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 us than powder detergents. They are divided in two main groups, namely water based liquid detergents and non-aqueous liquid detergent, 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 suface-active action and on the stain removing action on stains of protein type, whereas they do not act on oxidizable 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 base liquid detergent, comprising a mixture of non-ionic and anionic surfactants, ethyl alcohol, builders such as sodium tripolyphosphate, suspending agents such as calcinated silica or calcinated aluminum oxide, optical brighteners and sodium perborate.
• US-A-3 850 831 refers to essentialy anhydrous liquid detergent compositions, consisting of ionic, anionic and polyhydric solvents, stain removing agents of the persalt 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 solvents (pour point about 10°C), 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 (carboxymethyl cellulose), sodium borate, carbonate and bicarbonate, kaolin, bentonites etc. to obtain an essentially water free fine grain paste detergent.
• 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 (carboxymethyl cellulose), sodium borate, carbonate and bicarbonate, kaolin, bentonites etc.
• EP-B-0028 849 refers to a non-aqueous based liquid detergent containing a maleic anhydride copolimer 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-0120 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, carboxymethyl cellulose, 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 tripolyphsphate, sodium perborate, TAED and a copolymer such as SOKALAN CP5®.
• 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®- 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 protein stains, due to the absence of enzymes, particularly of the proteolytic type.
• EP-B-0 028 849, EP-B-0120 659, DE-A-3 511 515 and 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.
• said object is achieved by providing the said detergent in form of two physically separared phases, one containing the oxidizing agent and the other the bleach activator and the enzyme, in combination with surfactants, builders, optical brighteners, anti-redeponent 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 base.
• Said liquid base 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 consists of anhydrous salts of the kind of the polyphosphates, NTA (nitrilo-triacetic acid), sodium citrate, zeolites, bentonites, montmorillonites, and so on.
• the oxidizing agents are 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, percarbammide, peracids and organic peroxides and so on.
• the bleach activator which is used whenever inorganic persalts are employed, can consist of TAED (tetra-acetyl 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 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 are of the stilbene-morpholine, distril diphenyl and pyrazole type, and anyway of the type normally used in detergents.
• the preferred anti-redeponent 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 copolimers with methyl-vinyl ether, methyl propenyl ether and so on, are also employed.
• Persalt stabilizing agents are of type of the phosphonate and amino polycarboxylic complexants, such as EDTA (ethylen diamino tetracetyc acid), DTPA (diethylen triamino pentacetyc acid) etc.
• 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, borum organic and inorganic compounds such as boric acid and borates, nitrogenous compounds such as EDTA, NTA (nitrilo triacetyc 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 peracids or organic peroxides can give rise to interaction between activator and enzyme respectively, with a rapid decay of these compounds.
• the two phases 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 phases 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 unsolved solids In order to ensure a perfect physical stability in time, the unsolved solids must have a very fine grain size, for instance lower than 10 ⁇ m.
• Each phase consists of liquid components, solvents and ionic surfactants, solid components which can be dissolved in the system and suspended solid components, as well as 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 phase is composed of preferably non-ionic surfactants and polar solvents.
• the ratio between solvents and surfactants ranges between 1:9 and 3:1.
• C1 to C4 lower alcohols ethylene, propylene glycols, olygomers and copolymers thereof, even partly esterified with C1-C4 alcohol, glicerine 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 C6 and C22, and preferably between C8 and C18, condensed with ethylene oxide, having 3 to 25 monomer units and preferably 5 a 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 C1-C3 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 phases composing the detergent shall be suitably ensured by a limited presence of water in the two phases.
• the free water content shall not exceed 6% and preferably be lower than 3%.
• the liquid and solid components containing crystallization free water need to be dehydrated, in order to fulfill the above mentioned conditions.
• the two phases 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 100 mPa.s; in order to fulfill this requirement and in order to obtain the same viscosity for the two phases, to ensure a uniform delivery, the solid particles must be adequately fine, for instance smaller than 10 ⁇ m.
• This result is obtained by milling the suspension in a suitable machine, such as a ball mill or a bead mill, with a duration and a number of stages apt to ensure that the desired result is achieved.
• a suitable machine such as a ball mill or a bead mill
• a modification of the above procedure can consist in the previous milling in solid phase the single solid components, to be then added to the liquid, so as to obtain a fine suspension (grain size lower than 10 ⁇ m) stable to decantation.
• the physical stability that is to say, non-decantation of the suspensions corresponding to the two detergent phases, must be ensured for periods of time between 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 calcinated silica, calcinated allumina, 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%.
• Calcinated 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 superficial area comprised between 50 and 400 m2/g.
• Commercially available types of pyrogenic silica are the HDK® by Waker and AEROSIL® by Degussa.
• Polyvynil pyrrolidone is used in the 30,000 molecular weight range.
• Phase A the detergent phase containing the oxidizing agents
• Phase B that containing enzymes and the bleach activators
• Phase A and phase 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 phases are subsequently milled in a bead mill, until a 6.6 ⁇ m average value of the solid particles is obtained.
• composition of the two phases is the following, in % by weight:
• phase A and phase B are prepared, with the following compositions:
• Example 2 The two phases in Example 2 have the following chemical-physical characteristics:
• phase A and phase B of Example 1 are thoroughly mixed, in a 1:1 ratio, to obtain a single phase liquid detergent having the following composition:
• phase A and phase B preparations as per Example 2 After milling, two parts of phase A and phase B preparations as per Example 2, have been thoroughly mixed in a 1:1 ratio, to obtain a single phase liquid detergent, having the following composition, in weight %
• R% reflectivity % value measured by means of ELREPHO reflectometer - filter number 11.

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Cited By (18)

Citations (5)

• 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 FI FI873230A patent/FI873230A/fi not_active IP Right Cessation
  • 1987-07-23 DE DE8787110667T patent/DE3762242D1/de not_active Expired - Lifetime
  • 1987-07-23 AT AT87110667T patent/ATE51893T1/de not_active IP Right Cessation
  • 1987-07-23 ES ES87110667T patent/ES2014282B3/es not_active Expired - Lifetime
  • 1987-07-23 EP EP87110667A patent/EP0256343B1/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

Patent Citations (5)

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