FR2586697A1 - PHOSPHATE-FREE NON-AQUEOUS LIQUEFIING LIQUID COMPOSITIONS AND METHODS OF CLEANING LOW TISSUE USING THE SAME - Google Patents

Abstract

THE INVENTION RELATES TO A NON-AQUEOUS LIQUID DETERGENT COMPOSITION FOR LARGE BLEACHING WORK. THE COMPOSITION INCLUDES AT LEAST ONE LIQUID NON-IONIC SURFACTIVE DETERGENT IN WHICH IS SUSPENSIONED A DETERGENT ADJUSTING SALT WHICH IS A CARBOXYMETHYLOXYSUCCINATE. THE COMPOSITION MAY CONTAIN VARIOUS ADDITIVES AND ITS PHOSPHATE CONTENT IS LOW OR ZERO. APPLICATION: DETERGENTS.

Description

The present invention relates to composi-

  non-aqueous liquid solutions for the treatment of

  extra. More particularly, the present invention

  non-aqueous liquid detergent compositions

  its phosphate-free or low-phosphate products for laundering laundry, containing a suspension of a heptonate-type detergency builder salt,

  of a carboxymethyl-type detergency builder salt

  oxy-succinate or a builder salt of the ty-

  alginate in nonionic surfactants, which

  the compositions are stable vis-à-vis a separa-

  phase and gelling and can be easily poured, and the use of these compositions

for cleaning soiled fabrics.

  Liquid nonaqueous detergent compositions for heavy duty laundry are well known in the art. For example, such compositions may comprise a nonionic liquid surfactant in which particles of a detergency builder are dispersed, as described, for example, in U.S. patents. No. 4,316,812, No. 3,630,929 and No. 4,264,466 and in British Patents No. 1,205

711, No. 1,270,040 and No. 1,600,981.

  The cleaning power of surface detergents

  synthetic nonionic acids of the compositions

  laundry can be increased by adding

  detergency builders. Sodium tripolyphosphate is one of the preferred detergency builders. However, the use of sodium polyphosphate in dry powdered detergents involves

  disadvantages such as, for example, the

  polyphosphates to hydrolyze in pyro-

  ortho-phosphates which constitute adjuvants

tergence less interesting.

  In addition, the polyphosphate content of

  laundry detergents was held to be responsible

  the high phosphate content of surface water. Higher phosphate content in surface water has been shown to contribute to increased algal growth leading to harmful modification

  the biological balance of water.

  Recently, government legislation

  the promulgated have aimed to reduce the amount of

  lyphosphates present in detergents for linseed

  in some jurisdictions where polyphospha-

  were a problem, required that the deter-

  laundry workers do not contain any

  lyphosphates adjuvants detergents.

  Liquid detergents are often considered

  considered to be more practical to use than

  particulate or dry powder and, consequently,

  they have had significant success with consumers. They can be poured easily, they

  dissolve rapidly in the wash water, they can

  can be easily applied in solutions or

  concentrated on dirty parts of clothing in

  clean and do not give off dust, and they

  usually have little storage space. In-

  - the liquid detergents may contain, in their formulation, materials which could not withstand the drying operations without deterioration,

  which materials would often be used

  in the manufacture of detergent products

  particulate. Although they have many advantages

  in relation to unitary solids or

  ticularly, liquid detergents often

  certain inherent disadvantages that must be

  mounted to obtain acceptable detergent products

  in the trade. Thus, some of these products are

  parent to storage and others separate

  cold and can not easily be

  Persians. In some cases, the viscosity of the product changes and the product becomes too thick to be

  poured, so liquid as to resemble water.

  Some limpid products become cloudy and

very gel at rest.

  In addition to the problem of sedimentation or phase separation, nonaqueous liquid laundry detergents based on nonionic liquid surfactants have the disadvantage that nonionic surfactants tend to gel when they are

  added to cold water. This is a particular problem

  sharply acute during routine use of European automatic household washing machines in

  which the user places the detergent composition

  laundering in a dispensing device

  (for example, a dispensing drawer) of the machine.

  During operation of the machine, the detergent contained in the dispenser is subjected to a flow of cold water which transfers it into the main mass of the washing solution. In particular, during the winter months, when the detergent composition and

  water introduced into the dispenser are particularly

  cold, the viscosity of the detergent increases

  and a gel is formed. As a result, part of the composition is not completely swept out of the dispenser during operation of the machine,

  and a composition deposit accumulates during cy-

  repeated washing, ultimately forcing the use of

  to sweep the dispenser with hot water.

  The phenomenon of gelation can also

  pose a problem when washing in cold water, as may be recommended for certain synthetic and delicate

  tissues that can shrink in warm or hot water.

  The tendency of concentrated detergent compositions to gel during storage is aggravated by the storage of compositions in

  unheated storage areas or by trans-

  wearing compositions during the winter months in

  unheated transport vehicles.

  Partial solutions to the problem of gelling aqueous compositions substantially without detergency builder, have been proposed, for example by diluting the nonionic liquid surfactant with certain solvents acting on the viscosity and certain gelling inhibiting agents, such as

  lower alkanols, for example ethyl alcohol

  that (see U.S. Patent No. 3,953,380),

  alkali metal mates and adipates (see patent for

  U.S.A. 4,368,147), hexylene glycol, polyethyl-

  glycol, etc., and by a modification and optimization of

  the structure of nonionic surfactants.

  As an example of modification of nonionic surfactants

  a particularly good result has been

  by acidifying the hydroxyl-terminated portion

  than the nonionic molecule. The benefits of

  troduction of a carboxylic acid at the end of the

  nonionic facet comprising inhibition of

  lification at the time of dilution; a decrease in

  drop point of nonionic surfactants; and the

  anionic surfactant by neutralization in the wash liquor. The optimization of the structure

  non-ionic focus was on the chain length of the frag-

  hydrophobic-lipophilic effect and on the number and

  forming the alkylene oxide units (eg ethylene oxide) of the hydrophilic moiety. For example, it has been found that a C13 fatty alcohol ethoxylated with 8 moles of ethylene oxide has only a limited tendency

to the formation of a gel.

  Nevertheless, we want to improve both the

  stability and inhibition of gelation of

  non-aqueous liquid solutions without phosphates and

  phosphate content, for the treatment of tissues.

  According to the present invention, a

  highly concentrated non-aqueous liquid detergent composition

  low phosphate content, and more particularly

  is free of polyphosphoric detergency adjuvant

  phage by dispersing builder salts of the heptonate type, carboxymethyloxysuccinate, or alginate type in a non-surfactant detergent.

ionic liquid.

  The salts of heptonic acid used according to the present invention are well known. The acid

  heptonic acid derivative of an aldoheptose (mono-

  saccharide). Alkali metal salts of hep-acid

tonic are water soluble.

  The alkali metal salts of the heptonic acid used in the present invention are represented by the general formula:

H-C-OH

I

(H-C-OH) 5-

O = C-OM

  wherein M is an alkali metal or amine cation

  monium. The carboxymethyloxysuccinic acid salts used according to the present invention are known. The

  alkali metal and ammonium salts of the carbohydrate

  xymethyloxysuccinic are water soluble.

  The carboxymethyloxysuccinic acid salts used in the present invention are represented by the general formula:

MOOC-CH-COOM

I

CH 30-CH-COOM

  in which M e3t hydrogen, a metal cation

  alkali such as solium and potassium, or a

  ammonium, and at least one M is a cation of m -

alkali or ammonium.

  The alginic acid salts used according to the present invention are well known. Alginate is a polysaccharide extracted from marine algae. Salts

  alkali metals of alginic acid are hydrosolated

  lubles. Alginate is extracted from seaweeds in the form of mixed salts including calcium and magnesium. In order to improve the characteristics of

  viscosity of the composition, it is possible to add a surfac-

  nonionic tif with acid termination. To improve

  vantage the viscosity characteristics of the composition

  tion and storage properties of the composi-

  tion, we can add to the competition

  viscosity and anti-gel agents

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  such as monoalkyl ethers of alkylene glycol and antisedimentation agents such as phosphoric acid esters and aluminum stearate. In a preferred embodiment of the invention, the

  detergent composition contains a nonionic surfactant

  than acid-terminated and / or monoalkyl ether

  alkyl-glycol, and an anti-sedimentation agent.

  Sanitizers or bleaching agents

  and their activators can be added to improve the whitening and

cleaning the composition.

  In one embodiment of the invention,

  the adjuvant detergency components of the com-

  position are crushed to an inferior particle size

  less than 100 micrometers and preferably less than micrometers in order to further improve the stability of the suspension of the adjuvant detergency components

  in liquid nonionic surfactant detergent.

  In addition, other ingredients may be

  added to the composition, such as anti-inflammatory agents

  crustation, antifoaming agents, optical brighteners, enzymes, anti-redeposition agents,

perfumes and dyes.

  Washing machines currently manufactured for domestic use normally operate on

  washing temperatures up to 100 C.

  than 70 liters of water during the wash and rinse cycles. Normally 175 grams are used

detergent powder by washing.

  According to the present invention, when

  read the highly concentrated liquid detergent, it does not

  about 100 grams (77 ml) or less of

  liquid detergent solution to wash a complete

dirty laundry.

  Consequently, in one aspect, the present

  the invention provides a liquid composition for large laundry work without detergency adjuvant

  phosphate-like or substantially free from such an adjuvant

  detergency, consisting of a suspension of a salt

  of alkali metal of heptonic acid adjuvant detergent

  alkali metal salt of carboxymethyloxy acid

  succinic detergency builder, or an alkali metal salt of alginic acid detergency builder in a

nonionic liquid surfactant.

  In another aspect, the invention provides a concentrated liquid detergent composition with a

  low or no phosphate for heavy work

  chilling, which is stable, does not sediment itself

  poses and does not gel during storage and in use. The liquid compositions of the present invention can be easily poured, are easily dosed and are easily introduced into

washing machine.

  In another aspect, the invention provides a method for dispensing a detergent composition

  non-ionic laundry liquid with a phos-

  weak or no phat in and / or with cold water without causing gelation. In particular, there is provided a method for filling a container with a

  non-aqueous liquid laundry detergent composition

  wise in which the detergent is constituted, at least

  predominantly, a nonionic surfactant

  liquid solution free of polyphosphate adjuvant

  tergence and to distribute the composition from

  container in an aqueous wash bath, the distribution

  tion being carried out by directing a non-

  heated on the composition so that the composi-

  tion is driven by the current of water in the bath

washing.

  Detergent compositions free from

  polyphosphate adjuvant detergent eliminate the

  pollution of surface waters by phosphorus

  phosphates. Nonaqueous concentrated nonionic surfactant liquid laundry detergent compositions with low or no polyphosphate content,

  according to the present invention, combine the advantages

  to be stable, and not to undergo sedimentation

  warehousing and storage gelation

  ge. The liquid compositions are easy to pour,

  easy to dose and easy to introduce into the

China washing clothes.

  An object of the present invention is to provide a non-aqueous, non-polluting liquid non-aqueous detergent composition with low content, and in particular with a zero polyphosphate content, for

  heavy laundering work, containing as salt ad-

  a detergent, a heptonate, a carboxymethyl

  oxysuccinate or alginate suspended in an

nonionic factic.

  Another object of the invention is to provide

  liquid compositions for the treatment of

  low or no polyphosphate content which are suspensions of a detergency builder salt

  of the heptonate, carboxymethyloxy succinate or

  nate in a non-aqueous liquid and are stable in storage and are easy to pour and disperse

  in cold, warm or hot water.

  Another object of the present invention

  to formulate liquid detergent compositions

  non-aqueous strongly reinforced with non-ionic surfactant

  that, with low or no polyphosphate content, for heavy laundering work, which may be paid

  at all temperatures and which can be dispersed

  repeatedly from the distribution device.

  automatic washing machines

  European style without clogging or clogging the dispenser--

  even during the winter months.

  Another object of the present invention is to provide stable, non-gelling suspensions to

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  low or no polyphosphate content, of non-aqueous liquid non-ionic detergent composition reinforced for heavy laundering work, which includes a

  effective amount of heptonate, carboxymethyloxy-

  cinate or alginate as a detergency builder salt.

  Another object of the present invention is to provide non-gelling stable suspensions of non-aqueous liquid nonionic detergent composition

  reinforced for heavy laundering work, which

  take an alkanolic ester of phosphoric acid and /

  or an aluminum fatty acid salt as an anti-

  sedimentation, in an amount sufficient to increase

  the stability of the composition, that is to say,

  sedimentation of particulate adjuvant particles

  tergence, etc., preferably while reducing or at least not increasing the plastic viscosity of the composition. These objects of the invention as well as others

  which will emerge from the detailed description that will

  following of preferred forms of realization are

  the composition of a low or no polyphosphate detergency builder by adding to the nonaqueous liquid nonionic surfactant an effective amount of a detergency builder of

  alkali metal heptonate type, carboxymethyloxy-sucrose

  cinate, or alkali metal alginate and additives

  treatment of tissues, organic or inorganic, for example

  ples anti-gel agents and improving the vis-

  cosity, anti-sedimentation agents, anti-

  incrustation, bleaching agents,

  bleaching agents, antifoam agents, optical brighteners, enzymes,

  antiredeposition, perfumes and dyes.

  Nonionic surfactant detergent Non synthetic synthetic detergents

  ionic agents used in the practice of the invention.

  may be any of a large number

  such compounds, which are well known.

* As we know, organic detergents

  nonionic synthetics are characterized by the pre-

  of a hydrophobic organic group and a hydrophilic organic group and are generally produced by the condensation of an organic aliphatic or alkyl-aromatic hydrophobic compound with ethylene oxide

  (hydrophilic nature). In practice, any hy-

  containing a carboxy, hydroxy, amido or amino group having a free hydrogen atom attached to nitrogen, may be condensed with ethylene oxide

  or with its polyhydration product, polyethyl-

  enol glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to reach the ratio

  desired between the hydrophobic and hydrophilic groups.

  Representative examples of suitable nonionic surfactants are those described in the E. Patents.

U.S. 4,316,812 and 3,630,929.

  In general, nonionic detergents are lipophilic compounds alkoxylated by a group

  poly (lower alkoxy) in which the hydro-

  desired phile / lipophilic is obtained by the addition of a hydrophilic poly (lower alkoxy) group to a fragment

  lipophilic. A preferred class of nonionic detergents

  used consists of the higher alkanols

  alkoxylated with poly (lower alkoxy) groups

  wherein the alkanol has 9 to 18 carbon atoms.

  in which the number of moles of oxide of

  The lower alkylene (of 2 or 3 carbon atoms) is from 3 to 12. Among these materials, it is preferred to use those in which the higher alkanol is a higher fatty alcohol of 9 to 11 or 12 to 15 carbon atoms, and which contain 5 to 8 or 5 to 9 lower alkoxy groups per mole. Preferably, the lower alkoxy group is ethoxy, but in some cases it may be advantageously mixed with the propoxy group, the

258,669?

  presence is often only a proportional

minor (less than 50%).

  Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and which contains about 7 ethylene oxide groups per mole, for example Neodol 25-7 and Neodol 23-6.5, which are products manufactured by Shell Chemical Company, Inc. The first is a condensation product of a mixture of higher fatty alcohols averaging about 12 to

  15 carbon atoms, with about 7 moles of

  thylene, and the second is a corresponding mixture in which the carbon atom content of the fatty alcohol

  is 12 or 13, and the number of oxy-

  of ethylene present represents an average of about

  6.5. The higher alcohols are primary alkanols.

  Other examples of such detergents include

  take Tergitol 15-S-7 and Tergitol 15-S-9, which are

  both ethoxylates of linear secondary alcohols

  manufactured by Union Carbide Corporation. The first

  is a mixed ethoxylation product of a secondary alkanol

  Linear linear of 11 to 15 carbon atoms with seven moles of ethylene oxide, and the second is a similar product but nine moles of ethylene oxide reacted. Also useful in the composition

  of the invention as a component of the non-ionic detergent

  nonionic surfactants of higher molecular weight, such as Neodol 45-11, which are similar condensation products of ethylene oxide on

  fatty alcohols, the higher fatty alcohol

  carrying 14 or 15 carbon atoms, and the number of

  ethylene oxide groups per mole being about 11.

  These products are also manufactured by Shell Chemi-

Company cal.

  Other useful nonionic surfactants are represented by the well-known trade class

  nonionic surfactants sold under the brand name

  Mercial Plurafac. Plurafac products are the pro-

  reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and

  propylene oxide, completed by a hydro-

  xylE. Examples include Plurafac RA30 (a

  cool C13-C15 fat condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide), Plurafac RA40 (a C13-C15 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide), Plurafac D25 (a C13-C15 fatty alcohol fused with moles of propylene oxide and 10 moles of ethylene oxide). Another group of nonionic surfactants

  liquids are commercially available from

  Shell Chemical Company, Inc., under the trade name

  mercial Dobanol: Dobanol 91-5 is a C9-Cll ethoxylated fatty alcohol with an average of 5 moles of oxide

  ethylene and Dobanol 25-7 is a C12 fatty alcohol

  C15 ethoxylated with an average of 7 moles of

thylene per mole of fatty alcohol.

  In the lower alkanols alkoxylated with poly (lower alkoxy) groups, to obtain the

  better ratio between the hydrophilic and

  the number of lower alkoxy groups is generally 40% to 100% of the number of carbon atoms of the higher alcohol, preferably 40 to

  % of this number, and the nonionic detergent con-

  preferably at least 50% of such a preferred higher poly (lower alkoxy) alkanol. The alkanols of

  higher molecular weight and various other deter-

  normally solid nonionic substances and surfactants

  assets can contribute to gelation of the deter-

  liquid and, therefore, will preferably be removed or limited in the present compositions, although they may be used

  in minor proportions for their net properties.

2586697-

  cleaning, etc. Regarding non-detergents

  preferred and less preferred ionic

  kyle they contain are usually linear,

  although branching can be tolerated, for example

  ple at a carbon atom close to the terminal carbon atom of the right or the far chain of

  two carbon atoms of this terminal carbon atom

  nal and opposite of the ethoxylated chain, provided

  that such a branched alkyl group does not have a long

  more than three carbon atoms. Normally,

  the proportion of carbon atoms in such a con-

  branched figuration is minor and rarely exceeds

  % of the total carbon content of the group

  alkyl. Similarly, although linear alkyl groups that are end-joined to ethylene oxide chains are very preferable and are considered to provide the best combination of

  characteristics of detergency, biodegradability and

  and non-gelation, it may appear a medial or secondary junction with ethylene oxide

  chain. There is usually only a small proportion

  such alkyl groups, generally less than 20%, but, as in the case of the mentioned Tergitol, this proportion may be higher. Also, when

  lower alkylene oxide chain contains oxy-

  propylene oxide, the proportion of this propylene oxide

  is usually less than 20% and preferably

  less than 10% of this chain.

  When using higher proportions

  to those mentioned above of alkanols of which

  the alkoxylation is not terminal, alkoxyalkanols

  poly (lower alkoxy) groups containing propylene oxide and nonionic detergent with a lower hydro-lipophilic ratio, and when

  other nonionic detergents in place of

  preferred nonionic gents listed here, the product

  result may not be as good

  detergency, stability and non-gelatin

  than the preferred compositions, but the use of

  cation of compounds of the invention acting on the

  cosity and inhibiting gelation can also be

  improve the properties of detergents based on such nonionic compounds. In some cases, for example when using a lower poly (lower alkoxy) -alkanol of higher molecular weight, often for

  its detergency, its proportion is regulated or

  adjusted according to the results of experiments

  tine, to obtain the desired detergency and to obtain at the same time a non-gelling product and desired viscosity. Also, it has been found that

  Only rarely is it necessary to use higher molecular weight nonionic surfactants for their properties.

  detergents, because the non surfactants

  Preferred ionic compounds described herein are excellent deter-

  and, moreover, they make it possible to reach

  desired costivity in the liquid detergent without gelling

cation at low temperatures.

  Another useful group of nonionic surfactants is the "Surfactant T" series of

  nonionic surfactants proposed by British Petroleum.

  Surfactant T nonionic surfactants are obtained by ethoxylation of C13 secondary fatty alcohols

  with a narrow distribution of ethylene oxide.

  Surfactant T5 has an average of 5 moles of

  thylène; Surfactant T7 has an average of 7 moles of

  ethylene oxide; Surfactant T9 has an average of 9

  ethylene oxide and surfactant T12 has a medium-

  12 moles of ethylene oxide, per mole of alcohol

secondary fat in C13.

  In the compositions of the present invention

  tion, preferred nonionic surfactants include

  C13-C15 secondary fatty alcohols having

  relatively low ethylene oxide

  from 7 to 9 moles, and C 9 to C 18 fatty alcohols

258,669?

  xylated with about 5 to 6 moles of ethylene oxide.

  Mixtures of two or more liquid nonionic surfactants can be used and

  in some cases, we can benefit from the use of

such mixtures.

  Non-ionic surfactant with Acid Termination The properties of viscosity

  and gelling the liquid detergent compositions

  can be improved by including in the

  an effective amount of a nonionic surfactant

  acid-terminated liquid. Nonionic surfactants

  acid-terminated surfactants consist of a nonionic surfactant which has been modified to convert one of its free hydroxyl groups to a moiety having a free carboxyl group, such as an ester or partial ester

  non-ionic surfactant and an acid or

lycarboxylique.

  As described in the French patent application

  N 85 05319 filed on 9 April 1985, the surfac-

  nonionic acids, modified by a carboxyl group

  which can roughly be characterized as polyether carboxylic acids, act in a

  to lower the temperature at which the liquid surfactant

  Nonionic forms a gel with water.

  The addition of nonionic surfactants to

  acid termination to the liquid nonionic surfactant

  vorizes the ability of the composition to be dispensed, i.e., to be dispensed, and reduces the temperature at which the liquid nonionic surfactant forms a gel in water without decreasing their stability vis-avis

  sedimentation. The nonionic surfactant at

  Acidic acid reacts in the water of the washing machine

  with the alkalinity of the phase of sei adjuvant de

  dispersed tergence of the detergent composition and acts

as an effective anionic surfactant.

  Particular examples include the half-esters of Plurafac RA30 with succinic acid,

  the Dobanol 25-7 ester or half ester with the anhydrid

  succinic, and Dobanol 91-5 ester or hemi-ester with succinic anhydride. Instead of anhydride

  succinic, other acids or anhy-

  polycarboxylic acids, for example maleic acid

  that, maleic anhydride, citric acid, etc. The acid-terminated nonionic surfactants can be prepared as follows: Acid-terminated Plurafac 30: Mix 400

  g of nonionic surfactant Plurafac 30, which is a

  C13 to C15 canol which has been alkoxylated to introduce

  6 ethylene oxide units and 3 propylene oxide units

  by alkanol unit, with 32 g of succinic anhydride

  and heat for 7 hours at 100 C. Cool

  says the mixture and the filter to separate the material

  succinic that has not reacted. The infrared analysis

  about half of the nonionic surfactant has

  has been converted to its acid half-ester.

  Acid-terminated Dobanol 25-7: 522 g of Dobanol 25-7 nonionic surfactant, which is the ethoxylation product of a C12-C15 alkanol and

  has about 7 ethylene oxide units per molecule

  alkanol solution, with 100 g of succinic anhydride and

  0.1 g of pyridine (which acts as an ester catalyst)

  fication) and heated at 260 ° C for 2 hours,

  cools and filtered to separate the succinate material

  having not reacted. Infrared analysis shows that almost all the free hydroxyl groups in the

surfactant reacted.

  Acid-terminated 91-5 Dobanol: 1000 g of Dobanol 91-5 non-ionic surfactant, which is the ethoxylation product of a C 9 -C 14 alkanol, is mixed with

  about 5 units of ethylene oxide per

  alkanol solution, with 265 g of succinic anhydride and 0.1 g of pyridine as catalyst, and heated at 260 ° C. for 2 hours, cooled and filtered for

258,669?

  separate the unreacted succinic material. The-

  infrared analysis shows that almost all

  Free hydroxyl groups of the surfactant reacted.

  Other esterification catalysts, such as an alkali metal alkoxide (for example sodium methoxide) can be used instead

  pyridine or mixed with it.

  Polyether acid, that is to say, the

  acid-terminated nonionic filler, is preferably

  added to the dissolved state in the nonionic surfactant. Adjuvant Detergent Salts The nonaqueous liquid nonaqueous surfactant used in the compositions of the present invention contains, in the dispersed and suspended state, fine particles of organic detergency builder salts.

and / or minerals.

  The present invention encompasses, as a part of

  essential component of the composition, an adjuvant salt of

  organic pertussis of the carboxylate-type heptonate type

  methyloxysuccinate or alginate type.

  Organic Adjuvant Detergent Salts Preferred organic detergency builder salts include the alkali metal salts of heptonic acid, preferably the sodium and potassium salts. Other acid salts of monosaccharides

  that can be used are the salts of mono-

  saccharides formed with a longer chain. A particular example of monosaccharide acid salts

  is the sodium salt of heptonic acid.

  Other organic adjuvant salts of

  Preferred solutions include alkali metal salts

  carboxymethyloxysuccinic acid or ammonium

preferably the trisodium salt.

  Carboxymethyloxysuccinic acid salts

  that used in the detergent compositions of the

  The present invention is represented by the general formula

258,669?

following neral:

MOOC-CH-COOM

CH30-1H -COOM

  wherein M is selected from hydrogen, an alkali metal and ammonium cation, and at least one M is a

  alkali metal or ammonium. The preferred alkali metals

  res are sodium and potassium, sodium being

  favorite core. Mono-, di- and di-salts can be used

  trisodium, trisodium salt being still preferred.

  A particular example of carboxylic acid salts

  boxymethyloxysuccinic that can be used is

  represented by the formula: Na-OOC-CH-COO-Na

1

CH O-CH-COO-Na

  Other organic adjuvant salts of

  Preferred solutions include alkali metal salts

  alginic acid, preferably the salts of

  dium and potassium. Sodium alginate is a

  it is well known, it is readily available and has many known uses. Sodium alginate

  is also known as polymannuronate of

  dium. Polymannuronic acid may have a moderate weight

about 240,000 lecular.

  Alginic acid is extracted from seaweed

  brown giantine (giant kelp macrocystis pyrifus-

  ra (L.) Ag Lessoniaceae) in the form of mixed salts comprising calcium and magnesium salts of

  alginic. Alginates can also be ex-

  traits of fingered kelp (Laminaria digitata (L.) La-

  mour, Laminariaceae) and sugar kelp (Laminaria

  saccharina (L.) Lamour). Calcium salts and

  gnesium of alginic acid are easily transformed

  alkali metal salts, in particular in

  sodium ginate, by methods well known in the art. Sodium alginate is a powder of

  cream color that is soluble in water.

  A particular example of alkali metal salts of alginic acid that can be used is represented by the formula:

COOM OOM

H

OH OOM OH

M = Na (Manutex RH)

  Other organic detergent builders

  what can be used are polymers and copolymers

  polyacrylic acid and polymaleic anhydride and their alkali metal salts. More particularly, these detergency builder salts may consist of

  a copolymer which is the reaction product of a

  approximately equal parts of methacrylic acid and maleic anhydride, which has been completely neutralized to form its sodium salt. The detergency builder

  is commercially available under the trade mark

  cial Sokalan CP5. This detergency builder serves,

  when used even in small quantities, to

* an inlay, that is to say, it serves as an agent

antifouling.

  Since the compositions of the preface

  invention are generally very concentrated and,

  therefore, can be used in

  weakly, it is advantageous to supplement

  detergency builder with auxiliary adjuvant

  such as an alkali metal salt of polycarboxylic acid

  lower boxylic material with high fixation power

  calcium and magnesium to inhibit

  crustation that might otherwise be caused by the

  formation of insoluble calcium and magnesium salts.

  Suitable alkali metal salts of polyhydric

  carboxylic acids are the alkali metal salts of acids

  citric and tartaric acid, for example monosodium citrate

  (anhydrous), trisodium citrate, a salt of glutaric acid, a salt of gluconic acid and a salt of

diacid longer chalk.

  Examples of alkaline sequestering organic builder salts that can be used with builder salts of the heptonate, carboxymethyloxy succinate or alginate type, or in admixture

  with other organic detergency additives and half

  are the alkali metal aminopolycarboxylates

  example, ammonium or substituted ammonium, for example

  edetate (EDTA) of sodium and potassium, nitric

  sodium and potassium loacetates (NTA) and N- (2-

  hydroxy-ethyl) nitrilodiacetates of triethanolammonium.

  The mixed salts of these aminopolycarboxylates are suitable

also.

  Other suitable detergency builders

  of the organic type include carboxymethyl succinic

  are, tartranates and glycollates.

  Mineral salts Adjuvants of detergency The detergent compositions of the invention

  may also contain adjuvant salts of deter-

  minerals soluble in water and / or insoluble in water. Suitable alkaline mineral builder salts that can be used are the following:

  carbonates, borates, bicarbonates and silicate

  alkaline levels. (It is also possible to use ammonium salts

  monium or substituted ammonium). Specific examples

  such salts are sodium carbonate, sodium taboraborate, sodium bicarbonate,

  sodium sesquicarbonate and bicarbonate of potas-

  sium. The alkali metal silicates are

  useful adjuvant salts of detergency which also act

  to adjust or adjust the pH and to make the

  anticorrosive composition for the parts of the machine

  do not wash. Sodium silicates of Na 2 O / SiO 2 ratios of from 1.6: 1 to 1: 3, 2, in particular from about 1: 2 to 1: 2.8 are preferred. We can also use

  potassium silicates in the same ratios.

  Although it is preferable that the composi-

  detergent be free of phosphate or poly-

  phosphate or substantially free of polyphosphate,

  small amounts of polyphospha-

  the classics as detergency builder salts when local regulations permit such use. Particular examples of such detergency builder salts are sodium tripolyphosphate (TPP), sodium pyrophosphate, pyrophosphate, and the like.

  of potassium, potassium tripolyphosphate and heparin

  sodium xametaphosphate. Tripolyphosphate (TPP) from

  sodium is the preferred polyphosphate. In the formulas

  In which polyphosphate is added, it is added in an amount of from 0 to 50%; for example 0 to 30%, and in particular 5 to 15%. As mentioned

  previously, however, it is preferable that the

  mulations are free of polyphosphate or

free from polyphosphate.

  Other representative examples of suitable detergency builders include, for example, those described in US Pat. Nos. 4,316,812, 4,264,466 and 3,630,929. The alkaline mineral detergency builder salts can be used with the US Pat. surfactant detergent nonionic or mixed with

  other organic salts or mineral adjuvants

tergence.

  Zinc aluminosilicates can be used

  crystalline and amorphous litids insoluble in water.

  The zeolites generally have the formula: (M 20) x (Al 2 O 3) y '* (SiO 2) z' wH 2 O wherein x is 1, y is from 0.8 to 1.2, and is preferably 1, z is from 1.5 to 3.5 or more, and preferably is 2-3, and w is

  from 0 to 9, preferably from 2.5 to 6, and M is preferably

  sodium. A representative example of zeo-

  lite is a type A zeolite or similar structure

  Type 4A is particularly preferred.

  The preferred aluminosilicates have a power of exchange.

  calcium ion of about 200 milliequivalents per gram or more, for example 400 milliequivalents

per gram.

  Various crystalline zeolites (i.e.

  to say aluminosilicates) that can be used are described in British Patent No. 1,504,168,

  U.S. Patent No. 4,409,136 and in the US Pat.

  Canadian vets N 1,072,835 and N 1,087,477. An example

  lots of useful amorphous zeolites here can be found

in Belgian Patent No. 835,351.

  Other materials such as clays,

  particularly insoluble types in water, may

  may be useful additives in the compositions of the present invention. A particularly clay

  useful is bentonite. This material is mainly

  montmorillonite, which is an aluminum silicate

  hydrated minium in which about 1/6 of the atoms

  of aluminum may be replaced by

  gnesium and with which various amounts of hydrogen, sodium, potassium, calcium, etc., can be weakly combined. Bentonite in its form

  more purified (that is to say free of all sandstone,

  wheat, etc.) suitable for detergents contains at least 50% montmorillonite and thus its cation exchange capacity is at least about 50 to 75%.

  milliequivalents per 100 g of bentonite. Bentoni-

  Particularly preferred are bentonites from Wyoming or the western United States of America which have been sold under the names Thixo-jel 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textile materials, as

258,669?

  described in British Patents N 401 413 and N

461 221.

  Viscosity and Anti-Gel Control Agents

  Incorporation into the composition

  an effective amount of amphiphilic compounds

  low molecular weight agents acting as

  viscosity and gelling inhibition for the nonionic surfactant substantially improves

  the conservation properties of the composition.

  The amphiphilic compounds can be

  considered to have a chemical structure similar to that of liquid nonionic surfactants derived from ethoxylated and / or propoxylated fatty alcohols, but

  have hydrocarbon chain lengths relative to

  relatively short (C2 to C8) and low oxy-

  of ethylene (about 2 to 6 ethylene oxide groups

per molecule).

  Suitable amphiphilic compounds may be represented by the following general formula: RO (CH 2 CH 2 O) nH o R is a C 2 -C 8 alkyl group and n is a number

about 1 to 6 on average.

  In particular, the compounds are lower monoalkyl (C2-C5) ethers of lower alkylene glycols (C2-C3). More particularly, the compounds are

  lower monoalkyl ethers (C1 to C5) of mono-, di-

  or lower trialkylene glycols (C2-C3).

  Specific examples of amphiphilic compounds

  Suitable philes include ethylene glycol monoethyl ether C2H5-0-CH2CH pH, monobutyl ether

  diethylene glycol C4H9-O- (CH2CH2O) 2H, the monobasic ether

  tetraethylene glycol C4H7-0- (CH2CH2O) 4H and dipropyleneglycol monomethyl ether CH3-0- (CH2)

258,669?

  CHO) 2H. Especially preferred is monobutyl ether I CH 2

diethylene glycol.

  The incorporation into the composition of the lower alkylene glycol monoalkyl ether of

  low molecular weight decreases the viscosity of the compound

  easier to pour, improves stability against sedimentation and

  improves the dispersibility of the composition when

  is added to warm or cold water.

  The compositions of the present invention have better viscosity and stability characteristics and remain stable and versal to

  temperatures as low as about 5 C or less.

Stabilizing agents

  In one embodiment of the present

  the invention, the physical stability of the suspension of

  or adjuvant detergency compounds and any other

  suspended additive, for example the white

  chiment, etc., in the liquid vehicle is improved by the presence of a stabilizing agent which is an alkanol ester of phosphoric acid or an aluminum salt

of a higher fatty acid.

  In some formulations, it is possible

  improve the stability of the composition by incorporating

  a small but effective amount of a phosphorus compound

  acid organic phore having a -POH acid group, for example a phosphorous acid partial ester and

an alkanol.

  As described in the French patent application

  85.05319, the organic phosphorus compound

  that acid having a -POH acid group can increase the stability of the detergency builder suspension

  in the nonaqueous liquid nonaqueous surfactant.

  The acidic organic phosphorus compound may be, for example, a partial phosphoric acid ester and an alcohol such as an alkanol having a lipophilic character, for example having more than 5 atonims of

  carbon, for example 8 to 20 carbon atoms.

  A particular example is a partial ester of phosphoric acid and a C16 to C18 alkanol (Empiphos 5632 from Marchon); it consists of about

  % of monoester and 65% of diester.

  Incorporation of very small quantities

  of the acidic organic phosphorus compound makes the suspension

  much more stable vis-à-vis sedimentation

  at rest, while remaining versable, while

  for a low stabilizing concentration, for example

  less than about 1%, its plastic viscosity

usually increases.

  The stability and the anti-sedimentation properties of the composition can be further improved by the addition of a low and effective amount of a salt.

  of aluminum of a fatty acid greater than the composition.

  Stabilizers of the aluminum salt type

  are the subject of the French patent application

85.02815 of February 28, 1986.

  Higher aliphatic fatty acids

  preferred are about 8 to about 22 carbon atoms.

  preferably, about 10 to 20 carbon atoms, and more preferably about 12 to 18 carbon atoms. The aliphatic radical can be saturated or unsaturated, and it can be straight-chain or branched. As in

  the case of nonionic surfactants, it is also possible to

  mixtures of fatty acids, such as those

  from natural sources, such as tallow fatty acid, coconut fatty acid, etc. Examples of fatty acids from which the stabilizing aluminum salts can be formed include decanoic acid, dodecanol acid,

  palmitic acid, myristic acid, stearic acid,

  oleic acid, Eicosanoic acid, tallow fatty acid, coconut fatty acid, mixtures of these

258,669?

  acids, etc. The aluminum salts of these acids are generally commercially available, and they are preferably used in the form of three acid residues, for example aluminum stearate.

  in the form of Al aluminum tristearate (C17H35COO) 3.

  Salts with an acid residue, for example

  aluminum arate, Al (OH) C 17 H 35 COO) and salts with

  two acid residues, for example the distearate of

  luminium, Al (OH) (C17H35C00) 2 and mixtures of two

  or three of the aluminum salts with one, two or three

  Acid sidus can also be used. How-

  However, it is particularly preferred that the three-residue aluminum salt of the acid be at least 50%, preferably at least 50%, more preferably at least 80%, of the total amount of aluminum salt.

of fatty acid.

  Aluminum salts, as mentioned above,

  are commercially available and can be

  easily, for example by saponification of a fatty acid, for example animal fat, stearic acid, etc., and then treatment of the resulting soap with alum, alumina, etc. Although the Applicant does not wish to be bound to any particular theory as to how

  whose aluminum salt acts to prevent sediment

  In the case of suspended particles, it is assumed that the aluminum salt increases the wettability of the solid surfaces by the nonionic surfactant. This augmentation

  wettability therefore allows suspended particles to

  to stay more easily in suspension.

  It only takes very small amounts of

  stabilizing aluminum salt to obtain a clear

  improvement of physical stability.

  In addition to its action as a physical stabilizer, the aluminum salt has additional advantages over other physical stabilizers, is non-ionic and is compatible with the nonionic surfactant and does not adversely affect the detergency of the product. whole composition;

  it has some anti-foaming effect; he can meet

  force the action of fabric softeners and he

  gives suspensions a longer life

  laxation. Whitening Agents Bleaching agents are broadly classified for convenience into chlorine bleaches

  and oxygen bleaching agents. Agents of white

  Chlorinated chlorides are represented by hypochlorite

  sodium (NaOCl), potassium dichloroisocyanurate

  sium (59% available chlorine) and trichlo-

  isocyanuric (95% available chloride). Oxygen bleaches are preferred and they are represented by percompounds which release

  hydrogen peroxide solution. Preferable examples

  res include perborates, percarbonates and

  sodium and potassium phosphates and the monopersulphon

  potassium fate. Perborates, in particular sodium perborate monohydrate, are particularly preferred. The peroxygen compound is preferably used in admixture with an activator. Activators

  which can lower the operating temperature

  For example, US Pat. No. 4,264,466 or US Pat. No. 4,364,466 disclose the effectiveness of the peroxidic bleaching agent.

  N 4 430 244. Polyacetyl compounds are the active ingredients

  vaters we prefer; among them, we still prefer

  more compounds such as tetraacetyl-

  ethylene diamine ("TAED") and pentaacetyl glucose.

  Other useful activators include, for example, acetylsalicylic acid derivatives,

  ethylidene benzoate acetate and its salts, ethylidene

  n-carboxylate and its salts, alkyl- and alkenyl-succinic anhydrides, tetraacetylglycouril ("TAGU") and their derivatives. Other useful classes of activators are described, for example, in U.S. patents.

  A. Nos. 4,111,826, 4,422,950 and 3,401,789.

  The activator of the bleaching agent

  generally reacts with the peroxygen compound in

  a bleaching peroxyacid in the washing water

  ge. It is best to include a sequestering agent

  high complexing capacity in order to inhibit any reaction

  undesirable interaction between this peroxyacid and the hydrogen peroxide in the washing solution in the presence

of metal ions.

  Sequestering agents appropriate in

  this purpose include the sodium salts of the acid ni-

  trilacetic acid (NTA), ethylene-diamine

  tetraacetic acid (EDTA), diethylene triamine

  pentaacetic acid (DETPA), diethylene triamine

  pentamethylenephosphonic acid (DTP24P) sold under

  as commercial Dequest 2066; and the ethylene-acid

  diamine-tetramethylenephosphonic (EDITEMPA). The sequestering agents can be used alone or as a mixture. In order to avoid a loss of peroxide

  bleaching, for example sodium perborate, results

  For both enzyme decomposition, for example catalase enzyme, the compositions may further contain an enzyme inhibitor, i.e., a compound capable of inhibiting decomposition under the action of enzyme, bleaching peroxide. Suitable inhibitors are described in the US Pat.

U.S.A. 3,606,990.

  As a particular inhibitor of interest, mention may be made of hydroxylamine sulfate and other water-soluble hydroxylamine salts. In the preferred nonaqueous compositions of the present invention,

  appropriate amounts of the inhibitory hydroxylamine salts

  can be as low as about 0.01 to 0.4%. However, in general, appropriate amounts of enzyme inhibitor are up to about 15%, by

  0.1 to 10% by weight of the composition.

  In addition to detergency adjuvants,

  Other additives or detergent auxiliaries may be present in the detergent product in order to impart to it other desired functional or aesthetic properties. Thus, minor amounts of soil suspending or anti-redeposition agents may be included in the formulation, for example polyvinyl alcohol,

  fatty amides, sodium carboxymethylcellulose

  that, hydroxypropylmethylcellulose. An anti-agent

  preferred redeposition is carboxymethylcellulose (CMC) sodium having a 2: 1 ratio of CM / MC, which

  is sold under the trademark Relatin DM 4050.

  Optical brighteners can be used for cotton, polyamide and polyester fabrics. Suitable optical brightening agents include stilbene, triazole

  and benzidine sulphone, in particular triazinyl-

  sulfonated stilbene, sulfonated naphthotriazole-stilbene, benzidene-sulfone, etc., those

  prefers being the combinations of stilbene and triazole.

  Preferred brightening agents are Brithtener N4 which is a dimorphilinodianilino-stilbene sulphonate and

  Tinapal ATS-X that are well known in the tech.

  Enzymes can be used, preferably

  proteolytic enzymes, such as subtilisin, bromelain, papain, trypsin and pepsin, as well as amylase-type lipase enzymes and mixtures thereof. Preferred enzymes include a protease suspension, an esterase suspension and amylase. A preferred enzyme is Esperas SL8 which is a protease. It is also possible to add antifoam agents, for example silicone compounds, such as

  than Silicane L 7604 in small effective amounts.

  Bactericides can be used for

  tetrachlorosalicylanilide and hexchlorinated

  phenes, fungicides, dyes, pigments (water-dispersible), preservatives,

  ultraviolet absorbers, anti-yellowing agents

such as sodium carboxymethylcellulose, pH modifiers and pH buffers, color-preserving bleaches,

  perfumes and brighteners such as ultramarine blue.

  The composition may also contain an insoluble mineral thickener or dispersant of

  very large contact area, for example

  finely divided particle of ex-

  very small (for example, 5 microns in diameter, such as that sold under the name

  Aerosil) or other very large mineral substrates

  described in U.S. Patent No. 3,630,929,

  in proportions of 0.1 to 10%, for example 1 to 5%.

  However, it is preferred that the compositions which form peroxyacids in the wash bath (eg

  for example, compositions containing a peroxy compound

  gene and an activator for it) are sensitive

  free from such compounds and other silicates;

  It has been found, for example, that silica and silicas

  cates promote an undesirable decomposition of the

roxyacide.

  In one embodiment of the invention,

  the stability of the adjuvant detergency salts

  in the composition during storage and dispersion.

  sability of the composition in water are improved by grinding and reducing the particle size of

  solid detergency builders to less than 100 micro-

  meters, preferably less than 40 micrometers and more preferably less than 10 micrometers. Solid detergency builders, for example alkali metal polyphosphates, are generally provided in

  particle sizes of about 100, 200 or 400

  cromètres. The liquid nonionic surfactant phase can be mixed with detergency builders

  solid before or after the grinding operation.

  In a preferred embodiment of

  the invention, the mixture of liquid nonionic surfactant

  of solid ingredients is subjected to attrition milling in which the particle size

  solid ingredients are reduced to less than

  10 micrometers, for example to a particular dimension

  average of 2 to 10 micrometers or even lower

  re (for example 1 micrometer). Preferably, less than about 10%, especially less than about 5% of

  all the particles in suspension have dimensions

  particulate matter greater than 10 micrometers. The compositions whose dispersed particles are of such small size have a better stability vis-à-vis

  from separation or sedimentation to storage

  ge. The addition of the nonionic surfactant compound to

  acidification promotes the dispersibility of

  with no corresponding decrease in stability

  dispersions with respect to sedimentation.

  For the grinding operation, it is preferable

  that the proportion of solid ingredients is suf-

  high (eg at least about 40%,

  for example about 50%) so that the particles

  lides are placed in contact with each other and are not too isolated from each other by

  nonionic surfactant liquid. After the crushing step

  ge, all the liquid nonionic surfactant remaining at

  incorporate can be added to the ground formulation.

  Grinders that use grinding balls

  (ball mills) or mobile crushing elements if

  have given very good results. For example, a batch attrition laboratory mill employing batch

  grinding balls made of soapstone 8 mm in diameter.

  For an operation on a larger scale, you can -

  use a continuous mill in which there are grinding balls with a diameter of 1 mm or 1.5 mm operating in a very small gap between a stator and a rotor operating at a relatively high speed (for example a CoBall mill); when using such a mill, it is advantageous to pass the mixture of nonionic surfactant and solids firstly through a mill that does not perform such a fine grinding (for example a

  colloid mill) in order to reduce the

  less than 100 micrometers (for example at about 40 micrometers) before the milling step at a

  mean particle diameter less than about 10

  crometers in the ball mill working in con-

  tinu. In preferred liquid detergent compositions for heavy laundry

  the invention, typical proportions (percentages

  based on the total weight of the composition, unless otherwise specified) ingredients are as follows: Liquid nonionic surfactant detergent: in the range of about 10 or 20 to 60, for example

  or 25 to 50 and especially 30 to 40 percent.

  The nonionic surfactant with acid termination

  can be omitted; however, it is best to

  add it to the composition in an amount in the

  range from about 0 to 30, for example 5 to 25, and

  5 to 15 percent; carboxymethyloxysuccinic acid detergent builder salt in the range of about 5 to 50, e.g. 10 to 40, and especially 25 to 35 percent; or acid adjuvant adjuvant salt

  alginic in the range of about 5 to 50, e.g.

  10 to 40, especially 25 to 35 percent.

  Heptonic acid detergency builder salt

  that of carboxymethyloxysuccinic acid or of

  in the range of about 5 to 50, for example

  ple 10 to 40, and especially 25 to 35 percent.

  Polyphosphate-type detergency builder

  phate: in the range of about 0 to 50 percent,

  for example 0 to 30 and in particular 5 to 15 percent.

  Copolymer of polyacrylate and anhydride

  polymaleic acid and alkali metal salt. agent

  ti-incrustation: in the range of about 0 to 10,

  for example 2 to 8, and especially 2 to 6 percent.

  Monoalkyl alkylene glycol ether as

  anti-gelling agent: in a quantity in the inter-

  range from about 0 to 20, for example 5 to 15, in particular

8 to 12 percent.

  Phosphoric acid alkanole ester stabilizer: in the range of 0 to 2.0 or

  0.1 to 1.0, for example 0.10 to 0.5 percent.

  Fatty acid aluminum salt stabilizing agent: in the range of about 0 to 3.0, for example 0.1 to 2.0, and especially 0.5 to 1.5 percent. It is preferred that at least one of the stabilizing agents of the phosphoric acid ester type

  or aluminum salt is present in the composition.

  Bleaching agent: in the range of about 0 to 35, for example 5 to 30, and especially 8

at 15 percent.

  Activator of the bleaching agent: in the range of about 0 to 25, for example 3 to

, and especially 4 to 8 percent.

  Sequestering agent for the bleaching agent

  in the range of about 0 to 3.0, preferably

  0.5 to 2.0, and in particular 0.5 to 1.5 percent.

  Anti-redeposition agent: in the interval

  from about 0 to 3.0, for example 0.5 to 2.0, and especially

0.5 to 1.5 percent.

  Optical brightener: in the interval

  from about 0 to 2.0, for example 0.1 to 1.5, and especially

0.3 to 1.0 percent.

  Enzymes: in the range of about 0 to 3.0, for example 0.5 to 2.0, and especially 0.5 to 1.5

percent.

  Perfume: in the range of about 0 to 2.0, for example 0.10 to 1.0, and especially 0.5 to 1.0

percent.

  Colorant: in the range of about 0 to 1.0, for example 0.0025 to 0.050, and especially

0.25 to 0.0100 percent.

  The various additives previously mentioned

  may optionally be added to par-

  to the desired function of the added materials.

  Mixtures of surfac-

  acid-terminated nonionic acid and anti-

  gelling of the alkyl ether type of alkylene-gly-

  col and, in some cases, can benefit from

  the use of such mixtures alone, or with

  mixture of a stabilizing and anti-sedimentary agent

  cation, for example an alkanol ester of phosphoric acid. We will choose additives, so

  compatible with the main constitutions

  killers of the detergent composition. In the present

  As mentioned above, all the proportions and percentages are expressed by weight relative to the totality of the formulation or composition,

unless otherwise specified.

  The liquid nonionic detergent composition

  that, non-aqueous, concentrated, of the present invention

  is easy to distribute in the water of the machine to

  worm. Household washing machines currently in use normally use about 175 grams or

  250 grams of powdered detergent to wash a

  complete laundry. According to the present invention, only about 77 ml or about 100 grams of the

  concentrated liquid nonionic detergent composition.

  In a preferred embodiment of the invention, a typical detergent composition is

  formulated using the ingredients listed below

  under: Nonionic surfactant detergent Acid-terminated surfactant Alkali metal salt of heptonic acid detergency builder; metal salt

  carboxymethyloxysuccinic acid alkali

  as a detergency builder; or alkali metal salt of alginic acid detergency builder Anti-scale agent (Sokalan CP-5)

  Polyphosphate (adjuvant salt

  gence) Alkylene glycol monoalkyl ether Alkanolic phosphoric acid ester (Empiphos 5632) Anti-redeposition agent (Relatine

DM 4050)

  Perborate of bleaching alkali metal

  Activation of the bleaching agent

(TAED)

  Sequestering Agent (Dequest 2066) Optical Brightening Agent (ATS-X) Enzymes (Protease Escherase SL8) Fragrance% by weight -40 -15 -35 0-10 0-30 8-12

0,1-O, 5

  0-3.0 8-15 4-8 0-3.0 0.05 or 0.3-1.0

0.5-1.5

0.5-1.0

  The following nonlimiting examples illustrate

the present invention.

Sodium salt of Heptonic Acid

EXAMPLE 1

  A detergent composition of liquid, non-aqueous concentrated nonionic surfactant is formulated

  from the following ingredients in

diqu6es:

258,669?

% in weight

  A mixture of C13-C15 fatty alcohol

  densified with 7 moles of propylene oxide and 4 moles of ethylene oxide and C13-C15 fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide T7 Surfactant Surfactant T9 Product acid-terminated reaction

  of Bobanol 91-5 with succinate anhydride

  Sodium salt of heptonic acid

  Diethylene monobutyl ether

  glycol Ester alkanolic phosphoric acid (Empiphos 5632) Antiincrustation Agent (Sokalan CP-5)

  Sodium perborate monohydrate of white

  chiment Sodium carbonate Tetraacetylethylenediamine (TAED) as a bleach activator Sequestering agent (Dequest 2066) Optical brightener (Tinopal ATS-X) Anti-redeposition agent (Relatin DM 4050) Esterase suspension (Esperase SL8) Fragrance Colorant 13.5, 0, 0, 0 28.7, 0 0.3 4.0 9.0 0.9 4.5 1.0 0.5 1.0 1.0

.5925

0.0075

100.00

  The formulation is milled for about 1 hour to reduce the particle size of the detergency builder salts in suspension to less than microns. The formulated detergent composition is stable and non-gelling at storage and

  has a great detergency.

  The wording has a limit of

  5.0 Pa and an apparent viscosity of 1.1 Pa.s-1.

EXAMPLE 2

  In order to demonstrate the effect on the incrusta-

  substitution of sodium polyphosphate by an equivalent amount of detergency builder

  sodium heptonate, the formulation of the composition

  The detergent solution of Example 1, containing 28.7% by weight of sodium heptonate, is compared in a machine with

  wash with the same composition in which the heptona-

  is replaced by 28.7% by weight of poly-

sodium phosphate.

  The washing cycles are carried out with

  concentrations of 1 to 9 g / liter of each of the

  detergents containing respectively hepto-

  sodium nate and sodium polyphosphate.

  After 6 washing cycles

  with each of the detergent compositions in a

  China to wash, we measure the degree of incrustation,

  that is to say the percentage of ash deposited resulting

  As. The percentage of ash deposited is

  determined by calcination of washed parts.

  The observed results are indicated on the graph illustrated in Figure 1 of the drawings and

  show that at concentrations of

  from 1 to 5 g / l of washing water, the sodium heptonate

  dium is substantially greater than sodium polyphosphate to prevent scale or deposit of

  ashes. At concentrations of dftergenic composition

  From about 5 to 9 g / l of wash water, the behavior of sodium heptonate and sodium polyphosphate detergency builders is about the same as

  to their anti-incrustation properties.

EXAMPLE 3

  In order to demonstrate the effect on incrustation build-up of polyphosphate substitution

  sodium by an equivalent amount of sodium heptonate

  Detergent builder dium, the detergent composition of Example 1, containing 28.7 weight percent of sodium heptonate is compared in cycles of

  repeated washing in a washing machine with the same

  In which sodium heptonate is substituted

  28.7 percent by weight of sodium polyphosphate

  dium. Repeated washing cycles are carried out at concentrations in the wash water of 5 g / l of

  each of the detergent compositions for twelve cycles

  washing keys. The accumulation of incrustations,

  ie the ash accumulation percentage, is measured in each washing machine after 3, 6, 9 and

12 washes.

  The results obtained with regard to

  encrustations are shown on the graph

  illustrated in Figure 2. With regard to the accumu-

  the encrustations, there is no accumula-

  with sodium heptonate, while

  a slight accumulation with the polyphosphate of

dium adjuvant detergency.

  It is also possible to use alkali metal heptonates as detergency builder salts

  to replace in whole or in part the polyphosphoric

  phates in powdered detergent compositions, and in aqueous detergent compositions and in

  cream, while getting good results.

  Trisodium salt of Carboxymethyloxysuccinic acid

EXAMPLE 4

  A detergent composition is

  non-ionic, liquid, non-aqueous faction, concentrated at

  from the following ingredients in the quantities

  cated. % by weight Mixture of C13-C15 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide and C13-C15 fatty alcohol condensed with 5 moles of oxide

  of propylene and 10 moles of

  ene Surfactant T 7 Surfactant T 9 Acid-terminated reaction product

  of Dobanol 91-5 with succinic anhydride

picnic

  Trisodium salt of carboxymethyloxy acid

  succinic Diethylene Glycol Monobutyl Ether Phosphoric Acid Alkanolic Ester (Empiphos 5632) Anti-scale Agent (Sokalan CP5)

  Sodium perborate monohydrate of white

  Tetraacetylethylenediamine (TAED) as a bleach activator Sequestering agent (Dequest 2066) Optical brightener (Tinopal ATS-X) Anti-redeposition agent (Relatin DM 4050) Escherase suspension (Esperase SL8) Fragrance Colorant 13.5 , 0, 0, 0 29.6, 0 0.3 4.0 9, 0 4.5 1.0 0.5 1.0 1.0

.5925

0.0075

100.00

  The formulation is milled for about 1 hour to reduce the particle size of the builder salts in suspension to less than 40 microns. It is found that the detergent composition

  formulated is stable and does not gel at the storage

  wise and has great detergency.

  The wording has a limit of

  7.5 Pa and an apparent viscosity of 0.4 Pa.s-1.

EXAMPLE 5

  In order to disassemble the effect on the encrustation of the substitution of sodium tripolyphosphate by

  an amount equivalent to the adjuvant effect of deter-

  trisodium carboxymethyloxy succinate, the formulation of the detergent composition

  of Example 4 containing 29.6% by weight of carboxy-

  trisodium methyloxy-succinate for use in a washing machine with the same composition

  in which the trisodium carboxymethyloxy succinate

  that is replaced by 29.6% by weight of tripolyphos-

Sodium phate.

* Washing cycles are carried out at wash water concentrations of 1 to 9 mg / l of

  each of the respective detergent compositions.

  After using each composition

  detergent in a washing machine, measure the

  resulting incremental value, that is to say the percentage

  ash floor deposited. The measurement of the percentage of

  deposited ash is determined by calcining

these washed.

  The observed results are shown on

  the graph in Figure 3 and show that

  centrations of the detergent composition of 1 to 5 g / l in the washing water, carboxymethyloxy succinate

  trisodium is significantly greater than tripolyphos-

  sodium pest to prevent encrustation or ash deposition. At concentrations of detergent composition of about 5 to 9 g / l in the wash water,

  the behavior of trisodium carboxymethyloxy succinate

  that and sodium tripolyphosphate adjuvants de

  tergence is about the same when it comes to

anti-incrustation properties.

EXAMPLE 6

  In order to demonstrate the effect on the accumu-

  incrementation of the substitution of tripolyphos-

  sodium pest with an amount equivalent to the action of trisodium carboxymethyloxy succinate detergency builder, the detergent composition of

  Example 4 containing 29.6 percent by weight of car-

  trisodium boxymethyloxy-succinate in cycles of

  machine wash with the same composition in which

  trisodium carboxymethyloxy succinate is replaced by

  29.6 parts by weight of sodium tripolyphosphate

dium.

  Repeated wash cycles are performed

  at concentrations of 5 g / l in the wash water of each of the detergent compositions for twelve

  washing cycles. The accumulation of incrustation

  the percentage of ash accumulation is measured in each washing machine after 3, 6, 9 and

12 washes.

  The results of the accumulation of incrusta-

  obtained are shown on the graph below.

  4. With regard to incrustation accumulation,

  no accumulation with carboxymethyl was observed

  trisodium oxy-succinate, while a slight

  manages accumulation with sodium tripolyphosphate.

  The carboxymethyloxy-succinate of

  hog detergency builders may also be used to replace some or all of the polyphosphates in powder detergent compositions, and in aqueous detergent compositions

  and in creams, giving good results.

Sodium salt of Alginic Acid

EXAMPLE 7

  A nonionic, liquid, non-aqueous, concentrated surfactant detergent composition is formulated

  from the following ingredients in

cracked:% by weight

  Mixture of C13-C15 fatty alcohol

  densified with 7 moles of propylene oxide

  and 4 moles of ethylene oxide and

  cool C13-C15 fat condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide 13.5 Surfactant T 7 Surfactant T 9 Acid-terminated reaction product

  of Dobanol 91-5 with succinic anhydride

  Sodium salt of alginic acid

  Monobutyl ether of diethylen-gly-

  Col. Ester 4lcanolic phosphoric acid (Empiphos 5632) Antiincrustation Agent (Sokalan CP-5)

  Sodium perborate monohydrate of white

  tetraacetylethylenediamine (TAED) as, 0, 0, 0 29.6, 0 0.3 4.0 9.0 bleach activator 4.5 Sequestering agent (Dequest 2066) 1.0 Optical brightener (Tinopal) ATS-S) 0.5 Anti-Redeposition Agent (Relatin DM 4050) 1.0 Protease (Esperase SL8) 1.0 Fragrance 0.5925 Dye 0.0075.00 The formulation is milled for about 1 hour to reduce the particle size suspending builder salts in suspension at less than 40 micrometers. It is found that the formulated detergent composition is stable and does not gel

  storage and has great detergency.

  The wording has a limit of

  flow of 4.7 Pa and an apparent viscosity of

0.46 Pa.s-1.

EXAMPLE 8

  In order to demonstrate the effect on the incrusta-

  substitution of sodium tripolyphosphate

  by an equivalent amount with an adjuvant effect

  sodium alginate, the detergent composition formulation of Example 7, containing

  29.6% by weight of sodium alginate for use in

  China to be washed with the same composition in which sodium alginate is replaced by 29.6% by weight

of sodium tripolyphosphate.

  The washing cycles are carried out

  concentrations in the wash water of 1 to 9 g / liter of

  detergent compositions.

  After having used each composition de-

  in a washing machine, we measure the degree of incrustation resulting, that is to say the percentage

  ashes deposited. Measuring the percentage of cen-

  The amount deposited is determined by calcining washed parts. The observed results are shown on

  the graph in Figure 5 and show that

  concentration of detergent composition from 1 to 5 g / l

  in the washing water, sodium alginate is sensi-

  significantly higher than sodium tripolyphosphate to prevent encrustation or ash deposition. AT

  concentrations of detergent composition of

  5 to 9 g / l in wash water, the behavior

  sodium alginate and sodium tripolyphosphate

  detergency adjuvant lium is pretty much the same

  as regards the anti-incrustation properties.

EXAMPLE 9

  In order to demonstrate the effect on the accumu-

  incrementation of the substitution of tripolyphos-

  sodium pest with an equivalent amount, as a detergency builder, of sodium alginate,

  compare the detergent composition of Example 7

  holding 29.6 percent by weight of sodium alginate during repeated machine wash cycles with

  the same composition in which the alginate of

  dium is replaced by 29.6 per cent by weight of tri-

sodium polyphosphate.

  Repeated wash cycles are conducted at concentrations of 5 g / l of wash water of each of the detergent compositions for twelve wash cycles. The accumulation of incrustation, that is to say

  the percentage of ash accumulation is measured

  for each washing machine after 3, 6, 9 and 12

washings.

  The results concerning the incrustation accumulation obtained are indicated on the graph of Figure 6. As for the accumulation

  incrustation, there is hardly any evidence of

  with sodium alginate, while

  a slight accumulation with the tripolyphospha-

te of sodium. Alginates of alkali metal adjuvants of detergent can also

be used to

  replace, in whole or in part, the polyphospha-

  detergency builders in the compositions de-

  tergents in powder form, and in detergent compositions

  water and cream, giving good results.

  The formulations of Examples 1, 4 and 7 can be prepared without grinding the detergency builder salts and suspended solid particles to a small particle size, but the best results are obtained by grinding the formulation to

  to reduce the size of the solid particles

pension.

  The detergency builder salts can be used as supplied, or the detergency builder salts and the suspended solid particles can be milled or partially milled before being mixed with the nonionic surfactant. The grinding can be done in part before

  the end of mixing and to be completed after the

  ge, or the whole grinding operation can be done

  after mixing with the liquid surfactant.

  The formulations contain adjuvant particles

  detergents and suspended solids

  less than 100 microns, or preferably less than

  at 40 micrometers in diameter.

  It goes without saying that the invention is not

  adapted to the described embodiments and that it is capable of various variants without departing from

its frame.

Claims (11)

  1. Non-aqueous liquid detergent composition   for heavy laundry, characterized in that it comprises: at least one liquid nonionic surfactant detergent and   a carbohydrate additive adjuvant salt xyméthyloxy succinate.   2. A detergent composition according to the   cation 1, characterized in that it comprises at least one of the group consisting of: an anti-gelling agent of the acid-terminated nonionic surfactant type, an alkylene glycol monoether, and   a stabilizing agent of the alkano ester type phosphoric acid.   3. Detergent composition according to the   cation 1, characterized in that it comprises 5 to 50 percent of a carboxymethyloxy-succinate salt detergency builder.   4. laundry detergent composition according to claim 1, characterized in that it has a low or no polyphosphate content and in that it comprises: at least one liquid nonionic surfactant in an amount of about 25 to 50Z, an acid terminated nonionic surfactant in an amount of about 5 to 25X,   a carboxymethyloxy succinate salt   detergent builder in an amount of about 10 to Z,   an alkylene glycol monoether in a quantity   from about 5 to about 15Z, a builder polyphosphate in an amount of about 0 to about 30Z, and an alkanolic acid ester of phosphoric acid.   an amount of about 0.1 to 1.OZ.   5. laundry detergent composition according to claim 4, characterized in that it comprises: an alkali metal perborate monohydrate bleaching in an amount of about 5 to 30Z,   of tetraacetylethylenediamine   bleaching agent in an amount of about 3 to Z, and optionally one or more detergent additives selected from the group consisting of   anti-incrustation agent, an anti-redeposition agent.   a sequestering agent for the bleaching agent,   optical brighteners, enzymes and a perfume.   6. Detergent composition according to claim   cation 4, characterized in that carboxymethyloxy-   succinate is represented by the formula: NaOOC - CH - COONa t CH30 - CH COONa Laundry detergent composition according to claim 4, characterized in that the alkanolic phosphoric acid ester comprises a   C16-C18 alkanolic ester of phosphoric acid.   8. Detergent composition according to the   4, characterized in that it contains a polyphosphate detergency builder in a quantity about 5 to 15 percent.   9. Non-aqueous liquid detergent composition   is free from phosphate detergent builders for heavy duty laundry, characterized in that it comprises about 30 to 40Z of nonionic surfactant, about 5 to 15Z of acid-terminated surfactant, about 23 to 35X of trisodium salt of carboxymethyloxy acid -succiniqUe, about 8 to 12Z of alkylene glycol monobutyl ether, about 0.1 to 0.5X of C16-C18 alkanolic phosphoric acid ester, about 8 to 15Z of sodium perborate monohydrate bleaching, about 4 to 8Z of tetraacetylene diamine   (TAED) as a bleach activator.   10. Detergent composition according to the   9, characterized in that it comprises an anti-redeposition agent, an anti-incrustation agent and   a sequestering agent for the bleaching agent.   11. A method for cleaning soiled fabrics, characterized in that it consists in bringing the soiled fabrics into contact with the detergent composition of   laundry according to claim 9.