
Yet another preferred type of conventional cationic fabric softening agent includes the substantially water-insoluble materials which are the alkyl imidazolinium salts and alkyl pyrimiclinium salts believed to have the formula:
(( ) [CH ) --N~ R7 ~ X
l0 wherein the n's are, independently, an integer from about 2 to about 6, preferably n = 2 or 3; R5 is hydrogen or an alkyl, alkenyl or hydroxyalkyl group containing from 1 to about 4, preferably 1 or 2, carbon atoms, optionally substituted or interrupted by groups such as -O-, -CONH-, -COO-, 15 ethyleneoxy, propyleneoxy, etc.; R6 and R7 are, independently, alkyl or alkenyl groups containing from about 8 to about 30, preferably from about 12 to about 24, carbon atoms, optionally substituted or interrupted by groups such as -OH, -O-, -CONH-, -COO, ethyleneoxy, propyleneoxy, phenyl, benzyl, etc.; R8 is 20 hydrogen or an alkyl, alkenyl or hydroxyalkyl group containing from 1 to about 4 carbon atoms, uptionally substituted or inter-rupted by groups such as -O-, -CONH-, -COO-, ethyleneoxy, propyleneoxy, etc.; and X is the salt counteranion, preferably selected from halide, methylsulfate, ethylsulfate, and organic 25 anions. The number of certain optional functional groups (e.g., OH, -CONH-) present in the cationic fabric softening agent is limited such that the softening agent is substantially water-insoluble .
Representative examples of the fabric softening alkyl imida-30 zolinium salts include: 3-methyl-1-(tallowylamido) ethyl~2~tallowyl~
4,5-dihydroimidazolinium methylsulfate; 3-methyl-1-(palmitoyl~
amido)ethyl-2-octadecyl~4,5-dihydroimidazolinium chloride: 2-heptadecyl~3-methyl-1 -~2-stearylamido~-ethyl-4 ,S-dihydroimidazo-linium chloride; 2~-1auryl~3-hydroxyethyl-1-(oleylamido)ethyl~
35 4,5~dihydro imidazolinium chloride: and protonated 1-hardtallow amido ethyl-2-hardtallow imidazoline. Also suitable as conven-tional fabric softeniny agents herein are the imidazoiinium ~abricsoftening components of U.S. Patent No. 4,127,1l89, All o~ the foregolng types o~ conventlonal cationic fabric 5 softening agents can be readily syntheslzed in known manner.
Many of these materials are, in fact, commercially available.
Representative commercially available materials of the above classes inciude the quaternary ammonium compounds Adogen q48i~3 (tradem3rk of Sherex Chemical C:ompany, Inc., Dublin, Ohio 10 comprises approximately 85% ditallow dimethyl ammonium chloride) and Varisoft 110~) ~trademark of Sherex Chemical Company, Inc., Dublin, Ohio comprises methyl bis(hydr.tallowamidoethyl)2-hydroxyethyl ammonium methyl sulfate); and the imidazolinium compound Varisoft 475~) 5$rademark of Sherex Chemical Company, 15 Inc,, Dublin, Ohio; comprises methyl-1-tallow amido ethyl-2-tallow imiciazolinium methyl sulfate).
Particularly preferred speciflc compounds for use as the fabric softenlng agent in the compositions of the present invention are: ditallow dimethyl ammonium chloride (particularly Adogen 20 448E~)), ditallow dimethyl ammonium methyl sulfate, and methyl-1-tallow amido ethyl-2-tallow imidazolinium methyl sulfate.
The conventional cationic fabric softening agents useful in the present Invention are substantially water-insoluble. Such materlals are, however, freqùently water-dispersible and these 25 can readily be formulated into aqueous textile treating compositions .
The substantially water-insoluble cationic fabric softening agents are utilized In the textTle treating compositions herein in an amount of from about 0. i% to about 99.9% by weight, more 30 preferably from about 0.1% to about 30~ by welght, most preferably from about 1% to about i 0~ by weight of the composition. This fabric softening agent is also utilized In a particular welght ratio vis a vis the substantially saturated phosphoglyceride-containing lipid component as hereinafter 35 described In greater detail.
~f~
Substantially Saturated Phosph~ylyceride-Containing Lipicl Componen A second essential component of the textile treating com-positions herein comprises a substantially saturated, phospho-5 glyceride-containing lipid component. This lipid component will generally be anionic in nature and is thus distinct from the conventional, substantially water-insoluble cationic fabric softening agents hereinbefore described.
The substantially saturated, phosphoglyceride-containing 10 lipid component will generally contain at least about 50%, pref-erably from about 5096 to about 95%, and more preferably from about 55% to about 75%, by weight of lipid materials which are acetone insoluble. This acetone-insoluble lipid material itself comprises at least about 50%, more pr0ferably at least about 60~6, 15 by weight of one or more acetone-insoluble phosphoglycerides.
More particularly, such phosphoglyceride material wiil generally be selected from the group consisting of phosphatidyl choline (i.e., "pure lecithin"), phosphatidyl ethanolamine, phosphatidyl inositol, serine phosphoglyceride, phosphatidic acid, or mixtures 20 thereof. Preferably, the phosphoglycerides are di-acyl esters of fatty acids having at least about 8 carbon atoms, more preferably esters of C8-C30 fatty acids, and most preferably esters of C1 2-C24 fatty acids . The remainder of the acetone-insoluble lipid material present in the substantially saturated lipid component 25 typically comprises acetone-insoluble lipid materials such as phosphoglycolipids, phosphodiol lipids, phosphosphingolipids, glycolipids, or mbttures thereof.
The substantially saturated lipid component of the composi-tions herein may also contain acetone-soluble lipid material. Such 30 acetone-soluble material can include, for example, free fatty acids, fatty acid diglycerides, and/or fatty acid triglycerides.
The acetone-soluble lipid material should comprise less than about 50%, preferably from about 5% to about 50%, and more preferably from about 25% to about 45%, by weight, of the substantially 35 saturated lipid component of the compositions herein.
The substantially saturated lipid componen~ containiny the requ;site concentration of acetone-insoluble lipid materials can be derived from animal or vegetable svurces (e.g., soybeans, corn, - rapeseed, peanuts, sunflowers, safflowers, etc. ) . Preferred sources include egg yolk or soybean lecithin mixtures which are commercially available, with soybean lecithin mixtures being most preferred. The term lecithin mixtures, as used herein, means a material which is a mixture comprising more than one phosphoglyceride component, with at least one of the phospho-glyceride components being phosphatidyl choline (i.e., pure lecithin), phosphatidyl ethanolarr ine, phosphatidyl inositol, serine phosphoglyceride, or phosphatidic acid. For example, commercial-Iy available soybean lecithin mixtures Include Centrolex F~) (trademark of Central Soya, For~ Wayne, Indiana) which com-prises an approximately 95% acetone-insoluble fraction that con-tains at ieast approximately 60% phosphoglycerides~ Another example is Centrol 3F-DB(~ (trademark of Central Soya, Fort Wayne, Indiana) which comprlses an approximately 60% acetone-insoluble fraction that contains at least approximately 50~ phos-phoglycerides.
The acetone-lnsoluble lipid fraction present in soybean lecithln mixtures typically comprises: from about 2096 to about 30~
of phosphatidyl choline (i.e., pure lecithin ): from about 15% to about 25% of phosphatidyl ethanolamine; from about 10~ to about 20~ of phosphatidyl inositol; and from about 0% to about 15% of phosphatidic acid. The acetone-soluble lipid fraction present in commercially available soybean lecithin mixtures predominantly comprises a mixture of free fatty acids, fatty acid diglycerides, and fatty acid triglycerides. A more detailed description of the composition of lecithln mlxtures useful as sources of the lipid component of the present invention can be found In Kirk-Othmer Encyclopedia of Chemical_Technolociy, Third Edition, Vol. 14 pages 250-269 ~Grayson et al Editors; Wiley-lnterscience, New York, N.Y. 1981~.
- 1 o -It is necessary that the llpid material utllize~l in the compositions of the present invention be selectecl or modified, ,c referably modified by hydrogenation, such that the lipid cornpo-nent of the composition herein is substantially saturated. The 5 term "substantially saturated" as used herein means that the sub-stantially saturated lipid component has an iodine value (a well-known quantitative measure of unsaturation in lipid materiais) of less than about 75, preferably less than about 65, more prefer-ably tess than about S0, and most preferably less than about 30.
For optimum textile soften~ng performance to be realized wi~h the compositions of the present invention, it is preferred that the substantially saturated, phosphoglyceride containing lipid com-ponent be obtained by hydrogenating lecithin mixtures, preferably commercially avaiiable soybean lecithin mlxtures. Most preferred 15 are soybean lecithin mixtures comprising from about 5% to about 50~, preFerably from about 25% to about 45~6, by weight of acetone-soluble material. These particular types of soybean lecithin mixtures are preferably hydrogenated such that their iodine value is abou~ 50 or less, more preferably about 30 or 20 less.
Some types of hydrogenated phosphoglycerides-containing lipid mixtures are known in the art (see, for example, The Kirk-Othmer Encyclopedia of Chemical Technology. Hydrogena-tion processes which may be utilized to modify phospho-glyceride-containing lipid materials are also known. For example, U.S. Patent 3,026,341, to Da~is, issued March 20, 1962, discloses a process for hydrogenating lecithin mixtures. Hydrogenation procedures are more fully exempliEied hereinafter.
It should be recognized for purposes of the present Inven-tion that the substantially saturated lipid component of the com-positions herein may also be produced synthetically instead of being obtained or derlved from naturally-occurrlng sources.
Furthermore, the substantially saturated lipld component may comprise percentages of the varlous Indlvidual phosphoglyceride ~.~,.
components which differ from the component concentrations typi-cally found in commercially available lecithin mixtures. For example, the acetone-insoluble lipid material present in the sub--stantially saturated lipid component may comprise percentages of 5 phosphatidyl choline, phosphatidyl ethanolamine, phosphatidic acid, serine phosphoglyceride, and/or phosphatidyl inositol, which are, individually, greater ~han or less than those typically found in commercially available lecithin mixtures, as clescribed herein-before .
In addition, it should be recognized for purposes of the present invention that the substantially satura~ed lipid components of the compositions herein may also be obtained by combining, for example, acetone-insoluble phosphoglycerides or phosphoglyceride-containing acetone-insoluble lipid materials with açetone-soluble 15 lipid materials, such as by combining a hydrogenated or non-hydrogenated acetone-insoluble phosphoglyceride with hydrogenated or non-hydrogenated soybean oil (i.e., pre-dominantly di- and triglycerides). For example, the substantially saturated, phosphoglycaride-containing lipid component might be a 20 combination of hydrogenated Centrolex ~) (described more fully hereinafter) and non-hydrogenated soybean oil.
The compositions of the present invention, which utilize substantially saturated lipid components containing the above-described minimum amount of aceltone-insoluble phosphoglycerides, 25 provide surprisingly better softening performance under textile laundering conditions than do compositions in which the phospho-glycerides are not present. As noted above, for optimum textile softening performance, it i5 preferred that the substantially saturated, phosphoglyceride-containing lipi~ component be ob-30 tained by hydrogenating the lipid component, more preferably byhydrogenating lecithin mixtures, and most preferably by hydro-genating commercially available soybean lecithin mixtures.
The compositions of the present invention also provide unexpectedly superior performance relative to compositions which 35 comprise a phosphoglyceride-containing lipid component that is not substantialiy saturated on the basis of color and odor profiles for textiles which have been treated dl~ring a textile laundering operation and then stored for several weeks. In particular, textiles treated with compositions which comprise a conventional fabric softening agent and a phosphoglyceride-containing lipid 5 component which is not substantially-saturated tend to become yellow and develop a fatty odor after several weeks, whereas textiles treated with compositions of the present invention do not.
The substantially saturated lipid component of the composi-tions herein generally comprise from about 0.1% to about 99.9~ by weight, more preferably from about 0.1~ to about 30~6 by weight, and most preferably from about 1~ to about 10% by weight of the textile treating compositions of the present invention. Further-more, the subs~antially saturated lipid component of such composi-tions is generally present in an amount which is suffioient to provide a weight ratio of the acetone-insoluble lipid material (present in the substantially saturated lipid component) to the substantially water-insoluble cationic fabric softening agent within the range of from about 0.01 :1 to about 5:1, preferably from about 0.1 :1 to about 2.5:1, more preferably from about û.1 :1 to about 1.5:1, and most preferabnly about 0.5:1.
ptional components Although textile treating compositions herein need contain only the substantially water-insoluble cationic fabric softening agent and the substantially saturated, phosphoglyceride-contain-ing lipid component as hereinbefore described, such compositions can optionally contain a wide variety of additional ingredients.
The nature and amounts of such optional components are very much dependent upon desired final form and intended means of use of the textile treating compositions.
Most frequently, the textile treating compositions herein are in liquid form suitable for addition to the rinse water during the rinse cycle of a home laundering operation. Liquid compositions of this type will generally be prepared as an aqueous dispersion of the softening agent and lipid components, and accordingly, the most commonly employed optional component of the compositions herein will be water. Water can, in fact, comprise up to about 99 . 9% by weight of the compositions herein . More frequen tiy, liquld compositions of this type will comprise from about 50% to about 99.9~, preferably from abou~ 70~ to about 95%, by weight of water .
The compositions of the preser,t invention can also contain various other compatible optional components such as those mate-rials which are conventionally used in textile treating composi-tions. These componen~s can include, for example, colorants, perfumes, preservatives, optical brighteners, opacifiers, pH
buffers, electrolytes, viscosity modifiers, fabric conditioning agents, surfactants, stabilizers (such as polysaccharides, e.g., guar gum and polyethylene glycol ), anti-shrinkage agents, anti-wrinkle agents, fabric crispening agents, spotting agents, soil release agents, germicides, fungicides, anti-oxidants ~such as ~(-tocopherol and butylated hydroxy toluene), anti-corrosion agents, fabric softening agents which are not substantially water-insoluble cationic fabric softening agents, etc. While any or all of these optional components may be employed, the compositions of the present invention will most often include, in addition to the essential components, a dye, a perfume, and/or a preservative, with the remainder of the compositions being water.
Composition preparation The textile treating compositions herein may be prepared by simply combining the essential and desired optional components thereof in the requisite proportions. When prepared in the form of an aqueous dispersion, the combination of essential ingredients in soiid form are admixed with water, and this admixture is subjected to sufficient shear agitation to form the desired dis-persion. The mean particle size of the combination of active ingredients in such dispersions, to provide optimum softening performance, will generally range from about 0.01 micron to about 10 microns, prefera~ly within the range of from about 0.05 micron to about 1 micron. The pH of such compositions in aqueous form is not critical, and may be anywhere within the normal range for effective performance of the conventional fabric softening agent used. The natural pH of the mix components is ordinarily satisfactory. If adjustment in pH is desired for any reason, trace quantities of organic or inorganic aci~s or bases can bs used. A preferred range is 2.0-8.0; especially preferred is 3.0-7Ø
If the textile treating compositions of the present invention are to be employed in a laundry dryer, such compositions will generally be in solid ~orm. Frequently such compositions can be fashioned into dryer-added textile treating articles by combining such compositions with 3 substrate carrier. Textile tr~ating articles of this type are described in the a~rementioned U . S .
Patent 4,022,938, U.S. Patent 3,843,395 and U.5. Patent 3, 686, 025 .
Text le treating method The present invention also relates to methods for treating textiles to impart fabric softening and conditioning benefits to textiles so treated. Such a method in general is carried out by contacting textiles to be treated with a textile softening amount of a combination of the substantially water-insoluble cationic sof tening agent and substantially saturated, phosphoglyceride-containing lipid components of the textile treating composition hereinbefore described. Thus to carry out the textile treating methods herein, the compositions of this invention may be con-tacted directly with textiles to be treated or may be added to textile-containing aqueous solutions used in laundering operations.
The fabric softening compositions of the present invention are preferably used by adding such compositions to the rinse cycle during a conventionai home laundering operation. For optimun~ softening performance, detergent carry-over from the wash cycle to the rinse cycle containing the fabric softening composition should be minimized. Generally, rinse water in such operations has a temperature of about 5C to about 60C. The compositions of the present invention are used in the rinse such that the concentration of the actives ( i . e ., conventional cationic fabric softening agent plus lipid component) in the rinse is suf-ficient to impart a softening benefit to the textiles in the rinsing bath. Generally, such concentrations fall within the range of from about 10 ppm to about 1,000 ppm, preferably from about 10 5~
ppm to about 500 ppm, most preferably from about 50 ppm to about 100 ppm, wi~hin ~he aqueous rinsing bath. ~/hen multiple rinses are used, the textile treating composition is preferably added to the final rinse.
As indicated, the textile treating methods of this invention may also be carried out by adding the textile treating composi-tions herein to an automatic laundry dryer. Such compositions may aiso be added to the surfactant-containing a~ueous washing bath used in a horne laundering operation.
The following examples illustrate the fabric softening com-positions and methods of the present invention, and the benefits achieved by the utilization of such compositions and methods.
These examples are illustrative of the invention herein and are not to be construed as limiting thereof.
Com osition containin substantiallv saturated soybean lecithin mixture (959~ acetone-insoluble lipid) _ Compound Weight %
. ~
SBL " 2.81 Adogen 448E 2) 6.42 dye3 ) 0 .18 preservative0 . 02 perfume 0. 42 water balance 25 1 ) = soybean lecithin ~Centrolex F~9 from Central Soya, Fort Wayne, Indiana; approximately 9596 acetone-insoluble lipid which comprises at least approximately 60% phosphoglycer-ides; iodine value approximately 74)
Yi-Chang Fu BACKGROUND OF THE_INVENTI~)N
The present invention relates to textile treating cornposi-tions. In particular, the invention relates to concentrated textile treating compositions which provide improved fabric softening and conditioning benefits, especially when used in the rinse cycle of a textile laundering operation.
Textile treating compositions suitable for providing fabric softening and static ~ontrol benefits during laundering are well-known in the art, and have found wide-scale commercial applica-~ion. Conventionally, rins~addecl fabric softening compositions contain, as the active softening component, substantially water-insoluble cationic materials having two long alkyl chains. Typical of such materials are ditallow dimethyl ammonium chloride and imidazolinium compounds substituted with two tallow groups.
Other types of materials are also known as fabric treating and conditioning agents. One such type of fabric conditioning agent is lecithin. Thus, for example, Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Vol. 14, pages 250-269 (Grayson et al Editors; Wiley-lnterscience, New York, N.Y.;
1981 ), generally discloses the use of lecithin for emulsifying, wetting, softening and conciitioning textiles, specifically in the industrial sizing and finishing of textiles. Furthermore, U~S.
Patent 2,622,045, to Ester, Issued December 16, 1952, discloses compositions useful for lubricating and conditioning textile yarns, particularly cellulose derivatives, during industrial processing of these yarns. Some examples in this patent disclose "lecithin" as a component of yarn-treating compositions.
Textile treating compositions comprising quaternary ammonium salts in combination with other agents to provide addltional soft-ening and/or storage stability and/or static control are also known in the art. For example, U . S. Patent 2 ,372 ,985, to Roth, Issued April 3, 1945, discloses compositions containing a 35 "cation-active material" and a phosphatide. The cation-active materials preferred an~ specifically disclosed are water-soiuble amine salts. Specifically disclosed as the phosphatide component is egg-yolk lecithin and soybean lecithin, both which have unsat-urated fatty acid chains. This patent discloses that these com-5 positions have utility during industrial processing as softeningagents for wool and other textile fabrics. Furthermore, U.S, Patent 4,30~,151, to Cambre, Issued December 29, 1981, discloses detergent compositions which have fabric softening and anti-static properties. Disclosed in this patent is the use of soya-~erived 1n hydrogenated triglycerides as dispersion inhibitors in detergent compositions which also contain softening agents.
Notwithstanding the foregoing prior art developments, there remains a continuing need to identify additional textile treating compositions of these same types which are especially effective for 15 delivering fabric softening anci conditioning benefits to textiles treated therewith. it is accordingly an object of the present invention to provide improved textile treating compositions con-taining both conventional fabric softening agents and particular types of phospholipid materials. It is a further object of the 20 present invention to provide an improved textile treating method which employs such compositions to impart fabric softening and conditioning benefits.
SUMMARY OF THE INVENTION
The present invention relates to textile treating compositions 25 which provide improved textile softening and conditioning bene-fits. Such compositions comprise from about 0.1% to about 99. 9%
by weight of a substantially water-insoluble cationic fabric sof-tening agent and from about 0 .1 g6 to about 99 . 9% by weight of a substantially saturated, phosphoglyceride-containing lipid compo-30 nent. This substantially saturated lipid component comprises atleast about 50% by weight of an acetone-insoluble lipid material.
This acetone~insoluble lipid material itself comprises at least about 50% by weight of one or more acetone-insoluble phosphoglycerides.
The weight ratio of the acetone-lnsoluble lipid material in the lipid 35 component to the fabric softening agent component is in the range of from about 0.01:1 to about 5:1.
The present inventlon further reiates to a method for treat-ing textiles to impart fabric softening or conditioning benefits to textiies so treated. This method comprises contacting the textiles with a textile softenlng amount of a combination of a substantially 5 water-insoluble cationic fabric soFtening agent and a substantially saturated, phosphoglyceride-containing lipid component. The lipid component comprises at least 50~ by weight of acetone-insoluble lipid material, and the acetone-insoluble lipid material itself comprises at least about 50% by weight of one or 10 more acetone-insoluble phosphoglycerides. The weight ratio of the acetone-insoluble lipid material to fabric softening agent in the combination ranges from about 0.01:1 to about 5:1.
DETAILED DESCRIPTION OF THE INVENTION
-Substantially Water-inso!uble Gati~nic Fabric Softening Agent One essential component of the textile treating compositions useful in the present invention comprises a substantially water-insoluble, eationic fabric softening agent. Conventlonal fabric softening agents of this type are those which are known in the art to provide fabric softening and/or static eontrol benefits when ~0 used in textile laundering operations, especially, for example, during use in the rinse cycle of laundering with home laundry washing machines. A wide variety of such materials has been disclosed, for example, in such patents as Morton; U . S . Patent 3,686,025; Issued August 22, 1972; )iery et al; U.S. Patent 3,849,435; Issued November 19, 1974; Morton; U.S. Patent 3,843,395; Issued October 22, 1974: and Zaki; U.S. Patent 4,022,938; Issued May 10, 1977, Nonlimiting, general examples of classes of compounds which have been disclosed to have fabric softening properties are pri-mary, secondary, and tertiary amines, Imidazoles, imldazolines, oxazoles, pyrimidines, imidoethers, substituted pyridines, substituted ammonias, substituted ureas, substltuted thioureas, substituted guanidines, substttuted betaines, the phosphorus analogs of the foregoing types of materials, and the quaternary salts of the foregoing materlals. Conventional fabric softening agents from these classes of compounds generally possess a straight or branched, saturated or unsaturatecl, carbon chain of at least 8 carbon atoms, or an alipha~ic-aromatic group of at least 8 carbon atoms. Such compounds will furthermore frequently S have an amine nitrogen occurring either in a straigh~ chain as a primary, secondary, tertiary or quaternary nitrogen atom, or in a heterocyclic ring of 5 to 7 atoms as an imino group, tertiary nitrogen, or quaternary nitrogen~
For use in the compositions and methods of the present invention, ~he amines and amine derivatives are cationic and are substantially water-insoluble. Preferably the cationic amines and amine derivatives are used in the form of substantially water-insoluble salts, and most preferably are used as the tetraalkyl qua~ernary ammonium salts or alkyl imidazolinium salts. Gener-ally, therefore, the cationic amine and amine derivatives which have only one alkyl chain longer than about 8 carbon atoms are not useful as the substantially water-insoluble cationic fabric softening agents in the present invention.
Substantially water-insoluble cationic fabric softening agents include the softener materials which are di-C8-C30, preferably di-C12-C24, alkyl or alkenyl 'onium salts, especially mono- and poly-ammonium salts, and imidazolinium salts. Optionally, the alkyl or alkenyi groups may be substituted or interrupted by functional groups such as -OH, -()-, -CONH-, -COO-, ethylene-oxy, propyleneoxy, phenyl, benzyl, etc. The number of certain optional functional groups (e.g., -OH, -CONH-) present in the cationic fabric softening agent is limited such that the softening agent is substantially water-insoluble.
One preferred type of these cationic softeners includes the substantially water-insoluble, mono-ammonium compounds which are the quaternary ammonium and amine salt compounds having the forrnula:
rR1 R3- I ~
\ N/ X
R2/ \ R4 l whe ein R1 and R2 represent, independently, alkyl or alkenyl ~3Lr~
groups of from about 8 to about 30, preferahly from about 12 to about 24, carbon atoms, and optionally substituted or int~rrupted by groups such as -OH, -O-, -CONU-, -COO-, ethyleneoxy, propyleneoxy, phenyl, benzyl, etc.; R3 and R4 represent, inde-5 pendently, hydrogen, or alkyl, alkenyl or hydroxyalkyl groupscontaining from 1 to about 1~ carbon atoms, and optionally sub-stituted or interrupted by groups such as -O-, -CONH-, -COO-, ethyleneoxy, propyleneoxy, etc.; and X is the salt counteranion, preferably selected from halide, methylsulfate, ethylsulfate, and 10 organic anions. The number of certain optional functional groups ~e.g., -OH, -CONH-3 present in the cationic fabric softening agent is limited such that the softening agent is substantially water-insoluble .
Represen~ative examples of these quaternary softeners in-15 clude: ditallow dimethyl ammonium chloride ditallow dimethylammonium methyl sulfate; dihexadecyl dimethyl ammonium chloride:
di(hydrogenated tallow alkyl) dimethyl ammonium chloride; di-octadecyl dimethyl ammonium chloride; dieicosyl dimethyl ammonium chloride; didocosyl dimethyl ammonium chloride; di(hydrogenated 20 tallow) dimethyl ammonium methyl sulfate; dihexadecyl diethyl ammonium chloride; di(coconut alkyl) dimethyl ammonium chloride di(coconut alkyl) dimethyl ammonium methylsulfate; di(tallowyl amido ethyl) dimethyl ammonium chloride; di(tallowyl amido ethyl) dimethyl ammonium methylsulfate; cli(tallowyl amido propyl) di 25 methyl ammonium chloride; and di(tallowyl amido propyl) dimethyl ammonium methylsulfate.
Another preferred type of substantially water-insoluble cationic fabric softening agent includes compounds frorn the class of tri-C8-C30, preferably tri-C1 2~C24 ~ quaternary ammonium 30 salts. These compounds have structures similar to the di-C8-C30 alkyl or alkenyl quaternary ammonium salts immediately hereinbefore described, except that either the R3 or R4 group is a C8-C30, preferably a C1 2-C24, group selected from the same groups as can be used for the R and R groups. Representa-35 tive examples are tri(hardened tallowalkyl)methylammonium salts,trioleylmethylammonium salts, and tripalmitylmethylammonium salts.
f~
Yet another preferred type of conventional cationic fabric softening agent includes the substantially water-insoluble materials which are the alkyl imidazolinium salts and alkyl pyrimiclinium salts believed to have the formula:
(( ) [CH ) --N~ R7 ~ X
l0 wherein the n's are, independently, an integer from about 2 to about 6, preferably n = 2 or 3; R5 is hydrogen or an alkyl, alkenyl or hydroxyalkyl group containing from 1 to about 4, preferably 1 or 2, carbon atoms, optionally substituted or interrupted by groups such as -O-, -CONH-, -COO-, 15 ethyleneoxy, propyleneoxy, etc.; R6 and R7 are, independently, alkyl or alkenyl groups containing from about 8 to about 30, preferably from about 12 to about 24, carbon atoms, optionally substituted or interrupted by groups such as -OH, -O-, -CONH-, -COO, ethyleneoxy, propyleneoxy, phenyl, benzyl, etc.; R8 is 20 hydrogen or an alkyl, alkenyl or hydroxyalkyl group containing from 1 to about 4 carbon atoms, uptionally substituted or inter-rupted by groups such as -O-, -CONH-, -COO-, ethyleneoxy, propyleneoxy, etc.; and X is the salt counteranion, preferably selected from halide, methylsulfate, ethylsulfate, and organic 25 anions. The number of certain optional functional groups (e.g., OH, -CONH-) present in the cationic fabric softening agent is limited such that the softening agent is substantially water-insoluble .
Representative examples of the fabric softening alkyl imida-30 zolinium salts include: 3-methyl-1-(tallowylamido) ethyl~2~tallowyl~
4,5-dihydroimidazolinium methylsulfate; 3-methyl-1-(palmitoyl~
amido)ethyl-2-octadecyl~4,5-dihydroimidazolinium chloride: 2-heptadecyl~3-methyl-1 -~2-stearylamido~-ethyl-4 ,S-dihydroimidazo-linium chloride; 2~-1auryl~3-hydroxyethyl-1-(oleylamido)ethyl~
35 4,5~dihydro imidazolinium chloride: and protonated 1-hardtallow amido ethyl-2-hardtallow imidazoline. Also suitable as conven-tional fabric softeniny agents herein are the imidazoiinium ~abricsoftening components of U.S. Patent No. 4,127,1l89, All o~ the foregolng types o~ conventlonal cationic fabric 5 softening agents can be readily syntheslzed in known manner.
Many of these materials are, in fact, commercially available.
Representative commercially available materials of the above classes inciude the quaternary ammonium compounds Adogen q48i~3 (tradem3rk of Sherex Chemical C:ompany, Inc., Dublin, Ohio 10 comprises approximately 85% ditallow dimethyl ammonium chloride) and Varisoft 110~) ~trademark of Sherex Chemical Company, Inc., Dublin, Ohio comprises methyl bis(hydr.tallowamidoethyl)2-hydroxyethyl ammonium methyl sulfate); and the imidazolinium compound Varisoft 475~) 5$rademark of Sherex Chemical Company, 15 Inc,, Dublin, Ohio; comprises methyl-1-tallow amido ethyl-2-tallow imiciazolinium methyl sulfate).
Particularly preferred speciflc compounds for use as the fabric softenlng agent in the compositions of the present invention are: ditallow dimethyl ammonium chloride (particularly Adogen 20 448E~)), ditallow dimethyl ammonium methyl sulfate, and methyl-1-tallow amido ethyl-2-tallow imidazolinium methyl sulfate.
The conventional cationic fabric softening agents useful in the present Invention are substantially water-insoluble. Such materlals are, however, freqùently water-dispersible and these 25 can readily be formulated into aqueous textile treating compositions .
The substantially water-insoluble cationic fabric softening agents are utilized In the textTle treating compositions herein in an amount of from about 0. i% to about 99.9% by weight, more 30 preferably from about 0.1% to about 30~ by welght, most preferably from about 1% to about i 0~ by weight of the composition. This fabric softening agent is also utilized In a particular welght ratio vis a vis the substantially saturated phosphoglyceride-containing lipid component as hereinafter 35 described In greater detail.
~f~
Substantially Saturated Phosph~ylyceride-Containing Lipicl Componen A second essential component of the textile treating com-positions herein comprises a substantially saturated, phospho-5 glyceride-containing lipid component. This lipid component will generally be anionic in nature and is thus distinct from the conventional, substantially water-insoluble cationic fabric softening agents hereinbefore described.
The substantially saturated, phosphoglyceride-containing 10 lipid component will generally contain at least about 50%, pref-erably from about 5096 to about 95%, and more preferably from about 55% to about 75%, by weight of lipid materials which are acetone insoluble. This acetone-insoluble lipid material itself comprises at least about 50%, more pr0ferably at least about 60~6, 15 by weight of one or more acetone-insoluble phosphoglycerides.
More particularly, such phosphoglyceride material wiil generally be selected from the group consisting of phosphatidyl choline (i.e., "pure lecithin"), phosphatidyl ethanolamine, phosphatidyl inositol, serine phosphoglyceride, phosphatidic acid, or mixtures 20 thereof. Preferably, the phosphoglycerides are di-acyl esters of fatty acids having at least about 8 carbon atoms, more preferably esters of C8-C30 fatty acids, and most preferably esters of C1 2-C24 fatty acids . The remainder of the acetone-insoluble lipid material present in the substantially saturated lipid component 25 typically comprises acetone-insoluble lipid materials such as phosphoglycolipids, phosphodiol lipids, phosphosphingolipids, glycolipids, or mbttures thereof.
The substantially saturated lipid component of the composi-tions herein may also contain acetone-soluble lipid material. Such 30 acetone-soluble material can include, for example, free fatty acids, fatty acid diglycerides, and/or fatty acid triglycerides.
The acetone-soluble lipid material should comprise less than about 50%, preferably from about 5% to about 50%, and more preferably from about 25% to about 45%, by weight, of the substantially 35 saturated lipid component of the compositions herein.
The substantially saturated lipid componen~ containiny the requ;site concentration of acetone-insoluble lipid materials can be derived from animal or vegetable svurces (e.g., soybeans, corn, - rapeseed, peanuts, sunflowers, safflowers, etc. ) . Preferred sources include egg yolk or soybean lecithin mixtures which are commercially available, with soybean lecithin mixtures being most preferred. The term lecithin mixtures, as used herein, means a material which is a mixture comprising more than one phosphoglyceride component, with at least one of the phospho-glyceride components being phosphatidyl choline (i.e., pure lecithin), phosphatidyl ethanolarr ine, phosphatidyl inositol, serine phosphoglyceride, or phosphatidic acid. For example, commercial-Iy available soybean lecithin mixtures Include Centrolex F~) (trademark of Central Soya, For~ Wayne, Indiana) which com-prises an approximately 95% acetone-insoluble fraction that con-tains at ieast approximately 60% phosphoglycerides~ Another example is Centrol 3F-DB(~ (trademark of Central Soya, Fort Wayne, Indiana) which comprlses an approximately 60% acetone-insoluble fraction that contains at least approximately 50~ phos-phoglycerides.
The acetone-lnsoluble lipid fraction present in soybean lecithln mixtures typically comprises: from about 2096 to about 30~
of phosphatidyl choline (i.e., pure lecithin ): from about 15% to about 25% of phosphatidyl ethanolamine; from about 10~ to about 20~ of phosphatidyl inositol; and from about 0% to about 15% of phosphatidic acid. The acetone-soluble lipid fraction present in commercially available soybean lecithin mixtures predominantly comprises a mixture of free fatty acids, fatty acid diglycerides, and fatty acid triglycerides. A more detailed description of the composition of lecithln mlxtures useful as sources of the lipid component of the present invention can be found In Kirk-Othmer Encyclopedia of Chemical_Technolociy, Third Edition, Vol. 14 pages 250-269 ~Grayson et al Editors; Wiley-lnterscience, New York, N.Y. 1981~.
- 1 o -It is necessary that the llpid material utllize~l in the compositions of the present invention be selectecl or modified, ,c referably modified by hydrogenation, such that the lipid cornpo-nent of the composition herein is substantially saturated. The 5 term "substantially saturated" as used herein means that the sub-stantially saturated lipid component has an iodine value (a well-known quantitative measure of unsaturation in lipid materiais) of less than about 75, preferably less than about 65, more prefer-ably tess than about S0, and most preferably less than about 30.
For optimum textile soften~ng performance to be realized wi~h the compositions of the present invention, it is preferred that the substantially saturated, phosphoglyceride containing lipid com-ponent be obtained by hydrogenating lecithin mixtures, preferably commercially avaiiable soybean lecithin mlxtures. Most preferred 15 are soybean lecithin mixtures comprising from about 5% to about 50~, preFerably from about 25% to about 45~6, by weight of acetone-soluble material. These particular types of soybean lecithin mixtures are preferably hydrogenated such that their iodine value is abou~ 50 or less, more preferably about 30 or 20 less.
Some types of hydrogenated phosphoglycerides-containing lipid mixtures are known in the art (see, for example, The Kirk-Othmer Encyclopedia of Chemical Technology. Hydrogena-tion processes which may be utilized to modify phospho-glyceride-containing lipid materials are also known. For example, U.S. Patent 3,026,341, to Da~is, issued March 20, 1962, discloses a process for hydrogenating lecithin mixtures. Hydrogenation procedures are more fully exempliEied hereinafter.
It should be recognized for purposes of the present Inven-tion that the substantially saturated lipid component of the com-positions herein may also be produced synthetically instead of being obtained or derlved from naturally-occurrlng sources.
Furthermore, the substantially saturated lipld component may comprise percentages of the varlous Indlvidual phosphoglyceride ~.~,.
components which differ from the component concentrations typi-cally found in commercially available lecithin mixtures. For example, the acetone-insoluble lipid material present in the sub--stantially saturated lipid component may comprise percentages of 5 phosphatidyl choline, phosphatidyl ethanolamine, phosphatidic acid, serine phosphoglyceride, and/or phosphatidyl inositol, which are, individually, greater ~han or less than those typically found in commercially available lecithin mixtures, as clescribed herein-before .
In addition, it should be recognized for purposes of the present invention that the substantially satura~ed lipid components of the compositions herein may also be obtained by combining, for example, acetone-insoluble phosphoglycerides or phosphoglyceride-containing acetone-insoluble lipid materials with açetone-soluble 15 lipid materials, such as by combining a hydrogenated or non-hydrogenated acetone-insoluble phosphoglyceride with hydrogenated or non-hydrogenated soybean oil (i.e., pre-dominantly di- and triglycerides). For example, the substantially saturated, phosphoglycaride-containing lipid component might be a 20 combination of hydrogenated Centrolex ~) (described more fully hereinafter) and non-hydrogenated soybean oil.
The compositions of the present invention, which utilize substantially saturated lipid components containing the above-described minimum amount of aceltone-insoluble phosphoglycerides, 25 provide surprisingly better softening performance under textile laundering conditions than do compositions in which the phospho-glycerides are not present. As noted above, for optimum textile softening performance, it i5 preferred that the substantially saturated, phosphoglyceride-containing lipi~ component be ob-30 tained by hydrogenating the lipid component, more preferably byhydrogenating lecithin mixtures, and most preferably by hydro-genating commercially available soybean lecithin mixtures.
The compositions of the present invention also provide unexpectedly superior performance relative to compositions which 35 comprise a phosphoglyceride-containing lipid component that is not substantialiy saturated on the basis of color and odor profiles for textiles which have been treated dl~ring a textile laundering operation and then stored for several weeks. In particular, textiles treated with compositions which comprise a conventional fabric softening agent and a phosphoglyceride-containing lipid 5 component which is not substantially-saturated tend to become yellow and develop a fatty odor after several weeks, whereas textiles treated with compositions of the present invention do not.
The substantially saturated lipid component of the composi-tions herein generally comprise from about 0.1% to about 99.9~ by weight, more preferably from about 0.1~ to about 30~6 by weight, and most preferably from about 1~ to about 10% by weight of the textile treating compositions of the present invention. Further-more, the subs~antially saturated lipid component of such composi-tions is generally present in an amount which is suffioient to provide a weight ratio of the acetone-insoluble lipid material (present in the substantially saturated lipid component) to the substantially water-insoluble cationic fabric softening agent within the range of from about 0.01 :1 to about 5:1, preferably from about 0.1 :1 to about 2.5:1, more preferably from about û.1 :1 to about 1.5:1, and most preferabnly about 0.5:1.
ptional components Although textile treating compositions herein need contain only the substantially water-insoluble cationic fabric softening agent and the substantially saturated, phosphoglyceride-contain-ing lipid component as hereinbefore described, such compositions can optionally contain a wide variety of additional ingredients.
The nature and amounts of such optional components are very much dependent upon desired final form and intended means of use of the textile treating compositions.
Most frequently, the textile treating compositions herein are in liquid form suitable for addition to the rinse water during the rinse cycle of a home laundering operation. Liquid compositions of this type will generally be prepared as an aqueous dispersion of the softening agent and lipid components, and accordingly, the most commonly employed optional component of the compositions herein will be water. Water can, in fact, comprise up to about 99 . 9% by weight of the compositions herein . More frequen tiy, liquld compositions of this type will comprise from about 50% to about 99.9~, preferably from abou~ 70~ to about 95%, by weight of water .
The compositions of the preser,t invention can also contain various other compatible optional components such as those mate-rials which are conventionally used in textile treating composi-tions. These componen~s can include, for example, colorants, perfumes, preservatives, optical brighteners, opacifiers, pH
buffers, electrolytes, viscosity modifiers, fabric conditioning agents, surfactants, stabilizers (such as polysaccharides, e.g., guar gum and polyethylene glycol ), anti-shrinkage agents, anti-wrinkle agents, fabric crispening agents, spotting agents, soil release agents, germicides, fungicides, anti-oxidants ~such as ~(-tocopherol and butylated hydroxy toluene), anti-corrosion agents, fabric softening agents which are not substantially water-insoluble cationic fabric softening agents, etc. While any or all of these optional components may be employed, the compositions of the present invention will most often include, in addition to the essential components, a dye, a perfume, and/or a preservative, with the remainder of the compositions being water.
Composition preparation The textile treating compositions herein may be prepared by simply combining the essential and desired optional components thereof in the requisite proportions. When prepared in the form of an aqueous dispersion, the combination of essential ingredients in soiid form are admixed with water, and this admixture is subjected to sufficient shear agitation to form the desired dis-persion. The mean particle size of the combination of active ingredients in such dispersions, to provide optimum softening performance, will generally range from about 0.01 micron to about 10 microns, prefera~ly within the range of from about 0.05 micron to about 1 micron. The pH of such compositions in aqueous form is not critical, and may be anywhere within the normal range for effective performance of the conventional fabric softening agent used. The natural pH of the mix components is ordinarily satisfactory. If adjustment in pH is desired for any reason, trace quantities of organic or inorganic aci~s or bases can bs used. A preferred range is 2.0-8.0; especially preferred is 3.0-7Ø
If the textile treating compositions of the present invention are to be employed in a laundry dryer, such compositions will generally be in solid ~orm. Frequently such compositions can be fashioned into dryer-added textile treating articles by combining such compositions with 3 substrate carrier. Textile tr~ating articles of this type are described in the a~rementioned U . S .
Patent 4,022,938, U.S. Patent 3,843,395 and U.5. Patent 3, 686, 025 .
Text le treating method The present invention also relates to methods for treating textiles to impart fabric softening and conditioning benefits to textiles so treated. Such a method in general is carried out by contacting textiles to be treated with a textile softening amount of a combination of the substantially water-insoluble cationic sof tening agent and substantially saturated, phosphoglyceride-containing lipid components of the textile treating composition hereinbefore described. Thus to carry out the textile treating methods herein, the compositions of this invention may be con-tacted directly with textiles to be treated or may be added to textile-containing aqueous solutions used in laundering operations.
The fabric softening compositions of the present invention are preferably used by adding such compositions to the rinse cycle during a conventionai home laundering operation. For optimun~ softening performance, detergent carry-over from the wash cycle to the rinse cycle containing the fabric softening composition should be minimized. Generally, rinse water in such operations has a temperature of about 5C to about 60C. The compositions of the present invention are used in the rinse such that the concentration of the actives ( i . e ., conventional cationic fabric softening agent plus lipid component) in the rinse is suf-ficient to impart a softening benefit to the textiles in the rinsing bath. Generally, such concentrations fall within the range of from about 10 ppm to about 1,000 ppm, preferably from about 10 5~
ppm to about 500 ppm, most preferably from about 50 ppm to about 100 ppm, wi~hin ~he aqueous rinsing bath. ~/hen multiple rinses are used, the textile treating composition is preferably added to the final rinse.
As indicated, the textile treating methods of this invention may also be carried out by adding the textile treating composi-tions herein to an automatic laundry dryer. Such compositions may aiso be added to the surfactant-containing a~ueous washing bath used in a horne laundering operation.
The following examples illustrate the fabric softening com-positions and methods of the present invention, and the benefits achieved by the utilization of such compositions and methods.
These examples are illustrative of the invention herein and are not to be construed as limiting thereof.
Com osition containin substantiallv saturated soybean lecithin mixture (959~ acetone-insoluble lipid) _ Compound Weight %
. ~
SBL " 2.81 Adogen 448E 2) 6.42 dye3 ) 0 .18 preservative0 . 02 perfume 0. 42 water balance 25 1 ) = soybean lecithin ~Centrolex F~9 from Central Soya, Fort Wayne, Indiana; approximately 9596 acetone-insoluble lipid which comprises at least approximately 60% phosphoglycer-ides; iodine value approximately 74)
2) = trademark of Sherex Chemical Company, Inc., Dublin, Ohio;
comprises approximately 85% ditallow dimethyl ammonium chloride
comprises approximately 85% ditallow dimethyl ammonium chloride
3) = solution containing less than about 10% dye Use of this composition during the rinse cycle while laundering textiles in a home laundering machine, at a concen-tration of 70 ppm, followed by drylng in an automatic dryer, provides improved softening and condltioning benefits to the texti les .
Composition containing hydrogenated soybean lecithin mixture (95~ acetone-insoluble lipid) A. Hydrogenation of soybean lecithin mixture Commercially available soybean lecithin containlng 95 acetone-insoluble iipid material (1,500 g Centrolex F from Central Soya, Fort Wayne, Indiana; iodine value approximately 74;
phosphoglyceride content at least approximately 60% of the acetone-insoluble lipid content) in benzene (2,300 ml) is added to approximately 4-S grams of 10~ Pd/C in 500 ml of methanol. (The 10% Pd/C in methanol is allowed to sit for 1-1/2 hours prior to the addition of the lecithin under 200 psi of hydrogen gas. ) The resulting mixture is purged 4 times with hydrogen, and then the reaction is placed under approximately 200 psi of hydrogen gas.
The mixture is maintained at an average temperature of approxi-mately 50C (+ approximately 10C) under an average hydrogen gas pressure of approximately 200 psi for about 48 hours, after which time the rate of hydrogen uptake by the mixture is very slow. The reaction mixture is then filtered and the filtrate evaporated under partial vacuum to give the hydrogenated phosphoglyceride-containing lipid component (iodine value approximately 30) to be used in preparing the textile treating composition .
B. Preparation of the textile treating composition The hydrogenated phosphoglyceride-containing lipid material from par~ A above (approximately 60 grams) is combined with ditallow dimethyl ammonium chloride (approximately 140 grams of Adogen 448 E~ from Sherex Chemical Company, Inc., Dublin, Ohio; approximately R5% ditallow dimethyl ammonium chloride) in a weight ratio of approximately 0.5:1 (acetone-insoluble lipid material:ditallow dimethyl ammonium chloride). This solid com~
bination is heated to the point of melting (approximately 1 50F) and then stirred for about 5 minutes to mix the components. At this time approximately 196 grams of the hot melt is poured into approximately 1,800 grams of distilled water (pH approximately 5) containing about 0.4 grams Kathon~ (preservative made by Rohm and Haas, Philadelphia, PA) at approximately 150~F. This mix-ture is then subjected to high speed mechanical shearing for approximately 10 rnlnutes In a mixer ( Tekmar~q'SD-45, manufactured by Tekmar, Cincinnati, Ohio, and using a G-456 generator, manufactured by Tekmar, Cincinnati, Ohio set at speed setting of 60) . This mixture is then cooled to approximately 1 00F and approximately 9 grams of perfume is mixed in with slow speed stirring. The viscosity of the final product is approximateiy 24 cps and the mean particle size of the solid actlve combination is approximately 0. 2 microns .
Use of this composition during the rlnse cycle while launder-ing textiles in a home laundering machlne, at a concentration of 70 ppm, followed by drying the textiles in an automatic dryer, provides improved softening and condltionTng benefits to the 1 5 textiles.
ComposTtion containin~ hydroaenated eaa volk L-o~- phospha-tidyl choline A. Hydro~enation of egg yolk L~(-phosphatTdyl choline 100 grams of egg yolk L-~-phosphatidyl choline (i.e., pure egg yolk lecithin; Sigma Chemical Co., St. Louis, MO) is added to approximately 0.5-1 grams Pd/C in approxTmately 140 ml methanol. The Pd/C in methanol has been previously allowed to sit for 100 minutes under 180 psT of hydrogen gas at room temperature, exhausted of hydrogen gas and then flushed with nitrogen gas. Thls mixture is then flushed four times with hydrogen gas, and the reactTon mlxture then placed under approximately 100 psi of hydrogen gas. The mixture is maintained at a temperature between about 50-80C under an average hydrogen gas pressure of approximately 150 psi for about 26 hour~, after which time the rate of hydrogen gas uptake by the mixture is very slow. The reaction mixture is then filterecl and the filtrate evaporated under partial vacuum to give the hydrogenated egg yoik phosphatidyl choline to be used in the textile treatinci composltion.
~r~ 5 -- 18 ~
B, Textile treating composition containing hydro~3enated egg yolk phosphatidyl choline Utilizing a preparation procedure essentially the same as described in Example 2(B) hereinbe~re, the following textile treating composition is prepare~.
Component Weight EYLH 1 ) 2.94~
DTDMAC 2) 2.31%
Preservative 0. 02~
Perfume 0. 45%
Water balance 1 ) ~ hydrogenated egg yolk lecithin prepared as in Example 3(A).
2 ) = ditallow dimethyl ammonium chloride Use of this composition during the rinse cycle while 15 laundering textiles in a laundering machine, at a concentration of 230 ppm, followed by line drying the textile, provides impro~/ed softening and conditioning benefits to the textiles.
.
Composition containin~3 hydrogenated soybean lecithin mixture 20 (60% acetone-insoluble lipid).
Commercially available soybean lecithin containing a~proxi-mately 60% acetone-insoluble lipid material (Centrol 3F-DBU3) from Central Soya, Fort Wayne, Indiana; iodine value approximately 97;
phosphoglyceride content at least about 50% of acetone-insoluble 25 ~ipid content) is hyclrogenated using essentially the same pro-cedure as in Example 2(A~ (except that methanol is used as the solvent in place of benzene) to give a hydrogenated phospho-glyceride-containing lipid material (iodlne value approximately 68).
Preparation of a textile treating composition utilizing essentially 30 the same procedure as in Example 2(B) hereinbefore gives the following composition.
Component SBLH 1 J 5.34 Adogen 448E~32) 6.42 dye 0.18 _ 1 9 --preservative 0. 02 perfume 0. 42 water balance 1 ) = hydrogenated Centrol 3F-DBR
5 2) = trademark of Sherex Chemical Company, Inc., Dublln, Ohio;
comprises approximately 85% ditallow dime~hyl ammonium chloride 3 ) = solution containing less than about 10% dye Use of this composition during the rinse cycle while 10 laundering textiles in a home laundering machine, at a concentration of 430 ppm, followed by line drying, provides improved softening and conditioning benefits to the textiles.
Compositions containing hydroqena~ed soybean lecithin ~.
15 mixture 160% acetone-insoluble lipid) Weight %
Component Composition AComposition B
SBLH 1, 5.78 5.78 Adogen 448E~2) 4.63 2û di-hardtallow imidazoline 1.93 6.3 dye solution 4) 0.18 0.18 preservative 0 . 02 0 . 02 perfume 0 . 42 0 . 42 water balance 5)balance 6) 25 1 ) = hydrogenated Centrol 3F-DB ~) described in Example q 2) _ trademark of Sherex Chemical Company, Inc., Dublin, Ohio;
comprises approximately 85% ditallow dimethyl ammonium chloride 3) = approximately 90% 1-hardtallow amido ethyl-2-hardtallow imidazoline obtained from Sherex Chemical Company, Inc., Dublin, Ohio (comprises an equilibriurn mixture of the cyclic form as 1 hardtallow amido ethyl-2-hardtallow imidazoline, and the straight chain form as RCONHCH2CH2NHCH2CH2NH-COR, wherein the R's are hardtallow. j
Composition containing hydrogenated soybean lecithin mixture (95~ acetone-insoluble lipid) A. Hydrogenation of soybean lecithin mixture Commercially available soybean lecithin containlng 95 acetone-insoluble iipid material (1,500 g Centrolex F from Central Soya, Fort Wayne, Indiana; iodine value approximately 74;
phosphoglyceride content at least approximately 60% of the acetone-insoluble lipid content) in benzene (2,300 ml) is added to approximately 4-S grams of 10~ Pd/C in 500 ml of methanol. (The 10% Pd/C in methanol is allowed to sit for 1-1/2 hours prior to the addition of the lecithin under 200 psi of hydrogen gas. ) The resulting mixture is purged 4 times with hydrogen, and then the reaction is placed under approximately 200 psi of hydrogen gas.
The mixture is maintained at an average temperature of approxi-mately 50C (+ approximately 10C) under an average hydrogen gas pressure of approximately 200 psi for about 48 hours, after which time the rate of hydrogen uptake by the mixture is very slow. The reaction mixture is then filtered and the filtrate evaporated under partial vacuum to give the hydrogenated phosphoglyceride-containing lipid component (iodine value approximately 30) to be used in preparing the textile treating composition .
B. Preparation of the textile treating composition The hydrogenated phosphoglyceride-containing lipid material from par~ A above (approximately 60 grams) is combined with ditallow dimethyl ammonium chloride (approximately 140 grams of Adogen 448 E~ from Sherex Chemical Company, Inc., Dublin, Ohio; approximately R5% ditallow dimethyl ammonium chloride) in a weight ratio of approximately 0.5:1 (acetone-insoluble lipid material:ditallow dimethyl ammonium chloride). This solid com~
bination is heated to the point of melting (approximately 1 50F) and then stirred for about 5 minutes to mix the components. At this time approximately 196 grams of the hot melt is poured into approximately 1,800 grams of distilled water (pH approximately 5) containing about 0.4 grams Kathon~ (preservative made by Rohm and Haas, Philadelphia, PA) at approximately 150~F. This mix-ture is then subjected to high speed mechanical shearing for approximately 10 rnlnutes In a mixer ( Tekmar~q'SD-45, manufactured by Tekmar, Cincinnati, Ohio, and using a G-456 generator, manufactured by Tekmar, Cincinnati, Ohio set at speed setting of 60) . This mixture is then cooled to approximately 1 00F and approximately 9 grams of perfume is mixed in with slow speed stirring. The viscosity of the final product is approximateiy 24 cps and the mean particle size of the solid actlve combination is approximately 0. 2 microns .
Use of this composition during the rlnse cycle while launder-ing textiles in a home laundering machlne, at a concentration of 70 ppm, followed by drying the textiles in an automatic dryer, provides improved softening and condltionTng benefits to the 1 5 textiles.
ComposTtion containin~ hydroaenated eaa volk L-o~- phospha-tidyl choline A. Hydro~enation of egg yolk L~(-phosphatTdyl choline 100 grams of egg yolk L-~-phosphatidyl choline (i.e., pure egg yolk lecithin; Sigma Chemical Co., St. Louis, MO) is added to approximately 0.5-1 grams Pd/C in approxTmately 140 ml methanol. The Pd/C in methanol has been previously allowed to sit for 100 minutes under 180 psT of hydrogen gas at room temperature, exhausted of hydrogen gas and then flushed with nitrogen gas. Thls mixture is then flushed four times with hydrogen gas, and the reactTon mlxture then placed under approximately 100 psi of hydrogen gas. The mixture is maintained at a temperature between about 50-80C under an average hydrogen gas pressure of approximately 150 psi for about 26 hour~, after which time the rate of hydrogen gas uptake by the mixture is very slow. The reaction mixture is then filterecl and the filtrate evaporated under partial vacuum to give the hydrogenated egg yoik phosphatidyl choline to be used in the textile treatinci composltion.
~r~ 5 -- 18 ~
B, Textile treating composition containing hydro~3enated egg yolk phosphatidyl choline Utilizing a preparation procedure essentially the same as described in Example 2(B) hereinbe~re, the following textile treating composition is prepare~.
Component Weight EYLH 1 ) 2.94~
DTDMAC 2) 2.31%
Preservative 0. 02~
Perfume 0. 45%
Water balance 1 ) ~ hydrogenated egg yolk lecithin prepared as in Example 3(A).
2 ) = ditallow dimethyl ammonium chloride Use of this composition during the rinse cycle while 15 laundering textiles in a laundering machine, at a concentration of 230 ppm, followed by line drying the textile, provides impro~/ed softening and conditioning benefits to the textiles.
.
Composition containin~3 hydrogenated soybean lecithin mixture 20 (60% acetone-insoluble lipid).
Commercially available soybean lecithin containing a~proxi-mately 60% acetone-insoluble lipid material (Centrol 3F-DBU3) from Central Soya, Fort Wayne, Indiana; iodine value approximately 97;
phosphoglyceride content at least about 50% of acetone-insoluble 25 ~ipid content) is hyclrogenated using essentially the same pro-cedure as in Example 2(A~ (except that methanol is used as the solvent in place of benzene) to give a hydrogenated phospho-glyceride-containing lipid material (iodlne value approximately 68).
Preparation of a textile treating composition utilizing essentially 30 the same procedure as in Example 2(B) hereinbefore gives the following composition.
Component SBLH 1 J 5.34 Adogen 448E~32) 6.42 dye 0.18 _ 1 9 --preservative 0. 02 perfume 0. 42 water balance 1 ) = hydrogenated Centrol 3F-DBR
5 2) = trademark of Sherex Chemical Company, Inc., Dublln, Ohio;
comprises approximately 85% ditallow dime~hyl ammonium chloride 3 ) = solution containing less than about 10% dye Use of this composition during the rinse cycle while 10 laundering textiles in a home laundering machine, at a concentration of 430 ppm, followed by line drying, provides improved softening and conditioning benefits to the textiles.
Compositions containing hydroqena~ed soybean lecithin ~.
15 mixture 160% acetone-insoluble lipid) Weight %
Component Composition AComposition B
SBLH 1, 5.78 5.78 Adogen 448E~2) 4.63 2û di-hardtallow imidazoline 1.93 6.3 dye solution 4) 0.18 0.18 preservative 0 . 02 0 . 02 perfume 0 . 42 0 . 42 water balance 5)balance 6) 25 1 ) = hydrogenated Centrol 3F-DB ~) described in Example q 2) _ trademark of Sherex Chemical Company, Inc., Dublin, Ohio;
comprises approximately 85% ditallow dimethyl ammonium chloride 3) = approximately 90% 1-hardtallow amido ethyl-2-hardtallow imidazoline obtained from Sherex Chemical Company, Inc., Dublin, Ohio (comprises an equilibriurn mixture of the cyclic form as 1 hardtallow amido ethyl-2-hardtallow imidazoline, and the straight chain form as RCONHCH2CH2NHCH2CH2NH-COR, wherein the R's are hardtallow. j
4) = solution containing less than about 10% dye
5) = pH of final product approximately 2 by acidifying water with HCI
6) = pH of final product approximately 4 by acidifying water with HCI
Use of either of these compositions during -the rinse cycle while laundering textiles in a home laundering machine, at a concentration of 430 ppm, followed by line drying, provides improved softening and conditioning benefits to the textiles.
Composition containing hydrogenated soybean lecithin mixture ( 60% acetone- insoluble I ipid ) Commercially available fluid soybean lecithin containing approximately 60% acetone-insoluble lipid material lfluid soybean lecithin from Victory Soya, Toronto, Canada; iodine value approx-imately 93; phosphoglyceride content at least about 50% of acetone-insoluble lipid content) is hydrogenated using essentially the same procedure as in Example 2(A) (except that methanol is used as the solvent in place of benzene) to give a hydrogenated phosphoglyceride-containing lipid material (iodine value approxi-ma~ely 26)o Preparation of a textile treating composition utilizing essentially the same procedure as in Example 2(B) lexcePt that a Brookfield Counter-Rotating Mixer, Model L891, manufactured by Brookfield Engis~eering Lab, Stoughton, Massachusetts is utilized) gives the following composition.
Component Weight %
SBLH 1 5.28 Adogen 448E~192 ) 6 . 75 dye 3) 0.29 preservative 0. 02 perfume 0. 46 water balance 1 ) = hydrogenated Victory fluid soybean lecithin 2l = trademark of Sherex Chemical Company, Inc., Dublin, Ohio:
comprises approximately 85% ditallow dimethyl ammonium chloride 3) = solution containing less than about 10~ dye Use of this compasition during the rinse cycle while laun-dering textiles in a home laundering rnachine, at a concentration of 70 ppm, followed by drying the textiles in an automatic dryer, provides improves softening and conditioning benefits to the S texti I es .
Composition containing hydrogenated soybean lecithin mixture (60% acetone-insoluble lipid) Commercially available soybean lecithin containing ap~proxi-10 mately 60~ acetone-insoluble iipid material (Centrol 3F-DB~E3) from Central Soya, Fort Wayne, Indiana; iodine value approximately 97;
phosphoglyceride content at laast abou~ 50% of acetone-insoluble lipid content) is hydrogenated using essentially the same procedure as in Example 2(A) (except that methanol is used as 15 the solvent in place of benzene) to give a hydrogenated phospho-glyceride-containing lipid material (iodine value approximately 19).
Preparation of a textile treating composi~ion utilizing essentially the same procedure as in Example 2(B) hereinbefore gives the following composition.
Component Wei~ht %
SBLH 5.56 Adogen 448E 2) 6.69 dye 3) 0.18 preservative 0 . 02 2S perfume 0 . 42 water balance 11 = hydrogenated Centrol 3F-DB(3 2) = trademark of Sherex Chemical Company, Inc., Dublin, Ohio;
comprises approximately 85% ditallow dimethyl ammonium chloride 3) = solution containing less than about 10% dye Use of this composition during the rinse cycle while laun-dering textiles in a home laundering machine, at a concentration of 70 ppm, followed by drying the textiles in an automatic dryer, 35 provide improved softening and conditioning benefits to the texti les .
Use of either of these compositions during -the rinse cycle while laundering textiles in a home laundering machine, at a concentration of 430 ppm, followed by line drying, provides improved softening and conditioning benefits to the textiles.
Composition containing hydrogenated soybean lecithin mixture ( 60% acetone- insoluble I ipid ) Commercially available fluid soybean lecithin containing approximately 60% acetone-insoluble lipid material lfluid soybean lecithin from Victory Soya, Toronto, Canada; iodine value approx-imately 93; phosphoglyceride content at least about 50% of acetone-insoluble lipid content) is hydrogenated using essentially the same procedure as in Example 2(A) (except that methanol is used as the solvent in place of benzene) to give a hydrogenated phosphoglyceride-containing lipid material (iodine value approxi-ma~ely 26)o Preparation of a textile treating composition utilizing essentially the same procedure as in Example 2(B) lexcePt that a Brookfield Counter-Rotating Mixer, Model L891, manufactured by Brookfield Engis~eering Lab, Stoughton, Massachusetts is utilized) gives the following composition.
Component Weight %
SBLH 1 5.28 Adogen 448E~192 ) 6 . 75 dye 3) 0.29 preservative 0. 02 perfume 0. 46 water balance 1 ) = hydrogenated Victory fluid soybean lecithin 2l = trademark of Sherex Chemical Company, Inc., Dublin, Ohio:
comprises approximately 85% ditallow dimethyl ammonium chloride 3) = solution containing less than about 10~ dye Use of this compasition during the rinse cycle while laun-dering textiles in a home laundering rnachine, at a concentration of 70 ppm, followed by drying the textiles in an automatic dryer, provides improves softening and conditioning benefits to the S texti I es .
Composition containing hydrogenated soybean lecithin mixture (60% acetone-insoluble lipid) Commercially available soybean lecithin containing ap~proxi-10 mately 60~ acetone-insoluble iipid material (Centrol 3F-DB~E3) from Central Soya, Fort Wayne, Indiana; iodine value approximately 97;
phosphoglyceride content at laast abou~ 50% of acetone-insoluble lipid content) is hydrogenated using essentially the same procedure as in Example 2(A) (except that methanol is used as 15 the solvent in place of benzene) to give a hydrogenated phospho-glyceride-containing lipid material (iodine value approximately 19).
Preparation of a textile treating composi~ion utilizing essentially the same procedure as in Example 2(B) hereinbefore gives the following composition.
Component Wei~ht %
SBLH 5.56 Adogen 448E 2) 6.69 dye 3) 0.18 preservative 0 . 02 2S perfume 0 . 42 water balance 11 = hydrogenated Centrol 3F-DB(3 2) = trademark of Sherex Chemical Company, Inc., Dublin, Ohio;
comprises approximately 85% ditallow dimethyl ammonium chloride 3) = solution containing less than about 10% dye Use of this composition during the rinse cycle while laun-dering textiles in a home laundering machine, at a concentration of 70 ppm, followed by drying the textiles in an automatic dryer, 35 provide improved softening and conditioning benefits to the texti les .
Claims (20)
1. A textile treating composition suitable for imparting textile softening benefits to textiles treated therewith, which composition comprises:
(a) from about 0.1% to about 99.9% by weight of a substan-tially water-insoluble cationic fabric softening agent:
and (b) from about 0.1% to about 99.9% by weight of a substan-tially saturated, phosphoglyceride-containing lipid component comprising at least about 5096 by weight of an acetone-insoluble lipid material, with said acetone-insoluble lipid material comprising at least about 50% by weight of one or more acetone-insoluble phosphoglycerides:
the weight ratio of said acetone-insoluble lipid material to said fabric softening agent being in the range of from about 0.01:1 to about 5:1.
(a) from about 0.1% to about 99.9% by weight of a substan-tially water-insoluble cationic fabric softening agent:
and (b) from about 0.1% to about 99.9% by weight of a substan-tially saturated, phosphoglyceride-containing lipid component comprising at least about 5096 by weight of an acetone-insoluble lipid material, with said acetone-insoluble lipid material comprising at least about 50% by weight of one or more acetone-insoluble phosphoglycerides:
the weight ratio of said acetone-insoluble lipid material to said fabric softening agent being in the range of from about 0.01:1 to about 5:1.
2. A textile treating composition according to Claim 1 wherein the composition comprises:
(a) from about 0.1% to about 30% by weight of the substan-tially water-insoluble cationic fabric softening agent;
and (b) from about 0.1% to about 30% by weight of the substan-tially saturated, phosphoglyceride-containing lipid component:
and further wherein the ratio of the acetone-insoluble lipid material to the cationic fabric softening agent is in the range of from about 0.1:1 to about 2.5:1.
(a) from about 0.1% to about 30% by weight of the substan-tially water-insoluble cationic fabric softening agent;
and (b) from about 0.1% to about 30% by weight of the substan-tially saturated, phosphoglyceride-containing lipid component:
and further wherein the ratio of the acetone-insoluble lipid material to the cationic fabric softening agent is in the range of from about 0.1:1 to about 2.5:1.
3. A textile treating composition according to Claim 2 wherein the cationic fabric softening agent is selected from tetraalkyl quaternary ammonium salts, alkyl imidazolinium salts, alkyl pyrimidinium salts, or mixtures thereof; and wherein the acetone-insoluble phosphoglyceride component is selected from phosphatidyl choline, phosphatidyl ethanolamine, phosphatidyl inositol, serine phosphoglyceride, phosphatidic acid, or mixtures thereof.
4. A textile treating composition according to Claim 3 wherein the substantially saturated, phosphoglyceride-containing lipid component is derived from soybean or egg yolk.
5. A textile treating composition according to Claim 4 wherein the substantially saturated, phosphoglyceride-containing lipid component is a hydrogenated soybean lecithin mixture.
6. A textile treating composition according to Claim 3 wherein the substantially saturated, phosphoglyceride-containing lipid component has an iodine value of less than about 50.
7. A textile treating composition according to Claim 6 wherein the substantially saturated, phosphoglyceride-containing lipid component comprises from about 5% to about 50% by weight of acetone-soluble lipid material.
8. A textile treating composition according to Claim 7 wherein the substantially saturated, phosphoglyceride-containing lipid component is a hydrogenated soybean lecithin mixture.
9. A liquid textile treating composition suitable for addition to a textile-containing aqueous rinsing bath in order to impart softening benefits to textiles therein, said composition comprising:
(a) from about 0.1% to about 30% by weight of a cationic fabric softening agent selected from substantially water-insoluble tetraalkyl quaternary ammonium salts, substantially water-insoluble alkyl imidazolinium salts, substantially water-insoluble alkyl pyrimidinium salts, and mixtures thereof;
(b) from about 0.1% to about 30% by weight of a substan-tially saturated, phosphoglyceride-containing lipid com-ponent comprising at least about 50% by weight of an acetone-insoluble lipid material, with said acetone-insoluble lipid material comprising at least about 50% by weight of a phosphoglyceride selected from phosphatidyl choline, phosphatidyl ethanolamine, phosphatidyl inositol, serine phosphoglyceride, phosphatidic acid, or mixtures thereof; and (c) from about 50% to about 99.9% by weight of water;
the weight ratio of the acetone-insoluble lipid material to the fabric softening agent being within the range of from about 0.1:1 to about 2.5:1.
(a) from about 0.1% to about 30% by weight of a cationic fabric softening agent selected from substantially water-insoluble tetraalkyl quaternary ammonium salts, substantially water-insoluble alkyl imidazolinium salts, substantially water-insoluble alkyl pyrimidinium salts, and mixtures thereof;
(b) from about 0.1% to about 30% by weight of a substan-tially saturated, phosphoglyceride-containing lipid com-ponent comprising at least about 50% by weight of an acetone-insoluble lipid material, with said acetone-insoluble lipid material comprising at least about 50% by weight of a phosphoglyceride selected from phosphatidyl choline, phosphatidyl ethanolamine, phosphatidyl inositol, serine phosphoglyceride, phosphatidic acid, or mixtures thereof; and (c) from about 50% to about 99.9% by weight of water;
the weight ratio of the acetone-insoluble lipid material to the fabric softening agent being within the range of from about 0.1:1 to about 2.5:1.
10. A liquid textile treating composition according to Claim 9 wherein the composition is in the form of an aqueous dispersion of the softening agent/lipid material combination, and wherein the mean particle size of the softening agent/lipid component com-bination ranges from about 0.01 microns to about 10 microns.
11. A liquid textile treating composition according to Claim 10 wherein the substantially saturated, phosphoglyceride-contain-ing lipid component is derived from soybean or egg yolk.
12. A liquid textile treating composition according to Claim 11 wherein the substantially saturated, phosphoglyceride-contain-ing lipid component is a hydrogenated soybean lecithin mixture.
13. A liquid textile treating composition according to Claim 12 wherein the substantially saturated, phosphogiyceride-contain-ing lipid component has an iodine value of 50 or less, and where-in said component comprises from about 5% to about 50% by weight of acetone-soluble lipid material.
14. A method for treating textiles to impart fabric softening and conditioning benefits to textiles so treated, which method comprises contacting said textiles with a textile softening amount of a combination of:
(a) a substantially water-insoluble cationic fabric softening agent; and (b) a substantially saturated, phosphoglyceride containing lipid component comprising at least about 50% by weight of an acetone-insoluble lipid material, with said acetone-insoluble lipid material comprising at least about 50% by weight of one or more acetone-insoluble phosphoglycer-ides;
the weight ratio of said acetone-insoluble lipid material to said cationic fabric softening agent being in the range of from about 0.01:1 to about 5:1.
(a) a substantially water-insoluble cationic fabric softening agent; and (b) a substantially saturated, phosphoglyceride containing lipid component comprising at least about 50% by weight of an acetone-insoluble lipid material, with said acetone-insoluble lipid material comprising at least about 50% by weight of one or more acetone-insoluble phosphoglycer-ides;
the weight ratio of said acetone-insoluble lipid material to said cationic fabric softening agent being in the range of from about 0.01:1 to about 5:1.
15. A method for treating textiles according to Claim 14 wherein:
the substantially water-insoluble cationic fabric softening agent is selected from substantially water-insoluble tetraalkyl quarternary ammonium salts, substantially water-insoluble alkyl imidazolinium salts, substantially water-insoluble alkyl pyrimid-inium salts, and mixtures thereof;
the acetone-insoluble phosphoglyceride component is selected from phosphatidyl choline, phosphatidyl ethanolamine, phospha-tidyl inositol, serine phosphoglyceride, phosphatidic acid, or mixtures thereof; and the weight ratio of said acetone-insoluble lipid material to said cationic fabric softening agent is in the range of from about 0.1:1 to about 2.5:1.
the substantially water-insoluble cationic fabric softening agent is selected from substantially water-insoluble tetraalkyl quarternary ammonium salts, substantially water-insoluble alkyl imidazolinium salts, substantially water-insoluble alkyl pyrimid-inium salts, and mixtures thereof;
the acetone-insoluble phosphoglyceride component is selected from phosphatidyl choline, phosphatidyl ethanolamine, phospha-tidyl inositol, serine phosphoglyceride, phosphatidic acid, or mixtures thereof; and the weight ratio of said acetone-insoluble lipid material to said cationic fabric softening agent is in the range of from about 0.1:1 to about 2.5:1.
16. A method for treating textiles according to Claim 15 wherein the substantially saturated, phosphoglyceride-containing lipid component is derived from soybean or egg yolk.
17. A method for treating textiles according to Claim 16 wherein the substantially saturated, phosphoglyceride-containing lipid component is a hydrogenated soybean lecithin mixture.
18. A method for treating textiles according to Claim 17 wherein the substantially saturated, phosphoglyceride-containing lipid component has an iodine value of 50 or less, and comprises from about 5% to about 50% by weight of acetone-soluble lipid material.
19. A method for treating textiles according to Claim 14 wherein the textiles are contacted with the softening agent/lipid component combination in an aqueous bath containing from about 10 ppm to about 1000 ppm of said combination.
20. A method for treating textiles according to Claim 14 wherein the textiles are contacted with a textile softening amount of the softening agent/lipid component combination in a dryer.
KWZ/jmc KZAP3:3484
KWZ/jmc KZAP3:3484
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US827,131 | 1986-02-06 | ||
| US06/827,131 US4643919A (en) | 1986-02-06 | 1986-02-06 | Textile treating compositions and methods |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1266154A true CA1266154A (en) | 1990-02-27 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000528987A Expired - Fee Related CA1266154A (en) | 1986-02-06 | 1987-02-04 | Textile treating compositions and methods |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US4643919A (en) |
| EP (1) | EP0231973B1 (en) |
| JP (1) | JP2633242B2 (en) |
| KR (1) | KR870008078A (en) |
| AT (1) | ATE94202T1 (en) |
| AU (1) | AU583782B2 (en) |
| CA (1) | CA1266154A (en) |
| DE (1) | DE3787293T2 (en) |
| DK (2) | DK62487A (en) |
| FI (1) | FI870484A (en) |
| GB (1) | GB2186299B (en) |
| HK (1) | HK103992A (en) |
| IE (1) | IE60847B1 (en) |
| MX (1) | MX161265A (en) |
| NZ (1) | NZ219194A (en) |
| PT (1) | PT84251B (en) |
| SG (1) | SG99792G (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4735738A (en) * | 1985-10-21 | 1988-04-05 | The Procter & Gamble Company | Article with laminated paper orientation for improved fabric softening |
| US4808320A (en) * | 1986-08-14 | 1989-02-28 | Colgate-Palmolive Company | Fabric softening compositions based on lecithin and methods for making and using same |
| US4816170A (en) * | 1986-08-14 | 1989-03-28 | Colgate-Palmolive Company | Stable aqueous fabric softening compositions based on lecithin, saponin and sorbic acid and methods for making and using same |
| JPS6375167A (en) * | 1986-09-12 | 1988-04-05 | 落合 宏通 | Method for finish processing of clothing |
| ES2018605B3 (en) * | 1987-01-29 | 1991-04-16 | Unilever Plc | FABRIC CONDITIONING COMPOSITION. |
| JPH0742649B2 (en) * | 1987-05-26 | 1995-05-10 | 花王株式会社 | Softening agent |
| DE4132898A1 (en) * | 1991-10-04 | 1993-04-08 | Pfersee Chem Fab | WAITER LECITHINDISPERSIONS AND THEIR USE FOR THE TREATMENT OF FIBER MATERIALS |
| US5427696A (en) * | 1992-04-09 | 1995-06-27 | The Procter & Gamble Company | Biodegradable chemical softening composition useful in fibrous cellulosic materials |
| DE4220638A1 (en) * | 1992-06-24 | 1994-01-05 | Henkel Kgaa | Foam-regulated detergent |
| DE4338113A1 (en) * | 1993-11-08 | 1995-05-11 | Henkel Kgaa | Softening detergent with alkyl glycosides |
| WO1995025201A1 (en) * | 1994-03-15 | 1995-09-21 | Sequa Chemicals, Inc. | Paper opacifier |
| US6384005B1 (en) * | 1998-04-27 | 2002-05-07 | Procter & Gamble Company | Garment conditioning composition |
| US7041630B1 (en) | 1998-10-23 | 2006-05-09 | The Procter & Gamble Company | Fabric color care method for rejuvenating and/or restoring color to a faded fabric |
| JP2002528654A (en) * | 1998-10-23 | 2002-09-03 | ザ、プロクター、エンド、ギャンブル、カンパニー | Cloth color protection method |
| US7954190B2 (en) * | 2003-06-19 | 2011-06-07 | The Procter & Gamble Company | Process for increasing liquid extraction from fabrics |
| US7186318B2 (en) * | 2003-12-19 | 2007-03-06 | Kimberly-Clark Worldwide, Inc. | Soft tissue hydrophilic tissue products containing polysiloxane and having unique absorbent properties |
| US9016290B2 (en) | 2011-02-24 | 2015-04-28 | Joseph E. Kovarik | Apparatus for removing a layer of sediment which has settled on the bottom of a pond |
| GB2507752B (en) * | 2012-11-07 | 2017-09-13 | Intelligent Fabric Tech Plc | fabric softener |
| DE102016208403A1 (en) | 2016-05-17 | 2017-11-23 | Thyssenkrupp Ag | Speed limiter for a lift |
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| DE585724C (en) * | 1929-07-11 | 1933-10-10 | Oranienburger Chem Fab Akt Ges | Process for glazing, sizing, finishing and melting of textile fibers |
| DE649483C (en) * | 1930-11-04 | 1937-08-25 | I G Farbenindustrie Akt Ges | Process for treating cellulosic fibers |
| US2372985A (en) * | 1942-03-28 | 1945-04-03 | Richards Chemical Works | Compositions for treatment of fibrous materials |
| US2622045A (en) * | 1948-07-30 | 1952-12-16 | Eastman Kodak Co | Process of conditioning cellulose acetate yarn and product resulting therefrom |
| NL280642A (en) * | 1962-04-02 | |||
| JPS5431485B2 (en) * | 1972-12-30 | 1979-10-08 | ||
| JPS5443111A (en) * | 1977-09-12 | 1979-04-05 | Hitachi Ltd | Controlling method for temperature of heating furnace |
| DE2821494C2 (en) * | 1978-05-17 | 1983-04-28 | Bayer Ag, 5090 Leverkusen | Process and auxiliaries for dyeing polyester fibers or fiber mixtures containing them |
| US4213867A (en) * | 1978-12-29 | 1980-07-22 | Domtar Inc. | Fabric conditioning compositions |
| US4233164A (en) * | 1979-06-05 | 1980-11-11 | The Proctor & Gamble Company | Liquid fabric softener |
| JPS56306A (en) * | 1979-06-14 | 1981-01-06 | Fuji Boseki Kk | Production of water-soluble fiber |
| JPS6031944B2 (en) * | 1979-11-14 | 1985-07-25 | ライオン株式会社 | Household clothing smoothing agent composition |
| IT1128090B (en) * | 1980-02-01 | 1986-05-28 | Sandoz Spa | LECITHIN DERIVATIVES THEIR PREPARATION AND APPLICATION IN THE TEXTILE AND LEATHER INDUSTRY |
| US4308151A (en) * | 1980-05-12 | 1981-12-29 | The Procter & Gamble Company | Detergent-compatible fabric softening and antistatic compositions |
| US4511495A (en) * | 1980-05-16 | 1985-04-16 | Lever Brothers Company | Tumble dryer products for depositing perfume |
| EP0062352B1 (en) * | 1981-04-07 | 1986-07-30 | Mitsubishi Kasei Corporation | Soap composition |
| DE3129549A1 (en) * | 1981-07-27 | 1983-02-10 | Henkel KGaA, 4000 Düsseldorf | AGENT FOR TREATING WASHED LAUNDRY IN A LAUNDRY DRYER |
| US4493773A (en) * | 1982-05-10 | 1985-01-15 | The Procter & Gamble Company | Low phosphate, softening laundry detergent containing ethoxylated nonionic, alkylpolysaccharide and cationic surfactants |
| US4536316A (en) * | 1983-06-01 | 1985-08-20 | Colgate-Palmolive Co. | Fabric softening composition containing surface modified clay |
-
1986
- 1986-02-06 US US06/827,131 patent/US4643919A/en not_active Expired - Fee Related
-
1987
- 1987-01-27 AT AT87200123T patent/ATE94202T1/en not_active IP Right Cessation
- 1987-01-27 DE DE87200123T patent/DE3787293T2/en not_active Expired - Lifetime
- 1987-01-27 EP EP87200123A patent/EP0231973B1/en not_active Expired - Lifetime
- 1987-02-04 CA CA000528987A patent/CA1266154A/en not_active Expired - Fee Related
- 1987-02-04 MX MX5146A patent/MX161265A/en unknown
- 1987-02-05 AU AU68549/87A patent/AU583782B2/en not_active Ceased
- 1987-02-05 PT PT84251A patent/PT84251B/en not_active IP Right Cessation
- 1987-02-05 GB GB8702599A patent/GB2186299B/en not_active Expired - Lifetime
- 1987-02-05 IE IE30887A patent/IE60847B1/en not_active IP Right Cessation
- 1987-02-05 NZ NZ219194A patent/NZ219194A/en unknown
- 1987-02-05 FI FI870484A patent/FI870484A/en not_active Application Discontinuation
- 1987-02-06 KR KR870000952A patent/KR870008078A/en not_active Application Discontinuation
- 1987-02-06 JP JP62026205A patent/JP2633242B2/en not_active Expired - Fee Related
- 1987-02-06 DK DK062487A patent/DK62487A/en unknown
- 1987-02-06 DK DK062487D patent/DK169789B1/en active
-
1992
- 1992-09-29 SG SG997/92A patent/SG99792G/en unknown
- 1992-12-24 HK HK1039/92A patent/HK103992A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JP2633242B2 (en) | 1997-07-23 |
| US4643919A (en) | 1987-02-17 |
| EP0231973B1 (en) | 1993-09-08 |
| AU583782B2 (en) | 1989-05-04 |
| DK169789B1 (en) | 1995-02-27 |
| SG99792G (en) | 1992-12-04 |
| DE3787293D1 (en) | 1993-10-14 |
| EP0231973A3 (en) | 1990-03-21 |
| EP0231973A2 (en) | 1987-08-12 |
| HK103992A (en) | 1992-12-31 |
| IE60847B1 (en) | 1994-08-24 |
| GB8702599D0 (en) | 1987-03-11 |
| IE870308L (en) | 1987-08-06 |
| DE3787293T2 (en) | 1994-04-21 |
| NZ219194A (en) | 1990-06-26 |
| GB2186299A (en) | 1987-08-12 |
| DK62487A (en) | 1987-08-07 |
| ATE94202T1 (en) | 1993-09-15 |
| AU6854987A (en) | 1987-08-13 |
| MX161265A (en) | 1990-08-27 |
| KR870008078A (en) | 1987-09-24 |
| PT84251B (en) | 1989-09-14 |
| JPS62257463A (en) | 1987-11-10 |
| PT84251A (en) | 1987-03-01 |
| DK62487D0 (en) | 1987-02-06 |
| FI870484A0 (en) | 1987-02-05 |
| GB2186299B (en) | 1990-03-28 |
| FI870484A (en) | 1987-08-07 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |