CA2038640A1 - Laundry material - Google Patents
Laundry materialInfo
- Publication number
- CA2038640A1 CA2038640A1 CA002038640A CA2038640A CA2038640A1 CA 2038640 A1 CA2038640 A1 CA 2038640A1 CA 002038640 A CA002038640 A CA 002038640A CA 2038640 A CA2038640 A CA 2038640A CA 2038640 A1 CA2038640 A1 CA 2038640A1
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- Prior art keywords
- laundry
- material according
- laundry material
- oxidation
- oxidized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Lubrication Of Internal Combustion Engines (AREA)
- Woven Fabrics (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
LAUNDRY MATERIAL
A B S T R A C T
Laundry material having a phosphate content reduced to less than 5% by weight and even equal to zero, especially adapted for washing fabrics, comprising at least one zeolite and at least one oxidized polysaccharide selected from the group comprising:
a) the products resulting from the oxidation of disaccha-rides presenting a terminal function of the aldonic type, b) the products resulting from the oxidation of trisaccha-rides and of oligosaccharides presenting a terminal function of the aldonic type, c) the products resulting from the oxidation of starch hydrolysates, of cellulose and hemicelluloses present-ing a terminal function of the aldonic type, d) any mixtures of at least two of the above-identified oxidation products.
No figure.
A B S T R A C T
Laundry material having a phosphate content reduced to less than 5% by weight and even equal to zero, especially adapted for washing fabrics, comprising at least one zeolite and at least one oxidized polysaccharide selected from the group comprising:
a) the products resulting from the oxidation of disaccha-rides presenting a terminal function of the aldonic type, b) the products resulting from the oxidation of trisaccha-rides and of oligosaccharides presenting a terminal function of the aldonic type, c) the products resulting from the oxidation of starch hydrolysates, of cellulose and hemicelluloses present-ing a terminal function of the aldonic type, d) any mixtures of at least two of the above-identified oxidation products.
No figure.
Description
LAUNDRY MATERIAL
The present invention relates to a new laundry material, especially adapted for washing fabrics, the said laundry material presenting a phosphate content reduced to less than 5% by weight and even equal to zero and compris-ing at least one zeolite.
For a long time phosphates played a predominant role in laundry materials, especially as sequestrants of cations which form salts insoluble in water, in particular the calcium and magnesium ions; the excellent performance that they enable to be achieved resides in their particular structure.
However, one of the acute problems which the laundry materials industry must face, is the very pollut-ing character of said phosphates. In fact, thelr presence in waste water causes the well-known phenomenon of the eutrophisation; and for this reason the use of phosphates in laundry materials must comply with restrictions parti-cularly ecolog:Lcal which are more and more severe.
This ecological aspect is all the more pronounced as the powerful detergents currently employed and, in particular, the products used in industrial laundries, contain large amounts of phosphates which can exceed 30%.
Many attempts have therefore been made to elimi-nate entirely or at least partly the phosphates in laundry materials.
It has especially been proposed to use, as total or partial replacement agent for the phosphates, zeolites of natural or synthetic origin ; these products are well-known for their cation exchange power, particularly of calcium and magnesium, which are the source of the hardness of water and of mineral incrustation problems in the laundry or linen.
20~4a However, while zeolites contribute to the elimi-nation of these cations, their total substitution for phosphates does not permit a degree of washing compatible with the exigencies of practice to be achieved.
5Also, to improve the washing quality of laundry material based on zeolite and containing few or no phos-phates, it has been proposed to combine the said zeolites with various other agents such as notably nitrilotriacetic acid (NTA) and its salts, especially sodium nitrilotriace-10tate (European patents EP-A-0 070 079 and EP-A-0 319 053).
However, besides their imperfect biodegradability, the said products are surmised to fix heavy metals, which possibly could pass into drinking water. Consequently, it is generally recommended and even rendered compulsory today in certain countries, to limit to 5~ their propor-tion in detergent materials.
This 5~ proportion appears to be the optimum proportion of nitrilotriacetate of alkaline metal in the phosphates free compositions disclosed in the European Patent EP 0 319 053, which compositions contain from 20 to 35% by weight of zeolites.
It has also been proposed, as far as laundry mate-rials containing few or no phosphates are concerned, to associate the zeolites with special polycarboxylic poly-mers based on well-defined mixtures of mono- and dicarbo-xylic monoolefinic acids and of non-ionic esters of the said acids (European Patent EP 193 360). Among the monoolefinic derivatives of mono- and dicarboxylic acids, the derivatives of acrylic and/or methacrylic acid as well as the derivatives of maleic and/or itaconic acid, are especially mentioned.
It appears that such compositions may be free of phosphates and contain less than 20~ by weight of zeolites. However, in that case, the said zeolites are associated not only with the said polycarboxylic polymers but also with clays and with NTA.
~ ~3~ ri i~ ~
Among the polycarboxylic agents the most commonly recommended to improve the qua]ity of the laundry mate-rials based on zeolites and containing few or no phos-phates, there may be mentioned the acrylic polymers, and especially the homopolymers of acrylic and of methacrylic ~cids or of their salts, especially polyacrylic acid (PA) and sodium polyacrylates (NaP).
Compositions containing for example from 2 to 7~
by weight of polyacrylates and from 25 to 60% by weight of zeolites are disclosed in the German Patent DE 37 07 806.
Laundry materials associating zeolites and poly-acrylates are also disclosed in the German Patent DE
38 3~ 478.
It must however been recalled that acrylic poly-mers, especially polyacrylic acid and its salts, present the major drawback of not being biodegradable.
Consequently, it seems at present preferable to use these products at rates which do not exceed 4% by weight o~ the laundry material.
From the preceeding explanations, it appears that, generally speaking, there is a need for laundry materials presenting a reduced content of phosphates or which are even free of phosphates and which, while playing with efficiency the:Lr role without necess~ty of an overdosage in zeolites and without the use of ecologically unaccep-table additives, enable to reach global rates of polymers and/or polycarboxylic monomers non or weakly biodegradable and compatible with the present requirements of the environment protection and, especially, specific rates of nitrilotriacetic acid (NTA), polyacrylic acid (PA) or their salts which do not e~ceed 4~ by weight.
And Applicants have had the merit of finding that the said object is reached as soon as the laundry mate-rials of the kind in question comprise at least one oxi-dized polysaccharide selected from the group comprising:
~38~
a) the products resulting from the oxidation of disaccha-rides presenting a terminal function of the aldonic type, b) the products resulting from the oxidation of trisaccha-rides and of oligosaccharides presenting a terminal function of the aldonic type, c) the products resulting from the oxidation of starch hydrolysates, of cellulose and hemicelluloses present-ing a terminal function of the aldonic type, d) any mixtures of at least two of the above-identified oxidation products.
Advantageously, the oxidized polysaccharides which can be used within the scope of the present invention are those which are obtained startin~ from di-, tri- and oli~osaccharides, from starch hydrolysates, from cellulose and hemicellulose and of which only the terminal unction of the aldehyde type before oxidation (among their poten-tially oxidable functions) is substantiall~ oxidized into a function of the aldonic type.
Such oxidized polysaccharides can be obtained, especially if the intended oxidation is actually "selec-tive" at the level of the terminal function of the aldonic type by way of the catalytic oxidation process disclosed by the Applicants in their European Patent EP 232 202.
The polysaccharides whose process, disclosed in the above-mentioned European Patent EP 232 202, makes the selective oxidation possible comprise especially:
- disaccharides such as lactose, maltose, isomaltose, cellobiose, xylobiose and mannobiose, having a terminal function of the aldehydic type, - the starch hydrolysates obtained by acid and/or enzy-matic route, - the hydrolysis products of hemicelluloses such as the D-galacto-D-mannanes, the D-gluco-D-mannanes, the L-arabino-D-xylanes, the D-xylo-L-arabinanes.
The present invention relates to a new laundry material, especially adapted for washing fabrics, the said laundry material presenting a phosphate content reduced to less than 5% by weight and even equal to zero and compris-ing at least one zeolite.
For a long time phosphates played a predominant role in laundry materials, especially as sequestrants of cations which form salts insoluble in water, in particular the calcium and magnesium ions; the excellent performance that they enable to be achieved resides in their particular structure.
However, one of the acute problems which the laundry materials industry must face, is the very pollut-ing character of said phosphates. In fact, thelr presence in waste water causes the well-known phenomenon of the eutrophisation; and for this reason the use of phosphates in laundry materials must comply with restrictions parti-cularly ecolog:Lcal which are more and more severe.
This ecological aspect is all the more pronounced as the powerful detergents currently employed and, in particular, the products used in industrial laundries, contain large amounts of phosphates which can exceed 30%.
Many attempts have therefore been made to elimi-nate entirely or at least partly the phosphates in laundry materials.
It has especially been proposed to use, as total or partial replacement agent for the phosphates, zeolites of natural or synthetic origin ; these products are well-known for their cation exchange power, particularly of calcium and magnesium, which are the source of the hardness of water and of mineral incrustation problems in the laundry or linen.
20~4a However, while zeolites contribute to the elimi-nation of these cations, their total substitution for phosphates does not permit a degree of washing compatible with the exigencies of practice to be achieved.
5Also, to improve the washing quality of laundry material based on zeolite and containing few or no phos-phates, it has been proposed to combine the said zeolites with various other agents such as notably nitrilotriacetic acid (NTA) and its salts, especially sodium nitrilotriace-10tate (European patents EP-A-0 070 079 and EP-A-0 319 053).
However, besides their imperfect biodegradability, the said products are surmised to fix heavy metals, which possibly could pass into drinking water. Consequently, it is generally recommended and even rendered compulsory today in certain countries, to limit to 5~ their propor-tion in detergent materials.
This 5~ proportion appears to be the optimum proportion of nitrilotriacetate of alkaline metal in the phosphates free compositions disclosed in the European Patent EP 0 319 053, which compositions contain from 20 to 35% by weight of zeolites.
It has also been proposed, as far as laundry mate-rials containing few or no phosphates are concerned, to associate the zeolites with special polycarboxylic poly-mers based on well-defined mixtures of mono- and dicarbo-xylic monoolefinic acids and of non-ionic esters of the said acids (European Patent EP 193 360). Among the monoolefinic derivatives of mono- and dicarboxylic acids, the derivatives of acrylic and/or methacrylic acid as well as the derivatives of maleic and/or itaconic acid, are especially mentioned.
It appears that such compositions may be free of phosphates and contain less than 20~ by weight of zeolites. However, in that case, the said zeolites are associated not only with the said polycarboxylic polymers but also with clays and with NTA.
~ ~3~ ri i~ ~
Among the polycarboxylic agents the most commonly recommended to improve the qua]ity of the laundry mate-rials based on zeolites and containing few or no phos-phates, there may be mentioned the acrylic polymers, and especially the homopolymers of acrylic and of methacrylic ~cids or of their salts, especially polyacrylic acid (PA) and sodium polyacrylates (NaP).
Compositions containing for example from 2 to 7~
by weight of polyacrylates and from 25 to 60% by weight of zeolites are disclosed in the German Patent DE 37 07 806.
Laundry materials associating zeolites and poly-acrylates are also disclosed in the German Patent DE
38 3~ 478.
It must however been recalled that acrylic poly-mers, especially polyacrylic acid and its salts, present the major drawback of not being biodegradable.
Consequently, it seems at present preferable to use these products at rates which do not exceed 4% by weight o~ the laundry material.
From the preceeding explanations, it appears that, generally speaking, there is a need for laundry materials presenting a reduced content of phosphates or which are even free of phosphates and which, while playing with efficiency the:Lr role without necess~ty of an overdosage in zeolites and without the use of ecologically unaccep-table additives, enable to reach global rates of polymers and/or polycarboxylic monomers non or weakly biodegradable and compatible with the present requirements of the environment protection and, especially, specific rates of nitrilotriacetic acid (NTA), polyacrylic acid (PA) or their salts which do not e~ceed 4~ by weight.
And Applicants have had the merit of finding that the said object is reached as soon as the laundry mate-rials of the kind in question comprise at least one oxi-dized polysaccharide selected from the group comprising:
~38~
a) the products resulting from the oxidation of disaccha-rides presenting a terminal function of the aldonic type, b) the products resulting from the oxidation of trisaccha-rides and of oligosaccharides presenting a terminal function of the aldonic type, c) the products resulting from the oxidation of starch hydrolysates, of cellulose and hemicelluloses present-ing a terminal function of the aldonic type, d) any mixtures of at least two of the above-identified oxidation products.
Advantageously, the oxidized polysaccharides which can be used within the scope of the present invention are those which are obtained startin~ from di-, tri- and oli~osaccharides, from starch hydrolysates, from cellulose and hemicellulose and of which only the terminal unction of the aldehyde type before oxidation (among their poten-tially oxidable functions) is substantiall~ oxidized into a function of the aldonic type.
Such oxidized polysaccharides can be obtained, especially if the intended oxidation is actually "selec-tive" at the level of the terminal function of the aldonic type by way of the catalytic oxidation process disclosed by the Applicants in their European Patent EP 232 202.
The polysaccharides whose process, disclosed in the above-mentioned European Patent EP 232 202, makes the selective oxidation possible comprise especially:
- disaccharides such as lactose, maltose, isomaltose, cellobiose, xylobiose and mannobiose, having a terminal function of the aldehydic type, - the starch hydrolysates obtained by acid and/or enzy-matic route, - the hydrolysis products of hemicelluloses such as the D-galacto-D-mannanes, the D-gluco-D-mannanes, the L-arabino-D-xylanes, the D-xylo-L-arabinanes.
2~38~
According to another advantageous embodiment of the laundry material according to the invention, the oxidized polysaccharide used within the said product appears in the form of an oxidation product of starch hydrolysate having a DE (Dextrose Equivalent) from about 5 to about 90 and presents preferably an acid index I comprised between about 1 and about 20, the said acid index being expressed in number of grams of carboxylic function per 100 g of oxidized polysaccharide, and given by the formula:
DE x 45 I = 100 x 180 100 + DElx8o218 _ DE
According to the present invention, very particu-larly preferred are oxidized polysaccharides which have an acid index comprised between about 5 and about 14 and which are obtained by oxidation of starch hydrolysates having a DE comprised between a~out 20 and about 65.
Very particularly advantageous are oxidized polysaccharides which have an acid index comprised between about 8 and about 14 and which are obtained by oxidation of starch hydrolysates having a DE comprised between about 35 and about 650 According to another advantageous embodiment, the oxidized polysaccharide is an oxidized product having, especially due to its reducing sugars content, a good stability, especially from the point of view of its colour, when the said oxidized product is used (when preparing or using the laundry material according to the invention) at any moment and for example at the moment of 3 atomization or spraying, within an environment presenting an alkaline pH and/or a high temperature, environment which is adapted to colour (more or less pronounced yellowing) any composition containing lt.
In that connection, Applicants have elaborated new products consisting of "stabilized" oxidized polysaccha-rides which present low contents, generally lower than 2 ~
0.6%, preferably lower than about 0.1~ and still more preferably lower than 0.05% by weight, in reducing sugars.
In particular, Applicants have found that, when subiecting oxidized polysaccharides, in particular of the type constituted of oxidized starch hydrolysates to hydro-genation techniques, one obtains the intended products especially oxidized products which have a content in reducing sugars practically equal to zero and which are "stabilized" as far as a possible yellowing in the presence of a particular environment which favours such a yellowing (alkaline pH, high temperature) is concerned.
The abovesaid hydrogenation techniques comprise in particular catalytic hydrogenation techniques carried out continuously or not and using at least one catalyst selected from the groups IB, IIIB, IVB, VI, VII and VIII
of the periodical table and especially selected from the group comprising nickel, platine, palladium, cobalt, molybdenum and mixtures of the said metals.
Hydrogenation techniques using Raney nickel as a catalyser fixed or not on an inert carrier in the presence or not of an additional hydrogene source are particularly preferred.
Other hydrogenation techniques using, in the absence of any hydrogenation catalyst, hydrogen sources other than hydrogene gas, for example borohydrides of alkaline metals, especially sodium borohydride, may also be contemplated.
The oxidized polysaccharides, especially of the type of the oxidized starch hydrolysates, which are "stabilized" after such a hydrogenation treatment, in particular those having a D~ comprised between 5 and 90, an acid index I comprised between 1 and 20 and which are "stabilized" by catalytic hydrogenation, when used in laundry compositions and laundry materials furthermore provide the latter with performances which are comparable with the performances of the same oxidized products which st-~
are not "stabilized" and even performances improved in connection with certain parameters.
Moreover, it ~ust be recalled, at that precise state of the specification, that the characteristic use of at least one oxidized polysaccharide, especially of a polysaccharide, for instance a starch hydrolysate, "selec-tively" oxidized at the level of its aldehydic terminal function, within the laundry materials according to the invention, not only enables to substitute efficiently within the said materials at least part of the polycarbo-xylic compounds non-biodegradable or weakly biodegradable of the type NTA, PA or their salts, by products, i.e.
oxidized polysaccharides, with which no problems of biodegradability occur, but also does not necessitate in no case the concomitant increase of the rate of zeolite(s) contained within the said materials with respect to the rates at present used within laundry materials available in the trade, which are generally of about 21 to 25% by weight.
And it is remarkable to notice that, in an all the more surprising and unexpected manner, the characteristic presence of at least one oxidized polysaccharide, espe-cially a polysaccharide, notably a starch hydrolysate, "selectively" oxidized at the level of its aldehydic terminal function, enables the said materials which contain the said oxidized polysaccharide to be efficient:
- for constitutive zeolite(s) rates lower than 20% by weight and/or - for constitutive rates of polycarboxylic compounds of the type NTA, PA or their sal~s, not higher than 2%
by weight and even in the substantial absence of the said polycarboxylic compounds.
In addition to the advantages which have just been disclosed in connection with the laundry materials according to the invention, it must be noticed that the said materials, on the contrary to certain materials of ~ $~
the prior art, do not produce any substantial desactiva-ti~n of the bleaching agents, between which especially perborate, currently used in laundry materials for the elimination of oxidable stains and produce high levels of whiteness.
Without wishing to be bound by theory, Applicants attribute the excellence of these performances to the stabilizing effect played by the oxidized polysaccharides with respect to the oxidizing agents.
This result is particularly pronounced when the oxidising agent is a perborate, especially of sodium, and when the composition according to the invention comprises, as oxidized polysaccharide, an oxidized starch hydro-lysate.
According to an advantageous embodiment of the laundry material according to the invention, the latter comprises :
- a proportion from about 5 to about 35% by weight, pre-ferably from 10 to 25% and, still more preferably, from 15 to 20% by weight of at least one zeolite, - a proportion from about 3 to about 20~ by weight, pre-ferably from 5 to 20~ and, still more preferably, from 7 to 20% by weight of at least one oxidized polysaccha-ride, in particular of a polysaccharide "selectively"
o~idized in respect with its terminal function of the aldehydic type.
According to another advantageous embodiment of the above-mentioned material, the ratio by weight between, on the one hand, the zeolite and, on the other hand, the oxidized polysaccharide is comprised between about 0.5/1 and about 4/1, preferably between 1/1 and 2/1.
In connection with the present invention, the term "zeolite" comprises any ion exchanging material of the aluminosilicate type, of crystalline or amorphous nature and of natural or synthetic origin, such as disclosed for example in the above-mentioned European patents EP 70 079 and EP 193 360. Such products are for example available in the trade under the commercial names "zeolite A", "zeolite B", "zeolite X" or "zeolite HS".
In particular, a crystalline sodium silicoalumi-nate of the "zeolite A" type can be used.
In practice, the laundry materlal according to the invention, which constitutes a new industrial product, comprises also one or several other constituents which are selected in particular from the group comprislng the detergent agents, the surfactive agents, the antiredeposi-tion agents, the oxidizing agents, the structural agents, the anticorrosion agents, the antifoaming agents, the enzymes, the perfumes, the dyes, the solubilizing agents, etc., for example such as disclosed in the above-mentioned European patents EP 70 079 and EP 319 0530 The detergent agents may be, for example, selected among synthetic anionic detergent agents, such as hydro-soluble alkaline metal salts of organic sulphates and sulphonates comprising alkyl radicals having from about 8 to 22 carbon atoms, such as for example sodium or potas-sium dodecylbenzene sulphonates.
It is also possible to select the said agents among the non-ionic detergent agents, such as especially the alkylpolyg]ucosides or the ethoxylated fatty alcohols.
The oxidizing agents, i.e. the products which are adapted to set free peroxide ions in an amount sufficient to permit the bleaching of wine stains, of tea stains, of coffee stains, etc., may be in particular perborates, percarbonates, persilicates or perphosphates of alkaline metals and especially the sodium perborate.
The structural agents may in particular be select-ed, as recommended in the European patent EP 215 637, from the susars, the hydrogenated sugars and the mixtures of the above-mentioned products and especially those which consist of or which at least contain a monosaccharide such as glucose or fructose and/or a disaccharide such as 2 ~ 3 8 6 ~ ~
maltose or saccharose and/or their hydrogenation products.
The structural agents may especially consist of or contain, at least partially, sorbitol and especially consist of hydrogenated products obtained by hydrogenation of starch hydrolysates or glucose syrups.
Furthermore, the laundry material according to the invention may contain detergency additives normally used such as polyacrylic acid (PA), nitrilotriacetic acid (NTA) and/or their respective salts, especially their sodium salts.
However, as already indicated above, the charac-teristic presence of at least one oxidized polysaccharide wlthin the laundry materials according to the invention enables the said products to be, in a remarkable manner, while having a zeolite rate not higher and even lower than those of the materials of the prior art, efficient or constitutive rates of NTA, of PA or of their salts, lower than those currently encountered in the said materials of the prior art, especially for rates which are not higher than 2% by weight and which are even substantially equal to 0.
The laundry materials according to the invention, which are adapted in particular for the washing of tex-tiles as well in a machine or "hand-washed", are prefera-bly in the form of free-flowing particles, especially in the form of a powder or of granulates.
No special process and no special installation other than those normally used by those skilled in the art is necessary for the preparation of the above-mentioned materials; those skilled in the art may for example resort to classic techniques of drying of aqueous suspensions by spraying.
The mixture of the at least one zeolite and the at least one oxidized polysaccharide to be comprised by the laundry materials according to the invention can be carried out in various manners, the said products being in the form of powders, of liquids, or of mi~tures of powders/liquids, in the presence or not of all or part of the other constituents of the said materials.
For example, it is possible to mix the oxidized polysaccharide with a laundry "precomposition" already in the powder form and containing the ma~ority or even the totality of the other constituents of the final material.
The association of at least one zeolite and of at least one oxidized polysaccharide may also be realized within the laundry materials, the said materials being then in another form than that of free-flowing particles, in particular in the form of liquids, gels or pastes.
These products, which generally will present a dry matter content from about 15% to about 80%, and especially from 30 to 50~, can be obtained, for example, by increasing, by any possible manner and especially by mere dissolution or suspension in water or in another liquid, the water content of the laundry materials according to the invention previously prepared in the form of powders or of granulates.
They can also, in other cases, present a formula-tion substantially different of that used for the powders or granulates, especially as far as their content in tensio-active or surfactive additives is concerned.
The invention will be still better understood by means of the following examples relating to particularly advantageous embodiments of the products according to the invention.
To demonstrate the effectiveness of the laundry materials according to the invention, comparative trials were carried out using, on the one hand, a laundry mate-rial according to the prior art denoted by the letter "T"
whose constitution is given in the following Table I and, on the other hand, four laundry materials according to the invention, denoted respec~ively by the letters A, B, C and D, whose respective contents in zeolite(s), in o~idized polysaccharide(s) and possibly in sodium polyacrylates (PNa) are given in Table II.
In this first series vf trials, an oxidation product of a starch hydrolysate having a DE of about 61.5 and an acid index I of about 13.6 is ussd in the laundry materials according to the invention as ox~dized poly-saccharide.
TABLE I
Manufacturing Producing .
Constituentsbrand or formula Company by weight AntifoamingUKANIL 2136 ICI 0.2 dodecylbenzene sulphonate FLUKA 6 15 ethoxylated fatty alcohol KC 7/L
ethoxylated ceto-stearylic alcohol EMPILAN KM 11MARCHON 5 Sodium sulphate Na2 SO4PANREAC 21 Sodium metasilicate anhydrous SiO2Na2O PROLABO 3 20 Sodium carbonate Na2 CO3PANREAC 5 Sodium perborate Na BO3 4H2OFLUKA 18 Tetraacetylethylene diamine LEVER 2 Carboxymethyl-25 celluloseBLANOSE 7M65 AQUALON
Zeolite ANa2O Al2O~ 2SiO~
x H2O (x= 4 to 5) MONTEDISON 25 Sodium Polyacrylate SOKALAN C 245 BASF 4 EnzymeESPERASE NOVO 0.6 Water _ _ qsp 100 3o _ '~3~
TABLE II
_ Constituents Composition (% by weight~
T A B C D
Zeolite A 25 18 18 19 19 _ Polyacrylates 4 2 ~ _ Oxidized polysaccharide _ I0 18 14 10 The said comparative trials consist of washing trials which were performed by means of a washing machine of the VEDETTE 8596 SYSTEME CHOIX brand with top loading.
The trials were carried out at the two following temperatures: 40C and 60C.
For the trial at 40C, a rise of temperature of 13 minutes, then a plateau at 40C of 22 minutes was selected.
The complete cycle, that is to say including the fillings, rincings and spin-drying, lasts 80 minutes.
For the trial at 60C, there was provided a rise in temperature of 21 minutes, then a plateau at 60~C of 22 minutes. The complete cycle lasts 90 minutes.
In the two trials, the volume of washing water was 11 liters.
Two washings were carried out per temperature.
The hardness of the water was 30 TH.
The washing load was composed of 2.2 kg of pieces of white fabric (cotton) of which the sizes were 55 cm x 70 cm.
On each washing, there was included with a load of 2.2 kg of pieces of white fabric, a group of "soiled fabrics" of different natures and which include soilings predetermined and predeposited on these fabrics.
In practice, these "presoiled" fabrics which are pinned to the washing load, are as follows:
- 2 strips of grey polyest(er/cotton (64/35) of the KREFELD
brand ~ref. WFK 20 C), soiled by a mixture of an animal oil and carbon black, - 2 strips of cotton of the brand EMPA 103 constituted by eight pieces sewn together, namely:
- a piece of white cotton (of the EMPA 221 type), - a piece of grey cotton (of the EMPA 101 type soiled by a mixture of vegetable oil and carbon black), - a piece of cotton soiled with blood (of the EMPA 111 type), - a piece of cotton soiled with cocoa (of the EMPA 112 type), - a piece of COttOII soiled by a mixed stain of milk, blood, carbon blac~ (of the EMPA 116 type), - a piece of unbleached cotton (of the EMPA 222 type), - a piece of cotton soiled with wine (of the EMPA 114 type), - a piece of cotton soiled with sulphur black (not used in the present measurements), - 2 strips of polyester/cotton (65/35) soiled with tea, of the KREFELD brand (ref. WFK 20G), 20 - 2 strips of polyester/cotton (65/35) soiled with cocoa, of the KREFELD brand (ref. WFK 20F), - 2 strips of white polyester/cotton (65/35) of the EMPA
brand (ref. EMPA 213).
The dosle of laundry material was 8 g/l of water.
To evaluate the quality of the washing, on the one hand the removal of the soiling and o$ the stains and, on the other hand, the effect of the washings on the degree of bleaching were measured.
To evaluate the removal of the soiling and of the stains, procedure was by photometry (measurements of the amount of light reflected by the fabric); it was thus possible to calculate the percentages of removal of the soiling. A device for measuring the reflection of light, marketed under the brand ACS 1400 SPECTR0 was used.
The removal of the soiling is expressed by the formula Removal in ~ _ C - B x 100 (1) in which:
A = reflectance of the control white sample, B = reflectance of the control soiled sample, C = reflectance of the soiled sample after testing.
The reflectances were determined by means of the blue trichromatic component.
The number of measurements carried out per fabric was 4, which means 4 measurements (that is to say at four different places on the same piece of fabric) x 2 washings x 2 strips of fabric = 16 measurements per soiling, per formulation and per temperature.
Regarding the degree of bleaching, the effect of the washings was measured on two cuttings of EMPA 221 unsoiled white cotton and on two cuttings of EMPA 213 unsoiled white polyester/cotton, which were incorporated in the washing bath. On each cutting, 4 measurements were carried out, which therefore gave 16 measurements per formulation and per temperature studied.
If there are denoted :
- by Rbo, the blue trichromatic component obtained before washing, - by Rb, the blue trichromatic component obtained 25after washing, the degree of b]eaching is given by the formula BL = Rb - Rbo.
In the trials proper which will now be described, the effectiveness of the laundry materials according to the invention was studied successively on soilings based on oil and on carbon black, then on proteinic stains and oxidizable stains and finally the "degree of whiteness"
conferred by said materials on the treated fabrics was determined.
2~3~
Stains produced by mixtures of mineral, vegetable and/or animal oil with carbon black.
Washing trials were carried out, on the one hand, on grey cotton and, on the other hand, on synthetic fabrics (polye~ter/cotton~.
1) Trials on grey cotton By washing, there were treated successively each time two strips of grey cotton of the brand EMPA 101 soiled by a mixture of vegetable oil and carbon black.
This type of soiled cotton is representative of insoluble pigmentary soilings bound to the fabric by greasy film, as for example the collars of shirts and of coats, the rags and the greasy stains.
The two groups of tests carried out respectively at 40C and 60C gave for the products according to the invention A, B, C and D, on the one hand, and for the product T according to the prior art, on the other hand, from the point of view of removal of soiling represented by the abovesaid formula (1), the results collected respectlvely in Tables III and IV.
TABLE III
(Trial at 40C) -~rype Removal of soiling (in %) of fabric T A B C D
_ EMPA 101 17.4 17.5 16.3 16.7 16.1 TABLE IV
3 (Trial at 60C) I
Type Removal of soiling (in %) of fabric T A B C D
EMPA 101 17.7 18.8 23.1 16.9 17.1 _ ~8~
2) Trials on grey synthetic materials The synthetic fabric used here was a fabric of the polyester/cotton (dacron/cotton) type of the brand KREFELD; it was soiled with a mixture of animal oil with carbon black (ref. WFK 20C).
The two groups of the trials carried out respecti-vely at 40C and 60C gave for the compositions A, B, C
and D, on the one hand, and for the control product T, on the other hand, from the point of view of the removal of soiling represented by the abovesaid formula (l), the results which are collected respectively in Tables V and VI.
TABLE V
(Trial at 40~C) Type of ¦ Removal of soiling (in %) synthetic fabric 1 T A B D
Polyester/cotton 20.2 20.0 18.1 19.0 18.8 WFK 20C _ _ TABLE VI
(Trial at 60C) Type of Removal of soiling (in ~) 25 synthetic fabric T ~ _ _ C I D
Polyester/cotton l9.9 20.1 24.7 19.2 19.5 WFK 20C _ _ From Tables III to VI, it appears that the charac-teristic presence of at least one oxidized polysaccharide, especially of at least one polysaccharide "selectively"
oxidized at the level of its terminal function of the aldehydic type, in the laundry materials according to the invention, enables and that, for washing performances similar or even higher than those noticed with the prior art laundry material:
2038~
- to decrease the rate of incorporation of zeolite(s~
and/or - to decrease the rate of incorporation of a non-biode-gradable detergence additive currently used, such as polyacrylates, and even to suppress completely the incorporation of such an agent.
EXAMPL~ 2 Proteinic stains The action of the laundry materials according to the invention on proteinic stains is studied by using fabrics of the cotton type of EMPA b~and, namely: EMPA lll fabric soiled with blood, EMPA 112 fabric soiled with cocoa and EMPA 116 fabric soiled with a mixture of blood, milk and carbon black, and of the polyester/cotton type of the KREFELD type, namely: WFK 20F fabric soiled with cocoa.
These soilings are representative of stains of the blood, milk, egg, meat juice, mayonnaise, sauce type and the like.
Two groups of trials performed at 40~C and 60C
gave for the compositions A, B, C and D according to the invention and for the control product T, from the point of view of the removal of soiling represented by the above-said formula (l), the results collected in following Tables VII and VIII.
TABLE VII
(Trial at 40C) Type of Removal of soiling (in ~) ¦
fabric T A B C D
3o _ .
EMPA 111 (blood) 54.3 55.9 51.1 53.5 58.8 EMPA 112 (cocoa) 22.8 22.9 24.4 24.3 20.7 EMPA 116 (mixed) 20.3 19.9 16.6 16.0 22.0 Average cotton 32.5 32.9 30.7 31.3 33.8 35 WFK 20F (cocoa) 75.3 76.2 68.3 69.0 68.0 TABLE V _ (Trial at 60C) Type of Removal of soiling (in %) fabric T A B C D
EMPA 111 (blood) 65.4 75.3 64.8 57.5 66.0 EMPA 112 (cocoa) 25.8 24.5 30.3 21.3 20.6 EMPA 116 (mixed) 31.3 38.0 33.0 36.1 32.2 Average cotton 40.8 45.9 42.7 41.6 39.6 10 WFK 20F (cocoa) 76.3 76.5 80.0 73.3 77.2 From Tables VII and VIII, it appears that, in the case of the proteinic stains, the same conclusions as those previously made in connect~on with stains produced by mixtures of oil and carbon black, may be drawn as far as the efficiency of the laundry materials according to the invention is concerned as well as their interest comparatively with a material of the prior art which, while containing simultaneously more zeolite(s) and more polyacrylates, appears not to be more performant, espe-cially for a test temperature of 60C.
Oxidizable stains The effect of ~he laundry materials according to the invention on oxidizable stains was studied by using the following fabrics:
- polyester/cotton of the brand KREFELD soiled with tea (ref. WFK 20G) - cotton of the brand EMPA 222, that is to say unsoiled 3 unbleached cotton - cotton of the brand EMPA 114 soiled with wine.
The abovesaid fabrics are sensitive to chemical oxidation; the stains caused are those which the bleaching attenuates or causes to disappear (other stains of this type are those caused by fruits, coffee, vegetables and the like).
2 ~
A group of trials performed at 60C gave for the composition A, B, C and D and for the control product T, from the point of view of the removal of soil~ng repre-sented by the abovesaid formula (1), the results collected in Tables IX.
TABLE IX
Type of Removal of soiling (in %) fabric T A B C D
10 EMPA 222 (unbleached) 14.7 13.1 12.5 12.7 13.1 EMPA 114 (cocoa) 76.8 78.6 68.0 75.7 75.0 ~verage cotton 45.7 45.8 40.2 44.2 44 WFK 20G (tea) 85.9 85.4 65.6 82.0 83.5 15 The average of the results obtained on the stains of tea and wine and on unbleached cotton reflects the behaviour of the products tested on all stains of this family.
From Table IX, it appears that, in the specific case of oxidizable stains, the laundry materials according to the invention enable to reach a level of efficiency equal to that of the prior art laundry material. The laundry materials according to the invention fully respond to the criterium generally required as far as the elimina-tion of that type of stain is concerned.EXAMPLE 4 Degree of bleaching Unblued white cotton of the brand EMPA 221 and unblued polyester/cotton of the brand EMPA 213 were used 3 to determine whether a given laundry material was suitable for preserving, for increasing or for diminishing the initial degree of whiteness of the fabric.
The two groups of trials performed respectively at 40C and 60C gave for the compositions A, B, C and D, on the one hand, and for the control product T, on the other hand, from the point of view of degree of whiteness, the 20~8~0 results collected in Table X.
TABLE X
Variation (in ~) of the degree of whiteness Trial~ _______ ______. ______ ______ D
Cotton at 40C + 3.1 + 3.1 + 2.6 + 2.5 + ~.
________________________ ______ ,______. ____ __. ______ ____ I
Cotton at 60C + 4.5 + 4.3 + 5.7 + 4.3 + 4. l _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . _ _ _ _ _ _ . _ _ _ _ _ _ _ _ _ _ _ Polyester/cotton at 40C + 0.7 + 0.1 + 0.3 + 0.5 ~ 0. l __ _ _ __ _ _ _ _ _ _ _ _____ __ __ _ _ _ _ _ _ _ _ ___ _ __ . __ _ _ _ _. _ ___ _ _ _ _ _ _ I
Polyester/cotton at 60C + 1.2 + 0.~ + 1.6 + t.3 + 1.~
From Table X, it appears that, as far as the criterium under examination is concerned, the laundry materials according to the invention are globally as good as the prlor art laundry material, the said materials according to the invention enabling to obtain, after washing, a fabric whose degree of whiteness is higher than that which it had before washing.
In connection with a second group of trials, there were compared, according to tests identical to those previously disclosed, the efficiency of four laundry materials according to the invention referred to by E, F, G and H, and with respect to that of a prior art product containing 20% of zeolite and 10% of tripolyphosphates.
In order to prepare the said products E to ~, the 10% of tripolyphosphates of the composition of the control were substituted by the same weight respectively:
- of the product of oxidation of a starch hydrolysate having a DE close to 37, and presenting an acid index I
close to 8.6 as far as product E is concerned, - of the product of oxidation of a starch hydrolysate having a ~E close to 37, presenting an acid index I
close to 8.6 and "stabilized" by catalytic hydrogena-tion with nickel ~residual rate in reducing sugars SR
~$~0 lower than 0.1%) as far as product F is concerned, - of the product of oxidation of a starch hydrolysate having a DE close to 61.5, presenting an acid index I
close to 13.6 and "stabilized" by the action of sodium borohydrate (residual rate in SR lower than 1%) as far as product G is concerned, - of the product of oxidation of a starch hydrolysate having a DE close to 61.5 ~I close to 13.6) and "stabi-lized" by catalytic hydrogenation with nic~el (residual rate in SR lower than 0.~1%) as far as product H is concerned.
It appears from the said trials that, in a general manner, all of the laundry materials E to H according to the invention present performances which are similar and even higher in some cases with respect to those of a laundry material of the prior art in which zeolites and phosphates are associated.
In connection with a third group of trials, there is shown the interest of the laundry materials according to the invention by way of other trials than those disclosed previously and which will be disclosed in detail hereinafter.
In connection with these trials, the prior art control product was a laundry materlal denoted by the letter T whose constitution has been given in the above-mentioned Table I.
Three further laundry materials according to the invention, respectively denoted by the letters I, J and K, were tested, the respective rates in zeolite(s), in oxi-dized polysaccharide(s) and, if any, in sodium poly-acrylates (NaP) or in nitrllotriacetates (NTA), being indicated in the following Table XI.
~3~
TABLE XI
Constituents Composition ~% by weight) T I J K
Zeolite A 25 20 20 20 Polyacrylates 2 Nitrilotriacetates _ 2 _ 10 Oxidized Polysaccharide 10 In connection with these trials, there is used, as an oxidized polysaccharide contained within the laundry materials according to the invention, an oxidation product of a starch hydrolysate having a DE of about 37, and pre-senting an acid index I of about 8.6, the said oxidation product having moreover being subjected to catalytic hydrogenation with Raney nic~el (residual rate in reducing sugars lower than 0.05%).
The trials were carried out at 60C on a washing machine commercialized under the brand WASCATOR FOM 71, the amount of laundry material being 7 g/l, i.e. 154 g for every washing.
2.5 kg of fabrics containing two wear strips on the basis of pure cotton and a ballast of terry towels and dish towels of determined sizes or basis weight were washed (Standard NF T 73-600).
The tests which were carried out, were intended to measure, for every studied product (4 measures for each product), the chemical wear and the rate of organic incrustation obtained at the level of the fabrics being washed and that after 25 successive and cumulative washing cycles.
The chemical wear consists in measuring the ave-rage polymer$zation degree or DP of the cotton cellulosebeEore and after the 25 washings in order to evaluate the 2a3~o action on the macromolecular chain of cellulose of pro-ducts such as perborate and alkaline agents.
The determination of the DP of the cellulose is carried out by measuring the viscosity of a solution of a cotton sample subjected to the test within a convenient solvent (diamine cupriethylene) with respect to the viscosity of the solvent as such, said determination being carried out accordingly to the standard NF T 73-601, paragraph 3.6 or NF G 06-037.
The object sought for is that the detergent action does not cause a substantial decrease of the DP thus that the tear of the fabric thus washed is not facilitated.
In connection with the present tests, it is to be noticed that the cotton under test presents, before washing, a DP of 1925.
The organic incrustation permits to know the deposit of residual tensio-active(s) or soap(s) complexed by the calcium in the case of a sequestration of bad quality.
The test is carried out according to the standard NF T 73-601, paragraph 3.3 and ISO 4312, paragraph 6.
Generally speaking, one estimates that the rate of organic incrustation should not exceed about 1%.
In Table XII hereafter, the average degree of polymerization DP and the organic incrustation rate IO
obtained after 25 washings carried out at 60C are given in connection with the control laundry material T and with each one of the laundry materials I, J and K according to the invention.
TABLE XII
Laundry material T I J K
Degree of polymerization DP 1924 1865 1914 1892 _____________________________ ______ _______ ______. ._______ Organic incrustation rate IO (in ~) 1.05 0.59 0.64 0.41 2~38~4~1 The results recorded in Table XII globally show that the laundry materials according to the invention enable to obtain results which are similar with (from the standpoint of view of DP), and even higher (from the standpoint of view of I0) than those recorded with the prior art laundry material.
EXAMP$E 7 Using standard methods (Standards NF T 73-601, paragraph 3.4 et IS0 4312, paragraph 7), there is measured the rate of ashes of cotton strips which were subjected to a cycle of 25 successive washings at 60C using respecti-vely one or the other of the above-identified products T
(control), J and K (laundry materials according to the invention).
The measuring of the ash rate enables to know the importance of the deposit of mineral salts, especially of the calcium or magnesium carbonate, bicarbonate and sulphate, on the fabric at the end of the washing cycle.
In connection with laundry materials containing zeolites, it is generally agreed that an ash rate lower or equal to 1~ provides total satisfaction.
The results recorded in the following Table XIII
show, once again, that the laundry materials according to the invention enable to satisfy totally the requirements of the technique.
TABLE XIII
Laundry material T I J I K
3o Ashes rate (in %~ 0-74 ¦ 0-93 0.89
According to another advantageous embodiment of the laundry material according to the invention, the oxidized polysaccharide used within the said product appears in the form of an oxidation product of starch hydrolysate having a DE (Dextrose Equivalent) from about 5 to about 90 and presents preferably an acid index I comprised between about 1 and about 20, the said acid index being expressed in number of grams of carboxylic function per 100 g of oxidized polysaccharide, and given by the formula:
DE x 45 I = 100 x 180 100 + DElx8o218 _ DE
According to the present invention, very particu-larly preferred are oxidized polysaccharides which have an acid index comprised between about 5 and about 14 and which are obtained by oxidation of starch hydrolysates having a DE comprised between a~out 20 and about 65.
Very particularly advantageous are oxidized polysaccharides which have an acid index comprised between about 8 and about 14 and which are obtained by oxidation of starch hydrolysates having a DE comprised between about 35 and about 650 According to another advantageous embodiment, the oxidized polysaccharide is an oxidized product having, especially due to its reducing sugars content, a good stability, especially from the point of view of its colour, when the said oxidized product is used (when preparing or using the laundry material according to the invention) at any moment and for example at the moment of 3 atomization or spraying, within an environment presenting an alkaline pH and/or a high temperature, environment which is adapted to colour (more or less pronounced yellowing) any composition containing lt.
In that connection, Applicants have elaborated new products consisting of "stabilized" oxidized polysaccha-rides which present low contents, generally lower than 2 ~
0.6%, preferably lower than about 0.1~ and still more preferably lower than 0.05% by weight, in reducing sugars.
In particular, Applicants have found that, when subiecting oxidized polysaccharides, in particular of the type constituted of oxidized starch hydrolysates to hydro-genation techniques, one obtains the intended products especially oxidized products which have a content in reducing sugars practically equal to zero and which are "stabilized" as far as a possible yellowing in the presence of a particular environment which favours such a yellowing (alkaline pH, high temperature) is concerned.
The abovesaid hydrogenation techniques comprise in particular catalytic hydrogenation techniques carried out continuously or not and using at least one catalyst selected from the groups IB, IIIB, IVB, VI, VII and VIII
of the periodical table and especially selected from the group comprising nickel, platine, palladium, cobalt, molybdenum and mixtures of the said metals.
Hydrogenation techniques using Raney nickel as a catalyser fixed or not on an inert carrier in the presence or not of an additional hydrogene source are particularly preferred.
Other hydrogenation techniques using, in the absence of any hydrogenation catalyst, hydrogen sources other than hydrogene gas, for example borohydrides of alkaline metals, especially sodium borohydride, may also be contemplated.
The oxidized polysaccharides, especially of the type of the oxidized starch hydrolysates, which are "stabilized" after such a hydrogenation treatment, in particular those having a D~ comprised between 5 and 90, an acid index I comprised between 1 and 20 and which are "stabilized" by catalytic hydrogenation, when used in laundry compositions and laundry materials furthermore provide the latter with performances which are comparable with the performances of the same oxidized products which st-~
are not "stabilized" and even performances improved in connection with certain parameters.
Moreover, it ~ust be recalled, at that precise state of the specification, that the characteristic use of at least one oxidized polysaccharide, especially of a polysaccharide, for instance a starch hydrolysate, "selec-tively" oxidized at the level of its aldehydic terminal function, within the laundry materials according to the invention, not only enables to substitute efficiently within the said materials at least part of the polycarbo-xylic compounds non-biodegradable or weakly biodegradable of the type NTA, PA or their salts, by products, i.e.
oxidized polysaccharides, with which no problems of biodegradability occur, but also does not necessitate in no case the concomitant increase of the rate of zeolite(s) contained within the said materials with respect to the rates at present used within laundry materials available in the trade, which are generally of about 21 to 25% by weight.
And it is remarkable to notice that, in an all the more surprising and unexpected manner, the characteristic presence of at least one oxidized polysaccharide, espe-cially a polysaccharide, notably a starch hydrolysate, "selectively" oxidized at the level of its aldehydic terminal function, enables the said materials which contain the said oxidized polysaccharide to be efficient:
- for constitutive zeolite(s) rates lower than 20% by weight and/or - for constitutive rates of polycarboxylic compounds of the type NTA, PA or their sal~s, not higher than 2%
by weight and even in the substantial absence of the said polycarboxylic compounds.
In addition to the advantages which have just been disclosed in connection with the laundry materials according to the invention, it must be noticed that the said materials, on the contrary to certain materials of ~ $~
the prior art, do not produce any substantial desactiva-ti~n of the bleaching agents, between which especially perborate, currently used in laundry materials for the elimination of oxidable stains and produce high levels of whiteness.
Without wishing to be bound by theory, Applicants attribute the excellence of these performances to the stabilizing effect played by the oxidized polysaccharides with respect to the oxidizing agents.
This result is particularly pronounced when the oxidising agent is a perborate, especially of sodium, and when the composition according to the invention comprises, as oxidized polysaccharide, an oxidized starch hydro-lysate.
According to an advantageous embodiment of the laundry material according to the invention, the latter comprises :
- a proportion from about 5 to about 35% by weight, pre-ferably from 10 to 25% and, still more preferably, from 15 to 20% by weight of at least one zeolite, - a proportion from about 3 to about 20~ by weight, pre-ferably from 5 to 20~ and, still more preferably, from 7 to 20% by weight of at least one oxidized polysaccha-ride, in particular of a polysaccharide "selectively"
o~idized in respect with its terminal function of the aldehydic type.
According to another advantageous embodiment of the above-mentioned material, the ratio by weight between, on the one hand, the zeolite and, on the other hand, the oxidized polysaccharide is comprised between about 0.5/1 and about 4/1, preferably between 1/1 and 2/1.
In connection with the present invention, the term "zeolite" comprises any ion exchanging material of the aluminosilicate type, of crystalline or amorphous nature and of natural or synthetic origin, such as disclosed for example in the above-mentioned European patents EP 70 079 and EP 193 360. Such products are for example available in the trade under the commercial names "zeolite A", "zeolite B", "zeolite X" or "zeolite HS".
In particular, a crystalline sodium silicoalumi-nate of the "zeolite A" type can be used.
In practice, the laundry materlal according to the invention, which constitutes a new industrial product, comprises also one or several other constituents which are selected in particular from the group comprislng the detergent agents, the surfactive agents, the antiredeposi-tion agents, the oxidizing agents, the structural agents, the anticorrosion agents, the antifoaming agents, the enzymes, the perfumes, the dyes, the solubilizing agents, etc., for example such as disclosed in the above-mentioned European patents EP 70 079 and EP 319 0530 The detergent agents may be, for example, selected among synthetic anionic detergent agents, such as hydro-soluble alkaline metal salts of organic sulphates and sulphonates comprising alkyl radicals having from about 8 to 22 carbon atoms, such as for example sodium or potas-sium dodecylbenzene sulphonates.
It is also possible to select the said agents among the non-ionic detergent agents, such as especially the alkylpolyg]ucosides or the ethoxylated fatty alcohols.
The oxidizing agents, i.e. the products which are adapted to set free peroxide ions in an amount sufficient to permit the bleaching of wine stains, of tea stains, of coffee stains, etc., may be in particular perborates, percarbonates, persilicates or perphosphates of alkaline metals and especially the sodium perborate.
The structural agents may in particular be select-ed, as recommended in the European patent EP 215 637, from the susars, the hydrogenated sugars and the mixtures of the above-mentioned products and especially those which consist of or which at least contain a monosaccharide such as glucose or fructose and/or a disaccharide such as 2 ~ 3 8 6 ~ ~
maltose or saccharose and/or their hydrogenation products.
The structural agents may especially consist of or contain, at least partially, sorbitol and especially consist of hydrogenated products obtained by hydrogenation of starch hydrolysates or glucose syrups.
Furthermore, the laundry material according to the invention may contain detergency additives normally used such as polyacrylic acid (PA), nitrilotriacetic acid (NTA) and/or their respective salts, especially their sodium salts.
However, as already indicated above, the charac-teristic presence of at least one oxidized polysaccharide wlthin the laundry materials according to the invention enables the said products to be, in a remarkable manner, while having a zeolite rate not higher and even lower than those of the materials of the prior art, efficient or constitutive rates of NTA, of PA or of their salts, lower than those currently encountered in the said materials of the prior art, especially for rates which are not higher than 2% by weight and which are even substantially equal to 0.
The laundry materials according to the invention, which are adapted in particular for the washing of tex-tiles as well in a machine or "hand-washed", are prefera-bly in the form of free-flowing particles, especially in the form of a powder or of granulates.
No special process and no special installation other than those normally used by those skilled in the art is necessary for the preparation of the above-mentioned materials; those skilled in the art may for example resort to classic techniques of drying of aqueous suspensions by spraying.
The mixture of the at least one zeolite and the at least one oxidized polysaccharide to be comprised by the laundry materials according to the invention can be carried out in various manners, the said products being in the form of powders, of liquids, or of mi~tures of powders/liquids, in the presence or not of all or part of the other constituents of the said materials.
For example, it is possible to mix the oxidized polysaccharide with a laundry "precomposition" already in the powder form and containing the ma~ority or even the totality of the other constituents of the final material.
The association of at least one zeolite and of at least one oxidized polysaccharide may also be realized within the laundry materials, the said materials being then in another form than that of free-flowing particles, in particular in the form of liquids, gels or pastes.
These products, which generally will present a dry matter content from about 15% to about 80%, and especially from 30 to 50~, can be obtained, for example, by increasing, by any possible manner and especially by mere dissolution or suspension in water or in another liquid, the water content of the laundry materials according to the invention previously prepared in the form of powders or of granulates.
They can also, in other cases, present a formula-tion substantially different of that used for the powders or granulates, especially as far as their content in tensio-active or surfactive additives is concerned.
The invention will be still better understood by means of the following examples relating to particularly advantageous embodiments of the products according to the invention.
To demonstrate the effectiveness of the laundry materials according to the invention, comparative trials were carried out using, on the one hand, a laundry mate-rial according to the prior art denoted by the letter "T"
whose constitution is given in the following Table I and, on the other hand, four laundry materials according to the invention, denoted respec~ively by the letters A, B, C and D, whose respective contents in zeolite(s), in o~idized polysaccharide(s) and possibly in sodium polyacrylates (PNa) are given in Table II.
In this first series vf trials, an oxidation product of a starch hydrolysate having a DE of about 61.5 and an acid index I of about 13.6 is ussd in the laundry materials according to the invention as ox~dized poly-saccharide.
TABLE I
Manufacturing Producing .
Constituentsbrand or formula Company by weight AntifoamingUKANIL 2136 ICI 0.2 dodecylbenzene sulphonate FLUKA 6 15 ethoxylated fatty alcohol KC 7/L
ethoxylated ceto-stearylic alcohol EMPILAN KM 11MARCHON 5 Sodium sulphate Na2 SO4PANREAC 21 Sodium metasilicate anhydrous SiO2Na2O PROLABO 3 20 Sodium carbonate Na2 CO3PANREAC 5 Sodium perborate Na BO3 4H2OFLUKA 18 Tetraacetylethylene diamine LEVER 2 Carboxymethyl-25 celluloseBLANOSE 7M65 AQUALON
Zeolite ANa2O Al2O~ 2SiO~
x H2O (x= 4 to 5) MONTEDISON 25 Sodium Polyacrylate SOKALAN C 245 BASF 4 EnzymeESPERASE NOVO 0.6 Water _ _ qsp 100 3o _ '~3~
TABLE II
_ Constituents Composition (% by weight~
T A B C D
Zeolite A 25 18 18 19 19 _ Polyacrylates 4 2 ~ _ Oxidized polysaccharide _ I0 18 14 10 The said comparative trials consist of washing trials which were performed by means of a washing machine of the VEDETTE 8596 SYSTEME CHOIX brand with top loading.
The trials were carried out at the two following temperatures: 40C and 60C.
For the trial at 40C, a rise of temperature of 13 minutes, then a plateau at 40C of 22 minutes was selected.
The complete cycle, that is to say including the fillings, rincings and spin-drying, lasts 80 minutes.
For the trial at 60C, there was provided a rise in temperature of 21 minutes, then a plateau at 60~C of 22 minutes. The complete cycle lasts 90 minutes.
In the two trials, the volume of washing water was 11 liters.
Two washings were carried out per temperature.
The hardness of the water was 30 TH.
The washing load was composed of 2.2 kg of pieces of white fabric (cotton) of which the sizes were 55 cm x 70 cm.
On each washing, there was included with a load of 2.2 kg of pieces of white fabric, a group of "soiled fabrics" of different natures and which include soilings predetermined and predeposited on these fabrics.
In practice, these "presoiled" fabrics which are pinned to the washing load, are as follows:
- 2 strips of grey polyest(er/cotton (64/35) of the KREFELD
brand ~ref. WFK 20 C), soiled by a mixture of an animal oil and carbon black, - 2 strips of cotton of the brand EMPA 103 constituted by eight pieces sewn together, namely:
- a piece of white cotton (of the EMPA 221 type), - a piece of grey cotton (of the EMPA 101 type soiled by a mixture of vegetable oil and carbon black), - a piece of cotton soiled with blood (of the EMPA 111 type), - a piece of cotton soiled with cocoa (of the EMPA 112 type), - a piece of COttOII soiled by a mixed stain of milk, blood, carbon blac~ (of the EMPA 116 type), - a piece of unbleached cotton (of the EMPA 222 type), - a piece of cotton soiled with wine (of the EMPA 114 type), - a piece of cotton soiled with sulphur black (not used in the present measurements), - 2 strips of polyester/cotton (65/35) soiled with tea, of the KREFELD brand (ref. WFK 20G), 20 - 2 strips of polyester/cotton (65/35) soiled with cocoa, of the KREFELD brand (ref. WFK 20F), - 2 strips of white polyester/cotton (65/35) of the EMPA
brand (ref. EMPA 213).
The dosle of laundry material was 8 g/l of water.
To evaluate the quality of the washing, on the one hand the removal of the soiling and o$ the stains and, on the other hand, the effect of the washings on the degree of bleaching were measured.
To evaluate the removal of the soiling and of the stains, procedure was by photometry (measurements of the amount of light reflected by the fabric); it was thus possible to calculate the percentages of removal of the soiling. A device for measuring the reflection of light, marketed under the brand ACS 1400 SPECTR0 was used.
The removal of the soiling is expressed by the formula Removal in ~ _ C - B x 100 (1) in which:
A = reflectance of the control white sample, B = reflectance of the control soiled sample, C = reflectance of the soiled sample after testing.
The reflectances were determined by means of the blue trichromatic component.
The number of measurements carried out per fabric was 4, which means 4 measurements (that is to say at four different places on the same piece of fabric) x 2 washings x 2 strips of fabric = 16 measurements per soiling, per formulation and per temperature.
Regarding the degree of bleaching, the effect of the washings was measured on two cuttings of EMPA 221 unsoiled white cotton and on two cuttings of EMPA 213 unsoiled white polyester/cotton, which were incorporated in the washing bath. On each cutting, 4 measurements were carried out, which therefore gave 16 measurements per formulation and per temperature studied.
If there are denoted :
- by Rbo, the blue trichromatic component obtained before washing, - by Rb, the blue trichromatic component obtained 25after washing, the degree of b]eaching is given by the formula BL = Rb - Rbo.
In the trials proper which will now be described, the effectiveness of the laundry materials according to the invention was studied successively on soilings based on oil and on carbon black, then on proteinic stains and oxidizable stains and finally the "degree of whiteness"
conferred by said materials on the treated fabrics was determined.
2~3~
Stains produced by mixtures of mineral, vegetable and/or animal oil with carbon black.
Washing trials were carried out, on the one hand, on grey cotton and, on the other hand, on synthetic fabrics (polye~ter/cotton~.
1) Trials on grey cotton By washing, there were treated successively each time two strips of grey cotton of the brand EMPA 101 soiled by a mixture of vegetable oil and carbon black.
This type of soiled cotton is representative of insoluble pigmentary soilings bound to the fabric by greasy film, as for example the collars of shirts and of coats, the rags and the greasy stains.
The two groups of tests carried out respectively at 40C and 60C gave for the products according to the invention A, B, C and D, on the one hand, and for the product T according to the prior art, on the other hand, from the point of view of removal of soiling represented by the abovesaid formula (1), the results collected respectlvely in Tables III and IV.
TABLE III
(Trial at 40C) -~rype Removal of soiling (in %) of fabric T A B C D
_ EMPA 101 17.4 17.5 16.3 16.7 16.1 TABLE IV
3 (Trial at 60C) I
Type Removal of soiling (in %) of fabric T A B C D
EMPA 101 17.7 18.8 23.1 16.9 17.1 _ ~8~
2) Trials on grey synthetic materials The synthetic fabric used here was a fabric of the polyester/cotton (dacron/cotton) type of the brand KREFELD; it was soiled with a mixture of animal oil with carbon black (ref. WFK 20C).
The two groups of the trials carried out respecti-vely at 40C and 60C gave for the compositions A, B, C
and D, on the one hand, and for the control product T, on the other hand, from the point of view of the removal of soiling represented by the abovesaid formula (l), the results which are collected respectively in Tables V and VI.
TABLE V
(Trial at 40~C) Type of ¦ Removal of soiling (in %) synthetic fabric 1 T A B D
Polyester/cotton 20.2 20.0 18.1 19.0 18.8 WFK 20C _ _ TABLE VI
(Trial at 60C) Type of Removal of soiling (in ~) 25 synthetic fabric T ~ _ _ C I D
Polyester/cotton l9.9 20.1 24.7 19.2 19.5 WFK 20C _ _ From Tables III to VI, it appears that the charac-teristic presence of at least one oxidized polysaccharide, especially of at least one polysaccharide "selectively"
oxidized at the level of its terminal function of the aldehydic type, in the laundry materials according to the invention, enables and that, for washing performances similar or even higher than those noticed with the prior art laundry material:
2038~
- to decrease the rate of incorporation of zeolite(s~
and/or - to decrease the rate of incorporation of a non-biode-gradable detergence additive currently used, such as polyacrylates, and even to suppress completely the incorporation of such an agent.
EXAMPL~ 2 Proteinic stains The action of the laundry materials according to the invention on proteinic stains is studied by using fabrics of the cotton type of EMPA b~and, namely: EMPA lll fabric soiled with blood, EMPA 112 fabric soiled with cocoa and EMPA 116 fabric soiled with a mixture of blood, milk and carbon black, and of the polyester/cotton type of the KREFELD type, namely: WFK 20F fabric soiled with cocoa.
These soilings are representative of stains of the blood, milk, egg, meat juice, mayonnaise, sauce type and the like.
Two groups of trials performed at 40~C and 60C
gave for the compositions A, B, C and D according to the invention and for the control product T, from the point of view of the removal of soiling represented by the above-said formula (l), the results collected in following Tables VII and VIII.
TABLE VII
(Trial at 40C) Type of Removal of soiling (in ~) ¦
fabric T A B C D
3o _ .
EMPA 111 (blood) 54.3 55.9 51.1 53.5 58.8 EMPA 112 (cocoa) 22.8 22.9 24.4 24.3 20.7 EMPA 116 (mixed) 20.3 19.9 16.6 16.0 22.0 Average cotton 32.5 32.9 30.7 31.3 33.8 35 WFK 20F (cocoa) 75.3 76.2 68.3 69.0 68.0 TABLE V _ (Trial at 60C) Type of Removal of soiling (in %) fabric T A B C D
EMPA 111 (blood) 65.4 75.3 64.8 57.5 66.0 EMPA 112 (cocoa) 25.8 24.5 30.3 21.3 20.6 EMPA 116 (mixed) 31.3 38.0 33.0 36.1 32.2 Average cotton 40.8 45.9 42.7 41.6 39.6 10 WFK 20F (cocoa) 76.3 76.5 80.0 73.3 77.2 From Tables VII and VIII, it appears that, in the case of the proteinic stains, the same conclusions as those previously made in connect~on with stains produced by mixtures of oil and carbon black, may be drawn as far as the efficiency of the laundry materials according to the invention is concerned as well as their interest comparatively with a material of the prior art which, while containing simultaneously more zeolite(s) and more polyacrylates, appears not to be more performant, espe-cially for a test temperature of 60C.
Oxidizable stains The effect of ~he laundry materials according to the invention on oxidizable stains was studied by using the following fabrics:
- polyester/cotton of the brand KREFELD soiled with tea (ref. WFK 20G) - cotton of the brand EMPA 222, that is to say unsoiled 3 unbleached cotton - cotton of the brand EMPA 114 soiled with wine.
The abovesaid fabrics are sensitive to chemical oxidation; the stains caused are those which the bleaching attenuates or causes to disappear (other stains of this type are those caused by fruits, coffee, vegetables and the like).
2 ~
A group of trials performed at 60C gave for the composition A, B, C and D and for the control product T, from the point of view of the removal of soil~ng repre-sented by the abovesaid formula (1), the results collected in Tables IX.
TABLE IX
Type of Removal of soiling (in %) fabric T A B C D
10 EMPA 222 (unbleached) 14.7 13.1 12.5 12.7 13.1 EMPA 114 (cocoa) 76.8 78.6 68.0 75.7 75.0 ~verage cotton 45.7 45.8 40.2 44.2 44 WFK 20G (tea) 85.9 85.4 65.6 82.0 83.5 15 The average of the results obtained on the stains of tea and wine and on unbleached cotton reflects the behaviour of the products tested on all stains of this family.
From Table IX, it appears that, in the specific case of oxidizable stains, the laundry materials according to the invention enable to reach a level of efficiency equal to that of the prior art laundry material. The laundry materials according to the invention fully respond to the criterium generally required as far as the elimina-tion of that type of stain is concerned.EXAMPLE 4 Degree of bleaching Unblued white cotton of the brand EMPA 221 and unblued polyester/cotton of the brand EMPA 213 were used 3 to determine whether a given laundry material was suitable for preserving, for increasing or for diminishing the initial degree of whiteness of the fabric.
The two groups of trials performed respectively at 40C and 60C gave for the compositions A, B, C and D, on the one hand, and for the control product T, on the other hand, from the point of view of degree of whiteness, the 20~8~0 results collected in Table X.
TABLE X
Variation (in ~) of the degree of whiteness Trial~ _______ ______. ______ ______ D
Cotton at 40C + 3.1 + 3.1 + 2.6 + 2.5 + ~.
________________________ ______ ,______. ____ __. ______ ____ I
Cotton at 60C + 4.5 + 4.3 + 5.7 + 4.3 + 4. l _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . _ _ _ _ _ _ . _ _ _ _ _ _ _ _ _ _ _ Polyester/cotton at 40C + 0.7 + 0.1 + 0.3 + 0.5 ~ 0. l __ _ _ __ _ _ _ _ _ _ _ _____ __ __ _ _ _ _ _ _ _ _ ___ _ __ . __ _ _ _ _. _ ___ _ _ _ _ _ _ I
Polyester/cotton at 60C + 1.2 + 0.~ + 1.6 + t.3 + 1.~
From Table X, it appears that, as far as the criterium under examination is concerned, the laundry materials according to the invention are globally as good as the prlor art laundry material, the said materials according to the invention enabling to obtain, after washing, a fabric whose degree of whiteness is higher than that which it had before washing.
In connection with a second group of trials, there were compared, according to tests identical to those previously disclosed, the efficiency of four laundry materials according to the invention referred to by E, F, G and H, and with respect to that of a prior art product containing 20% of zeolite and 10% of tripolyphosphates.
In order to prepare the said products E to ~, the 10% of tripolyphosphates of the composition of the control were substituted by the same weight respectively:
- of the product of oxidation of a starch hydrolysate having a DE close to 37, and presenting an acid index I
close to 8.6 as far as product E is concerned, - of the product of oxidation of a starch hydrolysate having a ~E close to 37, presenting an acid index I
close to 8.6 and "stabilized" by catalytic hydrogena-tion with nickel ~residual rate in reducing sugars SR
~$~0 lower than 0.1%) as far as product F is concerned, - of the product of oxidation of a starch hydrolysate having a DE close to 61.5, presenting an acid index I
close to 13.6 and "stabilized" by the action of sodium borohydrate (residual rate in SR lower than 1%) as far as product G is concerned, - of the product of oxidation of a starch hydrolysate having a DE close to 61.5 ~I close to 13.6) and "stabi-lized" by catalytic hydrogenation with nic~el (residual rate in SR lower than 0.~1%) as far as product H is concerned.
It appears from the said trials that, in a general manner, all of the laundry materials E to H according to the invention present performances which are similar and even higher in some cases with respect to those of a laundry material of the prior art in which zeolites and phosphates are associated.
In connection with a third group of trials, there is shown the interest of the laundry materials according to the invention by way of other trials than those disclosed previously and which will be disclosed in detail hereinafter.
In connection with these trials, the prior art control product was a laundry materlal denoted by the letter T whose constitution has been given in the above-mentioned Table I.
Three further laundry materials according to the invention, respectively denoted by the letters I, J and K, were tested, the respective rates in zeolite(s), in oxi-dized polysaccharide(s) and, if any, in sodium poly-acrylates (NaP) or in nitrllotriacetates (NTA), being indicated in the following Table XI.
~3~
TABLE XI
Constituents Composition ~% by weight) T I J K
Zeolite A 25 20 20 20 Polyacrylates 2 Nitrilotriacetates _ 2 _ 10 Oxidized Polysaccharide 10 In connection with these trials, there is used, as an oxidized polysaccharide contained within the laundry materials according to the invention, an oxidation product of a starch hydrolysate having a DE of about 37, and pre-senting an acid index I of about 8.6, the said oxidation product having moreover being subjected to catalytic hydrogenation with Raney nic~el (residual rate in reducing sugars lower than 0.05%).
The trials were carried out at 60C on a washing machine commercialized under the brand WASCATOR FOM 71, the amount of laundry material being 7 g/l, i.e. 154 g for every washing.
2.5 kg of fabrics containing two wear strips on the basis of pure cotton and a ballast of terry towels and dish towels of determined sizes or basis weight were washed (Standard NF T 73-600).
The tests which were carried out, were intended to measure, for every studied product (4 measures for each product), the chemical wear and the rate of organic incrustation obtained at the level of the fabrics being washed and that after 25 successive and cumulative washing cycles.
The chemical wear consists in measuring the ave-rage polymer$zation degree or DP of the cotton cellulosebeEore and after the 25 washings in order to evaluate the 2a3~o action on the macromolecular chain of cellulose of pro-ducts such as perborate and alkaline agents.
The determination of the DP of the cellulose is carried out by measuring the viscosity of a solution of a cotton sample subjected to the test within a convenient solvent (diamine cupriethylene) with respect to the viscosity of the solvent as such, said determination being carried out accordingly to the standard NF T 73-601, paragraph 3.6 or NF G 06-037.
The object sought for is that the detergent action does not cause a substantial decrease of the DP thus that the tear of the fabric thus washed is not facilitated.
In connection with the present tests, it is to be noticed that the cotton under test presents, before washing, a DP of 1925.
The organic incrustation permits to know the deposit of residual tensio-active(s) or soap(s) complexed by the calcium in the case of a sequestration of bad quality.
The test is carried out according to the standard NF T 73-601, paragraph 3.3 and ISO 4312, paragraph 6.
Generally speaking, one estimates that the rate of organic incrustation should not exceed about 1%.
In Table XII hereafter, the average degree of polymerization DP and the organic incrustation rate IO
obtained after 25 washings carried out at 60C are given in connection with the control laundry material T and with each one of the laundry materials I, J and K according to the invention.
TABLE XII
Laundry material T I J K
Degree of polymerization DP 1924 1865 1914 1892 _____________________________ ______ _______ ______. ._______ Organic incrustation rate IO (in ~) 1.05 0.59 0.64 0.41 2~38~4~1 The results recorded in Table XII globally show that the laundry materials according to the invention enable to obtain results which are similar with (from the standpoint of view of DP), and even higher (from the standpoint of view of I0) than those recorded with the prior art laundry material.
EXAMP$E 7 Using standard methods (Standards NF T 73-601, paragraph 3.4 et IS0 4312, paragraph 7), there is measured the rate of ashes of cotton strips which were subjected to a cycle of 25 successive washings at 60C using respecti-vely one or the other of the above-identified products T
(control), J and K (laundry materials according to the invention).
The measuring of the ash rate enables to know the importance of the deposit of mineral salts, especially of the calcium or magnesium carbonate, bicarbonate and sulphate, on the fabric at the end of the washing cycle.
In connection with laundry materials containing zeolites, it is generally agreed that an ash rate lower or equal to 1~ provides total satisfaction.
The results recorded in the following Table XIII
show, once again, that the laundry materials according to the invention enable to satisfy totally the requirements of the technique.
TABLE XIII
Laundry material T I J I K
3o Ashes rate (in %~ 0-74 ¦ 0-93 0.89
Claims (13)
1. Laundry material having a phosphate content reduced to less than 5% by weight and even equal to zero, especially adapted for washing fabrics, comprising at least one zeolite and at least one oxidized polysaccharide selected from the group comprising:
a) the products resulting from the oxidation of disaccha-rides presenting a terminal function of the aldonic type, b) the products resulting from the oxidation of trisaccha-rides and of oligosaccharides presenting a terminal function of the aldonic type, c) the products resulting from the oxidation of starch hydrolysates, of cellulose and hemicelluloses present-ing a terminal function of the aldonic type, d) any mixtures of at least two of the above-identified oxidation products.
a) the products resulting from the oxidation of disaccha-rides presenting a terminal function of the aldonic type, b) the products resulting from the oxidation of trisaccha-rides and of oligosaccharides presenting a terminal function of the aldonic type, c) the products resulting from the oxidation of starch hydrolysates, of cellulose and hemicelluloses present-ing a terminal function of the aldonic type, d) any mixtures of at least two of the above-identified oxidation products.
2. Laundry material according to claim 1, wherein the oxidized polysaccharide is constituted by at least one product obtained from a di-, tri- or oligosaccharide, from a starch hydrolysate, from cellulose or hemicellulose of which only, among the whole of its potentially oxidizable functions, the terminal function (of the aldehydic type before oxidation) is substantially oxidized.
3. Laundry material according to claim 1, wherein the oxidized polysaccharide is an oxidation product of a starch hydrolysate obtained by the acid and/or the enzyma-tic route, having a DE from about 5 to about 90.
4. Laundry material according to claim 1, wherein the oxidized polysaccharide presents an acid index I
comprised between about 1 and about 20.
comprised between about 1 and about 20.
5. Laundry material according to claim 1, wherein the oxidized polysaccharide is an oxidation product of a starch hydrolysate having a DE from about 20 to about 65, the said oxidized polysaccharide having an acid index I
comprised between about 5 and about 14.
comprised between about 5 and about 14.
6. Laundry material according to claim 1, wherein the oxidized polysaccharide is an oxidation product of a starch hydrolysate having a DE from about 35 to about 65, the said oxidized polysaccharide having an acid index I
comprised between about 8 and about 14.
comprised between about 8 and about 14.
7. Laundry material according to claim 1, wherein the oxidized polysaccharide presents a content lower than about 0.6%, preferably lower than 0.1% and still prefera-bly lower than 0.05% by weight, in reducing sugars.
8. Laundry material according to claim 1, wherein the oxidized polysaccharide is subjected to a catalytic hydrogenation, the said catalytic hydrogenation being carried out, continuously or not, using at least one catalyst selected from the group consisting of nickel, platine, palladium, cobalt, molybdenum and mixtures of the said metals, and especially Raney nickel.
9. Laundry material according to claim 1, comprising:
- a proportion from about 5 to about 35% by weight, pre-ferably from 10 to 25% and, still more preferably, from 15 to 20% by weight of at least one zeolite, - a proportion from about 3 to about 20% by weight, pre-ferably from 5 to 20% and, still more preferably, from 7 to 20% by weight of at least one oxidized polysaccha-ride, in particular of a polysaccharide "selectively"
oxidized in respect with its terminal function of the aldehydic type.
- a proportion from about 5 to about 35% by weight, pre-ferably from 10 to 25% and, still more preferably, from 15 to 20% by weight of at least one zeolite, - a proportion from about 3 to about 20% by weight, pre-ferably from 5 to 20% and, still more preferably, from 7 to 20% by weight of at least one oxidized polysaccha-ride, in particular of a polysaccharide "selectively"
oxidized in respect with its terminal function of the aldehydic type.
10. Laundry material according to claim 1, wherein the ratio by weight between, on the one hand, the zeolite and, on the other hand, the oxidized polysaccharide is comprised between about 0.5/1 and about 4/1, preferably between 1/1 and 2/1.
11. Laundry material according to claim 1, wherein the zeolite is a sodium silico-aluminate, in particular of the zeolite A type.
12. Laundry material according to claim 1, com-prising one or several constituents selected from the group comprising the polycarboxylic detergent additives such as polyacrylic acid (PA), nitrilotriacetic acid (NTA) and/or their respective salts, the detergent agents, the surfactive agents, the antiredeposition agents, the oxidizing agents, the structural agents, the anticorrosion agents, the antifoaming agents, the enzymes, the perfumes, the dyes, the solubilizing agents.
13. Laundry material according to claim 1, com-prising at the most 4%, preferably at the most 2% by weight of a detergent additive selected from the group comprising polyacrylic acid (PA), nitrilotriacetic acid (NTA), their respective salts, especially their sodium salts, and the mixtures of the latter.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9003758 | 1990-03-23 | ||
| FR9003758A FR2659979B1 (en) | 1990-03-23 | 1990-03-23 | WASHING PRODUCT WITH REDUCED OR ZERO PHOSPHATE CONTENT. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2038640A1 true CA2038640A1 (en) | 1991-09-24 |
Family
ID=9395061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002038640A Abandoned CA2038640A1 (en) | 1990-03-23 | 1991-03-19 | Laundry material |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0455522B1 (en) |
| JP (1) | JPH05214367A (en) |
| AT (1) | ATE141323T1 (en) |
| CA (1) | CA2038640A1 (en) |
| DE (1) | DE69121286T2 (en) |
| DK (1) | DK0455522T3 (en) |
| ES (1) | ES2090268T3 (en) |
| FI (1) | FI911409A (en) |
| FR (1) | FR2659979B1 (en) |
| GR (1) | GR3020943T3 (en) |
| NO (1) | NO911157L (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015138283A1 (en) | 2014-03-11 | 2015-09-17 | E. I. Du Pont De Nemours And Company | Oxidized poly alpha-1,3-glucan as detergent builder |
| US10633683B2 (en) | 2015-04-03 | 2020-04-28 | Dupont Industrial Biosciences Usa, Llc | Gelling dextran ethers |
| US10787524B2 (en) | 2015-04-03 | 2020-09-29 | Dupont Industrial Biosciences Usa, Llc | Oxidized dextran |
| WO2021247810A1 (en) | 2020-06-04 | 2021-12-09 | Nutrition & Biosciences USA 4, Inc. | Dextran-alpha-glucan graft copolymers and derivatives thereof |
| WO2022178075A1 (en) | 2021-02-19 | 2022-08-25 | Nutrition & Biosciences USA 4, Inc. | Oxidized polysaccharide derivatives |
| WO2022235655A1 (en) | 2021-05-04 | 2022-11-10 | Nutrition & Biosciences USA 4, Inc. | Compositions comprising insoluble alpha-glucan |
| WO2022235735A1 (en) | 2021-05-04 | 2022-11-10 | Nutrition & Biosciences USA 4, Inc. | Compositions comprising oxidized insoluble alpha-glucan |
| EP4038172A4 (en) * | 2019-09-30 | 2023-06-21 | Ecolab USA Inc. | Ware washing solution containing oxidized starch |
| WO2023183284A1 (en) | 2022-03-21 | 2023-09-28 | Nutrition & Biosciences USA 4, Inc. | Compositions comprising insoluble alpha-glucan |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4134914A1 (en) * | 1991-10-23 | 1993-04-29 | Henkel Kgaa | DETERGENT AND CLEANING AGENT WITH SELECTED BUILDER SYSTEMS |
| DE4203923A1 (en) * | 1992-02-11 | 1993-08-12 | Henkel Kgaa | METHOD FOR PRODUCING POLYCARBOXYLATES ON A POLYSACCHARIDE BASE |
| US5437810A (en) * | 1994-04-26 | 1995-08-01 | Colgate-Palmolive Co. | Aqueous liquid detergent compositions containing oxidized polysaccharides |
| US9376648B2 (en) | 2008-04-07 | 2016-06-28 | The Procter & Gamble Company | Foam manipulation compositions containing fine particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE351431B (en) * | 1969-05-19 | 1972-11-27 | Lyckeby Staerkelsefoeraedling | |
| CA964216A (en) * | 1969-05-19 | 1975-03-11 | Lyckeby Starkelseforadling Ab | Modified saccharide materials |
| JPS6092239A (en) * | 1983-10-24 | 1985-05-23 | Kawaken Fine Chem Co Ltd | Preparation of gluconic acid |
| GB8522621D0 (en) * | 1985-09-12 | 1985-10-16 | Unilever Plc | Detergent powder |
| FR2597473B1 (en) * | 1986-01-30 | 1988-08-12 | Roquette Freres | PROCESS FOR THE OXIDATION OF DI-, TRI-, OLIGO- AND POLYSACCHARIDES TO POLYHYDROXYCARBOXYLIC ACIDS, CATALYST IMPLEMENTED AND PRODUCTS THUS OBTAINED. |
| DE3914293A1 (en) * | 1989-04-29 | 1990-10-31 | Kali Chemie Ag | DETERGENT AND DETERGENT COMPOSITIONS |
| FR2653442A1 (en) * | 1989-10-23 | 1991-04-26 | Roquette Freres | COMPOSITION FOR WASHING PRODUCTS, PROCESS FOR PREPARING SAME, AND WASHING PRODUCT CONTAINING SAME. |
| ATE124960T1 (en) * | 1989-11-10 | 1995-07-15 | Tno | METHOD FOR PRODUCING POLYDICARBOXYSACHARIDES. |
-
1990
- 1990-03-23 FR FR9003758A patent/FR2659979B1/en not_active Expired - Fee Related
-
1991
- 1991-03-19 CA CA002038640A patent/CA2038640A1/en not_active Abandoned
- 1991-03-21 DK DK91400773.7T patent/DK0455522T3/en active
- 1991-03-21 AT AT91400773T patent/ATE141323T1/en not_active IP Right Cessation
- 1991-03-21 EP EP91400773A patent/EP0455522B1/en not_active Expired - Lifetime
- 1991-03-21 ES ES91400773T patent/ES2090268T3/en not_active Expired - Lifetime
- 1991-03-21 DE DE69121286T patent/DE69121286T2/en not_active Expired - Fee Related
- 1991-03-22 FI FI911409A patent/FI911409A/en not_active Application Discontinuation
- 1991-03-22 NO NO91911157A patent/NO911157L/en unknown
- 1991-03-25 JP JP3216730A patent/JPH05214367A/en active Pending
-
1996
- 1996-09-04 GR GR960402301T patent/GR3020943T3/en unknown
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015138283A1 (en) | 2014-03-11 | 2015-09-17 | E. I. Du Pont De Nemours And Company | Oxidized poly alpha-1,3-glucan as detergent builder |
| US9695253B2 (en) | 2014-03-11 | 2017-07-04 | E I Du Pont De Nemours And Company | Oxidized poly alpha-1,3-glucan |
| US10072100B2 (en) | 2014-03-11 | 2018-09-11 | E I Du Pont De Nemours And Company | Oxidized poly alpha-1,3-glucan |
| US10633683B2 (en) | 2015-04-03 | 2020-04-28 | Dupont Industrial Biosciences Usa, Llc | Gelling dextran ethers |
| US10787524B2 (en) | 2015-04-03 | 2020-09-29 | Dupont Industrial Biosciences Usa, Llc | Oxidized dextran |
| EP4038172A4 (en) * | 2019-09-30 | 2023-06-21 | Ecolab USA Inc. | Ware washing solution containing oxidized starch |
| WO2021247810A1 (en) | 2020-06-04 | 2021-12-09 | Nutrition & Biosciences USA 4, Inc. | Dextran-alpha-glucan graft copolymers and derivatives thereof |
| WO2022178075A1 (en) | 2021-02-19 | 2022-08-25 | Nutrition & Biosciences USA 4, Inc. | Oxidized polysaccharide derivatives |
| WO2022235655A1 (en) | 2021-05-04 | 2022-11-10 | Nutrition & Biosciences USA 4, Inc. | Compositions comprising insoluble alpha-glucan |
| WO2022235735A1 (en) | 2021-05-04 | 2022-11-10 | Nutrition & Biosciences USA 4, Inc. | Compositions comprising oxidized insoluble alpha-glucan |
| WO2023183284A1 (en) | 2022-03-21 | 2023-09-28 | Nutrition & Biosciences USA 4, Inc. | Compositions comprising insoluble alpha-glucan |
| WO2023183280A1 (en) | 2022-03-21 | 2023-09-28 | Nutrition & Biosciences USA 4, Inc. | Compositions comprising insoluble alpha-glucan |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE141323T1 (en) | 1996-08-15 |
| NO911157D0 (en) | 1991-03-22 |
| JPH05214367A (en) | 1993-08-24 |
| FI911409A0 (en) | 1991-03-22 |
| EP0455522B1 (en) | 1996-08-14 |
| GR3020943T3 (en) | 1996-12-31 |
| DK0455522T3 (en) | 1996-12-30 |
| FR2659979B1 (en) | 1994-04-29 |
| FI911409A (en) | 1991-09-24 |
| DE69121286D1 (en) | 1996-09-19 |
| FR2659979A1 (en) | 1991-09-27 |
| NO911157L (en) | 1991-09-24 |
| EP0455522A1 (en) | 1991-11-06 |
| ES2090268T3 (en) | 1996-10-16 |
| DE69121286T2 (en) | 1997-02-20 |
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| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |