FR2475053A1 - NOVEL COMPOSITIONS BASED ON SAPONIFIED LECITHIN, THEIR PREPARATION AND THEIR APPLICATION IN THE TEXTILE, LEATHER AND PAPER INDUSTRY - Google Patents

Abstract

THE SUBJECT OF THE INVENTION IS NEW COMPOSITIONS CONTAINING PARTLY SAPONIFIED LECITHIN AND A POLYHYDROXYL COMPOUND, AND THEIR PREPARATION. THESE COMPOSITIONS MAY BE USED AS FINISHING AGENTS, DYING AUXILIARIES OR DETERGENTS IN THE TEXTILE, LEATHER OR PAPER INDUSTRY.

Description

The present invention relates to new compositions based on derivatives

  saponified from lecithin, their preparation and their use in the textile, leather and paper industry, in particular as dye auxiliaries and as agents for fining substrates consisting, in whole or in part, of natural fibers,

artificial or synthetic.

  The invention relates more particularly to a composition comprising a) a partially saponified lecithin having a saponification index of between 120 and 140, and

b) a polyhydroxy compound.

Component a) is a product obtained by partial saponification of lecithin with a basic compound at a temperature between 50 and 1150

in an aqueous medium.

  The basic compounds suitable for saponi-

lication of lecithin are for example carbonates or hydroxides of alkali or alkaline earth metal, such as carbonate or hydroxide of sodium, potassium, lithium or calcium, or amines

  organic such as monoethanolamine, diethanol-

  amine or triethanolamine, preferably hydroxide

sodium or potassium.

  The saponification of lecithin is carried out in an aqueous medium, the amount of water present

  being at least 12%, preferably 20 to 55% by weight.

The molar ratio of lecithin to the basic compound

  is 1: 1-3; 25, preferably 1: 2.

  The saponification of the lecithin is carried out under controlled conditions, so that the 2 fatty ester residues present in the lecithin are saponified, and the 2-trimethylammonioethylphosphoric group remains practically intact. The saponification is continued until the resulting product has a saponification index of between 120 and 140, preferably of the order of 130. The saponification index indicates the weight in mg of potassium hydroxide necessary to saponify one gram of lecithin and can be calculated according to the method described in Standard Methods of the Oils and Fats Division of the IUPAC, 5th ed., London Butterworths 1964. The reaction temperature is preferably between 85 and 1150. The duration of the reaction is between 1 hour and a half and two

hours and a half.

  The polyhydroxy compounds suitable as component b) are either sugars, for example aldoses or ketoses such as glucose, fructose,

or levulose, or disaccharides like saccha-

rose or maltose, either polyols, preferably polyols corresponding to the formula I HO-CH2 - (- CHOH) i, -CH20H (I) in which n signifies 1, 2, 3, 4 or 5, preferably 3 or 4. As examples of such polyols, mention may be made of arabitol, xylitol, adonitol, mannitol, sorbitol, dulcitol, iditol, talitol or glycerol,

preferably sorbitol.

  The compositions of the invention can be

  prepared according to known methods. We add

  the polyhydroxy compound is at the start of the saponi-

fication, with the basic compound, or during saponification

cation of lecithin. Thus, when a polyol is used, the lecithin and the basic compound can be heated together for 30 to 60 minutes at a temperature

  between 80 and 95, before adding the polyol.

The polyol can also be added at the same time as the basic compound, at the start of the saponification. In the case where a sugar is used, for example sucrose or glucose, the basic compound and the sugar are preferably added to the lecithin; in this case, the operation is preferably carried out at a temperature between 110-115 and, after cooling to 600, white spirit can be added to the mixture obtained. In each case, the polyhydroxy compound is added in a lecithin: polyhydroxy compound molar ratio of 1: 0.4 - 1.38, preferably 1: 0.7. When the polyhydroxy compound is added at the start of the saponification or during the saponification of the lecithin, the final composition may also contain the fatty acid residues released by the saponification; it is even possible that these fatty acid residues are slightly transesterified by the

polyhydroxylated compound.

The compositions of the invention have a pH of

9-9.5 when dissolved in water at 20.

  They preferably contain from 20 to 40% by weight of component b). The preferred compositions are those containing sorbitol as component b), in particular the compositions prepared by partial saponification of lecithin, as specified above, sorbitol

being added at the start or during saponification.

The lecithin used as starting material can be a lecithin of plant or animal origin, for example a lecithin from eggs or soybean oil. The preferred lecithin is a non-edible, water-dispersible soybean oil lecithin, as used in paints and varnishes, for example lecithin sold under the trademark Lecidris Toar by the company Chemicaltec, Italy or or by the Industria Italiana Centrale Italy Company,

  under the name Soy Lecithin FD.

  The compositions of the invention can be used as finishing agents in the textile, leather and paper industry; they give the treated substrates hydrophilic properties and

  flexibility as well as a full and swelling hand.

  The compositions of the invention are particularly indicated for treating textile materials made up,

in whole or in part, natural fibers, artificial

  these and / or synthetic, for example natural or regenerated cellulose such as cotton, natural or synthetic polyamides, for example wool, silk or nylon, polyolefins, for example polyethylene or polyisobutylene, vinyl polymers, polyesters, polyurethanes and polyacrylonitrile. The substrate to be finished can be in different forms, for example in the form of flock,

  carded, yarn, filament, woven, non

woven, closed or open loop fabrics, knitted or manufactured items, or

semi-manufactured.

The compositions of the invention are preferably used in the form of formulations. In addition to the composition, such a formulation may contain one or more components chosen from the agents

  emulsifiers, solvents and mineral oils.

Such formulations are also part of the invention. As suitable emulsifiers, there may be mentioned nonionic or anionic emulsifiers

  quickly giving a stable boiling emulsion.

As preferred nonionic emulsifiers,

  cite non-ionic polyglycolic ethers, in particular

  culier containing at least 4 alkylene units (preferably containing 2 to 3 carbon atoms), the upper limit being up to 100 units. The optimum number of alkyleneoxy units depends to some extent

  measurement of the polyglycolic compound. Alkylene units-

preferred oxy are ethyleneoxy units. The preferred nonionic polyglycolic ethers are the following compounds 1. Adducts of 5 to 20 moles, in particular 5 to 10 moles of alkylene oxide, in particular

  ethylene oxide, and an aliphatic alcohol containing

  from 5 to 20, preferably from 8 to 12 carbon atoms. Alcohol can be saturated or unsaturated. 2. Adducts of 5 to 20 Moles, in particular of to 10 Moles of Alkylene Oxide, in particular Ethylene Oxide, and of a Mono or Dialkyl Phenol in Which the Alkyl radical (s) Contain in total from 5 to 24,

  preferably 8 to 15 carbon atoms.

  3. Adducts from 2 to 100 moles, in particular

  bind from 5 to 30 moles of alkylene oxide, in particular ethyl oxide

lene, and saturated or unsaturated aliphatic acids containing from 12 to 20 carbon atoms, esters or amides of such acids, or similar fatty aids of vegetable or animal origin. The preferred anionic emulsifying agents are anionic polyglycolic ethers, for example the nonionic polyglycolic ethers mentioned above, in particular those of type 1 and 2, at least partially

carboxymethylated (for example by reaction with a chloro-

  sodium acetate). As other suitable compounds, mention may be made of sulfuric esters of saturated or unsaturated aliphatic alcohols containing from 14 to 20 carbon atoms, such as, for example, lauryl sulfate.

  sodium, alkylarylsulfonates, the alkyl residue of which

  holds from 1 to 20 carbon atoms such as for example

  sodium alkylphenylsulfonates or alkylnaphthylsul-

  sodium fonates, the alkyl residues of which each contain from 1 to 20 carbon atoms, or the alkyl sulfosuccinates, the

alkyl residue contains from 6 to 12 carbon atoms.

  It is possible to use mixtures of the nonionic polyglycolic ethers and / or the anionic emulsifying agents indicated above. Polyglycolic ethers and anionic emulsifiers mentioned above

are commercially available.

  The preferred emulsifiers are:

  Type 1 nonionic polyglycolic ethers, in particular

an aliphatic alcohol containing 10 to 12 carbon atoms and ethoxylated with 6 to 10 moles of ethylene oxide,

and polyglycolic ethers of carboxy alkylphenol

methylated in which the alkyl residue (s) contain from 8 to 13 carbon atoms and comprising an average of 6 to 7 ethyleneoxy units. The solvents suitable for the formulations of the invention are water or an organic solvent, for example an alcohol such as ethanol, isopropanol or isooctyl alcohol, dehydrated castor oil sold under the trademark Isoline (Wcburn Chem.

  Corp.), chlorinated hydrocarbons such as trichlorethylene, hy-

  armatic drocarbons or mixtures of these products.

  The preferred mineral oils are white spirit and paraffin oil, preferably white spirit. Depending on whether it is desired to operate in the presence or in the absence of foam, the formulation may contain, in addition to the composition of the invention, the emulsifying agent, a solvent and / or a mineral oil, an anti-foaming agent or a sequestering agent. In the case where it is desired to operate in the absence of foam, it is advantageous to use a formulation containing a commercial anti-foam agent, for example a silicone oil. When the presence of foam is desired, it may be appropriate to use a formulation containing a sequestering agent, for example ethylenediamine tetraacetic acid or one of its salts. You can also adjust the amount of foam desired using hard or soft water

for the finishing bath.

  The preferred formulations are those containing the composition of the invention, an emulsifying agent, a solvent and optionally a mineral oil and an anti-foaming agent. These formulations preferably contain from 5 to 50% by weight, in particular from 10 to 40%,

  more particularly from 20 to 30% by weight of the compound

tion of the invention, from 5 to 40%, preferably from 20 to 40% by weight of emulsifying agent and, optionally, from 8 to 12% by weight of a mineral oil and 1% by weight of an agent anti-foam, the rest being water or a mixture of water with an organic solvent,

preferably isooctyl alcohol.

The formulations of the invention can be prepared according to the usual methods. The preferred formulation can be prepared by adding, with stirring, the composition of the invention to the emulsifying agent at a temperature between 40 and 80 and, after cooling, the other components are preferably added in the following order: oil mineral and anti-foaming agent (when present> then the solvent. The pH of the final formulation is adjusted by

  preferably a value between 7 and 8.5.

The compositions of the invention, preferably in the form of the preferred formulation specified above, can also be used as dyeing or printing aids. Not only do they give the substrates the properties mentioned above, but they can also be used as solubilizers for dyes, in particular anionic dyes or dispersion dyes, as leveling agents,

  delaying agents or dismantling agents. The composi-

  tions of the invention also have lubricating properties and can be used, preferably in the form of a formulation as specified, as lubricants or slip agents for treatments in finishing machines, particularly machines in which the bath is strongly agitated, Z5 for example washing machines or dyeing machines such as turnstile boats and jet machines, where they

  prevent wrinkles. The compositions of the in-

  vention can also be used as detergents for washing the textile substrates mentioned above, in particular when they are used in the form of the formulations described. The compositions of the invention are particularly indicated for washing dyed substrates, more particularly substrates dyed with dispersion dyes, for example a substrate

  textile comprising polyester fibers. The composi-

tions can also be used to wash mixed textile substrates dyed with reactive dyes and dispersion dyes, for example a mixed substrate of polyester and cellulose fibers such as

the cotton.

  The invention comprises a method of finishing, dyeing or washing a substrate as specified, comprising the treatment of such a substrate in a bath containing the composition of the invention, preferably in the form of a formulation additionally containing an emulsifying agent, a solvent and, optionally, an oil

mineral and an anti-foaming agent.

The finishing treatment can be carried out according to known methods, for example by fading, impregnation, spraying or exhaustion, optionally before, during or after the dyeing of the substrate. As examples of embellishments, mention may be made of scouring, bleaching in the presence or absence of an optical brightener, peroxide bleaching and dyeing in a single bath, dyeing with anionic dyes (for example dyes

  direct, reactive, acid - or based on metal complexes -

lifères), cationic, tank or dispersion, or washing. Dyeing can be carried out according to the methods

  known, by exhaustion, continuously or by foular-

dage. Washing can be carried out according to the usual methods. The finishing or dyeing is carried out with a bath ratio of up to 20: 1, preferably of the order of 12: 0.5-1. The amount of composition of the invention to be used as a finishing agent, dye aid or detergent varies according to the

treatment process and the nature of the substrate. General-

ment, good results are obtained when 0.1 to 10%, preferably 0.3 to 2% of the formulation is used relative to the weight of the material to be finished. When using the formulation for the dismantling of dyes, it is used in proportions greater than 2%

by weight relative to the weight of the material to be treated.

As already mentioned, the invention also includes

  a formulation containing the composition of the invention

  tion in admixture with mineral oil as specified.

Such a formulation can be used as an anti-foaming agent. When using white spirit as a mineral oil, this component is added in addition to the

white spirit, which can be added at the end of the saponi-

lication of lecithin.

  The formulations of the invention containing the composition of the invention together with a solvent, for example an alcohol or a chlorinated hydrocarbon as specified, can also be used as

  detergent or as a dispersing agent.

The following examples illustrate the present invention without in any way limiting its scope. Parts and percentages are by weight. The temperatures

  are all indicated in degrees Celsius.

  Example 1 80 parts of soya lecithin (sold under the name Lecidris by the company Chemialtec, Italy) are introduced into a flask and the mixture is slowly heated to 50-600. Then add 32 parts of a 30% sodium hydroxide solution, heat the mixture to 90 and maintain this temperature

  for 1 hour. After adding 80 parts of a solution

tion at 70% sorbitol, the reaction mixture is kept at 90 (for approximately 1 hour) until a sample of the reaction mixture, dissolved in alcohol, has a neutral pH and, dissolved in water, gives a slightly marbled solution with a pH of 9-9.5. A waxy product is thus obtained which

softens around 50-60.

  Same product can be obtained by adding 70% sorbitol solution to lecithin

  heated to 50-60 at the same time as the basic compound.

The product obtained is put into the form of a formulation, by proceeding as follows: To a mixture composed of 300 parts of polyglycolic ether of tridecylphenol (comprising 6.5 ethylene oxy units), of 14 parts of a 30% solution % sodium hydroxide, 0.45 part sodium carbonate and 0.25 part water, slowly added to 37.7 parts of sodium chloroacetate; an exothermic reaction is formed, the temperature rises to 75 and this temperature is maintained for 90 minutes. To this mixture is then added to 75,200 parts of the saponification product prepared above and the mixture is heated for 30 minutes to 80. After cooling to 40-45, 90 parts of white spirit, 10 parts of silicone A (sold by the company Rhône Poulenc, France) and 80 parts of 2-ethylhexyl alcohol are added and the mixture is completed.

  to 1000 parts by adding water at slightly acidic pH.

  The final formulation has a pH of 7.88.

  Example 2 By proceeding as described in Example 1, 25 parts of soy lecithin are saponified with 10 parts of a 30% solution of sodium hydroxide.

in the presence of 20 parts of 70% sorbitol.

A formulation is then prepared having the following composition: It has 75 parts of a commercial emulsifying agent based on an alcohol containing from 10 to 12 carbon atoms, ethoxylated with 6 to 10 moles of ethylene oxide, add to 600 the saponified product prepared above. After cooling to 40-45 parts of white spirit containing 2.5 parts of silicone A, parts of isooctyl alcohol, and

parts of water.

  An analogous formulation can be prepared by replacing the emulsifying agent mentioned above.

by a commercial emulsifier based on an alkylaylsulfcnate.

Example 3

By proceeding as described in Example 1, 100 parts of lecithin are saponified with 35 parts of diethanolamine in the presence of 100 parts of

70% sorbitol.

  We can also carry out saponification

  by replacing diethanolamine with an equal amount

  valente of potassium hydroxide or monoethanolamine.

Example 4

To 8 parts of soy lecithin, 12 parts of sucrose or glucose, 4 parts of sodium hydroxide and 23 parts of water are added with stirring. The reaction mixture is kept at 1150 until a sample of the reaction mixture has a neutral pH when dissolved in alcohol and a pH of 9-9.5 when it is dissolved in water. After cooling to 600, add

  8 parts white spirit.

Example 5

  We proceed as described in Example 1 (saponifi-

cation and formulation), but by replacing sorbitol with mannitol or glycerol. A formulation is prepared as described in Example 1, but without adding any

silicone and white spirit.

  Example of Application A Unbleached cotton is treated at the boil in a bath containing, for 1000 parts, 1 part of the formulation prepared in Example 1 and 2 parts of caustic soda. The operation is carried out with a bath ratio of between 1: 5 and 1:20. When the scouring is finished, the cotton is rinsed. We thus obtain

  a scorched cotton with a soft touch.

  Application Example B A cotton knit is introduced into a bleaching bath containing, for 1000 parts, 0.8 part of the formulation prepared in Example 1, 2 parts of sodium carbonate and 2.5 parts of water. oxygenated to 130 volumes. The bath ratio is 1:12. The bath is brought to the boiling temperature and allowed to boil for 30 minutes. After rinsing and drying, we obtain a white cotton knit having

  excellent flexibility.

  Application example C Mercerized cotton thread is introduced at 80 in an aqueous bath containing, for 1000 parts, 1 part of the formulation prepared in Example 1, 1 part of sodium carbonate and 4 parts of hydrogen peroxide at 130 volumes. The pH of this bath is 11 and the bath ratio is 1:10. The bath is brought to the boiling point over the course of 10 minutes and the mixture is blanched for 40 minutes at boiling point. 1.5 parts of sodium thiosulfate are then added and, after 10 minutes, 1.5 parts of formic acid; a pH of 6.8 is thus obtained. To this bath is added 1 part of sodium m-nitro-benzene-sulfonate, a mixture of dyes comprising 0.8% of the dye CI Reactive Blue 52, 0.123% of the dye CI Reactive Red 55, and 0.166% of the dye CI Reactive Orange 10, and parts of sodium sulfate (added in

3 servings).

The mixture is boiled for 40 minutes, allowed to cool to 80 and after the addition of 10 parts of trisodium phosphate, the temperature is maintained at 80 for 10 minutes. After cooling, the cotton thread is washed at boiling point for 15 minutes with a bath containing, for 1000 parts, 0.5 part of the formulation prepared in Example 1. After rinsing hot then cold with a bath containing 1 part of acetic acid per 1000 parts of water, the substrate is dried. A cotton yarn dyed blue gray is thus obtained having excellent hydrophilic qualities and

a soft touch.

Application example D Mercerized cotton which has been previously bleached at 90 for 40 minutes with a dye bath containing, for 1000 parts, a mixture of dyes comprising 0.8% of the CI dye Reactive Blue 52, 0.123% of the CI dye Reactive Yellow 12 and 0.166% of the dye CI Reactive Red 20, parts of sodium sulfate, 1 part of the formulation prepared

example l1 and

1 part of m-nitro-benzene sulfonate

sodium.

  Then treat the substrate as described

in example C.

Example of application E In a jet machine, a cotton terry cloth is treated at 30 for 10 minutes with a bath containing 1 part of the formulation prepared in Example 1 per 1000 parts of water. The bath ratio is 1:12. The temperature is then raised to 40 and 21 parts of 36 Bé caustic soda and a mixture of dyes comprising 2.8% of the dye CI Solubilized Vat Blue 6 and 0.2% of the dye CI Vat Violet 1 are added. and, after having maintained this temperature for 20 minutes, 3.5 parts of sodium hydrosulfite are added and heating is continued at 60 for 20 minutes. The blue dyed terry cloth is then washed at the boil, with a solution containing 0.5 part of the formulation prepared in Example 1, per 1000 parts of water. After rinsing and drying, a terry cloth is obtained to the touch

soft and swelling.

Claims (24)

  1.- New compositions, characterized in that they contain a) a partially saponified lecithin having a saponification index of between 120 and 140, and b) a polyhydroxy compound.   2. A composition according to claim 1, characterized in that component a) is a product obtained by partial saponification of lecithin with a basic compound at a temperature between and 115 in an aqueous medium.   3. A composition according to claim 2, characterized in that the basic compound is chosen from sodium carbonate or hydroxide, potassium hydroxide,   lithium or calcium, monoethanolamine, diethanol- amine or triethanolamine.   4.- A composition according to any one of   claims 2 and $ 3 ca: activated in that the report basic compound lecithin molar is 13-3.25.   5.- A composition according to any one of   2 evlnieations 1 to 4, characterized in that the composition   health b) is a sugar or a polyol of formula I HO-CH 2- ± -CHOH) n-CH20H (I)   in which n signifies 1, 2, 3, 4 or 5.   6. A composition according to claim 5, characterized in that component b) is chosen parii glucose, sucrose, maltose, fructose, levulose, arabitol, xylitol, adonitol, mannitol, sorbitol, dulcitol, iditol, talitol or glycerol. 7.- A composition according to any one   of claims 1 to 6, characterized in that it contains 20 to 40% by weight of polyhydroxy compound b).   8.- A composition according to any one   of claims 1 to 7, characterized in that it   contains a) a product obtained by partial saponification of lecithin with a basic compound at a temperature between 80 and 950 in an aqueous medium, and b) sorbitol   the. sorbitol being added at the start or during saponification cation of lecithin.   9. A composition according to claim 8, characterized in that the molar ratio of lecithin sorbitol is 1: 0.4-1.38.   10.- Application of the specified compositions   to any of claims 1 to 9, such as finishing agents.   11.- Application of the specified compositions   to any of claims 1 to 9, such as auxiliary dyeing agents and detergents.   12.- A formulation, characterized in that it contains a composition as specified in one any of claims 1 to 9, an emulsifier and a solvent. 13.- A formulation according to claim 12, characterized in that it contains, as emulsifier, - an addition product of 5 to 20 moles of an alkylene oxide and of a saturated or unsaturated alcohol containing 5 with 20 carbon atoms, - an addition product of 5 to 20 moles of an alkylene oxide with a mono- or dialkyl-phenol, the alkyl radicals of which contain a total of 5 to 24 carbon atoms, - a Addition product of 2 to 100 moles of an alkylene oxide and of a saturated or unsaturated aliphatic acid containing from 12 to 20 carbon atoms, of an ester or amide of such an acid or of an acid analogous fatty acid of vegetable or animal origin, or a polyglycolic ether as specified above at least partially carboxymethylated, a saturated or unsaturated aliphatic alcohol sulfate containing 14 to 20 carbon atoms, an alkylarylsulfonate, the alkyl residue of which contains 1 to 20 carbon atoms, or an alkyl sulfosuccinate in which the alkyl residue contains from 6 to 12 carbon atoms bone, or their mixtures. 14. A formulation according to claim 13, characterized in that it contains, as an emulsifier, an addition product of 5 to 20 moles of ethylene oxide and of an aliphatic alcohol containing from 5 to 20 atoms of carbon, or a carboxymethylated polyglycolic ether of an alkylphenol in which the alkyl residue (s) contain from 8 to 13 carbon atoms and comprising from 5 to 10 ethyleneoxy units.   15.- A formulation according to any one of   claims 12 to 14, characterized in that it   contains as solvent, water, alcohol, hydro- chlorinated carbide or an aromatic hydrocarbon, or mixtures thereof. 16.- A formulation according to claim 15, characterized in that it contains, as alcohol, ethanol, isopropyl alcohol or isooctyl alcohol. 17.- A formulation according to any one   claims 12 to 16, characterized in that it also contains an anti-foaming agent. 18.- A formulation according to any one   claims 12 to 17, characterized in that it   contains from 5 to 50% by weight of a composition such as specified in any of the claims 1 to 9, and from 5 to 40% by weight of emulsifier. 19.- A formulation according to any one claims 12 to 18, characterized in that it   contains from 5 to 50% by weight of a composition such as   specified in any one of claims 1 to 9,   from 5 to 40%: by weight of emulsifier, a mixture of water and alcohol, and optionally an anti-foam silicone and white smirit. 20.- A process of finishing of substrates based on natural, artificial and / or synthetic fibers   ticks, characterized in that the said substrates are treated with a composition as specified in any one of claims 1 to 9 or by a formulation such as   specified in any one of claims 12 to 19. 21.- A process for dyeing substrates   based on natural, artificial and / or synthetic fibers   ticks, characterized in that said substrates are dyed or treated with a bath comprising a composition   as specified in any of the claims 1 to 9 or by a formulation as specified in   any one of claims 12 to 19. 22.- A process for washing substrates   based on natural, artificial and / or synthetic fibers ticks, characterized in that said - substrates by a bath comprising a composition   as specified in any of the claims 1 to 9 or by a formulation as specified in one   any of claims 12 to 19. 23.- Substrates based on natural, artificial and / or synthetic fibers, characterized in that they have been treated according to the finishing, dyeing or washing processes as specified in one   any of claims 20 to 22.   24.- Substrates made, in whole or in part, of natural or regenerated cellulose, synthetic or natural polyamides, polyethylene, polyisobutylene, polyvinyl derivatives, polyesters, polyurethanes or polyacrylonitrile, leather or paper, characterized in that they have been treated according to the finishing, dyeing and washing processes as speci ed in any of the claims 20 to 22. - :. 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