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
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38618—Protease or amylase in liquid compositions only
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/0017—Multi-phase liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds

Definitions

• the present invention relates to heavy duty and light duty liquid detergents.
• Liquid detergents have been gaining an ever increasing importance as they are more convenient to use than powder detergents. They are divided in two main groups, namely water based liquid detergents and non-aqueous liquid detergents, whose base is formed by an organic liquid medium.
• aqueous liquid detergents consists of solutions or microsuspensions of anionic, cationic and non-ionic surfactants, enzymes, perfumes, stabilizers and various adjuvants.
• stain removing agents of the peroxide type hydrogen peroxide, inorganic peroxides such as sodium perborate, organic peroxides, organic peracids etc.
• stain removing agents of the peroxide type hydrogen peroxide, inorganic peroxides such as sodium perborate, organic peroxides, organic peracids etc.
• Said aqueous based detergents for machine and hand washing are, therefore mainly founded on the surface-active action and on the stain removing action on stains of proteic type, whereas they do not act on oxidable stains, which constitute the main portion of the soils which are most frequently found.
• non-aqueous detergents consisting of an organic liquid medium based on polar solvents and surfactants containing in suspension an oxidizing agent of the organic or inorganic peroxide type, in conditions and in presence of other co-formulating agents such that interaction and therefore the decomposition of the oxidizing agent be impossible.
• the DE-C 1 279 878 (Unilever) relates to a non-aqueous based liquid detergent, comprising a mixture of non-ionic and anionic surfactants, ethyl alcohol, builders such as sodium tripolyphosphate, suspending agents such as calcined silica or calcined aluminum oxide, optical brighteners and sodium perborate.
• US-A 3 850 831 refers to essentially anhydrous liquid detergent compositions, consisting of ionic, anionic and polyhydric solvents, stain removing agents of the persait type, builders such as sodium tripolyphosphate and chelating agents such as polyamino-carboxylic acids.
• US-A 4 316 812 (Hancock et al.) refers to the use of non-ionic surfactants with no solvent (pour point about 1 COC), mixed with builders such as sodium tripolyphosphate, stain removing agents such as sodium percarbonate and perborate as well as with an alkalizing agent such as metasilicate and other typical detergent components, such as CMC (carboxymethyiceiiuiose), sodium borate, carbonate and bicarbonate, kaolin, bentonites etc. to obtain an essentially water free fine grain paste detergent.
• non-ionic surfactants with no solvent (pour point about 1 COC)
• builders such as sodium tripolyphosphate
• stain removing agents such as sodium percarbonate and perborate
• an alkalizing agent such as metasilicate and other typical detergent components, such as CMC (carboxymethyiceiiuiose), sodium borate, carbonate and bicarbonate, kaolin, bentonites etc.
• EP-B 0 028 849 refers to a non-aqueous based liquid detergent containing a maleic anhydride copolymer with ethylene or, methylvinyl ether, an essentially polyhydric solvent acting as a suspending agent together with non-ionic surfactants, as well as solid agents such as alkalizing agents, builders, oxidizing agents, bleach activators, enzymes and softeners.
• EP-B 0 120 659 (imperial Chemical Industries) relates to essentially anhydrous liquid detergent compositions, consisting essentially of a non-ionic surfactant, polar solvents with viscosity lowering functions and dispersing agents, builders, alkalizers, persalts, optical brighteners, carboxymethylcellulose, enzymes, such compositions being substantially anhydrous.
• DE-A 3 511 516 (Colgate-Palmolive) refers to a substantially anhydrous laundry detergent, comprising non-ionic surfactants, acid surfactants, sodium tripolyphosphate, sodium perborate, TAED and a copolymer such as SOKALAN CP5( R ).
• DE-A 3 511 515 (Colgate Palmolive) refers to a substantially anhydrous laundry detergent, comprising non-ionic surfactants, acid surfactants, sodium tripolyphosphate, sodium phosphonate, sodium perborate, SOKALAN CP5( R )-copolymer, sodium carbonate, TAED, optical brightener and protease.
• DE-C 1 279 878, US-A 3 850 831 and US-A 4 316 812 all refer to non-aqueous liquid detergent compositions, having a stain removing action based on non-activated persalts.
• Said compositions have a limited action on oxidizable stains at low temperatures due to the absence of bleach activators. Furthermore, they have a limited stain removal properties on proteic stains, due to the absence of enzymes, particularly of the proteolytic type.
• EP-B 0 028 849, EP-B 0 120 659, DE-A 3 511 515 and DE-A 3 511 516 are based on the combined use of oxidizing agents, bleach activators and enzymes to achieve the desired detergency effect.
• bleach activator and persalt if simultaneously present in solvents and polar surfactants based formulations, give rise to early reactions, with formation of peracid and water and possibly developing oxygen. Said reaction is assisted both by the partial solubility of the two components, but mainly by the presence of traces of water.
• GB-A 2 000 177 concerns a powder detergent composition made of two parts, separately packaged in a two-compartments non-woven sachet, one part containing acidic components rapidly soluble at cold temperature, the other one surfactants and coated alkali metal carbonates which dissolve only at temperatures higher than 40 ° C.
• EP-A 158 508 claims a special bleaching system consisting of a combination of a bleach and a bleach activator (chlorides/bromides mixtures), packaged separately, in a two-compartments multiple container, for controlled dosing off the activator such as to get a controlled, adjustable activation of the bleach at the time of laundering.
• a bleach activator chlorides/bromides mixtures
• said object is achieved by providing the said detergent in form of two physically separated base compositions, one containing the oxidizing bleaching agent and the other the bleach activator and the enzyme, in combination with surfactants, builders, optical brighteners, anti-redeposition agents, alkalizing substances, dyes, perfumes, stabilizing agents etc., all said components being dissolved and/or dispersed and/or emulsified in a suitable non-aqueous liquid vehicle, as outlined in claim 1.
• Said liquid vehicle preferably is formed by mixtures of liquid non-ionic surfactants and solvents of the polar type, the latter having the function of lowering the viscosity and the freezing point as well as that of enhancing the dispersibility in water during washing.
• Surfactants of the anionic or cationic type can be also included, if a textiles softening effect is desired.
• the builder may be an anhydrous salt of the kind of the polyphosphates, NTA (nitrilo-triacetic acid), sodium citrate, zeolites, bentonites, montmorillonites, and so on.
• NTA nitrilo-triacetic acid
• sodium citrate sodium citrate
• zeolites zeolites
• bentonites montmorillonites, and so on.
• the oxidizing bleaching agents may be chosen chosen among the inorganic persalts, of the kind of the monohydrate sodium perborate, tetrahydrate sodium perborate, sodium percarbonate, sodium, potassium and ammonium persulphate, sodium and potassium monopersulphate, perphosphate and organic per- compounds such as percarbamide, peracids and peroxides and so on.
• the bleach activator can consist of TAED (tetra-acetyl-ethylene diamine), PAG (penta-acetyl glucose), ESA (sorbitol hexa-acetate), TAGU (tetra-acetyl glycol urile), NAOFS (octyl phenol sulfonate sodium salt) and other known bleach activators.
• TAED tetra-acetyl-ethylene diamine
• PAG penenta-acetyl glucose
• ESA sorbitol hexa-acetate
• TAGU tetra-acetyl glycol urile
• NAOFS octyl phenol sulfonate sodium salt
• the enzymes are mainly of the proteolytic type, also in combination with lipase, amylase and cellulase.
• optical brighteners employed may be of the diamino stilbene, distyryl-diphenyl and pyrazole type, and anyway of the type normally used in detergents.
• the preferred anti-redeposition substances are of the cellulose derivative type, such as carboxymethyl cellulose and etherified non-ionic celluloses. Furthermore, acrylic acid homopolymers and acrylic acid copolymers with maleic anhydride and the maleic anhydride polar copolymers with methyl-vinyl ether, methyl propenyl ether and so on, are also employed.
• Persalt stabilizing agents may be of type of the phosphonate and amino polycarboxylic complexants, such as EDTA (ethylene diamino tetraacetic acid), DTPA (diethylene triamino pentaacetic acid) etc.
• EDTA ethylene diamino tetraacetic acid
• DTPA diethylene triamino pentaacetic acid
• protease, lipase, amylase, cellulase can be introduced in the detergent in solid form, as slurry, or in the form of solution, in the organic liquor.
• stabilizers such as calcium and magnesium organic and inorganic salts, polar solvents such as ethyl alcohol and polyglycols, boron organic and inorganic compounds such as boric acid and borates, nitrogen compounds such as EDTA, NTA (nitrilo triacetic acid), glycine, monoethanolamine, diethanolamine, triethanolamine, acetamide or glutamic acid can be suitably added.
• the proteolytic enzyme is introduced in form of a slurry in non-ionic surfactant or polar solvent, in fine particles, in post-admixture, to the residual composition, after milling, to avoid undesired degradation.
• oxidizing agents such as inorganic persalts and organic peracids or peroxides can give rise to interaction between activator and enzyme respectively, with a rapid decay of these compounds.
• the two base compositions can be prepared according to any suitable procedure.
• the dosing of the liquid detergent in the washing machine may be effected by using the dosing cup provided in the machine or directly into the washing machine.
• composition of liquids and solids of the two separate base compositions shall be such as to provide similar final density, viscosity and pour point, so as to ensure the same physical stability at low temperatures and constant supply ratio.
• the various solid components of the detergent can be partly soluble or insoluble in the liquid system.
• the undissolved solids In order to ensure a perfect physical stability in time, the undissolved solids must have a very fine grain size, lower than 10 wm.
• Each base composition consists of liquid components, e.g. solvents and non-ionic surfactants, solid components which can be dissolved in the system and suspended solid components, and, if present emulsified liquid components.
• liquid components e.g. solvents and non-ionic surfactants
• solid components which can be dissolved in the system and suspended solid components, and, if present emulsified liquid components.
• the ratio between solids and liquids ranges between 1:3 and 9:1, preferably between 1:1.5 and 3:1.
• the liquid vehicle is composed preferably of non-ionic surfactants and polar solvents.
• the ratio between solvents and surfactants ranges between 1:9 and 3:1.
• C 1 to C 4 lower alcohols ethylene, propylene glycols, oligomers and copolymers thereof, even partly esterified with Ct-C 4 alcohol, glycerine and aprotic polar solvents such as dimethyl sulphoxide are particularly suitable solvents.
• non-ionic surfactants are the primary and secondary, natural or synthetic alcohol derivatives, with a number of carbon atoms ranging between Cs and C 22 , and preferably between C 8 and C 18 , condensed with ethylene oxide, having 3 to 25 monomer units and preferably 5 to 15, or condensed with propylene oxide, with a monomer unit content between 2 and 10, and preferably between 3 and 6, or condensed together with oxyethylene and oxypropylene units.
• Non ionic surfactants of the mentioned type can contain the final hydroxyl esterified with C 1 -C 3 organic acids.
• non-ionic surfactants suitable for the formulation of the liquid detergents according to invention are those derived from condensation of alkyl phenols with alkylene oxides and where the type and content of monomer units is similar to those of the alcohol-based non-ionic ones mentioned above.
• the physical and chemical stability of the two base compositions shall be suitably ensured by a limited presence of water.
• the free water content must be lower than 2% and preferably be lower than 1%; as regards the base composition containing enzymes and bleach activators, the free water content must be lower than 5%, preferably lower than 3%.
• the liquid and solid components containing crystallization water need to be dehydrated, in order to fulfill the above mentioned conditions.
• the two base compositions forming the detergent are in form of suspensions of solids in liquids, having a viscosity ranging between 100 and 2000 mPa.s, and preferably between 500 and 1000 mPa.s; in order to fulfill this requirement and in order to obtain the same viscosity foor the two base compositions, to ensure a uniform delivery, the solid particles must be adequately fine, i.e. their particle size must be lower than 10 ⁇ m.
• a modification of the above procedure can consist in the previous milling in solid phase of the single solid components, to be then added to the liquid, so as to obtain a fine suspension (grain size lower than 10 wm) stable to decantation.
• the physical stability that is to say, non-decantation of the suspensions corresponding to the two detergent base compositions, must be ensured for periods of time between production and consumption, that is to say, at least for a period of time ranging between 6 and 12 months.
• suspending agents such as a calcined silica, calcined alumina, hydrosoluble polymers such as polyvinyl pyrrolidone, to the suspension, before or after milling.
• the added amounts range between 0.1 and 2.0%, and preferably between 0.3 and 1.0%.
• Calcined silica is silicium dioxide obtained through pyrohydrolisis of chlorosilanes and it is marketed as a low density powder unsoluble in water, with very small particles and surface area comprised between 50 and 400 m 2 /g.
• Commercially available types of silica are the HDK( R ) by Walker and AEROSIL( R ) by Degussa.
• Polyvinyl pyrrolidone is used in the 30,000 molecular weight range.
• Base (A) the base containing the oxidizing agents
• Base (B) the base containing enzymes and the bleach activators
• Base A and base B are separately prepared as described below, by mixing in a mixer provided with a stirrer the liquid and solid components.
• the solid components of the two bases are subsequently milled in a microsphere mill, until a 6.6 ⁇ m average value of the solid particles is obtained.
• composition of the two bases is the following, in % by weight:
• the two bases in Example 2 have the following chemical-physical characteristics:
• washing tests were carried out in a washing machine. Meanwhile, a washing test using a commercial water-based detergent containing enzymes was carried out under the same operating conditions. The results of the washing tests are shown in the following table:

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• Oil, Petroleum & Natural Gas (AREA)
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• 1986
  • 1986-08-12 IT IT12531/86A patent/IT1200285B/it active
• 1987
  • 1987-07-09 DK DK357187A patent/DK357187A/da unknown
  • 1987-07-15 IL IL83201A patent/IL83201A0/xx unknown
  • 1987-07-23 EP EP87110667A patent/EP0256343B1/en not_active Expired - Lifetime
  • 1987-07-23 ES ES87110667T patent/ES2014282B3/es not_active Expired - Lifetime
  • 1987-07-23 FI FI873230A patent/FI873230A/fi not_active IP Right Cessation
  • 1987-07-23 AT AT87110667T patent/ATE51893T1/de not_active IP Right Cessation
  • 1987-07-23 DE DE8787110667T patent/DE3762242D1/de not_active Expired - Lifetime
  • 1987-07-27 MC MC871902A patent/MC1840A1/xx unknown
  • 1987-08-11 NO NO873363A patent/NO873363L/no unknown
  • 1987-08-12 TN TNTNSN87097A patent/TNSN87097A1/fr unknown
• 1990
  • 1990-04-12 GR GR89400237T patent/GR3000431T3/el unknown

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