FR2689901A1 - Powdered composition for washing dishes. - Google Patents

Abstract

The subject of the invention is a powder detergent composition for dishwashing comprising, in percentage by weight: - 1 to 20.0% of a low molecular weight polyacrylate - 3.0 to 30.0% of a alkali metal silicate, - 1 to 12.0% of a nonionic surfactant, - 10.0 to 65.0% of a detergency builder, phosphate type - 0 to 1.5% of an agent defoamer, - 0.5 to 15% of a protease, and - 0.3 to 8.0% of an amylase, the pH of the composition being less than 11.0.

Description

The present invention relates to a composition

  powder detergent for automatic dishwashers.

  It has been found very useful to have enzymes in dish washing detergent compositions 14, because enzymes are very effective at removing food stains from the surface of glasses, dishes, pots, pans and cutlery. The

  enzymes attack these materials while other compounds

  However, for the enzymes to be highly effective, the composition must be chemically stable, and it must maintain a high level of activity.

  effective at the operating temperature of the washer

  automatic dishwashing Chemical stability is the property by which the detergent composition containing enzymes does not undergo significant degradation during storage This is also known as the "shelf life" The activity is the property of

  conservation of enzyme activity during use

  When a detergent is

  until it is used by the consumer.

  However, in the consumer's use of the dishwashing detergent composition, the dishwashing detergent

  activity unless the enzymes contained in the

  ters are maintained in an appropriate environment, they undergo degradation during storage

  which results in a product that has an active activity

  When enzymes are a part of the detergent composition, it has been found that the initial free water content of the composition should be as low as possible, and this low water content should be maintained during storage because water deactivates enzymes This deactivation causes a decrease in the initial activity of the detergent composition.

  After opening the container containing the detergent

  gent, the detergent is exposed to the environment that

  contains moisture During the moments during

  which detergent is exposed to the environment, it can

  absorb a certain amount of moisture This absorp-

  tion is made by components of the deter-

  This effect is increased when the container empties, because there is a larger volume of air in contact with the detergent, and therefore more Moisture available to be absorbed by the detergent composition. This generally accelerates the decrease in the activity of the detergent composition.

  the most effective way to avoid a significant decrease

  this activity is to start with a high initial enzymatic activity and to use

  in the dishwashing composition which does not

  do not react with enzymes or have a low affinity for water and will minimize the loss of activity

  when the detergent is stored or used.

  The powdered detergent compositions containing enzymes can be stabilized and their activity can be increased if the initial free water content of the detergent composition is less than 10% by weight, preferably less than 9%, by weight and preferably

less than 8%, by weight.

  In addition, the pH of a 1.0 wt.% Aqueous solution of the powdered detergent composition should be less than 11.0, preferably less than 10.5, and preferably less than 10.5.

  even lower than 10.3 This low alkalinity

  of the detergent washing composition of the

  The stool maintains the stability of the detergent composition containing a mixture of enzymes, thereby providing a higher initial activity of the enzyme mixture and maintaining this high initial activity.

  major in the use of washing compositions

  Automatic dishwashing is the formulation of automatic dishwashing dishwashing compositions

  which have a low alkalinity and can act

  ture while maintaining net performance.

  superior cleaning and taking care of the dishes

  The purpose of this invention is to prepare and utilize

  powder compositions for automatic dishwashers

  which contain phosphates and provide superior cleaning and protection of the dishes, and are

370 C to 600 C.

  It is an object of the present invention to provide an enzyme-containing automatic dishwashing phosphate detergent powder composition which has enhanced chemical stability and high activity at wash temperatures in the range of 400 C to 650 C, the composition can further be used for pre-soaking laundry This is achieved by controlling the alkalinity of the detergent composition and using a new enzyme mixture. An alkali metal silicate is used in the detergent compositions of the present invention. washing of

the dishes, powdered.

  The adjuvant detergent system of the composi-

  The present invention comprises at least one phosphate builder additive salt which can be used in conjunction with polymeric detergency builder salts and detergency builder salts.

containing no phosphates.

  The term "powder" in the present invention includes in its definition tablets, soluble capsules and soluble sachets. It is also possible to use the present compositions as a powder of the present invention.

soaking for the laundry.

  Automatic powder dishwashing compositions typically contain an agent

  surfactant with low foaming power, a bleaching agent

  Chlorine-based chlorine, alkaline detergency builders, and generally minor and additive ingredients The incorporation of a chlorine bleach requires special treatment and

  precautions during storage to protect the components

  components of the composition which are subject to deterioration

  The stability of the chlorine bleach is also critical and causes additional difficulties in processing and storage. In addition, it is known that

  detergent compositions for automatic dishwashers

  that can tarnish the silverware and cause damage to the metallic patterns on porcelain, due to the presence

  bleaching agent containing chlorine

  Therefore, there is a continuing need for detergent compositions for use in automatic dishwashers that are free of active chlorine and capable of

  to provide hard surface cleaning and

  the same or better aspects

  detergent compositions containing active chlorine.

  Such reformulation is particularly delicate in the context of the operations that take place in automatic dishwashers, because during these operations, the active chlorine avoids the formation and / or deposition of protein and protein-fat complexes on

  the hard surfaces of the dishes No system

  current activity is not able to achieve

appropriate this function.

  Various attempts have been made to formulate detergent compositions free of bleach, low foaming power for dishwashers

  automatic, containing particular nonionic agents

  low foaming agents, adjuvants

germs, fillers and enzymes.

  US Pat. No. 3,472,783 to Smille discloses that degradation may occur when an enzyme is added to a very alkaline automatic dishwasher detergent. FR-2,102,815 to Colgate-Palmolive, relates to washing and rinsing compositions for use in automatic dishwashers. The described compositions have a pH of 6 to 7 and contain an enzyme.

  amylolytic and, if desired, a proteolytic enzyme.

  which have been prepared in a particular manner from pancreas of animal origin and which exhibit a desired activity at a pH on the order of 6 to 7 DE-2,038,103 from Henkel & Co relates to aqueous cleaning compositions, liquid or pasty containing phosphate salts, enzymes and a component for stabilizing the enzymes US 3,799,879 to Francke et al, discloses a detergent cleaning composition of the

  dishes with a pH of 7 to 9 containing an amylo-

  lytic and possibly also a proteolytic enzyme

than.

  US 4,101,457 to Place et al discloses the use of a proteolytic enzyme having maximum activity at

  a pH of 12 in washing detergent compositions

automatic crockery.

  US Pat. No. 4,162,987 to Maguire et al. Discloses a granular or liquid automatic dishwashing detergent using a proteolytic enzyme having maximum activity at a pH of 12 and an amylolytic enzyme.

  having a maximum activity at a p H of 8.

  U.S. 3,827,938 to Aunstrup et al describes specific proteolytic enzymes that possess

  enzymatic enzymes in highly alkaline systems.

  Similar descriptions can be found in the

  British Patent 1,361,386 to Novo Terapeutisk Labora-

  torium A / S British Patent No. 1,296,839 to Novo

  Terapeutisk Laboratorium A / S describes amylolytic enzymes

  specific ticks that have a high degree of

  enzymatic life in alkaline systems.

  Thus, while the prior art clearly recognizes the disadvantages of using aggressive chlorine-based bleaching agents for washing operations in automatic dishwashers and also suggests compositions free of bleaching agents.

  bleaching, these descriptions of the prior art are

  silent on how to formulate whitening-free automatic dishwashing compositions that are effective and capable of providing

  superior performance during normal use.

  U.S. Patent Nos. 3,840,480, 4,568,476, and 3,821,118.

  and 4,501,681 and 4,692,260 describe the use of enzymes

  in automatic dishwasher detergents,

  as well as the Belgian patent N 0895 459, the French patents

  N 02 544 393 and 1 600 256, European Patent Nos. 0256 679, 266 904, 271 155, 139 329 and 135 226 and the patent

British N 021 86 884 -

  The prior art mentioned above has proved

  unable to provide a liquid detergent for washing

  automatic dishware containing phosphates as well as a mixture of enzymes and optionally a peroxide compound and an activator, for simultaneously degrading proteins and starches, wherein the combination of enzymes has

  a maximum activity at a p H less than 11.0 and in the

  which the automatic dishwasher powder detergent

  The present invention has the object of incorporating into a powdered dishwashing detergent compositions containing dishwashing phosphates a particular enzyme mixture which can be used in operations taking place in automatic dishwashers and which is capable of providing at least equal or improved performances at temperatures ranging from 450 ° C. to 650 ° C. The subject of the present invention is a powdered detergent composition for the washing of the dishes comprising in percentage by weight: 1 to 20% of a low molecular weight polyacrylate 3.0 to 30.0% of an alkali metal silicate, 1 to 12.0% of an agent nonionic surfactant, 0 to 65.0% of a 1.5% phosphate phosphate detergency builder, 0.5 to 15% protease, and 0.3 to 8% of an amylase, the pH of the composition being less than 1 1 0, and the apparent density of preference

less than 0.7 kg / l.

  Nonionic liquid surfactants that can be used in automatic dishwashing detergent powder compositions of the present invention are known. A wide variety of these agents

surfactants can be used.

  Non-synthetic organic detergents

  Ionic acids are generally described as ethoxylated propoxylated fatty alcohols which are low foaming and optionally capped surfactants, characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are

  generally obtained by condensation of an organic compound

  that hydrophobic aliphatic or alkyl aromatic with

  ethylene oxide and / or hydrophilic propylene oxide

  By nature Virtually any hydrophobic compound having a carboxy, hydroxy amido or amino group and having a free hydrogen bonded to the atom

  oxygen or nitrogen can be condensed with the ethylene oxide

  with its polyhydration product, polyethylene

  glycol, to form a nonionic detergent

  length of the hydrophilic or polyoxyethylene / pro-

  pylene can be easily adjusted to obtain the balance

  desired between the hydrophobic and hydrophilic groups.

  Particularly suitable nonionic surfactants are described in US Patents 4,316,812 and

3,630,929.

  Preferably the nonionic detergents which are

  used are lipophilic polyalkoxy detergents (inferred

  lower foaming capacity, in which the equi-

  hydrophilic / lipophilic desired free is obtained by adding

  poly (lower alkoxy) hydrophilic group to a lipophilic residue A preferred class of non-detergent

  the ionic values used is that of the higher polyalcohol

  koxy (lower) in which the alcohol has from 9 to 18 carbon atoms and in which the number of moles of lower alkylene oxide (from 3 to 2 carbon atoms) is from 3 to 15 Of these substances, those in which the higher alcohol is a fatty alcohol having from 9 to 11 or from 12 to 15 carbon atoms and which contain from 5 to 15 or from 5 to 16 lower alkoxy groups per mole are preferably used. Preferably, the alkoxy group lower is the ethoxy group, but in some cases it may be desirable to mix it with a propoxy group, the latter if it is present being usually in a minor proportion (not more than 50%) Of these compounds, those in which alcohol has 12 to 15 carbon atoms and which contain 7 groups

ethylene oxide per mole.

  Useful nonionic agents are those

  the low-foaming Plurafac series from BASF Chemical Company, which are the reaction products of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated with a hydroxyl group Examples include product A (a C 13 -C 15 fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide), product B ( a fatty alcohol of C 13 -C 15 condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide) and the product C (a C 13 -C 15 fatty alcohol condensed with 5 moles of propylene and 10 moles of ethylene oxide) Another group of low foaming liquid nonionic surfactants can be obtained from Shell Chemical Company, Inc. under the trade name Dobanol: Dobanol 91-5 is a C-fatty alcohol. Cl, ethoxylated low foaming having an average number of moles of ethylene oxide ylene and Dobanol 25-7 is an ethoxylated C 12 -IC 5 fatty alcohol

  having an average number of 7 moles of ethylene oxide.

  Another liquid nonionic surfactant that can

  to be used is sold under the brand name Lutensol SC 9713.

  Olin Poly-Tergent surfactants

  Organic Chemicals such as Poly-Tergent SLF-18, a

  Biodegradable, low foaming active ingredients are especially preferred for automatic dishwashing detergent powder compositions of the present invention. Poly-Tergent SLF-18 is also characterized as being water dispersible and having a

  low haze, and low surface tension.

  Synperonic LF D 25 or LF RA 30 nonionic surfactants marketed by ICI are especially preferred nonionic surfactants for use in the dishwasher powder detergent compositions.

the present invention.

  Other useful surfactants are Neodol-7 and Neodol 23-6 which are manufactured by Shell

  Chemical Company Inc The first is a condensation product

  A higher mixture of fatty alcohols having an average number of carbon atoms of 12 to 13 and an average number of ethylene oxide groups of 6.5. The higher alcohols are primary alcohols. Other examples such detergents include Tergitol 15-S-7 and Tergitol 15-S-9 (registered trademarks), both of which are ethoxylated linear secondary alcohols manufactured by Union Carbide Corp. The former is a mixed product of ethoxylation of secondary alcohols linear elements having from 1 to 15 carbon atoms with 7 moles of ethylene oxide and the latter is a similar product but obtained by

  reaction of 9 moles of ethylene oxide.

  Nonionic surfactants by weight

  high molecular weights such as Neodol 45-11 are also

  nonionic detergents constituting

  are also useful in the compositions of the pre-

  he feels invention, and are condensation products

  similar products obtained from ethylene oxide and alcohol

  higher fatty acids, the higher fatty alcohol having 14 to 15 carbon atoms and the number of ethylene oxide groups per mole being 11.

  also manufactured by Shell Chemical Company.

  To obtain the best balance between hydrophilic and lipophilic residues in the preferred higher polyalkoxy (lower) alcohols, the number of lower alkoxy groups is preferably 40 to 100% of the number of carbon atoms in the higher alcohol, preferably 40 to 60%, and the nonionic detergent contains

  preferably at least 50% of these higher polyalcohol

koxy (lower) preferred.

  The alkylated polysaccharide surfactants, which are used alone or in combination with a surfactant mentioned above and have a hydrophobic group containing from 8 to 20 carbon atoms, preferably from 10 to 16 carbon atoms and more preferably from

  12 to 14 carbon atoms, and the polyhydrophilic group

  saccharide containing from 1.5 to 10, preferably from 1.5 to 4, and more preferably from 1.6 to 2.7 saccharide units (for example galactoside, glucoside, fructoside, glucosyl, fructosyl and / or galactosyl units) are

  mixtures of these saccharic remains

  diques can be used in polyunsaturated surfactants.

  alkylated saccharides The number x indicates the number

  saccharide units in a polymeric surfactant

  Specific alkylated saccharide For a particular alkylated polysaccharide molecule, x can only represent whole values In a physical sample of an alkylated polysaccharide surfactant, there are generally molecules with different values of x. The physical sample can be characterized by the

  mean value of x and this average value can represent

  ter non integer numbers In this description the

  values of x are to be understood as mean values The hydrophobic group (R) can be attached in

  position 2-, 3-, or 4 instead of 1-, (provided

  for example a glucosyl or galactosyl group, rather than a glucoside or galactoside). However, the linkage at the 1-position, ie the glucosides and galactosides,

  fructosides, etc., is preferred.

  res, the additional saccharide units are

  mostly in position 2 of the sacchari-

  The link in position 3-, 4-, and 6-

  may also be encountered Possibly and in a less desirable manner, there may be a polyalkoxy chain

  joining the hydrophobic residue (R) and the polysaccharide chain

  The most preferred alkoxy radical is ethoxy.

  Preferred hydrophobic groups include alkyl groups, either saturated or unsaturated, linear or branched containing from 8 to 20, preferably from 10 to 16

carbon atoms.

  Preferably, the alkyl group is a saturated linear alkyl group. The alkyl group can contain up to three hydroxy groups and / or the polyalkoxy chain can contain up to 30, preferably less

of 10, alkoxy residues.

  Suitable alkylated polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl, di-, tri-, tetra-, penta and hexaglucosides, galactosides, lactosides, fructosides, fructosyls,

  lactosyls, glucosyls and / or galactosyls and their

  diapers. The alkylated monosaccharides are relatively less soluble in water than the higher alkylated polysaccharides When used in admixture with alkylated polysaccharides, the alkylated monosaccharides are solubilized to a certain extent The use of alkylated monosaccharides in combination with polysaccharides Alkyl chars are a preferred embodiment of the invention. Suitable mixtures include alkylated coconut di-, tri-, tetra-, and pentaglucosides.

  and alkylated tetra-, penta-, and hexaglucosides of tallow.

  Preferred alkylated polysaccharides are alkylated polyglucosides having the following formula: wherein Z is a residue derived from glucose, R is a

  hydrophobic group selected from alkyl groups,

  kylphenyl, hydroxyalkylphenyl and mixtures thereof, wherein said alkyl group contains from 10 to 18, preferably from 12 to 14 carbon atoms; N represents 2 or

  3, preferably 2, r represents from 0 to 10 and preferably

  0; and x is 1.5 to 8, preferably 1.5

  to 4 and even better from 1.6 to 2.7 To prepare these compounds

  A long chain alcohol (R 20 H) can be reacted with glucose in the presence of an acidic catalyst.

  to form the desired glucoside Alternatively, the polyglucosides

  alkylates can be prepared by a two-step process in which a short chain alcohol (R 1 OH) can be reacted with glucose in the presence of an acid catalyst to form the desired glucoside. Alternatively, the alkylated polyglucosides can be prepared by a two-step process, wherein a short chain alcohol (C 16) is reacted with glucose or a polyglucoside (x = 2 to 4) to obtain a short chain alkyl glucoside (x = 1 to 4) which can in turn be reacted with a longer chain alcohol (R 20 H) so

  to move the short chain alcohol and get the polyglut

  desired alkylated coside When this two-step process is used, the short-chain alkylglucoside content of the final alkylated polyglucoside is preferably less than 50%, more preferably less than 10% and most preferably less than 5%; it is particularly preferred

  it represents 0% of the alkylated polyglucoside.

  The amount of unreacted alcohol (the content

  free fatty alcohol) in the polysaccharide surfactant

  The desired alkylated ridate is preferably less than 2%, more preferably less than 0.5% by weight of the total alkylated polysaccharide. For some uses, it is desirable to have an alkylated monosaccharide content.

less than 10%.

  The term "alkylated polysaccharide surfactant" as used herein represents both preferred glucose and galactose derived surfactants and alkylated polysaccharide surfactants.

  less preferred throughout the description, the expression

  "Alkylated polyglucoside" (APG) is intended to include alkylated polyglycosides because the stereochemistry of the saccharide moiety is changed during the preparation reaction. A preferred APG glycoside surfactant is APG 625 glycoside manufactured by Henkel Corporation, Ambler, PA. APG 25 is a nonionic alkylated polyglycoside characterized by the formula: C n H 2 n + 1 O (C 6 H 1005) x H in which n = 10 (2%); n = 12 (65%); n = 14 (21-28%); n = 16 (4-8%) and n = 18 (0.5%) and x (degree of polymerization) = 1.6 APG 625 a: a pH of 6 to 8 (10% APG 625 in

  distilled water); a specific gravity at 25 C of 1, lg-

  / Ml; a density at 25 C of 0.91 kg / l; a BHL (hydrophilic / lipophilic balance) calculated of 12.1 and a Brookfield viscosity at 35 C, with a pin 21, at 5 to 10 rpm

3 to 7 Pa s.

  Mixtures of two or more liquid nonionic surfactants can be used and in some cases advantages can be obtained by

using such mixtures.

  The non-aqueous nonionic liquid surfactant is absorbed on a builder system comprising phosphate-based particles which is a salt of

  detergency and optionally a polyacrylate-type polymer

  low molecular weight and / or inorganic detergency builders as well as adjuvant salts of

  phosphates-free detergents such as alkaline carbonates

  for example sodium carbonate and citrate

  sodium or a mixture of carbonate and sodium citrate.

  The nonaqueous liquid nonaqueous surfactant has fine particles of organic and / or inorganic detergency builders dispersed therein.

  The preferred solid detergency builder salt is a poly-

  alkali metal phosphate such as sodium tripolyphosphate ("TPP") TPP is a mixture of anhydrous TPP and a small amount of TPP hexahydrate, such as

  the water content bound by chemical bonds

  One TPP of this type can be obtained by treating anhydrous TPP with a limited amount of water. The presence of hexahydrate decreases the speed of the dissolution rate of TPP in the water. 'water of

  washing and inhibiting caking Another TPP is

  is sold under the name THERMPHOS NW the particle size of the TPP NW, as sold, is generally

  The largest particles being 400 microns in place of all or part of the alkali metal polyphosphate, one or more other detergency builder salts can be used.

  Suitable detergency builder salts are carbohydrates

  nates, borates, phosphates, bicarbonates, silicates

  alkali metal, the lower polycarboxylic acid

  and polyacrylates, poly (maleic anhydride)

  polyacrylate and poly (co) copolymers

  maleic hydride) and poly (acetal carboxylates).

  Specific examples of such salts are

  detergents are sodium carbonate, potassium carbonate, sodium tetraborate,

  sodium pyrophosphate, sodium bicarbonate, hexa

  sodium metaphosphate, sodium sesquicarbonate,

  mono and diortho phosphate and potassium bicarbonate.

  The detergency builder salts may be used alone with the nonionic surfactant or in admixture with other detergency builders. Particular detergency builders also include those described in US Pat. Nos. 4,316,812,44,264,466. and 3, 630, 929 and those described in US Patents 4, 144, 226, 4,

, 092 and 4, 146, 495.

  Other detergency builder salts without

  may be added to the adjuvant salts

  phosphates, are gluconates, phosphonates, and

nitriloacetic acid salts.

  In combination with the adjuvant salts of detergents

  Alternatively, polyacrylates having a molecular weight of from 1,000 to 100,000 and preferably from 2,000 to about 80,000 may be used. A preferred low molecular weight polyacrylate is Sokalan CP 45 or

  Sokalan CP 5 manufactured by BASF having a molecular weight

  Another preferred low molecular weight polyacrylate is Acrysol LMW 45ND manufactured by

  ROHM and HAAS and having a molecular weight of 4,500.

* Norasol WL 2 is also preferred and com-

  takes 26% of LMW 45ND vaporized on soda burned at

74%

  Sokalan CP 45 or CP 5 is a copolymer of acrylic acid and maleic anhydride Such a substance has an absorption of water at 38 C, at a humidity

  78%, below 40% and preferably below

than 30%.

  Sokalan CP 45 is a partial copolymer-

  Neutralized solution of acrylic acid and sodium salt of maleic anhydride Sokalan CP 5 is classified as suspending and anti-redeposition agents This suspending agent has a low hygroscopicity Another detergency adjuvant salt is Sokalan CP 5 having a

  molecular weight of 70 000 which is a complete version

  A goal is to use suspending and anti-redeposition agents with low hygroscopicity. Polyacidic copolymers have this property, especially when partially neutralized. Rohm Haas Acusol 64 ND is other

useful suspending agent.

  The alkali metal silicates are useful anti-corrosion agents whose function is to render the anti-corrosive composition so as to minimize the

  damage to the cutlery and the parts of the washing machines

  automatic dishwashers The preferred sodium silicates are those having an Na 2 O / SiO 2 ratio of 1: 1 to 1: 2.4. Potassium silicates of the same ratios can also be used. Preferred alkali metal silicates,

  are sodium disilicate and sodium metasilicate.

  Another class of useful detergency builders are water-insoluble aluminosilicates, both crystalline and amorphous. Various crystalline zeolites (i.e., aluminosilicates) are described in British Patent 1,504,168, in which US Pat. No. 4,409,136 and Canadian Patents 1,072,835 and 1,087,477. An example of amorphous zeolites useful in the context of this invention can be found in Belgian Pat. No. 835,351. Zeolites generally have the formula (M 20) x (A 1203) y (If O 2) xw H ox represents 1, y represents from 0.8 to 1.2 and preferably 1, z represents from 1.5 to 3.5 or more and from

  preferably from 2 to 3 and W represents from 0 to 9, preferably

  from 2.5 to 6 and M is preferably sodium

  particular zeolite is type A or similar structure

  The preferred aluminosilicates have calcium ion exchange capacities of 200 milliequivalents per gram or more, eg

example 400 meq / g.

  Any anti-agent can be used

  Compatible Foam Preferred Antifoam Agents are Silicone Antifoam Agents These are alkylated polysiloxanes and include polydimethyl siloxanes, polydiethyl siloxanes, polydibutyl siloxanes, phenyl methyl siloxanes, trimethylsilane silicas and triethylsilane silicas. Suitable antifoam agent is TP-201 Silicon Carbide Union Other suitable antifoam agents are DB 700 and DB 100 silicones used at a rate of 0.2 to 1.0

  % by weight, the sodium stearate used at a concentration of

  from 0.5 to 1.0% by weight, and LPK N 158 (phosphoric ester) marketed by Hoechst, used at a concentration of 0% to 1.5% by weight, preferably 0.1 to 1%.

in weight.

  Perfumes that can be used include

  aromas of lemon and other natural essences.

  Any opacifying pigment which is compatible with the other components of the detergent formulation may also be used. A useful and preferred opacifier is the

  titanium at a concentration of 0 to 1.0% by weight.

  An important aspect of the present invention

  is to conserve open water (water that is not chemi-

  The absorbed water and the adsorbed water are two types of free water and include the free water usually encountered in detergent compositions.

  has the effect of deactivating the enzymes.

  The detergent composition of the present invention

  It may also comprise a peroxide-type bleaching agent at a concentration of 0 to 20% by weight, preferably from 0.5 to 17% by weight, and more preferably from 1 to 14% by weight. oxygen

  that can be used are perborate and percarbo-

  alkali metal nate, perphthalic acid, perphosphoric acid,

  phate, and potassium monopersulfate A compound

  preferred is sodium perborate monohydrate or dihydrate

  The peroxide bleaching agent is preferably used in combination with an activator at a

  concentration of 1 to 5% by weight. Appropriate activators

  are those described in U.S. Patent Nos. 4,264,466 or 1 in US Patent No. 4,430,244. Polyacetylated compounds are preferred

  Appropriate activators are also tetraacetyl-

  ethylene diamine ("TAED"), pentaacetyl glucose and

benzoate-ethylidine acetate.

  The activator generally interacts with the

  peroxide compound to form a bleach agent

  peracid type chime in the wash water.

  The detergent formulation also contains a mixture of a protease enzyme and an amylase enzyme and optionally a lipase that serves to attack and remove organic residues on the glasses,

  plates, pots, pans, and cutlery.

  Lipolytic enzymes can also be used

  in the laundry detergent powder composition

  Automatic stool of the invention Proteolytic enzymes

  eliminate protein residues, lipolytic enzymes and

  ticks, fatty residues and amylolitic enzymes starches Proteolytic enzymes include

  protease enzymes subtilisin, bromelain, papain, tryptic

  sine and pepsin Amylolitic enzymes include

  alpha-amylase enzymes Lipolytic enzymes include

  The preferred amylase enzyme is available under the tradename Maxamyl, derived from Bacillus lichenigormis supplied by Gist-Brocades, The Netherlands, in the form of granules having an activity of about 5,000 UAT / g. preferred protease is available under the

  brands Maxapem 15, 20, 30 or Maxapem 42 (PEM 42), derived from

  of Bacillus alkalophylus, and are proteomeric enzymes

  strongly alkaline mutants, marketed by Gist-Brocades, The Netherlands, in the form of granules (activity

about 15, 20, 30 or 40 UPM / g).

  Preferred enzymatic washing activities are 10 to 100 UPM / g for Maxapem and 4,000 UAT / g for Maxamyl 625. Another preferred protease is available under the trademark Maxatase, and is derived from a new Bacillus strain designated " PB 92 ", a culture of which

  was deposited in the Laboratory of Microbiology of the Univer-

  Delft and has the number R 60, and is marketed

  Gist-Brocades in the form of granules (activity of

  440 KUD / g) Preferred enzymatic activities are 200 to 700 KUD / g per wash for Maxatase The weight ratio of the proteolytic enzyme to the amylolytic enzyme

  in the laundry detergent powder composition

  automatic saddle according to the invention is between 8/1

  and 1/1, and preferably 4.5 / 1 to 1.1 / 1.

  The detergent composition of the present invention may have a relatively broad composition. The surfactant may comprise from 0 to 15% by weight of the composition, preferably from 0.1 to 15% and most preferably from 1 to 12% by weight. A soil-suspending agent which is preferably an acrylic acid copolymer may be present in amounts of from 0 to 20% by weight, preferably 3 to 15% by weight and most preferably 5 to 15% by weight. anti-foaming agent is present in an amount ranging from 0 to 1.5% by weight, preferably from 0.1 to 1.2% by weight, and more preferably from 0.3 to 1% by weight, the detergency builder which is preferably an alkali metal tripolyphosphate and / or an alkali metal pyrophosphate is present in an amount of from 2 to 40% by weight, preferably

  40% by weight and still more preferably 5 to 35% by weight.

  For a concentrated formulation, the alkali metal tripolyphosphate is present in an amount of 10 to 65% by weight, preferably 15 to 65% by weight, and more preferably

  15 to 62% by weight. The adjuvant system for deter-

  The process may also contain a low molecular weight polyacrylate polymer at a concentration of 1 to 20% by weight, preferably 1 to 17% by weight; and

better from 2 to 14% by weight.

  The alkali silicate, which is a corrosion inhibitor, and preferably sodium disilicate, is present in an amount of from 0 to 30% by weight, preferably from

  3 to 30% by weight and more preferably 4 to 28% by weight.

  The opacifier is present in an amount of 0 to 1% by weight, preferably 0.1 to 7% by weight, and more preferably 0.4% by weight.

  The enzymes are present in granular form

  Gist Brocades at a concentration of 0.8 to 22% by weight, preferably 0.9 to 20% by weight and better

  from 1.0 to about 18% by weight of the enzyme granules.

  my proteases are present in automatic dishwashing compositions at concentrations of 0.5 to% by weight, preferably 0.7 to 13% by weight and most preferably 0.8 to 11% by weight. The enzyme granules Amylase are present at concentrations of 0.3 to 8% by weight, preferably 0.4 to 7% by weight and most preferably 0.5 to 6% by weight. The lipase enzyme granules are present at concentrations ranging from 0.0 to 8.0% by weight of the detergent composition A preferred lipase enzyme is Lipolas 100 T from NOVO Nordisk, Denmark Lipase enzymes are especially beneficial for reducing fatty residues and problems of film formation on glasses and Related dishes Another useful lipase enzyme is Amaneo PS, supplied by Amanee International Enzyme Co. Inc. Other components such as fragrances are present at from 0.1 to about 5% by weight of the product.

detergent composition.

  One method of producing the powdered detergent formulation is first to vaporize and

  to absorb the nonionic surfactant on the salts

  phosphate absorbent and carbonate detergents and to mix intensively in a rotating drum The absorbed builder additive is then aged in the night to fully absorb the active ingredient.

  non-ionic and form a powder able to flow free-

  which is then mixed with the sulphate and

  sodium silicate in a double-sleeve mixer.

  Finally, the enzyme granules are added and mixed intensively to form a free flowing detergent powder. Another method of making the powdered detergent formulation having a bulk density of 0.9 is to dry vaporize all means

  the nonionic surfactant and the anti-

  foam on a perborate bleaching compound

  and the adjuvant salt of detergency These substances vaporize

  dried can be used immediately but

  it is better to put them to age for 24 hours.

  The dry vaporized substances are then dry blended into any known suitable blender such as a blender.

  drum at a temperature close to the am-

  biante with the other ingredients of the composition

  until a homogeneous mixture is obtained.

  The compositions of the present invention can also be obtained in the form of low density powder according to the process described in US 4,931,203,

  in which, these powders have an apparent density lower than

  than one-third of the apparent density of the powders

  standards that have an apparent density of 1, Okg / liter.

  The automatic nonionic dishwashing detergent powder compositions for automatic dishwashers of the present invention are readily dispersible in dishwasher water Domestic dishwashers presently used have a capacity of 80 cm 3 or 90 grams of detergent In normal use, for example for a full load of dirty plates, 60 grams of

  detergent powder are normally used.

  According to the present invention, it is sufficient to use 33 grams of the concentrated detergent composition, while for standard powder detergent compositions it is necessary to use about 50 cm 3 or about 50 grams. automatic dishwashing can include the following steps or cycles: washing, rinsing cycles with cold / hot water and rinsing cycles with hot water All washing and rinsing cycles requires 60 minutes The temperature of the washing water is 400 C at 650 ° C. and the temperature of the rinsing water is 550 ° C. to 650 ° C. The washing and rinsing cycles use about 4 to 7.5 liters of water for a washing cycle and about 4 to 7.5 liters of water. water for the

hot rinse cycle.

  Powdered automatic dishwasher detergent compositions show excellent

  cleaning properties and because of the high concentration

  When the detergent is removed from the composition, the detergent is not completely consumed during the wash cycle or completely removed during the rinse cycle, so that a sufficient amount of detergent remains during the rinse cycle to improve substantial rinsing Washed and dried dishes are free from undesirable trace, deposit or film, due to

  the use of hard water in the rinse cycle.

  The detergent powder composition of the invention

  In addition to the abovementioned components, this may include anti-scale agents, oxygen bleaches, agent activators and the like.

  bleaching and sequestering agents.

Example 1

  Detergent powder composition of density

  standard for automatic dishwasher.

  A standard density powder detergent,

  high solubility and freely flowing for washing

  automatic crockery was obtained by absorbing a

  Non-ionic surfactant (Union Carbide Tergitol MDS-42) on highly absorbing sodium tripolyphosphate Highly absorbent sodium silicate (PQ Corporation H 5240), granular sodium sulfate (Kerr-McGee Corporation Trona), granular sodium carbonate ( Allied Chemical

  dense soda ash) were also needed to confer

  detergent properties of the necessary free flow and high solubility The product was obtained by

  dry blending all the ingredients.

TABLE I

ingredients

  _ __________________________________

  Sodium tripolyphosphate (Oxychem HRS 3342)

  Anhydrous sodium sulphate Trona Gran.

  Anhydrous Sodium Carbonate Allied Dense Sodium Silicate Hydrated PQHS 240 Nonionic Surfactant Maxapem CX 30 MPU -Gist Brocade Maxamyl P 5000-Gist Brocade Concentration (% wt) o Specified amounts of Maxapem 30 and Maxamyl have been incorporated into the formulation. ADD powder, as exemplified in Table I by replacing an equivalent amount of sodium sulfate in the product Other ingredients and amounts were identical

in the product.

  The finished product was aged for a period of two days to obtain a beautiful free-flowing dry powder. The product was tested using a 50 g dose, and using the ASTM "stains and dandruff" test, combined with denatured egg stains (egg yolk denatured with 2.5M Ca C 12 solution) and substrates soiled with cooked oatmeal, and compared with an ADD powder not containing of enzyme and containing a bleaching agent and CASCADE, r = 1 a commercial ADD powder (dose of 50 g) and PALMOLIVE AUTOMATIC, a commercial liquid ADD (dose of 80 g) The cleaning performance tests were carried out with wash cycle temperatures of 490 C using tap water (about 115 ppm hardness).

TABLE II

  Automatic dishwasher test (product with enzyme c Product without enzyme c Bleach-based product) with tap water at a washing cycle temperature of 490 C Enzyme products conc Dose (g) Results (%) Dishwasher wash Maxapem 30 Maxamyl Denatured egg Cooked oatmeal

1 O O 50 6.5 60

2 O 1 50 30.5 99.5

3 2 O 50 98.0 60.0

4 2 1.5 50 99.0 99.5

2 0.5 50 95.0 98.5

6 1.5 0.25 50 94.0 95.5

7 1 0.5 50 93.0 100.0

8 1 0.25 50 94.5 100.0

9 1 0.25 50 68.5 100.0

Powder 50 91, 60.0

ADD 11614-90 B

  (containing 1.2% average C 1) CASCADE powder 50 63.0 60.0 (1% Cl average) Palm liquid 80 91.0 60.0 Auto (1% Cl average) N) os The product ADD without enzyme (1) did not allow

  practically no cleaning of oily soils

  euf and starch, while the incorporation of Protein Engineered 42 Maxacal and Maxamyl helped to completely eliminate egg and starch-based dirt from

  Powder containing enzymes (both

  pem 30 and Maxamyl) (2-9) were more efficient than the ADD powders containing a chlorine bleaching agent, such as PADD 11614-90 B, CASCADE, a commercial powder and PALMOLIVE AUTOMATIC, a commercial liquid product, for

  the cleaning of dirt based on egg and starch.

TABLE III

  Automatic dishwasher products, ASTM test results for "stains / films", water hardness 300ppm, wash cycle temperature 490C. Automatic Dishwashing Products Dishwashing Powder (3) ADD Powder 11614-90 B (with chlorine bleach) CASCADE powder (with chlorine bleach)

Liquid PALMOLIVE AUTOMA-

ICT (with white-collar

  Chlorinated Chlorine) Scale of Tasks Results Task / Screens Test l 2 e 3 e 4 e 1 st 2 nd 3 th 4 th 1 st 2 nd 3 th 4 th 1 st 2 nd 3 nd cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle A 3 A 3 A 3.4 A 2.3 B 5 B 5 B 5 B 3.4 A 5 A 6 AB 6 A 3

BC 3.4

CD 4 D 4,5

DE 2.3

  Good job quality B very little job C about 25% stained surface D about 50% stained surface E excessive stains Scale of film 1 no film 2 thin film 3 apparent film 4 significant film excessive film

Example 2

  The following concentrated formulation was obtained

  according to the process described in US 4,931,203.

TABLE IV

  Ingredients Concentration (%) Tripolyphosphate Sodium Beads 61.00

D CP 151-627

  Sodium Carbonate 10.00 (Allied Chemical Dense Soda Ash) Sodium Metasilicate 6.00 (1 Na 20: 1 Si 02, PQ Metsobeads 2048) Sodium Silicate 12.00 (1 Na 20: 1 Si 02, PQ Britesil LD 24) Nonionic surfactant 6.00 (Union Carbide Tergitol MDS-42) Maxapem CX 30 (Gist Brocades) 1 50 li 1 l Maxamyl P 5000 (Gist Brocades) The finished product is aged for two days to obtain a beautiful powder dry flowing freely. Laboratory tests of the compositions of Example 2 were carried out using dirt from

  varied nature This was done to show the differences

  Weaknesses between prototype formulations Egg-based dirt was prepared by mixing egg yolk with an equivalent amount of 2.5 N calcium chloride solution. This mixture was applied to the usable surface of plates. 20 cm diameter porcelain in the form of a thin film The plates were aged for one night at a relative humidity of 50% Oatmeal dirt was prepared by boiling 24 g Quaker Oats in 400 ml of running water for ten minutes Three grams of this mixture was dispersed as a thin film on a 20 cm porcelain plate The plates were aged for two hours at 80 C They were

  kept overnight at room temperature.

  Two plates, each with egg and oatmeal, were used for washing.

  placed in the same positions in the dish washer.

  33 g of the detergent were used as a single dose by washing All plates were noted by measuring the percentage of surface cleaned The results of the washing test with various dirt are reported below The results reported in Table V are averages over at least two tests The average results reflect the average performance obtained in 3 different types of water The product was tested, at a rate of 33 g using ASTM D 3556-79 test "tasks and combined with denatured egg stains (denatured egg yolk with a 2.5M Ca C 12 solution) and compared with a 50 g dose of commercial powder product. The prototype ADD powder containing Enzymes eliminated egg soils and the majority of oatmeal soils, while CASCADE, a commercial powder, virtually eliminated soiling. egg-based egg oatmeal.

TABLE V

  Cleaning test, enzyme-based product against

product without enzyme.

Example 3

  Detergent powder composition of density

  standard for automatic dishwasher.

  A high-solubility, free-flowing powder detergent for automatic dishwashers was obtained by absorbing a nonionic surfactant (Union Carbide Tergitol MDS-42) on highly absorbing sodium tripolyphosphate. Highly absorbent sodium silicate (PQ Corporation H 5240), Sodium sulphate Product Dose% Cleaning Egg Boiled Denatured Cooked oat Product ADD 33 g 100% 100% concentrated (Ex 2) CASCADE powder 50 g 40% 50% (commercial product) granular ( Kerr-McGee Corporation Trona), granular sodium carbonate (Allied Chemical dense soda ash) were also needed to give the detergent the necessary free flow and high solubility properties. The product was obtained by dry blending

all the ingredients.

TABLE VI

ingredients

  _____________________________________

  Sodium tripolyphosphate (Oxychem HRS 3342)

  Anhydrous sodium sulphate Trona Gran.

  Anhydrous Sodium Carbonate Allied Dense Sodium Silicate Hydrated PQHS 240 Nonionic Tergitol Surfactant

MDS-42

  Maxatase Gist Brocade Maxamyl P 5000-Gist Brocade Concentration (% wt)

_______________

  Specific amounts of Maxatase P 440,000 and Maxamyl P 5000 in granules have been incorporated into the ADD powder formulation, as exemplified in Table VI by replacing an equivalent amount of sodium sulfate in the product. The other ingredients and the

  quantities were identical in the product.

  The finished product was aged for a period of two days to obtain a beautiful free-flowing dry powder. The product was tested using a 50 g dose, and using the ASTM "stains and dandruff" test, combined with denatured egg stains (egg yolk denatured with 2.5M Ca C 12 solution) and substrates soiled with cooked oatmeal, and compared with an ADD powder not containing of enzyme and containing a bleaching agent and CASCADE, a commercial powder ADD (dose of 50 g) and PALMOLIVE AUTOMATIC, a liquid ADD commercial (dose of 80 g) The cleaning performance tests were carried out with temperatures of washing cycles of 490 C using

  tap water (about 115 ppm hardness).

TABLE VII

  Automatic dishwasher test (product with enzyme c Product without enzyme c Bleach-based product) with tap water at a washing cycle temperature of 490 C Enzyme products conc Dose (g) Results (%) Dishwasher wash Maxapem 30 Maxamyl Denatured egg Cooked oatmeal

1 O O 50 7.5 60

2 O 1 50 32.5 99

3 2 O 50 95.0 60.0

4 2 1.5 50 98.5 99.5

2 0.5 50 95.0 98.5

6 1.5 0.25 50 96.0 96.0

7 1 0.5 50 96.0 100.0

8 1 0.25 50 95.0 100.0

9 1 0.25 50 70.5 100.0

Powder 50 91, 60.0

ADD 11614-90 B

  (containing 1.2% Cl average) CASCADE Powder 50 63.0 60.0 (1% Cl average) Palm Liquid 80 91.0 60.0 Auto (1% Cl average) _ '-' The product ADD without enzyme (1) did not allow

  practically no cleaning of oily and starch-based soils, while the incorporation of Maxatase and Maxamyl has

  helped to completely eliminate egg and starch-based dirt respectively. Enzyme-containing powders (both Maxatase 30 and Maxamyl) (2-9) performed better than chlorinated bleach-containing ADD powders, such as that PADD 11614- 90 B, CASCADE, a commercial powder and PALMOLIVE

  AUTOMATIC, a liquid product of the trade, for the net-

  cleaning of dirt with egg and starch.

TABLE VIII

  Automatic dishwasher products, ASTM test results for "stains / films", water hardness

  300 ppm, washing cycle temperature 49 C.

  Products for Automatic Dishwasher Powder Dishwashers (3) Powder ADD 11614-90 B (with Chlorine Bleaching Agent) Commercial Powder (with

chlorine bleach

  d) Liquid (with chlorine bleaching agent) Results Task / film test 1st 2 3rd 3rd 4th 1st 2nd 3rd 4th 4th 2nd 3rd 3rd 4th 1st 2nd 3rd 3rd cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle A 3 A 3 A 3.4 A 2.3 B 5 B 5 B 5 B 3, 4 A 5 A 6 AB 6 A 3

BC 3.4

CD 4 D 4,5

DE 2.3

L __________________________________________________________________________ _________________

  Scale of tasks Right of tasks B very few tasks C about 25% stained surface About 50% stained surface E excessive stains ./ Scale of film 1 no film 2 thin film 3 film film 4 significant film 5 film excessive

Example 4

  The following concentrated formulation was obtained

  according to the process described in US 4,931,203.

TABLE IX

  Ingredients Concentration (%) Tripolyphosphate Sodium Beads 61.00

D CP 151-627

  Sodium Carbonate 10.00 (Allied Chemical Dense Soda Ash) Sodium Metasilicate 6.00 (1 Na 20: 1 Si 02, PQ Metsobeads 2048) Sodium Silicate 12.00 (1 Na 2 O: 1 Si O 2, PQ Britesil LD 24) Nonionic surfactant 6.00 (Union Carbide Tergitol MDS-42) Maxatase P 440 000 (Gist Brocades) 1.50 Maxamyl P 5000 (Gist Brocades) The finished product is aged for two days to obtain a beautiful powder dry flowing

freely.

  Laboratory tests of the compositions of Example 2 were carried out using dirt from

  varied nature This was done to show the differences

  Weaknesses between prototype formulations Egg-based dirt was prepared by mixing egg yolk with an equivalent amount of 2.5 N calcium chloride solution. This mixture was applied to the usable surface of plates. 20 cm diameter porcelain in the form of a thin film The plates were aged for one night at a relative humidity of 50% Oatmeal dirt was prepared by boiling 24 g Quaker Oats in 400 ml of running water for ten minutes Three grams of this mixture were dispersed as a thin film on a 20 cm porcelain plate The plates were aged for two hours at 800 C They were

  kept overnight at room temperature.

  Two plates, each with egg and oatmeal, were used for washing.

  placed in the same positions in the dish washer.

  33 g of the detergent were used as a single dose by washing All plates were noted by measuring the percentage of surface cleaned The results of the washing test with various dirt are reported below The results reported in Table IX are averages over at least two tests The average results reflect the average performance obtained in 3 different types of water The product was tested, at a rate of 33 g using ASTM D 3556-79 test "tasks and combined with denatured egg stains (denatured egg yolk with a 2.5M Ca C 12 solution) and compared with a 50 g dose of commercial powder product. The prototype ADD powder containing Enzymes completely eliminated egg stains and the majority of flour stains

  oatmeal, while commercial powder has practically

  it is not possible to eliminate egg stains and

oatmeal.

PAINTINGS

  Cleaning test, enzyme-based product against

product without enzyme.

* Product Dose% cleaning Egg Boiled denatured oat cooked Product ADD 33 g 100% 100% concentrated (Ex 2) CASCADE powder 50 g 40% 50% (Product of the trade)

Claims (7)

  A powdered dishwashing detergent composition comprising in percent by weight: 1 to 20.0% of a low molecular weight polyacrylate 3.0 to 30.0% of an alkali metal silicate, 1 to 12.0% of a nonionic surfactant, 0 to 65.0% of a phosphate builder O, 1.5% antifoaming agent, 0.5 to 15% d protease, and 0.3 to 8.0% of an amylase, the pH of the composition being less than 11.0.   2 A detergent powder composition for washing dishes according to claim 1, characterized in that it has a free water content of less than 8%, by weight. 3 Washing powder detergent composition   dishware according to any one of the claims   preceding, characterized in that it further comprises a lipase.   4 Detergent powder composition according to one   any of the preceding claims, characterized in that   it has an apparent density of less than 0.7 kg / l.   Powdered detergent composition for washing   dishware according to any one of the claims   preceding, characterized in that it comprises one or   several adjuvants selected from the anti-increment agents   tation, oxygen bleaching agents,   bleach activators, sequestrants   trants, anti-corrosion agents, anti-foaming agents, opacifiers and perfumes.   6 Washing powder detergent composition   dishware according to any one of the claims   preceding, characterized in that it comprises a perborate of alkali metal.   Dishwashing detergent composition according to claim 6, characterized in that it comprises an activator of the alkali metal perborate. 8 Washing powder detergent composition   dishware according to any one of the claims   preceding, characterized in that it comprises from 0.1 to   1.2% by weight of an antifoaming agent.   9 Washing powder detergent composition   dishware according to any one of the claims   preceding, characterized in that said protease is Maxacal and said amylase Maxamyl, the weight ratio of said protease to said amylase being 4.5 / about   1.1 / 1 and the pH of the detergent composition being lower than 10.5.   Powdered detergent composition for the   washing of dishes according to any of the claims   previous agreements, characterized in that the said   tase is Maxatase and said amylase is Maxamyl, the weight ratio of said protease to said amylase being from 5/1 to 1.1 / 1, the pH of said detergent composition being less than 10.5.   11 Method for washing dishes in a washing machine   automatic dishwashing, comprising washing said dishware at temperatures of 40 C to 650 C using a detergent composition as defined in one   any of the preceding claims.