CA1076914A - Process for washing textiles - Google Patents
Process for washing textilesInfo
- Publication number
- CA1076914A CA1076914A CA262,905A CA262905A CA1076914A CA 1076914 A CA1076914 A CA 1076914A CA 262905 A CA262905 A CA 262905A CA 1076914 A CA1076914 A CA 1076914A
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- CA
- Canada
- Prior art keywords
- alkali metal
- washing
- silicate
- detergent
- bath
- 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
- C11D3/02—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
-
- 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
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Detergent Compositions (AREA)
Abstract
PROCESS FOR WASHING TEXTILES
Abstract of the disclosure The process of the invention for the washing of textiles by treating the latter with an aqueous detergent-containing bath at a temperature of about 20 to 95°C, wherein the detergent substantially contains an organic surfactant, an alkali metal tripolyphosphate contaminated with alkali metal mono- or diphos-phates, a finely divided alkali metal aluminium silicate having a calcium sequestering power of at least 5 g Ca++ per 100 g of dehydrated silicate, and optionally additional washing adjuvants, consists in that with a content of about 0.5 to 2 g of alkali metal tripolyphosphate and about 0.5 to 4 g of alkali metal aluminium silicate in one litre of washing bath the latter simul-taneously contains not more than 0.1 g of alkali metal mono- or diphosphate per litre.
Abstract of the disclosure The process of the invention for the washing of textiles by treating the latter with an aqueous detergent-containing bath at a temperature of about 20 to 95°C, wherein the detergent substantially contains an organic surfactant, an alkali metal tripolyphosphate contaminated with alkali metal mono- or diphos-phates, a finely divided alkali metal aluminium silicate having a calcium sequestering power of at least 5 g Ca++ per 100 g of dehydrated silicate, and optionally additional washing adjuvants, consists in that with a content of about 0.5 to 2 g of alkali metal tripolyphosphate and about 0.5 to 4 g of alkali metal aluminium silicate in one litre of washing bath the latter simul-taneously contains not more than 0.1 g of alkali metal mono- or diphosphate per litre.
Description
~ 10769~
This invention relates to the washing of textiles (as herein de-fined) with an aqueous detergent-containing bath whose detergent substanti-ally comprises at least one organic anionic, non-ionic, ampholytic, or ampho-teric surfactant, an alkali metal tripolyphosphate ~which may be a technical grade) as water-soluble builder, and a finely divided alkali metal aluminium silicate as water-insoluble builder, with or without one or more additional detergent adjuvants. The word "textiles" is employed herein in a broad sense;
thus it includes knitted fabrics and non-woven fabrics, and also textile fibres, filaments, rovings and yarns, in addition to woven fabrics.
It is known that the washing and cleaning power of soaps and syn-thetic surfactants can be increased by the addition of certain substances known as builders.
The mechanism and precise nature of the action of these builders have not yet been completely elucidated, so that a prediction based on theo-retical principles as to which types of compound could be suitable for this purpose is not yet possible.
Having regard to the multiplicity of individual effects which can cooperate in increasing the washing power of surfactants, we consider that the requirements which must be imposed on a builder in the light of present knowledge are that the builder should be capable of:
1. forming water-soluble complexes with hardness-producing salts present in the water being used, e.g. with calcium and mag-nesium ions;
This invention relates to the washing of textiles (as herein de-fined) with an aqueous detergent-containing bath whose detergent substanti-ally comprises at least one organic anionic, non-ionic, ampholytic, or ampho-teric surfactant, an alkali metal tripolyphosphate ~which may be a technical grade) as water-soluble builder, and a finely divided alkali metal aluminium silicate as water-insoluble builder, with or without one or more additional detergent adjuvants. The word "textiles" is employed herein in a broad sense;
thus it includes knitted fabrics and non-woven fabrics, and also textile fibres, filaments, rovings and yarns, in addition to woven fabrics.
It is known that the washing and cleaning power of soaps and syn-thetic surfactants can be increased by the addition of certain substances known as builders.
The mechanism and precise nature of the action of these builders have not yet been completely elucidated, so that a prediction based on theo-retical principles as to which types of compound could be suitable for this purpose is not yet possible.
Having regard to the multiplicity of individual effects which can cooperate in increasing the washing power of surfactants, we consider that the requirements which must be imposed on a builder in the light of present knowledge are that the builder should be capable of:
1. forming water-soluble complexes with hardness-producing salts present in the water being used, e.g. with calcium and mag-nesium ions;
2. dispersing, in the washing bath, pigmentary soil particles representing a principal component of the soil carried by the textiles being washed;
3. stabilising detached soil in the washing bath in order to prevent soil particles from being redeposited upon by the textiles being washed;
4. inactivating any mineral constituents present in the washing bath;
5. reducing the adsorption of surfactants on the textiles being washed.
-`` 1076~14 In order to obtain information regarding the efficiency and suit-ability of particular products as builders, it is appropriate to determine their behaviour and efficiency in the washing process itself. It is thereby ensured that all factors affecting the builder action are taken into account, qualitatively and quantitatively.
Known builders comprise water-soluble alkali metal salts of mineral acids, e.g. alkali metal carbonates, borates, phosphates, polyphosphates, bi-carbonates, and silicates.
Among known builders a preferential position is occupied by the alk-ali metal polyphosphates, since these fulfil all the requirements indicated above, and exhibit, during washing, synergistic effects in combination with surface-active substances. Consequently they constitute at the present time the most important builders in light-duty, heavy-duty, and coloured-wash de-tergents. For this purpose pentasodium triphosphate is mainly used. The con-tent of this builder in detergents is commonly 25 to 65%, and in certain pre-parations this content is up to 90% by weight.
Because of the recent considerable increase in the consumption of phosphate-containing detergents and cleaning agents, both in the household field and in industry, the proportion of these phosphates present in natural waters has correspondingly increased. In discussions of the causes of the in-creasing eutrophication of waters, the water-soluble nitrate and phosphate salts have recently been said to possess the property of promoting the growth of certain species of algae under certain conditions and thus contributing towards the eutrophication of waters, whereby their oxygen balance is dis-turbed. Although at the present time it is not yet possible to make a def-initive assessment of the part played by phosphate-containing washing and cleaning agents in the eutrophication of waters, nevertheless it appears to be desirable to make available substitutes, containing no nitrogen or phosphates, for the builders used hitherto in detergent formulations; or alternatively, by blending alkali metal polyphosphates with certain other detergent components, to effect a reduction in the phosphorus contents of detergent formulations.
In this connection various organic compounds have already been .
. : :
proposed as builders, for example nitriloacetic acid, ethylene-diaminetetra-acetic acid, citric acid, oxydiacetic acid, oxydisuccinic acid, cyclocarboxyl-ic acids, and polymeric carboxylic acids, e.g. polymers of maleic acid and acryl:ic acid, and their copolymers with other unsaturated carboxylic acids, olefins, or short-chain unsaturated aliphatic ethers or alcohols.
The substances mentioned above have not proved to be satisfactory builders in every respect, however, inasmuch as they (1) have a strong ten-dency to form complexes with heavy metals and transition metals, so that in-creased contents of these metals are found in surface waters (whether as the result of direct sequestration or subsequent remobilisation of flow sedi-ment) and may pass into drinking water; or (2) do not to an adequate extent possess the previously mentioned properties of a builder, so that they do not give satisfactory washing results; or (3) are not sufficiently biodegradable.
It has recently been recognised that, by virtue of their ion ex-change capacity, the water-insoluble alkali metal aluminium silicates are also suitable for replacing part of the sodium tripolyphosphate in detergent form-ulations, and thus reducing the total phosphate content of the detergent. On completion of the washing process, these water-insoluble builders can readily be separated from the washing bath, but even if they are discharged in the waste water they do not give rise to any biologically undesirable loading of surface-waters, unlike the known organic builders.
A method of washing (e.g.) textiles in the presence of water-insol-uble alkali metal aluminium silicates, these being employed in conjunction with commonly used detergent components, has been described in German Pub-lished Specification ("Offenlegungsschrift") No. 2,412,837. The proportion of metaphosphates and polyphosphates in these detergent formulations is so regulated that the maximum phosphate content in the washing bath amounts to 0.6 gram of phosphorus per litre of washing bath. According to the examples given in this German Specification, 2.5 to 29.2 parts by weight of pentasodium triphosphate and 45 to 11.3 parts by weight of sodium aluminium silicate hav-ing a calcium sequestering power of 150 mg of CaO per gram of silicate would be employed per 100 parts by weight of detergent.
,,~
, The advantages attributed in the above-mentioned German Specifi-cation to the use of a blend of sodium tripolyphosphate and sodium aluminium silicate or sodium borosilicate in detergent formulations apply only to what is ca]led the primary washing action; this represents only a measure of the brightening effect achieved for an artificially soiled test fabric. In prac-tice, however, it has been found that what is called the secondary washing action of the detergent formulation, this being defined by the degree to which the fabric is loaded or "encrusted", is unsatisfactory. Nevertheless, in judging a washing process, the secondary washing action is of importance as well as the primary washing action. Heavily loaded or "encrusted" laundry loses some of its usefulness inasmuch as its absorptivity is reduced, it wears more rapidly, and it becomes less attractive because of its hard rough feel.
Another disadvantage of this prior detergent formulation results from the en-crustation occurring during the washing process on the heating elements in the washing machine used. Encrusted heating elements increase the energy cost of the washing process, and tend to necessitate unduly early servicing or replacement of the washing machine.
We have now found, to our surprise, that the disadvantages of the detergent compositions of the above-mentioned German Specification can be overcome if one ensures that the proportion of alkali metal mono- and/or di-phosphate(s3 in the washing bath is not more than 0.1 gram per litre. The presence of this alkali metal mono- or diphosphate in the washing bath results from the method of production of the alkali metal tripolyphosphate or of the detergent composition as a whole. If the proportion just mentioned is duly kept to 0.1 gram per litre or less, contents of approximately 0.5 to 2 grams of alkali metal tripolyphosphate and approximately 0.5 to 4 grams of alkali metal aluminium silicate per litre of washing bath are sufficient to obtain satisfactory primary and secondary washing actions.
In ordinary commercially available technical grade alkali metal tripolyphosphates, the proportion of alkali metal mono- and/or diphosphate(s) present may be as much as 20% by weight, according to which production pro-cess is employed. Moreover, if the detergent composition is produced by the 7691~
. .
hot spray drying process, which is very commonly employed, the content of alkali metal mono- and/or diphosphate~s) is additionally increased, in some cases to a considerable extent, by hydrolysis occurring during the prepara-tion of the slurry, and by pyrolysis of the tripolyphosphate during the hot spray drying; thus the final product may contain considerable proportions of mono- and/or diphosphate(s). Alkali metal mono- and diphosphates form in-soluble precipitates with calcium and magnesium ions present in the washing water, unless these hardness-producing ions are rendered ineffective by suitable measures. Ordinary detergent compositions which are produced with the use of ordinary commercial sodium tripolyphosphate by the methods of the prior art do give satisfactory washing results, despite their contents of , alkali metal mono- and/or diphosphate(s), because the content of the ordinary . -commercial sodium tripolyphosphate in the detergent composition is sufficient-ly high to ensure after the complexing of the calcium and magnesium ions has taken place, an excess of sodium tripolyphosphate is still available in the washing process, so that the precipitation of alkali metal mono- and/or di-phosphate(s) is avoided even at washing temperatures up to 90C. When deter-gent compositions according to the above-mentioned German Specification having a reduced alkali metal tripolyphosphate content are used, however, the precipitation of salts having an encrusting action naturally cannot be pre-vented.
According to the present invention, therefore, there is provided in the process of washing textiles by treating the textiles with an aqueous detergent-containing bath at a temperature of about 20 to 95C, wherein the detergent substantially contains an organic anionic, non-ionic, ampholytic or amphoteric surfactant, an alkali metal tripolyphosphate contaminated with alkali metal mono- or diphosphates as water-soluble builder, a finely divided -alkali metal aluminium silicate having a particle size of at most 40 u and a calcium sequestering power of at least 5 g Ca per 100 g of dehydrated silicate as water-insoluble builder, and optionally additional washing adjuvantsand wherein the bath contains the organic detergent in an amount of about 0.3 to about 1 g per litre of improvement consisting in that with a content of iC
- ~
7691~
about 0.5 to 2 g of alkali metal tripolyphosphate and about 0.5 to 4 g of alkali metal aluminium silicate in one litre of washing bath the latter simultaneously contains at most 0.1 g of alkali metal mono- or diphosphate per litre.
In a preferred form of the process of the invention the silicate should have a calcium sequestering power of approximately 10 to 14 grams of Ca per 100 grams of silicate. The alkali metal aluminium silicate may for example be represented by a crystalline zeolite which in its unactivated form substantially contains 18.2% Na20, 30.8 % A1203, 34.1 % SiO2 and 16.7 % H20, the balance being impurities.
The washing bath employed in the process of the invention may addi-tionally contain one or more of the following detergent adjuvants: sodium silicate; magnesium silicate; carboxymethylcellulose; sodium perborate tetra-hydrate; ethylenediaminetetraacetic acid, sodium sulphate, and mixtures there-of.
The surfactants which may be employed in the process of the inven-tion broadly comprise anionic, amphoteric, ampholytic, and non-ionic surfactants.
The "anionic" surfactants are to be understood to include water-soluble salts of higher fatty acids or resin acids, e.g. sodium or potassium soaps of hardened or unhardened coconut palm oil or rapeseed oil and also tallow and mixtures thereof. Also these anion-active substances which may be employed in the process of the invention are to be understood to include salts of higher-alkyl-substituted mononuclear aromatic sulphonates, e.g. alkyl-benzene sulphonates having 9 to 14 carbon atoms in the alkyl radical, alkyl naphthalene sulphonates, alkyl toluene sulphonates, alkyl xylene sulphonates, or alkylphenol sulphonates, and also salts of sulphated aliphatic alcohols or alcohol ethers, e.g. sodium or aluminium lauryl or hexadecyl sulphate, triethanolamine lauryl sulphate, sodium or potassium oleyl sulphate, and also sodium or potassium salts of lauryl sulphate ethoxylated with (e.g.) 2 to 6 moles of ethylene oxide. Other suitable anionic surfactants are secondary linear alkane sulphonates and also alpha-olefin sulphonates having a chain C
- - \
1~76914 length of 12 to 20 carbon atoms.
The non-ionic or non-ionogenic surfactants which may be employed in the present process are to be understood to include non-ionogenic compounds which contain an organic hydrophobic group and also a hydrophilic radical.
Examples of non-ionogenic surfactants are: condensation products of alkyl phenols with ethylene oxide, or of higher fatty alcohols with ethylene oxide;
condensation products of polypropylene glycol with ethylene oxide or propy-lene oxide; condensation products of ethylene oxide with a product of a reaction between ethylene diamine and propylene oxide; long chain tertiary amine oxides.
The ampholytic or zwitterionic surfactants which may be employed in the process of the invention include: derivatives of aliphatic secondary and tertiary amines or quaternary ammonium compounds containing 8 to 18 carbon atoms and having a hydrophilic group in the aliphatic radical, e.g. sodium-3-dodecylaminopropionate, sodium-3-dodecylaminopropane sulphonate, 3-(N,N-di-methyl-N-hexadecylamino)propane-l-sulphonate; fatty acid amino alkyl-N,N-dimethylacetobetaines, the fatty acid containing 8 to 18 carbon atoms and the alkyl radical containing 3 carbon atoms.
Detergent adjuvants (additives) which may be employed in the process of the invention include the following, for example: alkali metal or ammonium salts of sulphuric acid, silicic acid, carbonic acid, boric acid, or an alkylene-hydroxyalkylene- or amino alkylene phosphonic acid; bleaching agents;
stabilisers for peroxide compounds; water-soluble organic complexing agents.
More specifically, use may be made of: sodium perborate mono- or tetrahydrate; alkali metal salts or peroxymono- or disulphuric acid; alkali metal salts of perpyrophosphoric acid; precipitated water-insoluble magnesium silicate, alkali metal salts of iminodiacetic acid, nitrilotriacetic acid, ethylene diaminetetraacetic acid, methylene diphosphonic acid, hydroxyethane diphosphonic acid, or nitrilotrismethylene phosphonic acid.
Use may also be made of: substances which increase the soil-suspending power of washing baths, e.g. carboxymethylcellulose polyvinyl alcohol or polyvinylpyrrolidone; foam regulators, e.g. mono- or dialkyl phos-10769~4 phoric esters containing 16 to 20 carbon atoms in the alkyl radical; optical whitening agents; disinfectants; proteolytic enzymes. Detergent adjuvants (additives) which when employed with the other consitutents of the washing bath contribute towards an improvement of the detergent effect include in partic:ular: magnesium silicate; sodium silicate; sodium perborate tetra-hydrate; sodium sulphate; carboxymethylcellulose.
The detergent compositions having a low alkali metal mono- and/or diphosphate content which are suitable for use in preparing the washing bath employed in the process of the invention can for example be produced by the use of sodium tripolyphosphate which either has been purified by recrystal-lisation or has been produced from thermal phosphoric acid by a single-stage hot spray method, and which has an active pentasodium triphosphate content of at least 95 %, this tripolyphosphate being utilised in a hot spray drying process for the production of a detergent composition; it is also possible to use at least 90 % sodium tripolyphosphate in the production of the detergent composition by a dry mixing method. In this latter case there are no losses of sodium tripolyphosphate through hydrolysis and pyrolysis in the production of the detergent composition.
The invention is illustrated by the following example; however, it is not restricted thereto.
EXAMPLE
In order to determine the influence of tetrasodium diphosphate on the secondary washing action of blends of sodium tripolyphosphate and sodium aluminium silicate, washing tests were carried out in a domestic washing machine of the Miele 416 S type, using natural industrial water of 18dH.
The detergent components used were:
a) constant amounts of a basic detergent preparation, together with b~ variable amounts of sodium tripolyphosphate, tetrasodium di-phosphate, and sodium aluminium silicate.
The basic detergent preparation had the following composition:
7% by weight of dodecylbenzene sulphonate;
3% by weight of tallow fatty alcohol ethoxylate containing 11 moles ,C
1~7691~
of ethylene oxide per mole of tallow fatty alcohol;
3% by weight of hardened tallow soap;
4% by weight of magnesium silicate;
3% by weight of sodium silicate;
1% by weight of carboxymethylcellulose;
25% by weight of sodium perborate tetrahydrate;
0.2% by weight of ethylenediaminetetraacetic acid;
8% by weight of water; and sodium sulphate to make 100% by weight.
The sodium tripolyphosphate used in the washing tests was obtained by recrystallisation of technical sodium tripolyphosphate, the purity of which amounted to 94.2 %, in accordance with the information given by O.T. Quimby in J. Phys. Chem. 58 (1954) page 603. The purified sodium tripolyphosphate still contained 0.1 % by weight of disodium hydrogen phosphate and 0.2 % by weight of tetrasodium diphosphate.
The tetrasodium diphosphate used in the washing tests was a commer-cial product and still contained 1 % by weight of disodium hydrogen phosphate and also 0.5 % by weight of sodium tripolyphosphate.
The sodium aluminium silicate used was a finely divided crystalline zeolite of the "molecular sieve A" type. The exchange capacity of this product for Ca ions at 90 C was 14 g of Ca per 100 g of substance.
Molecular sieve A had the following composition:
18.2 % By weight of Na20, 30.8 % by weight of A1203, 34.1 % by weight of SiO2, and 16.7 % by weight of H20. The mole ratio amounted to 0.97 Na20 . A1203 . 1.9 SiO2 . 3.1 H20. The maximum particle size of the molecular sieve A was 40 ~
The dosage of the basic detergent preparation in the washing bath amounted to 5 grams per litre of washing bath for each washing test. The amount of the other components of the detergent varied, as can be seen from the Table below. The washing tests were carried out in accordance with the washing programme for a boiling wash with prewash and clear wash. The maximum temperature in the prewash stage was 40C and in the clear wash stage about _ g _ C
- - ~
1~7691~
85 to 90C. Following the clear wash the material washed was rinsed five times and subjected to a new washing cycle without intermediate drying, since in preliminary tests no difference was found in the washing results when the goods washed were previously dried in the clothes dryer.
Based on the procedure proposed by Schweizerische Gesellschaft fUr analytishe und angewandte Chemie in "Seifen und Waschmittel", Berne, 1955, page 116, unsoiled "Renforcé" cotton fabric of Eidgenossische Material-prufungsanstalt ~Federal Material Testing Institute) of St. Gallen, Switzerland, was used as test fabric and ballast, in stitched strips of 40 x 80 cm. The weight of the fabric amounted to 1.2 kg, so that there was a bath ratio of 1:12.5. After 50 washing cycles, the fabric was washed at 900C and the encrustation of the fabric was ascertained as percentage of ignition residue. After 50 washing cycles, the heating bar elements were also examined for encrustation, for which purpose they were removed from the washing machine.
The results obtained in the individual series of tests, each comprising 50 washing cycles, are shown in the Table.
C
1~7~91~
TAsLE
Test Dosage of detergent components (g/l) Series No. I II III IV V VI
1 5 2 0 0 7.6 heavy 2 5 1 1 0 3.4 light 3 5 1 1 0.05 3.8 light 4 5 1 1 0.1 4.6 light 1 1 0.15 6.7 medium
-`` 1076~14 In order to obtain information regarding the efficiency and suit-ability of particular products as builders, it is appropriate to determine their behaviour and efficiency in the washing process itself. It is thereby ensured that all factors affecting the builder action are taken into account, qualitatively and quantitatively.
Known builders comprise water-soluble alkali metal salts of mineral acids, e.g. alkali metal carbonates, borates, phosphates, polyphosphates, bi-carbonates, and silicates.
Among known builders a preferential position is occupied by the alk-ali metal polyphosphates, since these fulfil all the requirements indicated above, and exhibit, during washing, synergistic effects in combination with surface-active substances. Consequently they constitute at the present time the most important builders in light-duty, heavy-duty, and coloured-wash de-tergents. For this purpose pentasodium triphosphate is mainly used. The con-tent of this builder in detergents is commonly 25 to 65%, and in certain pre-parations this content is up to 90% by weight.
Because of the recent considerable increase in the consumption of phosphate-containing detergents and cleaning agents, both in the household field and in industry, the proportion of these phosphates present in natural waters has correspondingly increased. In discussions of the causes of the in-creasing eutrophication of waters, the water-soluble nitrate and phosphate salts have recently been said to possess the property of promoting the growth of certain species of algae under certain conditions and thus contributing towards the eutrophication of waters, whereby their oxygen balance is dis-turbed. Although at the present time it is not yet possible to make a def-initive assessment of the part played by phosphate-containing washing and cleaning agents in the eutrophication of waters, nevertheless it appears to be desirable to make available substitutes, containing no nitrogen or phosphates, for the builders used hitherto in detergent formulations; or alternatively, by blending alkali metal polyphosphates with certain other detergent components, to effect a reduction in the phosphorus contents of detergent formulations.
In this connection various organic compounds have already been .
. : :
proposed as builders, for example nitriloacetic acid, ethylene-diaminetetra-acetic acid, citric acid, oxydiacetic acid, oxydisuccinic acid, cyclocarboxyl-ic acids, and polymeric carboxylic acids, e.g. polymers of maleic acid and acryl:ic acid, and their copolymers with other unsaturated carboxylic acids, olefins, or short-chain unsaturated aliphatic ethers or alcohols.
The substances mentioned above have not proved to be satisfactory builders in every respect, however, inasmuch as they (1) have a strong ten-dency to form complexes with heavy metals and transition metals, so that in-creased contents of these metals are found in surface waters (whether as the result of direct sequestration or subsequent remobilisation of flow sedi-ment) and may pass into drinking water; or (2) do not to an adequate extent possess the previously mentioned properties of a builder, so that they do not give satisfactory washing results; or (3) are not sufficiently biodegradable.
It has recently been recognised that, by virtue of their ion ex-change capacity, the water-insoluble alkali metal aluminium silicates are also suitable for replacing part of the sodium tripolyphosphate in detergent form-ulations, and thus reducing the total phosphate content of the detergent. On completion of the washing process, these water-insoluble builders can readily be separated from the washing bath, but even if they are discharged in the waste water they do not give rise to any biologically undesirable loading of surface-waters, unlike the known organic builders.
A method of washing (e.g.) textiles in the presence of water-insol-uble alkali metal aluminium silicates, these being employed in conjunction with commonly used detergent components, has been described in German Pub-lished Specification ("Offenlegungsschrift") No. 2,412,837. The proportion of metaphosphates and polyphosphates in these detergent formulations is so regulated that the maximum phosphate content in the washing bath amounts to 0.6 gram of phosphorus per litre of washing bath. According to the examples given in this German Specification, 2.5 to 29.2 parts by weight of pentasodium triphosphate and 45 to 11.3 parts by weight of sodium aluminium silicate hav-ing a calcium sequestering power of 150 mg of CaO per gram of silicate would be employed per 100 parts by weight of detergent.
,,~
, The advantages attributed in the above-mentioned German Specifi-cation to the use of a blend of sodium tripolyphosphate and sodium aluminium silicate or sodium borosilicate in detergent formulations apply only to what is ca]led the primary washing action; this represents only a measure of the brightening effect achieved for an artificially soiled test fabric. In prac-tice, however, it has been found that what is called the secondary washing action of the detergent formulation, this being defined by the degree to which the fabric is loaded or "encrusted", is unsatisfactory. Nevertheless, in judging a washing process, the secondary washing action is of importance as well as the primary washing action. Heavily loaded or "encrusted" laundry loses some of its usefulness inasmuch as its absorptivity is reduced, it wears more rapidly, and it becomes less attractive because of its hard rough feel.
Another disadvantage of this prior detergent formulation results from the en-crustation occurring during the washing process on the heating elements in the washing machine used. Encrusted heating elements increase the energy cost of the washing process, and tend to necessitate unduly early servicing or replacement of the washing machine.
We have now found, to our surprise, that the disadvantages of the detergent compositions of the above-mentioned German Specification can be overcome if one ensures that the proportion of alkali metal mono- and/or di-phosphate(s3 in the washing bath is not more than 0.1 gram per litre. The presence of this alkali metal mono- or diphosphate in the washing bath results from the method of production of the alkali metal tripolyphosphate or of the detergent composition as a whole. If the proportion just mentioned is duly kept to 0.1 gram per litre or less, contents of approximately 0.5 to 2 grams of alkali metal tripolyphosphate and approximately 0.5 to 4 grams of alkali metal aluminium silicate per litre of washing bath are sufficient to obtain satisfactory primary and secondary washing actions.
In ordinary commercially available technical grade alkali metal tripolyphosphates, the proportion of alkali metal mono- and/or diphosphate(s) present may be as much as 20% by weight, according to which production pro-cess is employed. Moreover, if the detergent composition is produced by the 7691~
. .
hot spray drying process, which is very commonly employed, the content of alkali metal mono- and/or diphosphate~s) is additionally increased, in some cases to a considerable extent, by hydrolysis occurring during the prepara-tion of the slurry, and by pyrolysis of the tripolyphosphate during the hot spray drying; thus the final product may contain considerable proportions of mono- and/or diphosphate(s). Alkali metal mono- and diphosphates form in-soluble precipitates with calcium and magnesium ions present in the washing water, unless these hardness-producing ions are rendered ineffective by suitable measures. Ordinary detergent compositions which are produced with the use of ordinary commercial sodium tripolyphosphate by the methods of the prior art do give satisfactory washing results, despite their contents of , alkali metal mono- and/or diphosphate(s), because the content of the ordinary . -commercial sodium tripolyphosphate in the detergent composition is sufficient-ly high to ensure after the complexing of the calcium and magnesium ions has taken place, an excess of sodium tripolyphosphate is still available in the washing process, so that the precipitation of alkali metal mono- and/or di-phosphate(s) is avoided even at washing temperatures up to 90C. When deter-gent compositions according to the above-mentioned German Specification having a reduced alkali metal tripolyphosphate content are used, however, the precipitation of salts having an encrusting action naturally cannot be pre-vented.
According to the present invention, therefore, there is provided in the process of washing textiles by treating the textiles with an aqueous detergent-containing bath at a temperature of about 20 to 95C, wherein the detergent substantially contains an organic anionic, non-ionic, ampholytic or amphoteric surfactant, an alkali metal tripolyphosphate contaminated with alkali metal mono- or diphosphates as water-soluble builder, a finely divided -alkali metal aluminium silicate having a particle size of at most 40 u and a calcium sequestering power of at least 5 g Ca per 100 g of dehydrated silicate as water-insoluble builder, and optionally additional washing adjuvantsand wherein the bath contains the organic detergent in an amount of about 0.3 to about 1 g per litre of improvement consisting in that with a content of iC
- ~
7691~
about 0.5 to 2 g of alkali metal tripolyphosphate and about 0.5 to 4 g of alkali metal aluminium silicate in one litre of washing bath the latter simultaneously contains at most 0.1 g of alkali metal mono- or diphosphate per litre.
In a preferred form of the process of the invention the silicate should have a calcium sequestering power of approximately 10 to 14 grams of Ca per 100 grams of silicate. The alkali metal aluminium silicate may for example be represented by a crystalline zeolite which in its unactivated form substantially contains 18.2% Na20, 30.8 % A1203, 34.1 % SiO2 and 16.7 % H20, the balance being impurities.
The washing bath employed in the process of the invention may addi-tionally contain one or more of the following detergent adjuvants: sodium silicate; magnesium silicate; carboxymethylcellulose; sodium perborate tetra-hydrate; ethylenediaminetetraacetic acid, sodium sulphate, and mixtures there-of.
The surfactants which may be employed in the process of the inven-tion broadly comprise anionic, amphoteric, ampholytic, and non-ionic surfactants.
The "anionic" surfactants are to be understood to include water-soluble salts of higher fatty acids or resin acids, e.g. sodium or potassium soaps of hardened or unhardened coconut palm oil or rapeseed oil and also tallow and mixtures thereof. Also these anion-active substances which may be employed in the process of the invention are to be understood to include salts of higher-alkyl-substituted mononuclear aromatic sulphonates, e.g. alkyl-benzene sulphonates having 9 to 14 carbon atoms in the alkyl radical, alkyl naphthalene sulphonates, alkyl toluene sulphonates, alkyl xylene sulphonates, or alkylphenol sulphonates, and also salts of sulphated aliphatic alcohols or alcohol ethers, e.g. sodium or aluminium lauryl or hexadecyl sulphate, triethanolamine lauryl sulphate, sodium or potassium oleyl sulphate, and also sodium or potassium salts of lauryl sulphate ethoxylated with (e.g.) 2 to 6 moles of ethylene oxide. Other suitable anionic surfactants are secondary linear alkane sulphonates and also alpha-olefin sulphonates having a chain C
- - \
1~76914 length of 12 to 20 carbon atoms.
The non-ionic or non-ionogenic surfactants which may be employed in the present process are to be understood to include non-ionogenic compounds which contain an organic hydrophobic group and also a hydrophilic radical.
Examples of non-ionogenic surfactants are: condensation products of alkyl phenols with ethylene oxide, or of higher fatty alcohols with ethylene oxide;
condensation products of polypropylene glycol with ethylene oxide or propy-lene oxide; condensation products of ethylene oxide with a product of a reaction between ethylene diamine and propylene oxide; long chain tertiary amine oxides.
The ampholytic or zwitterionic surfactants which may be employed in the process of the invention include: derivatives of aliphatic secondary and tertiary amines or quaternary ammonium compounds containing 8 to 18 carbon atoms and having a hydrophilic group in the aliphatic radical, e.g. sodium-3-dodecylaminopropionate, sodium-3-dodecylaminopropane sulphonate, 3-(N,N-di-methyl-N-hexadecylamino)propane-l-sulphonate; fatty acid amino alkyl-N,N-dimethylacetobetaines, the fatty acid containing 8 to 18 carbon atoms and the alkyl radical containing 3 carbon atoms.
Detergent adjuvants (additives) which may be employed in the process of the invention include the following, for example: alkali metal or ammonium salts of sulphuric acid, silicic acid, carbonic acid, boric acid, or an alkylene-hydroxyalkylene- or amino alkylene phosphonic acid; bleaching agents;
stabilisers for peroxide compounds; water-soluble organic complexing agents.
More specifically, use may be made of: sodium perborate mono- or tetrahydrate; alkali metal salts or peroxymono- or disulphuric acid; alkali metal salts of perpyrophosphoric acid; precipitated water-insoluble magnesium silicate, alkali metal salts of iminodiacetic acid, nitrilotriacetic acid, ethylene diaminetetraacetic acid, methylene diphosphonic acid, hydroxyethane diphosphonic acid, or nitrilotrismethylene phosphonic acid.
Use may also be made of: substances which increase the soil-suspending power of washing baths, e.g. carboxymethylcellulose polyvinyl alcohol or polyvinylpyrrolidone; foam regulators, e.g. mono- or dialkyl phos-10769~4 phoric esters containing 16 to 20 carbon atoms in the alkyl radical; optical whitening agents; disinfectants; proteolytic enzymes. Detergent adjuvants (additives) which when employed with the other consitutents of the washing bath contribute towards an improvement of the detergent effect include in partic:ular: magnesium silicate; sodium silicate; sodium perborate tetra-hydrate; sodium sulphate; carboxymethylcellulose.
The detergent compositions having a low alkali metal mono- and/or diphosphate content which are suitable for use in preparing the washing bath employed in the process of the invention can for example be produced by the use of sodium tripolyphosphate which either has been purified by recrystal-lisation or has been produced from thermal phosphoric acid by a single-stage hot spray method, and which has an active pentasodium triphosphate content of at least 95 %, this tripolyphosphate being utilised in a hot spray drying process for the production of a detergent composition; it is also possible to use at least 90 % sodium tripolyphosphate in the production of the detergent composition by a dry mixing method. In this latter case there are no losses of sodium tripolyphosphate through hydrolysis and pyrolysis in the production of the detergent composition.
The invention is illustrated by the following example; however, it is not restricted thereto.
EXAMPLE
In order to determine the influence of tetrasodium diphosphate on the secondary washing action of blends of sodium tripolyphosphate and sodium aluminium silicate, washing tests were carried out in a domestic washing machine of the Miele 416 S type, using natural industrial water of 18dH.
The detergent components used were:
a) constant amounts of a basic detergent preparation, together with b~ variable amounts of sodium tripolyphosphate, tetrasodium di-phosphate, and sodium aluminium silicate.
The basic detergent preparation had the following composition:
7% by weight of dodecylbenzene sulphonate;
3% by weight of tallow fatty alcohol ethoxylate containing 11 moles ,C
1~7691~
of ethylene oxide per mole of tallow fatty alcohol;
3% by weight of hardened tallow soap;
4% by weight of magnesium silicate;
3% by weight of sodium silicate;
1% by weight of carboxymethylcellulose;
25% by weight of sodium perborate tetrahydrate;
0.2% by weight of ethylenediaminetetraacetic acid;
8% by weight of water; and sodium sulphate to make 100% by weight.
The sodium tripolyphosphate used in the washing tests was obtained by recrystallisation of technical sodium tripolyphosphate, the purity of which amounted to 94.2 %, in accordance with the information given by O.T. Quimby in J. Phys. Chem. 58 (1954) page 603. The purified sodium tripolyphosphate still contained 0.1 % by weight of disodium hydrogen phosphate and 0.2 % by weight of tetrasodium diphosphate.
The tetrasodium diphosphate used in the washing tests was a commer-cial product and still contained 1 % by weight of disodium hydrogen phosphate and also 0.5 % by weight of sodium tripolyphosphate.
The sodium aluminium silicate used was a finely divided crystalline zeolite of the "molecular sieve A" type. The exchange capacity of this product for Ca ions at 90 C was 14 g of Ca per 100 g of substance.
Molecular sieve A had the following composition:
18.2 % By weight of Na20, 30.8 % by weight of A1203, 34.1 % by weight of SiO2, and 16.7 % by weight of H20. The mole ratio amounted to 0.97 Na20 . A1203 . 1.9 SiO2 . 3.1 H20. The maximum particle size of the molecular sieve A was 40 ~
The dosage of the basic detergent preparation in the washing bath amounted to 5 grams per litre of washing bath for each washing test. The amount of the other components of the detergent varied, as can be seen from the Table below. The washing tests were carried out in accordance with the washing programme for a boiling wash with prewash and clear wash. The maximum temperature in the prewash stage was 40C and in the clear wash stage about _ g _ C
- - ~
1~7691~
85 to 90C. Following the clear wash the material washed was rinsed five times and subjected to a new washing cycle without intermediate drying, since in preliminary tests no difference was found in the washing results when the goods washed were previously dried in the clothes dryer.
Based on the procedure proposed by Schweizerische Gesellschaft fUr analytishe und angewandte Chemie in "Seifen und Waschmittel", Berne, 1955, page 116, unsoiled "Renforcé" cotton fabric of Eidgenossische Material-prufungsanstalt ~Federal Material Testing Institute) of St. Gallen, Switzerland, was used as test fabric and ballast, in stitched strips of 40 x 80 cm. The weight of the fabric amounted to 1.2 kg, so that there was a bath ratio of 1:12.5. After 50 washing cycles, the fabric was washed at 900C and the encrustation of the fabric was ascertained as percentage of ignition residue. After 50 washing cycles, the heating bar elements were also examined for encrustation, for which purpose they were removed from the washing machine.
The results obtained in the individual series of tests, each comprising 50 washing cycles, are shown in the Table.
C
1~7~91~
TAsLE
Test Dosage of detergent components (g/l) Series No. I II III IV V VI
1 5 2 0 0 7.6 heavy 2 5 1 1 0 3.4 light 3 5 1 1 0.05 3.8 light 4 5 1 1 0.1 4.6 light 1 1 0.15 6.7 medium
6 5 1 1 0.3 7.8 heavy
7 5 2 1 0 2.2 light
8 5 2 1 0.1 2.4 light
9 5 2 1 0.3 3.8 heavy 4 1 0 1.4 light 11 5 4 1 0.1 1.6 light 12 5 4 1 0.3 2.2 medium 13 5 1 2 0 0.8 none .
14 5 1 2 0.1 0.9 none 1 2 0.4 1.9 medium 16 5 0 1 0 10.8 heavy '¢`
10769i4 The column headings in the Table should be interpreted as follows:
Column I: Amount of basic detergent preparation in grams per litre of washing bath.
Column II: Amount of sodium aluminium silicate (molecular sieve A) in grams per litre of washing bath .
Column III: Amount of sodium tripolyphosphate in grams per litre or washing bath.
Column IV: Amount of tetrasodium diphosphate in grams per litre of washing bath.
Column V: Loading of fabric after 50 washing cycles in ~%).
Column VI: Encrustation of heating bars after 50 washing cycles in (%).
The series of experiments 2-4, 7, 8, 10, 11, and 14 correspond to the process of the invention, while the other series of experiments serve for comparison. From the Table it can be seen that the washing tests carried out under the washing conditions of the invention result in substantially less loading of the fabrics washed and substantially less encrustation of the heating bar elements of the washing machine than in the comparison tests.
The process of the invention can thus be said to be a technical improvement in relation to the process of DT OS 2,412,837.
lfC
.
:, . ' . ` . '
14 5 1 2 0.1 0.9 none 1 2 0.4 1.9 medium 16 5 0 1 0 10.8 heavy '¢`
10769i4 The column headings in the Table should be interpreted as follows:
Column I: Amount of basic detergent preparation in grams per litre of washing bath.
Column II: Amount of sodium aluminium silicate (molecular sieve A) in grams per litre of washing bath .
Column III: Amount of sodium tripolyphosphate in grams per litre or washing bath.
Column IV: Amount of tetrasodium diphosphate in grams per litre of washing bath.
Column V: Loading of fabric after 50 washing cycles in ~%).
Column VI: Encrustation of heating bars after 50 washing cycles in (%).
The series of experiments 2-4, 7, 8, 10, 11, and 14 correspond to the process of the invention, while the other series of experiments serve for comparison. From the Table it can be seen that the washing tests carried out under the washing conditions of the invention result in substantially less loading of the fabrics washed and substantially less encrustation of the heating bar elements of the washing machine than in the comparison tests.
The process of the invention can thus be said to be a technical improvement in relation to the process of DT OS 2,412,837.
lfC
.
:, . ' . ` . '
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In the process of washing textiles by treating the textiles with an aqueous detergent-containing bath at a temperature of about 20 to 95°C, wherein the detergent substantially contains an organic anionic, non-ionic, ampholytic or amphoteric surfactant, an alkali metal tripolyphosphate contaminated with alkali metal mono- or diphosphates as water-soluble builder, a finely divided alkali metal aluminium silicate having a particle size of at most 40 µ and a calcium sequestering power of at least 5 g Ca++
per 100 g of dehydrated silicate as water-insoluble builder, and optionally additional washing adjuvants and wherein the bath contains the organic detergent in an amount of about 0.3 to about 1 g per litre the improvement consisting in that with a content of about 0.5 to 2 g of alkali metal tripolyphosphate and about 0.5 to 4 g of alkali metal aluminium silicate in one litre of washing bath the latter simultaneously contains at most 0.1 g of alkali metal mono- or diphosphate per litre.
per 100 g of dehydrated silicate as water-insoluble builder, and optionally additional washing adjuvants and wherein the bath contains the organic detergent in an amount of about 0.3 to about 1 g per litre the improvement consisting in that with a content of about 0.5 to 2 g of alkali metal tripolyphosphate and about 0.5 to 4 g of alkali metal aluminium silicate in one litre of washing bath the latter simultaneously contains at most 0.1 g of alkali metal mono- or diphosphate per litre.
2. The process as claimed in claim 1, wherein the calcium sequestering power of the alkali metal aluminium silicate amounts to about 10 to about 14 g Ca++ per 100 g of silicate.
3. The process as claimed in claim 1, wherein the alkali metal aluminium silicate is a crystalline zeolite which in the unactivated form contains 18.2%
Na2O, 30.8 % A12O3, 34.1 % SiO2 and 16.7 % H2O, the balance being impurities.
Na2O, 30.8 % A12O3, 34.1 % SiO2 and 16.7 % H2O, the balance being impurities.
4. The process as claimed in claim 1, wherein the washing bath contains, as washing adjuvants, sodium silicate, magnesium silicate, carboxymethyl-cellulose, sodium perborate tetrahydrate, ethylenediaminetetraacetic acid, sodium sulphate, and mixtures thereof.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2544949A DE2544949B2 (en) | 1975-10-08 | 1975-10-08 | Method of washing textiles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1076914A true CA1076914A (en) | 1980-05-06 |
Family
ID=5958566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA262,905A Expired CA1076914A (en) | 1975-10-08 | 1976-10-07 | Process for washing textiles |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS5249377A (en) |
| AT (1) | ATA743076A (en) |
| BE (1) | BE847023A (en) |
| CA (1) | CA1076914A (en) |
| CH (1) | CH624442A5 (en) |
| DE (1) | DE2544949B2 (en) |
| DK (1) | DK146781C (en) |
| FI (1) | FI762847A (en) |
| FR (1) | FR2327352A1 (en) |
| GB (1) | GB1518600A (en) |
| GR (1) | GR61267B (en) |
| IT (1) | IT1069078B (en) |
| NL (1) | NL7610965A (en) |
| NO (1) | NO763426L (en) |
| SE (1) | SE421273B (en) |
| TR (1) | TR18979A (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1963898A1 (en) * | 1969-10-13 | 1971-07-15 | Henkel & Cie Gmbh | Powdery to granular detergent containing perborate and process for its production |
| AT330930B (en) * | 1973-04-13 | 1976-07-26 | Henkel & Cie Gmbh | PROCESS FOR THE PRODUCTION OF SOLID, SPILLABLE DETERGENTS OR CLEANING AGENTS WITH A CONTENT OF CALCIUM BINDING SUBSTANCES |
-
1975
- 1975-10-08 DE DE2544949A patent/DE2544949B2/en not_active Ceased
-
1976
- 1976-09-28 GB GB40209/76A patent/GB1518600A/en not_active Expired
- 1976-09-28 SE SE7610735A patent/SE421273B/en unknown
- 1976-10-04 NL NL7610965A patent/NL7610965A/en unknown
- 1976-10-06 FI FI762847A patent/FI762847A/fi not_active Application Discontinuation
- 1976-10-06 IT IT51594/76A patent/IT1069078B/en active
- 1976-10-06 AT AT743076A patent/ATA743076A/en not_active Application Discontinuation
- 1976-10-07 GR GR51870A patent/GR61267B/en unknown
- 1976-10-07 TR TR18979A patent/TR18979A/en unknown
- 1976-10-07 CA CA262,905A patent/CA1076914A/en not_active Expired
- 1976-10-07 DK DK451776A patent/DK146781C/en active
- 1976-10-07 BE BE171300A patent/BE847023A/en not_active IP Right Cessation
- 1976-10-07 CH CH1272176A patent/CH624442A5/en not_active IP Right Cessation
- 1976-10-07 NO NO763426A patent/NO763426L/no unknown
- 1976-10-08 JP JP51121199A patent/JPS5249377A/en active Pending
- 1976-10-08 FR FR7630357A patent/FR2327352A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NO763426L (en) | 1977-04-13 |
| DK451776A (en) | 1977-04-09 |
| DK146781B (en) | 1984-01-02 |
| SE421273B (en) | 1981-12-14 |
| FI762847A (en) | 1977-04-09 |
| NL7610965A (en) | 1977-04-13 |
| GR61267B (en) | 1978-10-17 |
| JPS5249377A (en) | 1977-04-20 |
| DE2544949B2 (en) | 1978-05-11 |
| DE2544949A1 (en) | 1977-04-14 |
| SE7610735L (en) | 1977-04-09 |
| IT1069078B (en) | 1985-03-25 |
| BE847023A (en) | 1977-04-07 |
| FR2327352B1 (en) | 1980-05-23 |
| GB1518600A (en) | 1978-07-19 |
| ATA743076A (en) | 1979-07-15 |
| CH624442A5 (en) | 1981-07-31 |
| TR18979A (en) | 1978-02-06 |
| FR2327352A1 (en) | 1977-05-06 |
| DK146781C (en) | 1984-06-12 |
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