FR2586424A1 - NONAQUEOUS LIQUID LAUNDRY DETERGENT COMPOSITIONS AND METHODS FOR CLEANING LOW TISSUE USING SAME - Google Patents

Abstract

THE INVENTION RELATES TO A NON-AQUEOUS LIQUID DETERGENT COMPOSITION FOR LARGE BLEACHING WORK, WITH LOW OR NO PHOSPHATE CONTENT. THE COMPOSITION CONSISTS OF A STABLE SUSPENSION, IN A NON-IONIC LIQUID SURFACTANT, OF A POLYMER OF HYDROXY-ACRYLIC ACID OR OF A SALT OF HYDROXY-ACRYLIC ACID AS A DETERGENCY ADHESIVE OR OF A POLYACETAL-CARBOXYLIC ADDITIONAL OF SALT . VARIOUS ADDITIVES MAY BE INCLUDED INCLUDING IN PARTICULAR A NON-IONIC SURFACTANT WITH ACID TERMINATION AS ANTI-SEDIMENTATION AGENT, A MONOALKYL ETHER OF ALKYLENE-GLYCOL AND AN ANTI-SEDIMENTATION AGENT. APPLICATION: DETERGENTS.

Description

The present invention relates to composi-

  non-aqueous liquid solutions for the treatment of tissues. More particularly, the present invention relates to phosphate-free or low-phosphate non-aqueous liquid detergent compositions for laundering laundry, containing a suspension of a hydroxy-acrylic acid polymer or a salt of a such acid as a detergent builder or

  of a polyacetal carboxylate as an adjuvant salt of

  tergence in nonionic surfactants, which compositions are stable to phase separation and gelation and can be easily poured, and the use of these compositions

for cleaning soiled fabrics.

  Nonaqueous liquid detergent compositions for heavy laundry work are

  well known in practice. For example, composi-

  such a type may include a surfactant

  non-ionic quid in which particles are dispersed

  particles of a detergency builder, as described, for example, in U.S. No. 4,316,812, N'3

  Nos. 630,929 and 4,264,466 and in British patents

  Nos. 1 205 711, 1 270 040 and 1 600 981.

  The U.S. Patent No. 4,450,089 discloses a particulate detergent whitening composition

  comprising a mineral bleaching agent of the type

  oxygenated and a hydroxyl acrylate polymer to stabilize

  the bleaching agent, and the U.S. Patent.

  No. 4,445,249 discloses a detergent composition of

  particulate bleaching comprising a bleaching agent

  organic chorant of the peroxyacid type and a polymer

  of hydroxy acrylate to stabilize the bleaching agent

  chiment. The U.S. Patent No. 3,825,498 describes

  the use of a polyhydroxy-carboxylic acid polymer

  xyl as a substitute for the salts

  phosphates or polyphosphate detergents used in aqueous or particulate powder detergent compositions for washing dishes.

  The U.S. Patent No 3 706 672 and the patent

  United States vet No. 3,922,230 discloses the use of polyacrylic polymers as substitutes for phosphate or phosphate-based detergency builder salts.

  polyphosphate in detergent compositions.

  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 tendency

  polyphosphates to hydrolyze in pyro-

  ortho-phosphates which constitute adjuvants

tergence less interesting.

  In addition, the polyphosphate content of

  laundering tergents was held responsible

  the high phosphate content of

  face. Higher phosphate content in surface water has been shown to contribute to increased growth

  algae resulting in a harmful modification of the

biological balance of water.

  Recently, government legislation

  promulgated aimed at reducing the amount of poly-

  phosphates in laundry detergents and, in some jurisdictions, polyphosphates

  were a problem, required that the deter-

  laundry workers do not contain any

  polyphosphate builder additives.

  Liquid detergents are often considered

  are considered more convenient to use than particulate or dry powder products and, as a result, have been a significant success for consumers. They can be dosed easily, they dissolve quickly in the water of

  washing, they can be easily applied in

  concentrated dispersions or dispersions on

  clothes & clean and do not give off dust, and they usually occupy little space to

  storage. In addition, liquid detergents can

  to contain, in their formulation, materials that could not withstand the drying operations

  without deterioration, which materials would be

  advantageously used in the manufacture of

  particulate detergent products. Although they have

  Many advantages over single or particulate solids, liquid detergents often have some inherent disadvantages that must be overcome to achieve

  commercially acceptable detergents.

  Thus, some of these products are separated at

  posage and others separate upon cooling and can not easily be redispersed. In some cases, the viscosity of the product changes and the product becomes either too thick to be poured or liquid to the point of resembling water. Some limpid products become cloudy and others become

gel at rest.

  In addition to the problem of sedimentation or phase separation, liquid detergents

  non-aqueous laundering-based surfactants

  Non-ionic materials have the disadvantage that nonionic surfactants tend to gel when added to cold water. This is a

  particularly acute problem during

  of European automatic washing machines in which the user places the

  detergent laundry composition in a

  dispensing system (eg a dispensing drawer

  tribution) of the machine. During the 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

  particularly during the winter months, when

  detergent position and water introduced into the dis-

  tributor are particularly cold, the viscosity

  detergent increases strongly and a gel is formed.

  As a result, part of the composition is not com-

  completely swept out of the dispenser during the

  operation of the machine, and a deposit of

  accumulates during repeated washing cycles,

  finally forcing the user to scan the disc

tributor with hot water.

  The phenomenon of gelation can also

  This may be a problem when washing in cold water, as may be recommended for certain synthetic and delicate fabrics or fabrics that may 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 problems of the felification have been proposed, for example by diluting the ionic liquid surfactant with certain solvents.

  acting on viscosity and certain inhibiting agents

  Examples of gelling agents, such as lower alkanols, for example ethyl alcohol (see US Pat. No. 3,953,380), alkali metal formates and adipates (see US Pat. No. 4,368,147), are incorporated herein by reference. hexylene glycol, polyethylene glycol, etc., and

  by a modification and an optimization of the.

  structure of nonionic surfactants. For example

  modification of nonionic surfactants, we have

  had a particularly advantageous result in

  modifying the hydroxyl-terminated portion of the nonionic molecule. Advantages of introducing a carboxylic acid at the end of the nonionic surfactant include inhibition of gelation at the time of dilution; a decrease in the drop point of nonionic surfactants; and forming anionic surfactant by neutralization in the wash liquor. Optimization of the nonionic structure focused on the chain length of the hydrophobial moiety and the number and constitution of 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 slight tendency to

limited to the formation of a gel.

  Nevertheless, we want to improve both the

  stability and inhibition of gelation of

  nonaqueous liquid solutions without phosphate and

  phosphate content, for the treatment of tissues. According to the present invention, a

  very non-aqueous liquid detergent composition

  centric low-phosphate laundry

  and more particularly free of adjuvant deter-

  polyphosphate type, by dispersing a polymer of hydroxyacrylic acid or a salt of such an acid

  as a detergency builder or a polyacetal-carboxy-

  as a detergency adjuvant salt in a detergent

a liquid nonionic surfactant.

  Hydroxyacrylic acid polymers or a salt of such acid as detergency builders used in accordance with one embodiment of the present invention are well known. The method of making the hydroxy acrylic acid polymer and salt of such an acid and its use for stabilizing peroxygen bleaches or bleach peroxyacids in detergent compositions are described in U.S. Pat. No. 4,450,089 and

  No. 4,455,249, which are hereby incorporated by reference.

  Lower molecular weight polymers of hydroxy acrylic acid or salt of such acid are readily biodegradable. The hydroxy acrylic acid and salt polymers of such an acid are good stabilizers for bleaching agents and serve as effective anti-scaling agents. Polymers

  of hydroxy acrylate are adjuvant salts of deter-

  particularly good because of their high

  see sequestering calcium and magnesium ions in

washing water.

  The hydroxy-acrylate polymer used as detergency builder according to the present invention contains monomeric units of formula:

R1 0011

  Wherein R1 and R2 are the same or different and represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and M represents hydrogen, or an alkali metal, alkaline earth metal or alkali metal cation. 'ammonium. The degree of polymerization, i.e. the value of n, is generally determined by the limit compatible with solubility.

polymer in water.

  The polyacetal carboxylates used according to

  another embodiment of the present invention

  are also well known. The manufacturing process

  cation of builder salts is described in U.A. Nos. 4,315,092 and 4,144,226 and the use of the polyacetal carboxylate as

  adjuvant detergency salts is described in the literature.

United States vet No. 4,146,495.

  The polyacetal carboxylates are hydrosolu

  rapidly depolymerize in a neutral or non-alkaline medium to form

  Molecular weights that are easily biodegradable.

  The polyacetal carboxylates are therefore used in formulations which, at the time of addition to washing water, normally have a pH greater than 7, for example from about 8 to 10, for example 9 to 10. Although the polyacetal carboxylates as used in an alkaline medium are effective detergency builder salts, when the waste water of the bath

  aqueous wash is discharged to the sewer or other system.

  wastewater collection and that the washing water is neutralized, the polyacetal carboxylates

  are depolymerized into small fragments that are easily

  biodegradable. The polyacetal carboxylates are particularly good builder salts of detergency because of their high sequestering power

  calcium and magnesium ions in the wash water.

  The polyacetal carboxylate builders used in the present invention are represented by the general formula: wherein M is an alkali metal or ammonium cation, n is at least 4, and R 1 and R 2 are chosen to be individually stable groups that stabilize the polymer against alkaline solution depolymerization and are selected to be compatible with the ingredients of the nonionic liquid detergent composition of the present invention. A commercially available polyacetal carboxylate builder is sold by Monsanto Chemical Company under the trademark

  Commercial Builder U and it's a sodium salt.

  In order to improve the characteristics of

  viscosity of the composition, it is possible to add a

  Nonionic acidic facade with acid termination. To improve

  further the viscosity characteristics of the com-

  position and storage properties of the

  Viscosity improvers and anti-icing agents such as monoalkyl alkylene glycol ethers and anti-settling agents such as phosphoric acid esters and aluminum stearate can be added to the composition. In a preferred embodiment of the invention, the

  detergent composition contains a nonionic surfactant

  than acid-terminated and / or monoalkyl ether

  alkylene 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 detergency builder components of the composition are comminuted to a particle size.

  less than 100 micrometers and preferably less than

  less than 10 micrometers in order to further improve the stability of the suspension of detergency builder components in the liquid nonionic surfactant detergent. In addition, other ingredients may be

  added to the composition, such as anti-inflammatory agents

  crustation, anti-foam agents, aviation

  optics, enzymes, anti-reductive agents,

perfumes and dyes.

  Washing machines currently manufactured for domestic use normally operate at wash temperatures up to 95 ° C. About 20 liters of water are used during the wash cycles

and rinsing.

  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 80 grams (67 ml) or less of

  liquid detergent for washing a

a lot of dirty clothes.

  Therefore, in one aspect, the present invention provides a liquid composition for fattening

  laundry work without the adjuvant

  phosphate type or substantially free from

  a detergency builder, consisting of a suspen-

  alkali metal hydroxyl acrylate polymer detergent builder or alkali metal salt of polyacetal carboxylic acid detergency adjunct

  in a nonionic liquid surfactant.

  In another aspect, the invention provides a concentrated liquid detergent composition with low or no phosphate content for heavy duty laundry, which is stable, does not sediment to

  storage and does not freeze during storage.

  wise and in use. The liquid compositions of the present invention can be easily poured, are easily dosed and are easy to

  introduce in the 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

  in which the detergent consists, at least predominantly, of a liquid nonionic surfactant free of adjunctive polyphosphate

  detergent and to distribute the composition

  firing the container in an aqueous wash bath, the dispensing being carried out by directing a stream of unheated water on the composition so that the composition is entrained by the stream of water

in the wash bath.

  Detergent-free detergent-builder polyphosphate detergent compositions eliminate the problem of surface water pollution by phosphates. Non-aqueous concentrated non-aqueous surfactant laundering liquid 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 gelling and storage. The liquid compositions are easy to pour,

  easy to dose and easy to introduce into

China washing clothes.

  An object of the present invention is to provide

  a nonaqueous, non-ionic detergent composition

  liquid, non-polluting, low-grade, and in particular

  zero-polyphosphate content, for gross

  laundry, containing a polymer of hydroxy-

  acrylate as a detergency builder or a polyace-

  tal-carboxylate as a detergency builder salt in

a nonionic surfactant.

  Another object of the invention is to provide

  liquid compositions for the treatment of

  low or no polyphosphate content, which are suspensions of hydroxy-acrylate polymer

  as a detergency builder or polyacetal-carbon

  xylate as a detergency builder salt in a

  non-aqueous and are stable in storage, and are easy to pour and disperse in water

cold, warm or hot.

  Another object of the present invention

  to formulate strong non-ionic surfactant, non-aqueous liquid detergent compositions with low or no polyphosphate content, for heavy laundering work, which can be poured at any temperature and can be repeatedly dispersed from the device distribution of automatic washing machines

  European style without clogging or obstructing

  tributor even during the winter months.

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

  low or no polyphosphate content,

  non-ionic liquid non-ionic detergent detergent

  for heavy laundering work, which includes

  an effective amount of a hydroxyl polymer

  acrylate as a detergency builder or a polyaceutical

  tal-carboxylate 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 phosphoric acid ester and / or an aluminum fatty acid salt in an amount

  sufficient to increase the stability of the composi-

  to prevent the sedimentation of

  detergency builder particles, 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

  affected by preparing a specific composition

  low or no polyphosphate content, by adding to the nonaqueous liquid nonionic surfactant an effective amount of an alkali metal hydroxyacrylate polymer as a detergency builder or

  polyacetal carboxylate of alkali metal as the salt

  detergents and fabric treatment additives, organic or inorganic, for example anti-gelling and viscosity improvers,

  anti-sedimentation agents, anti-incrusta-

  bleaching agents, activators of

  bleaching agents, antifoam agents, optical brighteners, enzymes, agents

  anti-redeposition, perfumes and dyes.

  Will deinterent non-ionic surfactant Non synthetic synthetic detergents

  ions 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

  synthetic nonionic are characterized by the.

  the presence of a hydrophobic organic group and a hydrophilic organic group and they are generally produced by the condensation of an organic compound

  aliphatic or alkyl-aromatic hydrophobic with oxy-

  of ethylene (of hydrophilic nature). Virtually any hydrophobic compound having a carboxy, hydroxy amido or amino group having a free hydrogen atom attached to the nitrogen can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, to form a detergent no

  ionic. The length of the hydrophilic or poly-

  oxyethylene can easily be adjusted to

  dye the desired ratio between the hydro-

  phobic and hydrophilic. Representative examples of suitable nonionic surfactants are those described in U.S. patents. Nos. 4,316,812 and 3,630,929. In general, the nonionic detergents are

  lipophilic compounds alkoxylated by a poly-

  (lower alkoxy) in which the hydrophilic ratio

  the desired lipophilicity 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 by poly (lower alkoxy) groups.

  in which the alkanol has 9 to 18 carbon atoms and in which the number of moles of lower alkylene oxide (of 2 or 3 carbon atoms) is 3 to 12. Among these materials, it is preferred to use

  those in which the higher alkanol is an al-

  cool fat greater than 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 group

  lower alkoxy is the ethoxy group, but in some cases

  In some cases, it can be advantageously mixed with the propoxy group, the possible presence of which often represents only a minor proportion (less than%). 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 condensate

  of a mixture of higher fatty alcohols having in

  average about 12 to 15 carbon atoms, with about

  7 moles of ethylene oxide, and the second is a corresponding mixture in which the carbon atom content of the higher fatty alcohol is 12 to 13, and the number of ethylene oxide groups present is an average about 6.5. Alcohols

  higher 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. Meadow-

  is a mixed ethoxylation product of a linear secondary alkanol of 11 to 15 carbon atoms with seven moles of ethylene oxide, and the second is a

  similar product but o nine moles of ethylene oxide

have not reacted.

  Also useful in the composition of the invention as a component of the nonionic 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

Chemical Company.

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

  nonionic surfactants sold under the trade name

  Plurafac. Plurafac products are the reaction product of a higher linear alcohol and a mixture of oxides of ethylene and propylene, containing

  a mixed chain of ethylene oxide and

  pylene, terminated with a hydroxyl group. Examples include products which are (A) a C13-C15 fatty alcohol fused with 6 moles of ethylene oxide and 3 moles of propylene oxide, (B) a C13-C15 fatty alcohol condensed with 7 moles propylene oxide and 4 moles of ethylene oxide, (C) a C 13 -C 15 fatty alcohol condensed with 5 moles of propylene oxide and moles of ethylene oxide and (D) a mixture 1: 1 of

(B) and (C).

  Another group of nonionic surfactants

  liquids are commercially available from

  from the Shell Chemical Company, Inc., under the brand name Dobanol: Dobanol 91-5 is a C9-C11 fatty alcohol ethoxylated with an average of 5 moles of ethylene oxide and Dobanol 25-7 is a fatty alcohol in C12-C15 ethoxylated with an average of 7 moles of oxide

  of ethylene per mole of fatty alcohol.

  In the lower alkanols alkoxylated with poly (lower alkoxy) groups, preferred for obtaining

  keep the best ratio between the hydrophilic

  and lipophilic, the number of lower alkoxy groups

  is usually equal to 40% to 100% of the

  of carbon atoms of the higher alcohol, preferably

  40 to 60% of this number, and the nonionic detergent preferably contains at least 50% of such a preferred higher poly (lower alkoxy) alkanol. The

  alkanols of higher molecular weight and various

  very normally solid nonionic detergents and

  surfactants may contribute to the gelation of the liquid detergent and, therefore, will be

  preference or they will be in limited quantities in the present compositions, although they may be used in minor proportions for their cleaning properties, etc. With regard to preferred and less preferred nonionic detergents,

  the alkyl groups they contain are generally

  linear, although one can tolerate

  cation, for example at a carbon atom adjacent to the terminal carbon atom of the straight chain or away from two carbon atoms of this terminal carbon atom and at the opposite of the chain

  ethoxylated, provided that such an alkyl group

  does not have a length of more than three atoms

  carbon. Normally, the proportion of carbon atoms

  in such a branched configuration is minor and rarely exceeds 20% of the total carbon atom content of the alkyl group. Similarly, although linear alkyl groups which are end-joined to the ethylene oxide chains are very preferable and are considered to provide the best combination of detergency, biodegradability and non-gelling characteristics, they can appear a middle or secondary junction with the ethylene oxide of the chain. There is usually only a minor proportion of such alkyl groups, generally less than 20%, but, as in the case of the mentioned Tergitol, this proportion may be higher. Also, when the lower alkylene oxide chain contains propylene oxide,

  the proportion of this propylene oxide is generally

  less than 20%, and preferably less than

%, of this chain.

  When using higher proportions

  to those mentioned above of alkanols of which

  the alkoxylation is not terminal, of alkanols

  xylated by poly (lower alkoxy) groups

  propylene oxide and non-detergent

  with a lower hydro-lipophilic ratio, and

  other nonionic detergents are used in place of the preferred nonionic detergents listed herein, the resulting product may not exhibit such good detergency, viscosity stability and non-gelling properties as the preferred compositions , but the use of the compounds of the invention acting on viscosity and inhibiting gelation can also 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

  detergent, its proportion is adjusted or limited in accordance

  to the results of routine experiments, to obtain the desired detergency and to obtain at the same time a non-gelling and viscosity product

  desired. It has also been found that it is only

  necessary to use non-ionic surfactants

  of the higher molecular weight for their detergent properties, since the preferred nonionic surfactants described herein are excellent detergents and,

  Moreover, they make it possible to reach the desired viscosity.

  in liquid detergent without gelling

low temperatures.

  Another useful group of non-ionic surfactants

  The "Surfactant T" series consists of nonionic surfactants proposed by British Petroleum. Surfactant T Nonionic Surfactants

  are obtained by ethoxylation of secondary fatty alcohols

  C13 dies with a narrow distribution of ethylene oxide. Surfactant T5 has an average of 5 moles of ethylene oxide; Surfactant T7 has an average of 7 moles of ethylene oxide; Surfactant T9 has an average of 9 moles of ethylene oxide and T12 Surfactant has an average of 12 moles of ethylene oxide, per mole

of secondary fatty alcohol in C13.

  In the compositions of the present invention

  tion, preferred nonionic surfactants include

  C13-C15 secondary fatty alcohols having

  relatively low ethylene oxide

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

  ethoxylated 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 of liquid detergent compositions

  can be improved by including in the composi-

  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 a partial ester of a nonionic surfactant and a acid or

polycarboxylic anhydride.

  As described in the patent application

  85 05 319 filed on 9 April 1985, the sur-

  non-ionic facets modified with a free carboxyl group, which can be broadly characterized as polyether carboxylic acids, act as

  to lower the temperature at which the sur-

  Nonionic liquid facifier forms a gel with water.

  Addition of acid-terminated nonionic surfactants to liquid nonionic surfactant

  promotes the ability of the composition to be

  steam, that is to say, to be paid, and reduces the temperature

  at which the liquid nonionic surfactant

  form a gel in water without reducing their

  with respect to sedimentation. The acid-terminated nonionic surfactant reacts in the water of the washing machine with the alkalinity of the salt phase

  dispersed detergency builder of the composition

  tergents and acts as an effective anionic surfactant.

  Specific examples include

  half-esters of the product (A) with succinic anhydride

  the Dobanol 25-7 ester or half ester with succinic anhydride, and the 91-5 Dobanol ester or hemi ester with succinic anhydride. In the place of succinic anhydride, other polycarboxylic acids or anhydrides, for example

  maleic acid, maleic anhydride,

  citric acid, etc. The acid-terminated nonionic surfactants can be prepared as follows: Acid-terminated product (A): 400 g of nonionic surfactant product (A) which is an alkanol are mixed

  which has been alkoxylated to introduce 6 mo-

  ethylene oxide and 3 propylene oxide units per alkanol unit, with 32 g of succinic anhydride and heated for 7 hours at 100.degree. We cool

  the mixture and the filter to separate the suc-

  cinique who has not reacted. Infrared analysis shows that about half of the nonionic surfactant 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 comprises about 7 ethylene oxide units per molecule of d alkanol, with 100 g of succinic anhydride and 0.1 g

  pyridine (which acts as a catalyst for esterification

  and heated at 260 ° C for 2 hours,

  cold and filtered to separate the succinic material

  that did not react. Infrared analysis - shows that

  almost all the free hydroxyl groups on the

factive reacted.

  91-5 acid-bound Dobanol: 1000 g mixed

  Dobanol 91-5 non-ionic surfactant, which is the

  ethoxylation solution of a C 9 to C 11 alkanol and

  It contains about 5 ethylene oxide units per molecule of alkanol, with 265 g of succinic anhydride and 0.1 g of pyridine as catalyst, and is heated to 260.degree.

  for 2 hours, cooled and filtered to separate

  the unreacted succinic material. Infrared analysis shows that almost all groups

  hydroxyl free surfactant reacted. Other cata-

  Esterification lysers, such as an alkali metal alkoxide (eg sodium methoxide) can be used in place of pyridine or in admixture

  with her. Polyether acid, that is to say the surfac-

  acid-terminated nonionic tif is preferably

  added in the dissolved state in the nonionic surfactant.

  Debiting Adjuvant 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

  organic acid polymer type hydroxy-acrylate

  salt or salt of such acid or an adjuvant salt of

  organic detergency of the polyacetal carboxylate type.

  The preferred organic detergency builder salt of the hydroxyl-acrylonic acid polymer type is one of the alkali metal salts of the hydroxy-acrylic acid polymer, preferably the

sodium and potassium salts.

  In short, the hydroxy-acrylic acid polymer

  and salt of such an acid, used in the present invention as a detergency builder, contains monomeric units of formula:

R OH

_C CC-

R2 COOM

r2hi

  wherein R1 and R2 may be the same or different

  and represent hydrogen or an alkyl group

  comprising 1 to 3 carbon atoms, such as methyl, ethyl and propyl. The preferred substituents for R 1 and R 2 are both hydrogen. M represents

  hydrogen or an alkali metal, such as

  dium or potassium, or an alkaline earth metal such

  than calcium, magnesium or barium. The substitute

  killed favorite for M is sodium. The groups

  polymers are not critical and can;

  be H, OH, CH3 or a hydrocarbon chain.

  The degree of polymerization, i.e. the value of n, is usually determined by the limit

  compatible with the solubility of the polymer in water.

  The value of n can be from 10 to 10,000, from

  preferably from 10 to 1000, and more preferably from 20 to 200.

  The hydroxy-acrylic acid or salt polymer of such an acid may have a molecular weight of 1000 to

6 5

  Preferably from 1000 to 105, and more preferably from

  2000 to 20,000. See, for example, U.S. patents.

  Nos. 3,920,570 and 4,101,411 which describe procedures

dice of manufacturing polymers.

  Polvacetal-Carboxylic Acid Salts detergent additives

  Other organic adjuvant salts of detergent

  Preferred examples include the alkali metal salts of polyacetal carboxylic acid, preferably the

sodium and potassium salts.

  In general, polyacetal carbons

  xylates detergency builders used in the pre-

  This invention is represented by the following general formula:

R CHO R2

ICOOMN

  wherein M is selected from an alkali metal, ammonium, alkyl groups of 1 to 4 carbon atoms; tetralkylammonium groups and alkanolamine groups having 1 to 4 carbon atoms in the alkyl chain; alkali metals, for example sodium and potassium, are preferred; not

  is equal to & at least 4; and R1 and R2 are individually

  all chemically stable groups. R1 and R2

  may be the same or different groups.

  The end groups R 1 and R 2 can be chosen from a wide range of materials, provided that they stabilize the polyacetal carboxylate against rapid depolymerization.

  alkaline. The terminal groups R1 and R2 are also

  selected to be compatible with the ingredients used to formulate the nonaqueous liquid non-ionic composition of the present invention, particularly the nonionic surfactant and

  anti-gelling and anti-settling agents.

  The number of recurring groups,

  to say the value of n, is an important factor because

  the effectiveness of the polyacetal carboxylate as a

  Detergent detergency is affected by the length of the polymer chain. When n = 4, the polymer is effective as a sequestering agent, a chelating agent and a detergency builder. The value of n can be as high as 400. However, there does not seem to be any advantage in having n

value greater than about 200.

  When the value of n exceeds about 100,

  there is no significant improvement in

  sequestering, chelating and detergency adjuvants. Thus, the polyacetal carboxylate may contain 10 " units, i.e., n may be 10-400, preferably n = 50 to 200, and better

  still n = 50 to 100 recurring patterns.

  When n has a value of 50 to 200, the effi-

  the sequestering capacity of calcium and magnesium ions is very satisfactory and the adjuvant properties of

detergency are very good.

  For example, end groups

  appropriate chemically stable ones include fragments

  stable substituents derived from compounds with

  elsewhere stable, such as alkanes, such as

  thane, ethane, propane and butane; alkenes such as ethylene, propylene and butylene; saturated and unsaturated branched chain hydrocarbons such as 2-methylbutane and 2-methylbutene; alcohols such as methanol,

  ethanol, 2-propanol, cyclohexanol, poly-

  alcohols such as 1,2-ethanol-diol and 1,4-benzene

  not-diol; ethers such as methoxyethane, methyl ether, ethyl ether, ethoxypropane and

  cyclic ethers such as ethylene oxide; the PI-

  chlorohydrin and tetramethylene oxide; aldé

  hydes and ketones such as ethanal, acetone, propanal and methylethylketone; and compounds containing carboxylate groups such as alkali metal salts of carboxylic acids, carboxylic acid esters and anhydrides. Particularly suitable end groups include alkyl groups and cyclic alkyl groups containing oxygen such as oxyalkyl groups such as methoxy, ethoxy, carboxylic acids; and

  aldehydes, ethers and other alkyl groups

oxygen.

  The polyacetal carbokylates may contain polymeric moieties, and therefore the polymer may be a linear homopolymer or copolymer, or it may be branched. A number of chain extenders may be copolymerized with the polyacetal carboxylates. It is sufficient if the chain extender provides at least two reactive sites and does not cause the

  depolymerization of the polyacetal carboxylates in

  alkaline solution and that it is compatible with surfac-

  non-ionic tif and anti-gelling agents and,

  anti-sedimentation of the present invention.

  Chain extender agents suitable for

  These include: polyalcohols such as ethylene oxide, propylene oxide and epihalohydrin epoxysuccinates; aldehydes such as formaldehyde and acetaldehyde. It is particularly advantageous that the extender

  of chain contains carboxy substituent groups.

  Aliphatic chain extending agents having 1 to 4 carbon atoms, such as ethylene oxide

  and propylene oxide, are particularly

  ferred. When acetal-carboxylic esters are copolymerized with a chain extender, the amount of acetal-carboxylate should be at least about 50 percent by weight, based on the total weight of the polymer, to ensure that the polymer effectively sequesters calcium and magnesium ions

  and retains its detergency builder properties.

  It is preferred that the amount of acetal carboxylate is from 50 to 80 percent, for example about 80 percent by weight, based on the total weight of the

polymer, or even higher.

  In a preferred embodiment of the invention, R1 is chosen from:

/ CH2- CH2

OCH CH2

0 - CH2

  -OCH3. -0c H5. HO (CHCCH2O>, 4 H3C it COOM H3 '

RC - CR

I!

H5C20 COOM

  and mixtures thereof, and R2 is selected from:

-CH3, -C2H5, - (CH2CH20 * 1_4H,

H3C RC- H5C20 W

/ C 'CH2 \

-CH CH2

  embedded image where R is hydrogen or an alkyl group of 1 to 8 carbon atoms, and M is such

as defined above.

  It is particularly preferable that R1 is:

OCH2CH3

  -CH CH3 C001 or -C-CH3 I COOM1 or mixtures thereof, and R2 is: f? 2c CH H3.

  where M is sodium and n is 50-200.

  Other organic detergency builders that can be used are polymers and copolymers of polyacrylic acid and polymaleic anhydride and their alkali metal salts. More particularly, these detergency builder salts may be a copolymer which is the reaction product of about the same number of moles of methacrylic acid and maleic anhydride, which has been completely neutralized to form its sodium salt. The detergency builder is available in

  trade under the trademark Sokalan CP5.

  This detergency adjuvant serves, when used

  in even small amounts, & inhibit an encrustation.

* Since the detergent compositions

  of the present invention are generally very

  centered, and therefore, can be used in relatively small amounts, it is advantageous to supplement the adjuvant. detergency using an auxiliary adjuvant such as an alkali metal salt of lower polycarboxylic acid having a high binding capacity of calcium and magnesium to inhibit incrustation that might otherwise be caused by the formation of insoluble salts of calcium and magnesium. Suitable alkali metal salts of polycarboxylic acids are the alkali metal salts of citric and tartaric acids, for example

  example, monosodium citrate (anhydrous), tartrates

  monosodium, disodium and dipotassic processes.

  They may be added to, and used with, the alkali metal salt of hydroxyacrylic acid builder additive and the alkali metal salts of polyacetal carboxylic acid

-2586424

  detergency builders (eg Builder U), which

are also described here.

  Examples of alkaline sequestering gold builder additive salts which can be used with the hydroxyacrylic acid builder adjuvant polymer or the salt of such acid or

  with the polyacetal carboxylates adjuvants

  of the present invention, or in admixture with other organic and inorganic detergency builders are alkali metal, ammonium or substituted ammonium aminopolycarboxylates, for example edetate (EDTA) of sodium and potassium, nitrilotriacetates (NTA) of sodium and potassium

  and N- (2-hydroxyethyl) nitrilodiacetates of trietha-

  nolammonium. The mixed salts of these aminopolycar-

boxylates are also suitable.

  Other suitable detergency builders

  of the organic type include carboxymethyl

  succinates, tartronates and glycolates.

  Mineral Salts Adiuvants of Devenir The detergent compositions of the invention may also contain adjuvant salts of

  - mineral detergents soluble in water and / or insoluble

  lubles in the water. Suitable alkaline mineral detergency builder salts that can be used

  are carbonates, borates, bicarbonates and silicates

  alkali metal cates. (It is also possible to use the ammonium or substituted ammonium salts). Particular examples of such salts are sodium carbonate, sodium tetraborate, sodium bicarbonate,

  sodium sesquicarbonate and bicarbonate of potas-

  sium. Alkali metal silicates are useful detergency builder salts which also act to adjust or adjust the pH and to render the composition anticorrosive to the parts of the washing machine. Sodium silicates having an Na 2 O / SiO 2 ratio 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 the conventional polyphosphates can be added as adjuvant detergency

  local regulations allow this use

  tion. Specific examples of such adjuvant salts

  detergents are the tripolyphosphate (TPP) of

  dium, sodium pyrophosphate, pyrophosphate

  potassium, potassium tripolyphosphate and hexahydrate

  sodium metaphosphate. Tripolyphosphate (TPP) from

  sodium is the preferred polyphosphate. In the formulas

  in which the polyphosphate is added, it is added in a proportion of 0 to 20 or 30%

example 5 to 15%.

  As mentioned earlier, however, it is preferable that the formulations are free of

  polyphosphate or substantially free of polyphosphate

phate.

  Other representative examples of suitable detergency builders include, for example, those described in U.S. patents. Nos. 4,316,812, 4,264,466 and 3,630,929. The alkaline inorganic detergency builder salts may be used with the nonionic detergent surfactant or in admixture with other organic or inorganic detergency builder salts.

  The zeolite aluminosilicates can be used

  crystalline and amorphous ticks insoluble in water.

  The zeolites generally have the formula: (M 20) x (Al 2 O 3) y '(SiO 2) ZwH 2 O wherein x is 1, y is from 0.8 to 1.2, and is preferably 1, z is 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 zeolite is a type A zeolite or similar structure,

  type 4A being particularly preferred. Alumina

  Preferred nosilicates have a calcium ion exchange capacity of about 200 milliequivalents per gram or

  more, for example 400 milliequivants per gram.

  Various crystalline zeolites (i.e.

  aluminosilicates) that can be used are de-

  British Patent Specification No. 1,504,168, U.S. Pat. No. 4,409,136 and in Canadian Patents 1,072,835 and 1,087,477. An example of amorphous zeolites useful herein can be found in US Pat.

Belgian Patent No. 835,351.

  Other materials such as clays, particularly water insoluble types, may be useful additives in the compositions of the present invention. A particularly useful clay is bentonite. This material is mainly montmorillonite which is a hydrated aluminum silicate in which about 1/6 of the aluminum atoms can be replaced by magnesium atoms and with which various amounts of hydrogen, sodium,

  potassium, calcium, etc ..., may be low-

  combined. Bentonite in its purest form

  (ie, free from sandstone, sand, etc ...) suitable for detergents contains at least 50% montmorillonite and thus its cation exchange capacity is at least about 50-75.

  milliequivalents per 100 g of bentonite. Benton

  Particularly preferred are the bentonites from Wyoming or from 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 the textile materials, as described in British Patent Nos. 401,413 and N '

461 221.

  Aaents of Realaae of Viscosity and Anti-Gelation

  Incorporation into the composition

  an effective amount of alkylene glycol monoalkyl ether low molecular weight amphiphilic compounds acting as viscosity control and gelling inhibition agents for the

  non-ionic surfactant significantly improves

  properties of preservation 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 they have relatively short (C2 to C8) hydrocarbon chain lengths and a low ethylene oxide content ( about 2 to 6 oxide groups

ethylene 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 alkyl monoalkyl ethers (C2 to C5) of alkylene glycols

lower (C2-C3).

  More particularly, the compounds are lower mono (C1-C5) monoalkyl ethers,

  lower di- or trialkylene glycols (C2-C3).

  Specific examples of amphiphilic compounds

  Suitable philes include ethylene glycol monoethyl ether C2H5-O-CH2CH20H, diethylene glycol monobutyl ether C4H9-O (CH2CH2O) 2H, tetraethylene glycol monobutyl ether C4H7-O- ( CH2

  CH 2 O) 4H and dipropylene monomethyl ether

  glycol (CH3-O- (CH2CHO) 2H). We particularly prefer

H3

  the monobutyl ether of diethylene glycol.

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

  low molecular weight decreases the viscosity of the com-

  position, so that it is easier to pour, improves stability against sedimentation and

  improves the dispersibility of the composition during

  it is added to warm or cold water.

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

  temperatures as low as about 5C or less.

  Stabilizing Agents In one embodiment of the present invention the physical stability of the suspension of the detergency adjuvant compound (s) and any other

  suspended additive, for example the white

  chiment, etc., in the liquid vehicle is

  the presence of a stabilizing agent which is an alkanol ester of phosphoric acid or a salt

  of aluminum of a higher fatty acid.

  The stability of the composition can be improved.

  sition by incorporating a small amount but ef-

  of an acidic organic phosphorus compound having an acid group -POH, for example an ester

  partial phosphorous acid and an alkanol.

  As described in the patent application

  No. 85 05 319 cited above, the phosphorus compound

  acid organic phore having an acidic -POH group

  may increase the stability of the suspension of

  detergency in non liquid surfactant

non-aqueous ionic.

  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 carbon atoms, for example 8 at 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

  about 35% monoester and 65% diester.

  The incorporation of very small quantities of

  organic acid phosphorus compound makes the suspension

  much more stable vis-à-vis a sediment

  at rest, while remaining pourable, while at a low stabilizing

  less than about 1%, its plasma viscosity

tick generally decreases.

  It is possible to further improve the stability and the antisedimentation properties of the

  composition by the addition of a small amount of

  ficace of an aluminum salt of a higher fatty acid

to the composition.

  Stabilizers of the aluminum salt type

  mium is the subject of the French patent application 86

  02815 filed February 28, 1986.

  Preferred higher aliphatic fatty acids have 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 use mixtures of fatty acids, such as those from natural sources, such as

  tallow fat, coconut fatty acid, etc ...

  Examples of fatty acids from which the stabilizing aluminum salts can be formed include decanoic acid, dodecanoic acid,

  palmitic acid, myristic acid, stearic acid,

  oleic acid, eicosanoic acid, tallow fatty acid, coconut fatty acid, mixtures of these acids, etc. The aluminum salts of these acids are generally commercially available. , and they

  are preferably used in the three-fold form.

  Acid sidus, for example aluminum stearate

  in the form of aluminum tristearate A1 (C17H35C00) 3.

  Salts with an acid residue, for example monosaccharide,

  aluminum tetra, Al (OH) 2 (C17H35C00) and salts with

  two acid residues, for example aluminum distearate

  minium, Al (OH) C 17 H 35 Cl 2) and mixtures of two or three of the aluminum salts with one, two or three acid residues can also be used. However,

  it is particularly preferable that the aluminum salt

  at least 30% by weight, preferably at least 50%, more preferably at least 80%

  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 Claimant does not wish to be

  related to any particular theory of the

  Since the aluminum salt acts to prevent sedimentation of the suspended particles, it is assumed that the aluminum salt increases the wettability of the solid surfaces by the nonionic surfactant. This

  increased wettability therefore allows the particles

  in suspension to stay more easily suspended

  if we. It only takes very small amounts of the stabilizing aluminum salt to get a clear

  improvement of physical stability.

  In addition to its action as a phy-

  However, 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 overall detergency of the composition; it has a certain anti-foam effect; it can enhance the action of fabric softeners and it

  gives suspensions a longer period of

  fixation. Bleaching Agents Bleaching agents are broadly classified, for convenience, as chlorine bleaches

  and oxygen bleaching agents. Agents of white

  Chlorinated chlorides are represented by sodium hypochlorite (NaOCl), potassium dichloroisocyanurate

  (59% available chlorine) and trichloroiso-

  cyanuric (95% available chloride). The agents

  Oxygen bleaching is preferred and they are

  presented by peroxide compounds that release peroxide

  of hydrogen in solution. Preferred examples include

  take perborates, percarbonates and perphospha-

  sodium and potassium and potassium monopersulphate. Perborates, in particular sodium perborate monohydrate, are particularly preferred. Peroxyacids such as diperoxyazelaic acid can also be used as bleaching agents,

  diperoxydodecanedioic acid, monoperoxidic acid

  succinic acid, monoperoxyphthalic acid (MPPA) and

diperoxyterephthalic acid.

  The peroxygen compound is preferably used

  mixed with an activator. Activators

  which can lower the operating temperature

  The effectiveness of the peroxide bleaching agent is described, for example, in U.S. Pat. No. 4,264,466 or column 1 of the U.S. Patent. No. 4

  430 244. Polyacetyl compounds are the active ingredients

  we prefer; among them, we still prefer

  more compounds such as tetraacetylethyl

  lene diamine ("TAED") and pentaacetyl glucose.

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

  ethylidene benzoate acetate and its salts, ethyl

  dienecarboxylate and its salts, alkyl- and alkenylsuccinic anhydrides, tetraacetylglycouril ("TAGU")

  and their derivatives. Other useful classes of

  are described, for example, in the patents of the

  - E.U.A. Nos. 4,111,826, 4,422,950 and 3,661,789.

  The bleach activator generally reacts with the peroxygen compound to form a bleach peroxy acid in the wash water. It is preferable to include a sequestering & high complexing agent in order to inhibit any adverse reaction between this peroxy acid and the hydrogen peroxide in the wash solution.

presence of metal ions.

  Sequestering agents appropriate in this

  purpose include the sodium salts of nitric acid

  Lotriacetic acid (NTA), ethylene-diamine

  tetraacetic acid (EDTA), diethylene triamine

  pentaacetic acid (DETPA), diethylene triamine

  pentamethylenephosphonic acid (DTPMP) sold under the

  that 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 white peroxide

  chiment, for example sodium perborate, resulting

  decomposition under the action of enzymes, for example

  the catalase enzyme, the compositions may contain

  In addition, an enzyme inhibitor, ie a

  compound capable of inhibiting decomposition, under the

  enzyme, bleaching peroxide. Inhibitions

  appropriate devices are described in the patent for

USA. No. 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 hydroxylamine salts

  ibitors 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 builders, various other detergent additives or auxiliaries may be present in the detergent product to impart other desired functional or aesthetic properties. Thus, in the formulation, minor amounts of

  suspension or anti-redeposition of soil

  for example, polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropylmethylcellulose. A preferred anti-redeposition agent is sodium carboxymethylcellulose having a ratio of 2: 1 of CM / MC, which is sold under the trademark

Commercial Relatin DM 4050.

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

  and benzidine sulphone, in particular triazinyl-

  substituted sulphonated stilbene, sulphonated naphtotriazole-stylbene, benzidene sulphone, etc ..., those which are

  prefers being the combinations of stilbene and

  zole. A preferred brightener is "Stilbene

  Brightener N4 "which is a dianilino-dimorpholino-

stilbene sulfonate.

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

  that Silicane L7604 in small effective amounts.

  Bactericides can be used for

  tetrachlorosalicylanilide and hexchlorinated

  phene, fungicides, dyes, pigments

  (dispersible in water), preservatives,

  ultraviolet absorbers, anti-yellowing agents, such as sodium carboxymethylcellulose, pH modifiers and pH buffers, color-preserving bleaches, perfumes, dyes 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 silica of extremely large particle size.

  small (for example with a diameter of 5 to 100 micro-

  meters, such as that sold under the name Aerosil) or the other very large mineral carriers described in U.S. Pat. No. 3,630,929, in proportions of 0.1 to 10%, for example 1 to 5%. However, it is preferred that compositions which form peroxyacids in the wash bath (e.g. compositions containing a peroxygen compound and an activator therefor) are substantially free of such compounds and other silicates have been found by example, that silica and silicates favor

  undesirable decomposition of the peroxy acid.

  In one embodiment of the invention,

  the stability of the adjuvant detergency salts

  in the composition during storage and dis-

  Persistence of the composition in the water are improved.

  grinding and reducing the particle size.

  solid detergency builders less than 100 micrometers, preferably less than 40 micrometers

  and better still less than 10 micrometers. The adjutants

  Solid detergency products are generally provided in particle sizes of about 100, 200 or 400 micrometers. The phase of nonionic surfactant

  liquid can be mixed with the adjuvants

  tergence solids before or after the grinding operation. In a preferred embodiment of

  the invention, the mixture of nonionic surfactant

  quide and solid ingredients is subjected to attrition grinding in which 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 less than

  higher (for example 1 micrometer). Preferably, less than about 10%, especially less than about 5% of all suspended particles have

  particle sizes greater than 10 micrometers.

  Compositions whose dispersed particles are so small have better stability against separation or sedimentation in storage. The addition of the acid-terminated nonionic surfactant promotes the dispersibility of the dispersions without correspondingly reducing the stability of the dispersions with respect to sedimentation.

  For the grinding operation, it is preferable

  that the proportion of solid ingredients is sufficiently high (for example at least about 40%, especially about 50% so that the solid particles are brought into contact with one another and are not too isolated from each other by the

  nonionic surfactant liquid. After the crushing step

  ge, all the liquid nonionic surfactant remaining at

  incorporate can be added to the ground formulation.

  Grinders using grinding balls (grinders) or similar moving grinding elements have given very good results. For example, a batch attrition laboratory mill employing batch

  grinding balls made of soapstone 8 mm in diameter.

  For a larger-scale operation, a continuous mill can be used in which there are grinding balls with a diameter of 1

  mm or 1.5 mm operating in a very small

  be 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 first through a mill which does not perform such a fine grinding (for example a colloid mill). ) to reduce the particle size to less than 100 micrometers (e.g., to about 40 micrometers) prior to the grinding step to an average particle diameter of less than about 10 micrometers in the continuous bead mill. In preferred liquid detergent compositions for heavy duty laundry

  the invention, typical proportions (the percentages

  based on the total weight of the composition

unless otherwise specified) the ingredients are as follows: Liquid nonionic surfactant detergent: in the range of about 20 to 60, e.g.

percent.

  The acid-terminated nonionic surfactant may be omitted; however, it is preferable to add it to the composition in an amount in the range of about 2 to 30, for example 2 to 20 or

at 25 percent.

  Polymer of hydroxyacrylic acid or salt of such acid or polyacetalcarboxylate detergency builder in the range of about 5 to 50, by

example 10 to 30 percent.

  Polyphosphate-type detergency builder

  phate: in the range of about 0 to 30 percent, for example O & 20, and especially 5 to 15 percent. Polyacrylate Copolymer and Metal Salt

  alkali metal of polymaleic anhydride as an anti-

  incrustation: in the range of approximately 0 to 10,

example 2 to 8 percent.

  Alkylene glycol monoalkyl ether such as: anti-gelling agent: may be omitted; however, it is best to add it to the composition in one

  amount in the range of about 0 to 20, e.g.

  5 to 30 percent, including 5 to 15 or 20 percent

hundred.

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

  0.1 to 2.0, e.g. 0.10 to 0.5 or 1.0 percent.

  A fatty acid aluminum salt stabilizing agent in the range of about 0 to 3.0, for example 0.5 to 2.0 percent, especially 0.1 to 1.0 percent. It is preferable 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 40 percent,

especially 5 or 10 to 30 percent.

  Activator of the bleaching agent: in the range of about 0 to 25, for example 2 to 25 for

percent, including 5 to 20 percent.

  Sequestering agent for the bleaching agent

  in the range of about 0 to 3.0, preferably

0.5 to 2.0 per cent.

  Anti-redeposition agent: in the meantime

  from about 0 to 3.0, preferably 0.5 to 2.0 percent.

  Optical brightener: in the meantime

  from about 0 to 2.0, preferably from 0.1 to 1.5 percent.

  Enzymes: in the range of approximately 0 to

  3.0, preferably 0.5 to 2.0 percent.

  Fragrance: in the range of about 0 to

  2.0, preferably 0.10 to 1.0 percent.

  The various additives previously mentioned may optionally be added to achieve

  the desired function of the added materials.

  Surfactant mixtures can be used

  acid-terminated nonionic acid and anti-gel agents

  alkylene glycol alkyl ether type

  in some cases, we can benefit from the use of

  such mixtures alone, or with addition to the

  mixture of a stabilizing and anti-settling agent.

  The additives will be selected so that they are compatible with the main constituents of the detergent composition. In the present application, as mentioned above, all the proportions and percentages are expressed by weight relative to

  the totality of the formulation or composition, except

otherwise.

  The liquid nonionic detergent composition

  The non-aqueous concentrate of the present invention is easy to distribute in the water of the washing machine. Household washing machines currently in use normally use about 175 grams of powdered detergent to wash a full load of

  machine. According to the present invention, it is only necessary to

  viron 67 ml or about 80 grams of the composition

  concentrated liquid nonionic detergent.

  In a preferred embodiment of the invention, the typical detergent composition is formulated using the ingredients enumerated below: Alkali metal salt polymer of hydroxypropyl acid acrylonitrile Adiuvant Deionic% ioids Surfactant nonionic detergent 30-55 Surfactant acid-terminated 1-10 Alkylene glycol monoalkyl ether 3-15 Hydroxyacrylate polymer 7-22 Phosphoric acid alkanolic ester 0.1-0.9 Alkali metal bleaching perborate 10-22 Agent activator bleaching (TAED) 4-15 Optical brightener 0.10.6 Enzymes 0.5-1.5 Fragrance 0.1-0.8 In another preferred embodiment

  of the invention, the detergent composition of

  Typical formulation is formulated using the ingredients listed below: Alkaline Salt of AcidPolvacetal-Carboxvliaue Adiuvant of Deteraemce Surfactant Nonionic Surfactant Detergent & Acid Termination

  Alkali metal salt of polyacetal acid

  carboxylic detergency builder Polyphosphate detergency builder alkanolic phosphoric acid alkali metal alkaline bleaching agent bleaching agent (TAED) optical brightening agent (Stilbene Brightener N4))% by weight -55 2-18 -22 0-20

0.1-0.9

7-22 4-12

0.1-0.8

  Enzymes (Protease-Esperase SL8) 0.5-1.5 Fragrance 0.1-0.8

  The following nonlimiting examples illustrate

the present invention.

EXAMPLE 1

  A liquid detergent composition not

  concentrated aqueous solution with a nonionic surfactant

  trimmed with the following ingredients

quantities indicated.

  % by weight Surfactant T9 Surfactant T7 Dobanol 91-5 acid terminated reaction product with succinic anhydride 4.0 Diethylene glycol monobutyl ether 10 Sodium alpha-hydroxyacrylate polymer 17.0 Alkanolic acid ester phosphoric 0.3 Sodium perborate monohyrate bleaching 17.0 Tetraacetylethylene diamine (TAED) as bleach activator 10.0 Stilbene brightener 0.4 Esperase suspension 1.0 Fragrance 0.3 Aqueous prepared quantities

EXAMPLE 2

  A nonionic surfactant concentrated liquid detergent composition from the following ingredients is indicated: no is xei Nonionic surfactant, product D, Dobanol 91-5 acid terminated reaction product with succinic anhydride Sodium salt of polyacetal carboxylic acid ( Builder U) Alkanolic acid phosphoric acid Sodium perborate monohydrate bleaching Tetraacetylethylene diamine (TAED) as bleach activator Stilbene Brightener N4 Esperase suspension Fragrance in oids, 0 14.0 17.0 0.3 17, 0, 0 0.4 1.0 0.3

100.0

  The compositions of Examples 1 and 2 are or can be milled for about one hour to reduce the particle size of the adjuvant salts

  detergency in suspension at less than 10 micrometers.

  It is found that the prepared detergent compositions are stable and do not gel on storage and

it has a high detergency power.

  The compositions can be prepared without

  grinding of the detergency builder salts and the

  solid particles in suspension at a small particle size, but the best results are obtained

  by grinding the composition to reduce the size

  particulate matter of suspended solid particles

  if we. They may be used as builder salts in suspension builder salts may be supplied, or detergents and solid particles may be crushed or partially

2586-424

  milled before being mixed with the nonionic surfactant. The grinding may be carried out in part before mixing and grinding may be completed after mixing, or all grinding may be carried out after mixing with the liquid surfactant. The compositions of the present invention, containing an alkali metal hydroxyacrylate polymer as a detergency builder, may be thickened by conventional thickeners such as Bentonite and Aerosil to form a cream or paste and be used as a cleaning degreasing agent. .

Claims (16)

  1. Non-aqueous liquid detergent composition   for heavy laundering work, characterized in that it contains: at least one liquid nonionic surfactant detergent, a hydroxyacrylic acid polymer or hydroxy-acrylic acid polymer type detergency builder or an adjuvant salt organic detergent composition of the polyacetal carboxylate type, at least one component selected from an acid-terminated nonionic surfactant anti-gelling agent and an alkylene glycol monoalkyl ether, and an anti-settling agent.   2. A detergent composition according to the   cation 1, characterized in that it comprises 5 to 50 percent of a polymer-type detergency builder   of hydroxy-acrylic acid or hydroxy-acid salt   acrylic or a polyacetal carboxylate builder salt.   3. Detergent composition according to the   cation 1, characterized in that the hydroxy-acrylic acid adjuvant detergency polymer contains monomer units of formula: FR, OH l 25.o -CI -2.M   wherein R1 and R2 may be the same or different   and are selected from hydrogen and alkyl groups of 1 to 3 carbon atoms, and M is selected from hydrogen, an alkali metal cation,   of alkaline earth metal and ammonium.   4. A detergent composition according to the   cation 1, characterized in that it comprises at least   a nonionic liquid surfactant in a quantity of   25 to 50%, a nonionic surfactant with a final   its acid in an amount of about 2 to 20%, a monoalkyl ether of alkylene glycol in an amount of about 5 to 20%, a hydroxy-acrylate adjuvant detergent polymer in an amount of about 10 to %, and an alkanolic ester of phosphoric acid in an amount of about 0.1 to 1.0%   5. A detergent composition according to claim   cation 4, characterized in that the hydroxy-acrylic acid detergency builder polymer contains monomeric units of formula: R2 COM   wherein R1 and R2 may be the same or different   fers and are selected from hydrogen, the groups   methyl, ethyl and propyl, M is selected from among   dium and potassium, and the value of n is chosen from   so that the polymer is soluble in water.   6. Non-aqueous liquid detergent composition   phosphate-free detergent, which is   characterized in that it comprises about 30 to 55% of nonionic surfactant, about 1 to 10% of surfactant to   acid termination, about 3 to 15% monoalkyl ether   alkylene glycol, about 7 to 22% sodium hydroxyl acrylate builder polymer, about 0.1 to 0.9% C16 to C18 alkanolic phosphoric acid ester, about 10 to 22% sodium perborate monohydrate bleaching, and about 4% tetraacetylethylene diamine as activator bleaching agent.   7. A detergent composition according to claim   cation 6, characterized in that the hydrophilic polymer   xy-acrylate has a molecular weight of 2000 to 20000.   8. Detergent composition according to the   cation 1, characterized in that the polyacetal-carbon   xylate is represented by the formula: R 1 "2P   Wherein M is selected from an alkali metal, ammonium, alkyl groups of 1 to 4 carbon atoms; tetraalkylammonium groups and alkanolamine groups of 1 to 4 carbon atoms in the alkyl chain: n has a value of at least 4, and   R1 and R2 are chosen to be individual groups   dually stable which stabilize the polymer at   against depolymerization in alkaline solution and are chosen to be compatible with the ingredients   of the nonionic liquid detergent composition.   9. Laundry detergent composition according to claim 1, characterized in that it has a low or no content or polyphosphate and in that it comprises at least one nonionic surfactant   in an amount of about 25 to 50%, an over-   nonionic acid-free faction in an amount   from about 10 to 25%, a polyacetal carboxylate adju-   detergency in an amount of about 10 to 30%,   a polyphosphate adjuvant detergent in a quantity   from about 0 to 20%, and an alkanolic phosphoric acid ester in an amount of about 0.1 to 1.0%.   10. Detergent composition according to claim   section 9; characterized in that the polyacetal carboxylate is represented by the formula: R1 i-HO t GROOMS   wherein M is an alkali metal; n has a value of 50 to 200, and R1 and R2 are chosen to be individually stable groups that stabilize the   polymer against a depolymerization in solution.   alkaline solution and are chosen in such a way as to   the ingredients of the detergent composition liquid nonionic gente.   11. A non-aqueous liquid detergent detergent phosphate-free detergency builder composition, characterized in that it comprises about 30 to 45%   nonionic surfactant, about 2 to 18% of   acid-terminated filler, about 5 to 22 of polyacetal carboxylic acid sodium salt, about 0.1 to 0.9% of C16 to C18 alkanolic phosphoric acid ester, about 7 to 22% of perborate of sodium monohydrate bleaching, and about 4 to 12% tetraacetylethylenediamine (TAED) as an activator bleaching agent.   12. Detergent composition according to claim   cation 11, characterized in that the polyacetal.   carboxylate is represented by the formula: ## STR2 ## wherein M is selected from sodium and potassium; n is 50 to 200; R1 is OCH2CH3 or COOM 1I -CH -C -CH I I CH3 COOH or their mixtures, and R2 is OCH CH 1 2 3 -CH I CH3   and the polyacetal carboxylate segments constitute   80 per cent by weight of the totality of the poly- tal-carboxylate.   13. A detergent composition according to claim   12, characterized in that the polyacetal-carbon   xylate is the sodium salt and the R1 groups are stabilizing end groups.   14. A detergent composition according to claim   cation 3 or 11, characterized in that it comprises an alkali metal perborate monohydrate bleaching   in an amount of about 5 to 30%, tetraacetyl-   ethylene diamine as a bleach activator   in an amount of about 5 to 20%, and   one or more detergent additives   selected from optical brighteners, enzymes, my and a perfume.   15. A method for cleaning soiled fabrics, characterized in that it consists in putting the soiled fabrics in contact with the detergent composition of   laundry according to claim 6.   16. A method for cleaning soiled fabrics, characterized in that it consists in putting the soiled fabrics in contact with the detergent composition of   laundry according to claim 11.