FR2619393A1 - DETERGENT COMPOSITION BASED ON ETHOXYLATE AND A COPOLYMER OF TEREPHTHALATE FACILITATING SOIL DECOLUTION AND METHOD FOR USE THEREOF - Google Patents

Abstract

The invention relates to a detergent composition which facilitates the detachment of greasy soiling in the washing in cold water of laundry containing in particular polyester fabrics when this laundry is washed several times with said composition. The composition contains a narrow range ethoxylate nonionic detergent, which is a lipophilic compound polyethoxylated with an average of 5 to 10 ethylene oxide groups per molecule and in which at least 70% of the ethylene oxide is found in polyethoxy groups having 4 to 12 ethylene oxide groups, unlike a conventional nonionic detergent of the wide range ethoxylate type, and a soil release facilitator which is a polyethylene terephthalate-polyoxyethylene terephthalate copolymer, these two components exerting a synergistic effect of aid in the detachment of the dirt. Area of application: laundry detergents.

Description

The present invention relates to composi-

  detergents based on synthetic organic detergents

  nonionic theics, the properties of which help to detach stains are improved. The invention relates more particularly to such detergent compositions, both in particulate solid form and

  in liquid form, which contain as a

  the soiling of the dirt is a tere-

  polyethylene terephthalate phthalate

  (PET-POET) and, as a non-ionic detergent, an etho-

  narrow-range xylat (EGE) which acts as a detergent

  but also significantly improves the aid effect of

  staining caused by the copolymer PET-

  POET. The best soil release aid activity exerted by the described compositions is particularly marked when the subject laundry

  washing (and simultaneously treated by the facilitator

  as the detachment of dirt) consists of a

  or more tissues comprising one or more

  fibrous synthetic organic polymers, in particular polyesters, and when the washing is carried out at low temperature, for example between 10 and

 C, or between 15 and 25vC.

  Prior to the present invention,

2 6 1 9393

  knew how to make particular detergent compositions

  based on synthetic organic detergents

  reinforced with detergency builders, using

  nonionic detergents and adjuvants

  phosphated and / or non-phosphated detergents. The adjutants

  non-phosphate detergents that have been used

  include those of both types, soluble in

  water and insoluble in water. Adjuvants of deter-

  water-soluble solutions include silicates,

  alkali metal carbonates, bicarbonates and borates

  and water-insoluble detergency builders include zeolites, all of which are well known in the art. These compositions are described in a number of U.S.A. patents issued to the assignee of the present application, Colgate-Palmolive Company, and products of this type, in which dried detergency adjuvant salt base beads.

  by atomization contain, in the absorbed and liquid

  of, a nonionic detergent, have been marketed by this company under the trademark FRESH

START).

  PET-POET polymers have been proposed

  constituents of particular detergent compositions

  in which they help take off clothes from

  fouling applied later. Patents

  Such polymers and their role include British Patent No. 1,088,984 and U.S. Patent No. 3,962,152. U.S. Patent No. 3,962,132 discloses

  state of a polyacrylate in detergent compositions

  zeolite-reinforced and U.S. Patent No. 4,283,299 discloses a polyacrylate in nonionic detergent compositions reinforced with

  a phosphate for its anti-redeposition effect.

  In the prior art, it has also been established that soil release facilitating polymers, analogous to those used in the present invention (PET-POET), can be incorporated into liquid detergent compositions. It was also known that nonionic detergents are constituents

  useful detergents for liquid detergent compositions.

  In some liquid detergents, it has been used in

  both a PET-POET copolymer and non-ionic detergents

  wide range ethoxylate (EGL).

  U.S. Patent No. 4,441,881 discloses that

  detergent compositions based on detergent

  nonionic EGE gels containing a detergency adjuvant

  and a small proportion of cellulosic

  for example, hydroxypropylmethylcellulose

  or methyl cellulose, as "dirt screens"

  In this patent, the described nonionic detergent is a narrow-range polyethoxylate (EGE) of alcohol.

  fat that is presented as being less sus-

  can be released into smoke from the top of a spray tower when a mixture of kneader containing

  such a nonionic detergent is spray dried.

  This patent also mentions that the EGE of composi-

  described therein, gives these compositions superior cleaning power compared to

  similar compositions in which are used

  as non-ionic detergents, gamma ethoxylates

  me wide classics (EGL). It should be noted that in the

  preceding sentence and thereafter, in order to avoid a

  petition of the expression "nonionic detergent", EGE

  and EGL refers to such detergents, and not only

  to the types of their ethoxy moieties.

  U.S. Patent Nos. 4,569,772 and

  4,571,303 both describe compositions

  similar to some of those of the present invention, with the difference that none of these patents

  mentioned by EGE and does not describe or suggest that the use

  EGE in place of EGL in these compositions 4.

  can synergistically improve the characteristics

  aid in the removal of dirt from the copolymer

  PET-POET contained in these compositions.

  Although the prior art knows the various components of the present compositions, it is considered

  detergent compositions comprising a combination of

  of EGE and a PET-POET copolymer are new.

  and, by the unpredictably advantageous effects

  obtained with these compositions (improvement of

  stain), compared to other

  of this type based on EGL, the non-obviousness

  of the present invention has been established.

  Although the prior art described above,

  found during research on the technology

  related to the field of the present invention,

  various combinations of the necessary components

  compositions of the invention, it does not teach an ordinary specialist the use of EGE

  instead of EGL in the detergent compositions

  which contain PET-POET polymers which are

  the removal of dirt, with or without poly-

  stabilizing acrylate (in the particular compositions

  reinforced, and certainly this art does not teach

  not suggest or suggest that the compositions of the Application-

  have a better activity of decolon-

  the presence of dirt in these compounds

  positions, nonionic detergents EGR instead

EGL nonionic detergents.

  According to the present invention, a detergent composition facilitating the removal of stains, having improved properties of helping to remove stains in the washing with cold water of fabrics

  containing polyester which has been contaminated with

  this improvement in the detachment of

  due to the presence in the composition of a narrow range ethoxylate (EGE) as a detergent

  nonionic and a polyterephthalate copolymer of

  Plyoxyethylene polyethylene terephthalate (PET-POET) facilitates soil release in place of a broad-range ethoxylate (EGL) as a non-detergent

  ionic material and a PET-POET copolymer, comprises a

  detergent portion of such an EGE type of detergent

  non-ionic gent, which is a poly-lipophilic compound

  ethoxylated with an average of 5 to 10 oxide groups

  per mole and of which at least 70% of the

  thylene is in polyethoxy groups with 4 to 12 ethylene oxide groups, and an effect ratio facilitating the removal of dirt from a

  PET-POET copolymer as an agent facilitating

  stains. The invention also contemplates a method for washing laundry and imparting to the laundry properties of aid in detaching stains after

  repeated washing with the composition of the invention.

  The active detergent component of the composi-

  The methods and methods of the present invention are primarily

  a non-ionic detergent. The detergents

  Anionic synthetic chemicals may have

  this to inactivate PET-POET copolymers or they can inhibit their action to aid in the detachment of dirt, probably by opposing the deposition of these

  copolymers on the linen from the washing water.

  However, anionic detergents can sometimes be used in relatively small proportions in substantially nonionic detergent compositions

  without detracting from the action of helping to detach

  sures offered by the PET-POET copolymer.

  Among the nonionic detergents, it is preferable to use those which are EGE products of reaction and condensation of ethylene oxide and G

  of a suitable lipophilic compound or substance. Sal-

  Higher cools, generally fatty alcohols of 12 to 18 carbon atoms per molecule, are the preferred reactants for their reaction with ethylene oxide to produce the desired nonionic detergents for the compositions of the present invention, but Oxo type alcohols and phenols

  medium alkyl chain, for example nonyl-phenyl

  nols, can also be interesting to use.

  Other members of this well-known class of deter-

  Nonionic materials, for example the higher fatty acid esters of ethylene oxide, may also be useful in certain compositions and for particular applications. Preferably, we use

  a higher fatty alcohol as a source of lipopolysaccharide

  phile, and the condensation product of the oxide of

  thylene is a nonionic detergent of the ethoxy-

  narrow range lat (EGE). By the expression "ethoxy-

  "narrow range" means a lipophilic compound polyethoxylated with ethylene oxide so that at least 70% of the ethylene oxide of the nonionic detergent is in the form of polyethoxy groups having n to (n + 8) moles of ethylene oxide per mole, n being able to have a value of 1 to 10, although it is

  preferable that n be 3 - 5, better eareàevicn4.

  Thus, preferably at least 70% of the ethylene oxide

  binds nonionic detergent consisting of the ethoxylate

  narrow range (EGE) is found in

  ethoxy having 4 to 12 ethoxy groups. Even better,

  these groups have 5 to 10 ethoxy groups and consis-

  at least 80 or 85% of the ethoxy content of the EGE. Instead of ethylene oxide, one can

  use in some cases mixtures of ethylene oxide

  and propylene oxide in these EGEs, provided that the final product has the desired properties and

  unpredictably advantageous, together with the copoly-

  PET-POET, which will be described in more detail in the following

  of this memorial, so that the action of

  the removal of dirt is improved, compared

  to compositions containing the same copoly-

  PET-POET, but using wide-range ethoxylates (EGLs) as nonionic detergents, which

  are the usual nonionic detergents of the

  than. Although it may be preferable

  EGE type xylates are within certain ethoxy content limits of their polyethoxy moieties,

  the manufacturing processes usually give rise to

  of polymers, so that it is possible to specify

  average contents in ethoxy groups. Thus, the deter-

  EGE nonionic gels can contain an average of 4 to 12 or 5 to 10 ethylene oxide groups per molecule, for example about 6 or 7 ethylene oxide groups per molecule.

  molecule. The preferred lipophilic compound is the one

  of a higher fatty alcohol and, therefore, the ethylene oxide content of the EGE nonionic detergents is such that at least 70% of the ethylene oxide is in higher alcohol fatty alcohol ethoxylates. on average 5 to 10 ethylene oxide groups per

  molecule and, preferably, at least 80 to 85% of the oxy-

  of ethylene is in such ethoxylates of

  cool fat superior. This compares with the 50%

  or fewer such polyethoxy groups

  EGL. Also, the higher fatty alcohol of ethoxylates

  lats of higher fatty alcohol preferably has from 12 to 14 carbon atoms, although sometimes fatty alcohol

  may have from 10 to 16 or from 12 to 16 carbon atoms.

  The invention contemplates the use of synthetic lipophilic compounds such as those derivable from higher fatty alcohols having odd numbers of carbon atoms.

  within the limits indicated, or those which may

  river of higher fatty alcohols with even numbers of carbon atoms, as in natural products,

  and mixtures thereof can also be used.

  The currently available EMTs are pre-

  of condensation produced by condensation reactions

  talysées which favor the production of a narrow range of

  instead of the more conventional broad range of polyethoxylates in the alkoxylated lipophilic detergent. Catalytically produced products are characterized by a normal distribution curve when the percentage by weight (ordinate) is traced

  depending on the ethylene oxide content (abscissa

  its), but the maximum of the "bell curve" is much higher for EGE nonionic detergents than for EGL nonionic detergents. Similar products with similar distribution curves can be made by removing the "heads" and "tails" of EGLs or other EGEs, for example by removing the higher and lower polyethoxylates.

  by solvent extractions, distillations and

  appropriate physical processes. Detergents

  EGL nonionic agents contain lower

  of a narrow range of desired polyethoxylates

  like those with 4 to 12 or 5 to 10 ethylene groups

  xy, often less than 50%, compared to more than% for EMTs. They also contain at least

  approximately 1% of each of the individual degrees of etho-

  xylation of 1 to 16 or 1 to 20, although it is desired that the average ethylene oxide content is 7 moles per mole, for example. However, an EGE that has an average of 7 moles of ethylene oxide per mole

  usually contains no ethylene oxide polymer

  contains more than 15 ethoxy groups, and the proportions of polyoxyethylene in the range of 4 to 12 and 5 to 10

  ethoxy groups are significantly increased. This increase

261 9393

  and the narrower range of distribution of frag-

  Polyethoxy compositions clearly alter the properties of EGE in a good way when it is incorporated into a detergent composition containing a PET-POET copolymer. The reason for this effect is not fully understood at present, but may be related to less interference of the nonionic detergent in PET-POET copolymer deposition on the

  linen considered as a substrate, before the dirtying

  and final disposal by subsequent washing.

  In the vicinity of the "maximum" of the distribution curve presented by EGEs, for example in the range of 5 to 10 ethoxy groups per polyoxyethylene moiety,

  the percentages of fragments of 5 to 10 ethylene groups

  xy for EMTs, compared to EGLs, can

  from 15% and over to 60% or more, the differences

  maxima of interest for 7-polyethoxylates

and 8 ethoxy groups.

  Of the nonionic detergents EGE preferred

  res usable according to the present invention include the nonionic surfactant Tergitol & 24-L-60N, which has the formula RO (CH2CH20) nH o R is a mixture of linear alcohols C12 and C14 and n has a value

  average of about 7.0. This product has a point of

  60 C for a 1% aqueous solution, and this is

  a narrow range ethoxylate. Its properties are de-

  written in a product documentation leaflet

  Union Carbide Corporation, dated April 1987. Other surfactants

  non-ionic Tergitol class which can also be

  use, at least in part, with 24-L-60N, include 26-LGO60N, 24-L-45N and 24-L-75N, o 60, 45

  and 75 indicate cloud points, in degrees

  tigrades. In addition, it is considered that similar products manufactured by Shell Chemical Company, which have been named Shell 23-7P and Shell-23-7Z, may replace them, although the results may not be accurate.

to be so satisfying.

  The distribution of ethoxylates in various

  EGEs are indicated in Bulletins of the Tech-

  Tergitol Surfactants entitled "Ethoxylate Distribution of Tergitol 24-L Nonionic Surfactants by

  Gas Chromatography ", published by Ethylene Oxide Deri-

  Vacant Division of Union Carbide Corporation. The Your-

  The following table, Table 1, summarizes the distribution of ethoxylates (by gas chromatography) in two of the preferred EEMs mentioned above, and in

EGL comparable.

TABLE 1

  Weight Percentage RO (CIH2CH20) n1 n Tergitol 24-L-60N Tergitol 24-L60 Tergitol 24-L-75N Tergitol 24-L-75

0 0.6 1.3 0.3 0.9

1 0.2 0.9 0.0 0.6

2 0.4 1.8 0.2 1.2

3 1.1 3.1 0.4 2.0

4 2.7 5.4 1.4 3.6

6.6 7.0 3.1 5.3

6 13.1 9.0 7.6 6.8

7 19, .5 10.3 14.3 8.6

8 21.5 11.1 20.3 10.6

9 16.3 11.2 20.6 10.9

9.5 10.0 15.5 10.5

11 4.1 8.0 8.8 9.4

12 1.3 6.3 3.9 7.6

13 0.4 4.3 0.9 5.5

14 1.8 2.2

  Total * 97.3 91.5 97.1 85.6 The entire sample can not be recovered because of the

  retention of the higher ethoxylates in the gas chromatography column.

  The PET-POET copolymers of the present invention are

  usually have molecular weights in the

  from 19,000 to 43,000, preferably about 19,000 to 25,000, for example about 22,000, depending on the molecular weight determinations made on samples of such copolymers which are generally

  used here. These molecular weights are moderate weights

  average leculars by weight, to the distinction of weights

  number of molecular molecules, which, in the case of

  The polymers used in the invention are often

  laughing. In the polymers used, the polyoxyethylene generally has a molecular weight in the range of about 1,000 to 10,000, preferably about 2,500 to 5,000, and more preferably 3,000 to 10,000, for example 3,400. In such polymers, the molar ratio of polyethylene terephthalate units to polyoxyethylene terephthalate units (considering oo - OCH2CH20 - C - - and

- (OCH2CH2) 0- o- C - -

  such units) is in the range of 2: 1 to 6: 1, preferably 5: 2 to 5: 1, more preferably 3: 1

  at 4: 1, for example about 3: 1. The proportion of frag-

  ethylene oxide compared to the phthalate fragments

  in the polymer is normally at least 10: 1 and often 20: 1 or more, preferably in

  the range of 20: 1 to 30: 1, and more preferably approximately

* 22: 1. So we see that the polymer can be con-

  considered to be essentially an oxide polymer

  of modified ethylene, the phthalic fragment does not constitute

  a secondary component, whether calculated on a molar basis or a weight basis. It is astonishing that with such a small proportion of

  ethylene terephthalate or polyethylene terephthalate

  ethylene in the copolymer, it is sufficient

  similar to the polymer of the polyester fiber substrate (or other polymers to which it adheres,

  for example polyamides), so as to be

  held during washing, rinsing and drying.

  Although the PET-POET copolymer describes

  the one normally used by the United Kingdom

  according to the present invention and is the one which it prefers by far for its desired effects, other PET-POET polymers, for example some of those described in US Pat.

  3,962,152 and British Patent No. 1,088,984, may

  can also be used and are considered

  can sometimes be effective agents of

  of soil release in the compositions of the present invention. However, it is estimated that

  properties of aid in the detachment of dirt pre-

  These polymers are generally lower than

  to those of the preferred polymers.

  PET-POET copolymers useful in the practice of the present invention are available from Alkaril Chemicals, Inc. in the form of an aqueous powder or dispersion as Alkaril.

  QCF (powder) and Alkaril QCJ (aqueous liquid). evident

  However, to make liquid detergent compositions, it is preferred to use the QCJ product. Other copolymers, which also contain a polyacrylate as a stabilizer (generally in a ratio of

  polyacrylate copolymer weight of 4: 1) are

  by this company under the designations Alkaril

Base C and Alkaril Velvetol 251-C.

  Various detergency and combination adjuvants

  sounds of these, which serve to complete the action

  synthetic organic detergent (s)

  and improve this action, particularly in particulate detergent compositions, include both soluble and insoluble detergency builders.

  in water. Among the water-soluble detergency adjuvants

  Organic and inorganic detergency builders may be useful, but inorganic builders, generally in the form of one or more alkali metal salts, are preferred. Among the adjuvants

  of water-soluble mineral detergents, those which are

  They include: various phosphates, generally polyphosphates such as tripolyphosphates and pyrophosphates, especially sodium tripolyphosphates and sodium pyrophosphates, for example pentasodium tripolyphosphate and pyrophosphate

  tetrasodium; sodium carbonate; the bicarbonate

  sodium te; sodium silicate; the borate of

  dium or borax, and mixtures thereof. Instead of a mixture of sodium carbonate and sodium bicarbonate, one

  can sometimes substitute sodium sesquicarbonate.

  The alkali metal or sodium silicate, when used, normally has an M 2 O: SiO 2 ratio

  or Na 2 O: SiO 2 in the range of 1: 1.6 to 1: 3, preferably

  1: 2.0 to 1: 2.8, for example 1: 2.4 (or 1: 2.35).

  Among the adjuvant salts of mineral detergency

  water-soluble metals, phosphates can be used

  when they do not constitute a disadvantage,

  times with a lower proportion of sodium silicate.

  In preferred compositions without phosphates, carbonates can be used with bicarbonates

  and sometimes with borates and / or smaller amounts

  sodium silicates. Silicates are rare-

  used alone. Instead of using polyphospheres

  individual phates, it may sometimes be preferable to use mixtures of sodium tripolyphosphate and sodium pyrophosphate in proportions

  the range of 1:10 to 10: 1, preferably 1: 5 to 5: 1.

  Naturally, it is recognized that changes in

  the chemical structure of phosphates can occur

  during mixing and spray drying.

  ensure that the final product can have a

  phosphate, differing somewhat from that

  on the basis of the phosphate components loaded in the mixer, which are those described in

  present invention. Although we can also use

  sometimes additives of organic detergency hy-

  such as trisodium nitrilotriacetate

  (NTA), detergency adjuvants are generally preferred.

  water-soluble minerals, as indicated previously

  is lying. The various adjuvant salts of water-based detergents

  lubles can be used in hydra-

  which are sometimes preferable, and the salts

  water-soluble, hydrated or anhy-

  are normally sodium salts, or

  alkali metal salts, but sodium salts are generally preferred. In some cases,

  for example when producing compositions de-

  slightly acidic tergents, the acidic forms of detergency builders may be preferable, but normally the salts are of a neutral or basic nature, and in general the pH of an aqueous solution

  1% of the detergent composition is in the

  from 9 to 11.5, for example from 9 to 10.5.

  Insoluble detergency builders,

  typically zeolite A, usually hydrated,

  for example with 15 to 25% water of hydration, can

  can be used to advantage in composi-

  of the present invention. The hydrated X and Y zeolites can also be useful, as can the 16.

  zeolites and zeolitic materials

  and other insoluble ion exchange compounds that can act as detergency builders. Among the various zeolites A, zeolite 4A has often proved preferable. These materials are well known in the art and their manufacturing methods do not need to be described here. In general, these compounds are represented by the formula: (Na 2 O) x. (A1203) y. (Sio2) z.w H20

  where x is 1, y is 0.8 to 1.2, preferably

  Preferably, about 1, z is 1.5 to 3.5, preferably 2 to 3 or about 2, and w is 0 to 9, preferably 2.5 to 6.

  The zeolite used as adjuvant to determine

  should be a cation exchange zeolite

  novalents, that is to say that it must be an alumino-

  silicate of a monovalent cation such as sodium, potassium

  sium, lithium (where possible), or other alkali metal, or ammonium. Preferably, the monovalent cation of the type of zeolite mentioned is an alkali metal cation, in particular sodium or potassium.

  sium, and even better sodium, as indicated in the previous formula. The zeolites they

  crystalline or amorphous, are capable of

  gir quite quickly with calcium ions in hard water so that, alone or in conjunction with

  other water softening compounds of the com

  detergent position, they soften the wash water before harmful reactions occur between

  the ions responsible for the hardness of the water and the

  components of the detergent composition based on synthetic organic detergent. The zeolites used

  can be characterized as having a strong ability to

  calcium ion exchange city, which is normally about 200 to 400 milligrams equivalents or more of hardness reduced to calcium carbonate per gram of the aluminosilicate, preferably 250 to 350 mg equivalents / g, based on of anhydrous zeolite. Also, they preferably reduce the hardness of the wash water rapidly,

  usually in the first 30 seconds to five

  after they have been added to the wash water, and they can lower the hardness to less than one milligram of

  CaCO3 per liter, at the same time. The hyaline zeolites

  The dairies generally have a moisture content or water of hydration in the range of 5 to 30%, preferably about 15 to 25% and more preferably 17 to 22%,

  for example about 20%. Zeolites, such as

  brewing material from which base beads may be manufactured shall be in the finely divided state, the final particle diameters being not more than 20 micrometres, for example

  0.005 to 20 micrometers, preferably with a

  average particle size of 0.01 to 8 micrometers,

  for example 3 to 7 micrometers, if they are crystal-

  lines, and 0.001 to 0.1 micrometer, for example 0.01 to 0.05 micrometer, if they are amorphous. even though

  final particle sizes are very much lower than

  zeolite particles generally have di-

  mensions in the range of 0.037 to 0.140

  mm, preferably 0.044 to 0.105 mm, such as

  in the mixer for the production of

  the basic ones. In the base pearls, the zeolite (s)

  These are often and advantageously accompanied by one or more suitable detergency builder salts,

  for example, sodium tripolyphosphate and silicon

  sodium carbonate (in relatively low proportion),

  or sodium carbonate and sodium bicarbonate.

  Sodium silicate may tend to agglomerate

  with the zeolites, so that its proportion in the zeolite-reinforced base beads is limited, or the sodium silicate

  omitted, especially in

  carbonate, but sometimes the final detergent compositions may contain as much as%, for example in the absence of another binder or

appropriate anticorrosive agent.

  Polyacrylate used to stabilize the

  PET-POET copolymer in the particulate compositions

  res is a low molecular weight polyacrylate, for example an alkali metal polyacrylate, such as sodium polyacrylate, whose molecular weight is generally in the range of about 1,000 to 5,000, preferably 1,000 to 3,000 and more preferably from 1,000 to 2,000, for example 2,000. The average molecular weight is generally in the range of from 1,200 to 2,500, for example 1,300 to 1,700. Although other water-soluble polyacrylates may sometimes be present. partially replace the described sodium polyacrylate, including some other alkali metal polyacrylates, with

  potassium polyacrylate, it is preferable

  such substitutions, where

  are limited to a minor proportion of the material, and preferably the polyacrylate used

  is a total sodium polyacrylate. These materials

  res are available from Alco Chemical Corporation

  as AlcosperseW. Polyacrylates of

  dium are available in the form of powders or

  light amber, the powders being total-

  are soluble in water, solutions with

  from about 25 to 40% solids, by

  30%, and the pH of these solutions or a solution

  30% aqueous solution of a powder being 7.5 to 9.5.

  Among these products, the ones we prefer are currently

  sold under the names Alcosperse 104, 107, 107D, 109 and 149, of which

  Alcosperse 107D, a 100% powder of

  Although Alcosperse 107, a 30% aqueous solution, can be substituted for it, there is little difference in the results (provided that it is dehydrated first). In both cases, it is sodium polyacrylate, the liquid form (107) having a pH in the range of 8.5 to 9.5 and the pH of the powder (107D) being in the range of 7.0 to 8.0 at a concentration of 30% in water. The

  powder is preferably anhydrous but can contain

  a small proportion of water, normally less than

  %, which is mostly eliminated during

  the melting operation performed, for example when the PETPOET copolymer and the polyacrylate are melted

  together then cooled until solidification.

  To manufacture the polymeric components sta-

  bilized facilitating the removal of dirt from

  compositions of the invention, by following the

  In a normal manner, the PET-POET polymer is melted by bringing it to a temperature above its melting point and preferably in the range of 70.degree.

   C, in order to liquefy it, and then add a po-

  scdaimsolieenpure lyccrylate. When a homogeneous melt is obtained, it can be cooled, and the solidified melt can be crushed by any suitable means. Preferably, a cryogenic grinding or transformation operation is carried out

  in flakes so that the product is under

  of a finely divided powder or flakes which are easily miscible with other powdered particulate components of a reinforced detergent composition and do not unfavorably separate from said composition. Cryogenic crushing, often operated at a temperature below OC, and sometimes below -50 C, can be achieved by grinding or other crushing in the presence of liquid nitrogen or

  other cryogenic material. Alternatively, it can be used

  use a suitable grinder, such as a hammer mill, a Raymond Imp cage mill or grinder, and instead of liquid nitrogen or other cryogenic refrigerant

  liquid, it is possible to mix carbon dioxide

  lidified (dry ice) with the resins being milled, or other cooling means can be used to prevent overheating of the material and to keep it in a cold, easy state

  to break. Instead of crushing devices

  other products with equivalent effects, including the Raymond Ring-Roll crusher

  contains an internal separator and is capable of

  to obtain very finely divided resinous materials.

  Instead of using equipment from

  cryogenic or low-temperature grinding for crushing

  After the solidified melt of the PET-POET copolymer and the polyacrylate has been completed, the melt can be spray-cooled to form beads of desired dimensions, which generally pass through a 2.00 mm mesh screen, and preferably a 0 mesh screen. , 59 mm. The resulting products of the disclosed methods of the present invention can be considered as

  PET-POET copolymers carrying a polyacrylate.

  Since the proportion of the polyacrylate is

  latively weak (although its effect is appreciated

  the PET-POET copolymer constitutes a medium for

  distribute the polyacrylate throughout a composition

  any detergent solution with which he is

  diapered. Thus, in addition to the stabilizing effect that the

  polyacrylate exerts on the PET-POET copolymer, the

  lymere promotes the dispersion of polyacrylate, although

  that it can be more evenly distributed in the

  of the detergent composition and can therefore

  more uniformly to this composition the

  advantageous properties of the polyacrylate, which comprise

  improving the elimination of clay soils

  during the washing and the inhibition of soil redeposition on the laundry during washing. The fact that the polyacrylate is transported by the stabilized polymer also avoids the necessity

  to spray a solution of polyacrylate on

  detergent composition or base beads to distribute it more evenly throughout

the detergent composition.

  The stabilized PET-POET copolymers, in

  Intimate contact with the preferred stabilizing polyacrylate is used in the present invention to exert a soil release aid action in the described detergent compositions. It has been found that linen, in particular linen consisting of

  polyester fabrics or blends of poly-

  ester (often with cotton), make it easier to

  various soils in the washing water during

  the washing operation with the detergent compositions

  synthetic organic compounds, in particular

  bind those based on non-ionic detergents

  if the dirtying of the laundry took place after

  was washed with such a detergent composition

  holding the PET-POET copolymer. Some proportion

  of the copolymer is retained on the laundry during the washing operation, so that it is present

  when the laundry is dirtied later, and its

  sence facilitates the removal of dirt and / or stains applied later during the wash

  following. Polyacrylate could be expected to

  late, being in the same particles as the co-

  polymer PET-POET, promotes the dispersion of the polymer and inhibits its deposit on the laundry, but such is not

  the case. On the contrary, polyacrylate increases the activity

  help with the soil.

  PET-POET polymer in detergent compositions. A mechanism that accounts for this increase is

  inhibition, by the polyacrylate, of the decomposition

  degradation of the polymer when it is in contact with alkaline materials, as in the reinforced detergent compositions in which the detergency builder salt is alkaline (such as

  this is the case for a large number of them),

  especially at high temperatures.

  In addition to EGE, detergency adjuvant

  and PET-POET copolymer, or in addition to the three

  cited and stabilizing polyacrylate; the particulate detergent compositions of the invention

  also contain water (or human

  midity) and one or more additives. We can use

  a wide range of additives in the products

  such as those normally

  in detergent compositions of various types.

  but, in the compositions of the invention, the

  Preferred additives include enzymes such as

  the mixed proteolytic and amylolytic enzymes

  fluorescent brightening agents, such as stilbene brighteners, dyestuffs

  such as dyes and pigments,

  mixing agents, such as citric substances

  and magnesium sulphate, and perfumes. In

  in some cases fabric softeners are used,

  for example, bentonite or ammonium halides

  quaternary nium or amines, and sometimes flow improvers, which are often clays

26 1 9393

  special, We can include in the compositions of

  the invention of bleaching agents such as

  sodium borate, and bleach agent activators

  chiment, often in higher proportions than other additives, and they are often very useful in detergent compositions for washing

  in hot water. Charges, for example Na2SO4, may be

can also be present.

  In particular detergent compositions

  In accordance with the invention, there is normally from 10 to 35% of the nonionic detergent EGE, preferably from 15 to 25%, and most preferably about 20%. Content

  detergency adjuvant is usually found in the

  from 30 to 75%, preferably 55 to 70%, and

  even better 58 to 61%, for example 58% and 61%.

  When the detergent composition is a phosphate-reinforced composition, the phosphate content is generally in the range of 30 to 75%,

  with from 0 to 10% of water-soluble silicate, preferably

  this in the range of 50 to 65% sodium tripolyphosphate with 2 to 10% sodium silicate, and

  more preferably about 58% of tripolyphosphate

  dium and about 5% sodium silicate. For phosphate-free reinforced detergent compositions, the builder content is normally 30 to 75%, comprising 15 to 40% zeolite

  ion exchanger, from 10 to 30% of sodium carbonate

  dium and 5 to 20% of sodium bicarbonate,

  preferably being 55 to 70% in total, with 20 to 40% zeolite, 15 to 25% carbonate and 5 to% bicarbonate, and more preferably about 61% total, with 30% zeolite ( anhydrous base), 20% carbonate and 11% bicarbonate. For both types of detergent compositions, the percentage of

  PET-POET copolymer is usually found in the

  range from 0.5 to 10%, preferably 2 to 6% and better

  still about 4%, and the percentage of poly-

  Stabilizing acrylate is normally found in the

* range from 0.1 to 5%, preferably 0.5 to 5% and better

  still it is about 1%. The ratio of polyacrylate

  the PET-POET copolymer is normally

  in the range of 1: 6 to 1: 2, preferably 1: 5

  at 1: 3 and better yet it is about 1: 4. Additives

  present, apart from the bleaching agents and fillers which may constitute in total from 5 to 40% of the detergent composition, the required components being reduced proportionally to compensate, not

  generally not more than 10% of the total

  overall, preferably less than 5%, the

  preferred range being from 1 to 4%, for example 2% and 4% for particulate detergent compositions

  phosphate-reinforced and phosphate-free,

  tively. Individual additives (other than bleaches, bleach activators and fillers) normally constitute less than 2% of the composition and often less than

1.5%.

  To make the detergent compositions

  in particulate form, base pearls are prepared

  killed of mineral detergency adjunct by mixing

  an aqueous mixer mixture containing such an admixture

  detergency or a mixture of adjuvants

  tergence, usually with a solids content

  from 40 to 75%, at a temperature in the range of 40 to 75 C, and

  by spray drying it in an atomic tower

  at a temperature in the range of 250 to 450 ° C, to produce substantially globular beads of particle sizes in the range of 0.149 to 2.00 mm. If spray drying also results in the production of larger and smaller particles, these can be screened or classified by air up to

  the desired interval, or any other interval

  as acceptable for the intended purposes. The nonionic liquid detergent is then absorbed into the spray-dried beads,

  after cooling, by spraying the detergent

  desired liquid nonionic gent, in this case

  a non-ionic detergent EGE, on the surface of

  moving them. An advantage of the present invention

  It has been found that EGEs tend to be liquid, or at least are more easily liquefied by heating near room temperature (25 C) than EGLs, and therefore penetrate better to the spray-dried base beads, which improves treatment

  and results in products flowing better. The copoly-

  The PET-POET mother can be dispersed and / or dissolved in the nonionic detergent and can be absorbed in the spray dried base beads together with the nonionic detergent but especially when using a stabilizing polyacrylate to improve the

  properties of aid in detaching dirt from the co-

  PET-POET polymer, the copolymer can be melted with the polyacrylate, after which the melt can be solidified, either by spray cooling to form particles of similar dimensions to those of the base beads, or by being crushed to these dimensions by cryogenic or a

  other appropriate way. For a description more

  of the manufacture of the stabilized copolymer,

  see U.S. Patent No. 4,569,772 (Cial-

  lella, yielding to Colgate-Palmolive Company) incorporated

  here by reference. Atomic dried base pearls

  containing the nonionic detergent, and the co-

  stabilized polymer, can then be mixed

  and various other additives, not previously incorporated in these components, can be added after the fact, by mixing and / or spraying, as appropriate. Generally, these additives include

  enzymes and perfumes, agents that improve

  are optional. In some cases, antistatic agents are also added afterwards, either

  in the form of solid particles, either in the liquid state.

  These after-the-fact additions are normally executed

  in a suitable mixing apparatus, such as a mixture of

  inclined drum, but in general we can use

  any suitable type of mixing apparatus.

  The particulate compositions of the invention

  are used in essentially the same manner as described in US Pat. No. 4,571,303.

  (Ciallella, ceding to Colgate-Parmolive Company), incor-

  pored here by reference, and their testing to determine

  terminating their suitability for commercial use is against a wide variety of stains on normal laundry, including engine oil

  dirty, because a prime advantage of the deter-

  reinforced non-ionic detergent or heavy duty laundering agents is that they are effective in removing oily stains from

  linen, including linen containing

  polyester bristles. In tests aimed at determining

  their effectiveness in these applications, parts of the test material, for example knitting

  polyester, double polyester knit, poly-

  woven ester and polyester / cotton blends, are preferably

  laundered during a normal wash cycle of

  minutes using an automatic washing machine

  than top-loading capacity of 67 liters

  very water with a hardness of 150 mg / liter (p.p.

  m.) reduced to calcium carbonate (mixed hardness of

  calcium and magnesium), - after which the laundry is rinsed

  This is spin-dried and then dried in a

  automatic laundry chute (with a drying cycle of minutes). Then, the luminous reflectances of the

  test pieces are measured and their average is calculated

  EEA. Subsequently, the test pieces are stained, as with dirty engine oil (usually

  three drops per test piece) and undergo an old

  overnight. The next day, the reflections

  stained areas of these tissues are measured and the stained test pieces are washed and dried

  previously described, after which the reflec-

  these previously stained areas are measured. If it is posited that the reflectance of the unsplotted part is Rd1, that of the stained part before washing is Rd2, and that the final reflectance is Rd3, the percentage of soil detachment is Z (Rd3-Rd2) / ( Rdl-Rd2) x 100. Obviously, we take averages calculated on several test pieces used, so as to be able to

  obtain the average percentage of soil detachment

  for a particular spot on a particular

  for various stains on such a material, for a particular stain on various materials or for

  various stains on various matters.

  The activity of helping to detach soil

  of the detergent composition can thus be

  compared to that of another composition, in com-

  parrying the percentages of soil release

  obtained under identical washing conditions. nor-

  incorrectly, washing in cold water is the hardest test for a detergent composition and, therefore, comparisons made

  under these conditions are more indicative of

  28- with experimental detergent compositions, and

  experimental compositions that eliminate the

  The best cold water is often the one that consumers prefer the most. In addition, washing in cold water is more energy efficient, less expensive and affordable for more people in both industrialized and industrialized countries.

  third world, so that better performance

  these removal of stains and dirt in from

  Such washing conditions are extremely desirable.

  ble. By the test described above, the EGE nonionic detergents of the present invention are

  synergistically and strongly improve the effects of

  from the peeling off of the PET-copolymer

  POET, compared to similar compositions

  in which EGL non-ionic detergents replace

  hundred EGE components. In comparative tests, in the absence of PET-POET copolymer, the same types

  detergent compositions do not show any

  riority of compositions containing non-detergents

  ionic EGE on the compositions containing the deter-

  EGL non-ionic agents. It appears clearly

  the significant improvement in the aid effect

  adhesion of soiling of the compositions (and

  dice) of the invention is due to a combined action of

  PET-POET copolymer used as an agent to assist

  adhesion of dirt and nonionic detergent EGE, this conjugated action or synergy not being

  evident from the prior art.

  In liquid detergent compositions

  of the present invention, the compound or compounds of

  The fluorescent geometries that are present have a sub-

  washing clothes and they are used to convert

  shooting the invisible radiation in visible light, to make appear whiter the surfaces of the linen on which they were deposited. Such agents

  fluorescent brighteners are a class of sub-

  stances well known in the detergent technique and there is no need to describe them here. Suffice it to say that they will normally be of the stilbene type and, more particularly, of the stilbene-sulphonic acid type or the salt of such an acid. Among such brighteners used in the compositions of the present invention are those manufactured by Mobay Chemical Corp. and sold under the brands of

  manufactures Phorwite HRS and Phorwite BHC which are, respec-

  Finally, 4,4'-bis (4-anilino-6- (methylamino) -

  s-triazin-2-ylamino) -2,2'-stilbene-disulphonic acid and the potassium salt of 4,4'-bis (4-phenyl-2N-1,2,3-triazol-2-yl) ) -1,2'-stilbenedisulfonic. Although the fluorescent brightening agents mentioned act very effectively in the present compositions,

  considers that other types of substantial brightening agents

  These elements can be used in their place, without loss of the unexpected advantageous improvement of the soil release which is characteristic of the compositions of the invention.

  Anionic detergent may also be

  cluded in the preferred forms of implementation of

  liquid tergents of the invention in order to improve the

  substantivity of the fluorescent brightening agent, and

  add detergent properties to the

  (the anionic detergents being particularly

  effective in removing particulate matter

  tissues). The anionic detergent is preferably

  sulfate or sulfonate type, normally in the form of a water-soluble salt, such as a metal salt

  alkali, for example a sodium salt. Such deter-

  These subjects are extensively described in various texts, including Schwartz and Perry's Surface Active Agents (Their Chemistry and Technology), and John W. McCutcheon's various annual editions of Detergents and Emulsifiers. Although higher fatty alcohol sulphates and various other

  sulphates and sulphonates, it is preferable that the

  or a (higher alkyl) benzenesulfonate, especially such a compound whose alkyl group has from 12 to 18 carbon atoms. More preferably, the alkyl group is linear and has 12 to 16 carbon atoms, such as the dodecyl group, and the cation is

sodium.

  An enzymatic component of the present

  positions can be any suitable enzyme that is effective against a type of soils likely

  to be met on washing clothes with the deter-

  liquid gent. The most important of these enzymes are proteolytic and amylolytic enzymes, and

  their mixtures are preferable. These mixtures contain

  normally a part of the proteolytic enzyme

  for 0.5 to 2 parts of amylolytic enzyme,

  roughly equal portions are often preferred. A suitable commercial product is that sold under the brand name of

  Alcamyl O, which is manufactured by Novo Industrii, but other products of the type

  Maxatase (may also be acceptable.

  may be mixed with carriers or may be dissolved or dispersed in liquid media

  to facilitate weighing and further formulation

  cises. In the manufacture of compositions of the pre-

  invention, it is generally preferable to use

  liquid preparations of the mentioned double enzymes, which dissolve more easily than

powders.

  A stabilizing agent or a stable combination

  bilisante is normally present with the enzyme (s)

  my; it helps prevent a decrease in activity

  enzymatic after storage of the composition

  liquid tergent containing the enzyme or the mixture of enzymes. Suitable stabilizers include lower carboxylic acid salts, typically 1 to 3 carbon atoms, which are preferably

  alkali metal salts, for example salts of

  dium. Of the lower carboxylic acid salts, formates are preferred, the most preferred of these

  stabilizers being sodium formate. Preferably

  this again, the enzyme stabilizer mentioned is

  in one or more water-soluble salts of calcium and / or magnesium, preferably salts of strong organic acids, such as calcium chloride, magnesium chloride and / or magnesium sulfate. This or these salts form a stabilizing system with the one or more

  salts of lower carboxylic acids, and they improve

  the stabilization of the enzyme or enzymes

paths.

  Since it is recognized that

  Although not all of the liquid detergent compositions of the present invention are readily soluble in the aqueous medium of these compositions, it is often advantageous to use a co-solvent to facilitate the dissolution of these components (such as

  the fluorescent brightening agent) and to help

  to fish for a stratification of the liquid detergent composition or a deposit of its components. The co-solvent

  can also perform antifreeze function, by

  to maintain the composition uniformly liquid even when temperatures fall below the freezing point. The preferred co-solvents are

  polar organic compounds of low molecular weight

  which are preferably lower alkanols such as ethanol or isopropanol, ethanol (which

  is normally denatured) being preferred. Such a co-

  solvent can be mixed with another solvent, such as a diol or a polyol, to form a system

  more complex co-solvent. Among the diols and polyols

  Suitable ols are glycerol and glycols.

  The water used may be tap water, distilled water or deionized water, or

  may be treated water such as feed water

  boiler supply from the feed system

  of the boilers in the manufacturing facility

  tion. It is normally desirable that the hardness of this water be relatively low, and the hardness of the water should normally be less than 100 mg / liter (eg mC), expressed as CaCO 3, preferably lower than

  at 50 mg / liter, and even more preferably about zero.

  Various additives may be included in the liquid compositions of the invention, often the same as those for particulate products, the most commonly used of these additives being a perfume and a colorant. The perfume is normally lipophilic but is easily solubilized by the surfactant components and solvents of the composition. The

  dye may be a finely divided pigment

  sand in water, but it is generally preferable to use a water-soluble dye or a mixture of such suitable dyes, dye mixtures

  pigments and pigments are also possible.

  Other components of the composition of the invention that may be considered additives are the alkaline and acidic substances that can be used to adjust the pH of the liquid detergent to a desired range. Normally, it is not necessary to use both acidic substances

  and alkaline, for pH adjustment, but this modality

  sometimes it may be desirable. An active substance

  preferred is citric acid, which is preferably

  this used in the form of an aqueous solution, for example

  to 50% citric acid in water, and a preferred alkaline neutralizing agent is aqueous sodium hydroxide, which is generally at a concentration of

  38% NTa20 in the water. Another additive that is often

  preferably used in the present

  is an additive intended to inhibit the corrosion of

  metal material in which the composition is

  stored, processed or transported. Among these agents

  ticorrosion, the most effective for the present

  positions are the alkali metal nitrates, by

for example, sodium nitrate.

  -15 The proportions of the various components of the

  liquid detergent compositions of the present invention.

  are maintained in certain intervals in order to

  to obtain a product with the desired characteristics

  with a better detergent power vis-à-

  oily spots, for example

  dirty, on various tissues, in particular poly-

  esters and cotton / polyester blends, and of which

  the appearance and physical characteristics are acceptable. The main component of the liquid detergent compositions of the invention is water, the proportion of which is normally a sufficiently solubilizing proportion (together with any cosolvent that may be present) for EGE, PET-POET copolymer and any other components of the composition. Content

  water is in the range of 50 to 85%, preferably

  60 to 80%, more preferably 65 to 75%, and most preferably 70% or about 70%. The proportion of EMT is a detergent proportion, which is

  generally in the range of 10 to 30%, preferably

  preferably 12 to 20%, more preferably 14 to 18%, and most preferably 34, preferably 16% or about 16%. The proportion of PET-POET copolymer is a helper proportion

  the detachment of soiling, which is generally

  within the range of 0.2 to 3%, preferably 0.5

  at 2%, better still 0.7 to 1.5%, and most preferably

1% or about 1%.

  When a fluorescent brightening agent or a mixture of fluorescent brighteners is present, its proportion is a brightening effect proportion, in the range of 0.05 to 2%, preferably 0.05 to

  0.3%, and more preferably 0.2% or about 0.2%. The pro-

  portion of anionic detergent is an

  the substantivity of the brightening agents in the range of 1 to 10%, preferably 2 to 5%, and

  more preferably 3.5% or about 3.5%.

  The proportion of the enzyme (s) is an enzymatic proportion, in the range of 0.1 to 5%, preferably 0.3 to 3%, and more preferably 0.8% or about 0.8%. These proportions are based on the enzymes as commercially available, including any supports. The stabilizer or enzyme stabilizer system is present in a stabilizing ratio in the range of 0.5 to 6%, preferably 2 to 4%, and more preferably

  this proportion is about 3%, for example 3.2%.

  The co-solvent present is in a proportion with a dissolving effect in the range of 3 to 15%, preferably 4 to 10%, and more preferably 5%.

  or about 5%. The totality of the additive (s)

  in the range of 0.1 to 5%, preferably between

  0.2 to 2%, for example 1% or about 1%.

  As for the individual additives, the content of the anticorrosive compound is in the range of 0.2 to 2%,

  preferably 0.3 to 1%, and more preferably 0.5% or more

  0.5% viron. The proportion of perfume is in the range of 0.1 to 1.5%, preferably 0.2 to 1%, and more preferably 0.35% or about 0.35%. The content of neutralizing or pH-adjusting agents is

  in the range of 0.05 to 0.5%, preferably

  this 0.1 to 0.3%, and more preferably 0.15% or about 0.15%. The content of dye or other dyestuff may range from 0.00001 to 1%, preferably 0.00002 to 0.01%, and more preferably 0.00004%.

or about 0.00004%.

  The liquid detergent composition facilitating the removal of dirt obtained is normally

  in appearance, and sometimes it can be translucent

  of. It can be made deliberately opaque,

  creates, or more cloudy, through the use of additives

  propriate. The pH of the product is normally in the range of 7.3 to 8.1, preferably about 7.7, and the viscosity is normally in the range of 65 to 115 centipoises at 25 ° C. preferably

at about 90 mPa.s.

  The manufacture of the liquid composition of

  the invention is relatively simple, practically

  a critical operation is not necessary. In general, the proportion of water of the formula or about 80% or more of this proportion is introduced by pumping

  in a mixing vessel or tank and the various

  detergent composition components are mixed

  in the aqueous medium, then the rest of the water is added. Sometimes the co-solvent may be added first, and other times some or all of it may be retained for later addition with the rest of the water, at the same time.

  end or near the end of the mixing process. In beautiful

  case, special components such as

* kind of fluorescent brightening, are dissolved first in

  the co-solvent or in part of the water containing

  part or all of the co-solvent. Although these techniques may facilitate the faster manufacture of the liquid detergent having the state and appearance

  desired product, the desired product is generally

  naked without having recourse to these operative variants, ex-

  cepted for the preliminary dissolution of the agent of

  fluorescent living. When the mixture of all

  If the components are finished, the rest of the water can be added, also with stirring, and

  adjust the pH. After pH adjustment and check

  relied on the viscosity to make sure it is in

  standards, the product can be bottled

  rectly. The use of the liquid compositions of the invention is simple and satisfactory, from the point of view of the user, who has little to

  if not to dose the desired amount of

  liquid detergent and add it to the water of the

  of an automatic washing machine. These machines contain 60 to 70 liters of water, usually 67 liters, and one will use 1/2 cup of detergent

  liquid, which corresponds to about 120 g,

  This quantity may vary according to the load to be washed and the degree of dirt of the articles to be washed. The laundry (usually about 3 kg + 50%) is added to the wash water and the machine is started. The wash water normally has a hardness of not more than 300 mg / liter (ppm) expressed as CaCO3, and the water temperature is normally 10 to 90 C. It is known that, according to US practice, the temperature of the water is the washing water seldom, if ever, approaches boiling, but the

  processes for washing and assisting in detaching

  The seals according to the present invention are usable at such high temperatures. However, the best comparative effects of separation assistance are obtained

  dirt at the lowest temperatures. Preferably

  the water hardness is not more than 200 mg / liter, the range of 100 to 200 mg / liter being

  considered normal. Of course, we can also

  use waters of lower hardness. In the above-mentioned wide range of temperatures, a preferred range is 10 to 50 ° C, and to achieve the most markedly improved effects of soil release and the resulting detergent action,

  compared to those obtained using composi-

  similar EGL, this range is 10 to 25 C,

for example, about 20 to 21 C.

  Normally, the wash cycle (during the

  the PET-POET copolymer is applied simultaneously to the laundry) is from 5 to 30 minutes, the rinsing cycle being from 1 to 5 minutes in the case where one uses a

  automatic washing machine, and sometimes you can use

  several rinsing cycles, usually 2 or 3.

  Drying times range from 10 to 60 minutes, generally

  20 to 40 minutes and the drying will generally be

  This is done at "normal" drying temperatures of automatic tumble dryers rather than "high" settings. Naturally, the conditions of washing and drying will be determined by the nature of the laundry, dirt and / or stains present on the laundry, and depending on the characteristics of the laundry.

  washing and drying apparatus used. We use

  will usually be automatic washing machines to

  loading from above, but charging machines-

  side effects are also acceptable, and

  also comes to the benefits mentioned by a manual washing

  laundry and drying on clothesline.

  In the washing-treatment process, it is

  particularly advantageous to introduce the

  liquid detergent described in the washing machine, but it is also possible to introduce its various constituents, alone or in mixtures, into the washing machine.

  to wash, to produce essentially the same

  washing water. The resulting wash water will contain a detergent proportion of EGE and

  a proportion with an effect of aid to the detachment

  PET-POET copolymer seals. Such proportions are in the ranges of 0.01 to 0.1% and 0.0002 to 0.01%, respectively, preferably 0.01 to 0.05% and 0.0005 to 0.006%, respectively, and better

  still 0.02 to 0.04% and 0.001 to 0.005%, respectively

  for example about 0.03% and about 0.003%, respectively. The concentration of fluorescent brightening agent is in the range of 0.0001 to 0.01%, preferably 0.0002 to 0.001%, for example 0.0003%. The concentration of anionic detergent is

  is in the range of 0.001% to 0.03%, preferably

  from 0.002 to 0.02%, for example about 0.007%.

  The concentrations of the other components of the compound

  liquid detergent (except water)

  in the wash water and their intervals of use.

  percentage in relation to the washing water,

  can be obtained by multiplying the concentrations

  examples given for the 0.0018 liquid detergent composition, which gives their ideal concentrations in the wash water, or

  the percentage intervals can be calculated

  higher and higher levels of these concentrations in

  the percent concentrations given for the liquid detergent composition by 0.0010 (for the lower limit) and 0.0030 (for the

  upper limit). Although it is more preferable

  In order to utilize the liquid detergent composition at a concentration in the wash water of about 0.18%, this concentration may be, depending on the nature of the laundry, in the range of 0.10 to 0.30%. or in a

  narrower preferred range of 0.15 to 0.25%.

  The following nonlimiting examples illustrate

  the invention. Unless otherwise indicated, in these

  examples and in the specification, all

  are expressed in weight and all temperatures

in C.

EXAMPLE 1

  Component Percent Sodium Tripolyphosphate 57.3 Narrow Range Ethoxylated Fatty Alcohol K 20.0 Water 10.0 Sodium Silicate (Na2O: SiO2 = 1: 2.35) 4.5 PET-POET Copolymer ** 3.6 Proteolytic Enzymes and mixed amylolytic (Maxatase MP) 1,3 Sodium sulphate 1,1 Fluorescent brightening agent (Tinopal Z BM highly concentrated) 1,0 Sodium polyacrylate (Alcosperse

107D) 0.9

Perfume 0.2

100.0

  x Condensation product of a linear alcohol in

  C12-C14 and an average of 6-7 moles of ethylene oxide

  per mole of alcohol, about 88% of the ethylene oxide

  ethylene in polyoxyethylene groups of 5 to 10 ethoxy groups (Tergitol 24-L-60N, manufactured by

Union Carbide Corporation).

  * PET-POET copolymer of average molecular weight

  by weight of about 22,000, the molecular weight of the

  lyoxyethylene is about 3,400 and the ratio of

  polyethylene terephthalate units

  polyoxyethylene terephthalate being about 3: 1 (Alkaril QCF, manufactured by Alkaril Chemicals,

  Inc., and provided by that company in the form of

  ticles, in a ratio of 4: 1 with polyacrylate

  sodium, under the name Alkaril Base C at

state beforehand).

  A detergent composition is prepared

  having the formula above by mixing a

  mixture of kneaders with 45% solids

  killed by tripolyphosphate, silicate, sulphate,

  fluorescent brightener and dye, in tap water, at a temperature of about 60C and spray-drying it in a hot desiccant gas at a temperature of about 4000 C in a tower

  atomization to form pearls of al-

  0.140 to 2.00 mm, having a moisture content of 13.5%. After cooling, 74 parts of these base beads are sprayed with 20 parts of the nonionic detergent EGE in the liquid state at elevated temperature, for example about 40 C, which detergent is absorbed into the beads. Next, 4.5 parts of a 4: 1 QCF / Alcosperse mixture (in particulate form, having approximately the same particle size as the spray-dried beads) and 1.3 parts of

  mixture of enzymes with the detergency adjuvant beads

  containing the nonionic detergent and then

  smokes the product by spraying 0.2 parts of liquid perfume, the materials being kept in motion in an inclined drum mixer during all these

operations.

  The effect of helping to detach stains

  the detergent composition described, containing the

  synergistic cation of the EGE nonionic detergent and the PET-POET copolymer, is measured by the HMS method

  (dirty engine oil) previously described in this

  description. Test pieces made of different materials are first washed in a machine

  automatic washing with the detergent composition ex-

  perimental at a concentration of 0.15% in wash water at 21 C with a hardness of 150 mg / liter, expressed as calcium carbonate, then dried

  in an automatic dryer, we spot each of the

  these test with three drops of dirty engine oil (HMS), let them rest for one night, and

  again washed with the detergent composition ex-

  perimentally in the same conditions. We measure

  reflectance of the test pieces after the first wash

  after staining and after the second wash

  and we calculate the percentages of separation of

  cracks according to the previously given formula.

  A control composition containing the same proportion of nonionic detergent is prepared, but it is an EGL (Neodol 25-7) having essentially the same

  same average ethylene oxide content and

  the same fatty alcohol component, the only difference

  between the detergents residing in the

  the broad-range ethylene oxide polymer in the narrow-range EGL detergent in EGE detergent. For such a control product, the same

  basic pearls and additives, and in the same proportion

  tions, but the different nonionic detergent is

sorbed in these pearls.

  The following table compares the percentages

  removal of dirt (or removal of

observed):

TABLE I

  Peeled dirt (%) Ccmposition Ccaposition Fabric type of the Experimental Part T & min Dacron double knit 88.7 73.1

26 1 9393

  Single knit in Dacron 94.0 91.1 Woven polyester 91.5 80.8 Blend 65:35 Dacron: cotton 47.3 35.7 Blend 50:50 Dacron: cotton 32.2 26.7 Knit Nylon 79.4 59 , 4 Jersey acetate 81.9 72.1 Since a difference of 5% in the dirt separation is considered as

  significant in the conditions of the test, we obtain

  holds significant differences for all test pieces except the simple Dacron knit, but even in this case, the experimental composition

  is significantly better than the control composition.

  The average improvement is 10.9%. Observations

  The visual effects of the test pieces are even more convincing of the unpredictably advantageous soil detachment effect of the synergistic composition of the present invention. It must be remembered that the indicated test is carried out

  with stronger stains than normal

  encountered and under washing conditions

  (cold water) which are considered unfavorable.

  Thus, it is possible to achieve a detachment of

  even better using warm or hot wash water. Moreover, when several washes, for example 2 to 6, with the compositions, precede

  the staining of HMS stains, the decol-

  The fouling of the composition of the invention is even more pronounced. The soil release effects obtained for HMS are also obtained when using various other types of soiling.

  in the described essay and the improvements in terms of

  Witnesses are also important.

EXAMPLE 2

  Components Percent Sodium Zeolite (Zeolite 4A, Anhydrous Base) 30.1 Sodium Carbonate (Anhydrous) 20.1 Nonionic Detergent EGE * 20.0 Sodium Bicarbonate 10.8 Water 9.5 White Montmorillonite (Anhydrous) 1.4 Mixture of enzymes (Maxatase MP) 1.3 Fluorescent brightening agent (Tinopal 5B ™ highly concentrated) 1.0 Copolymer PET-POET * 4.0 Sodium polyacrylate (Alcosperse 107D) 1.5 Perfume 0.2 Coloring matter (mixture of dyes) 0.1

100.0

See Example 1

  - See Example 1 (Alkaril Velvetol 251-C used at

place of Alkaril Base C).

  Two control compositions, A and B, were prepared, A being identical to the above experimental formula except for the substitution of Neodol 25-7 for Tergitol 124-L-60N, and this EGL substitution also being carried out for the control B for which QCF and 1% of the Alcosperse 107D stabilizer (the

  Remainder of Alcosperse 107D is added to the mixture of

  laxeur). The test pieces are washed, stained and washed again with the experimental compositions,

  Witness A and Witness B, respectively, the results of

  States being collected on the following table.

TABLE II

  % soil release Composition Fabric Type of Parts Experimental Witness A Witness B

26 1 9393

  Double Knit Dacron 66.0 27.9 3.6 Blend 65:35 Dacron: Cotton 40.2 31, 8 13.8 Knit Nylon 39.3 17.4 26.7 Acetate Jersey 48.8 33.5 10 8

  The results above show that the

  The experimental mule of the present invention is clearly

  better than any of the formulas

  less to facilitate peeling on parts

  described, an oily soiling more

  this, namely a motor oil even dirtier than that used for the tests of Example 1. If one

  considers that a difference of 5% is quite

  significant, it is clear that we are achieving differences

  these very appreciable compared to the best of

  controls, for which the non-ionic detergent is

  that EGL instead of the nonionic detergent EGE of

  compositions of the present invention. Thus, the improvement

  The ratio of soil release to the four listed materials is 20.9%. Visual examinations of the test pieces confirm that the

  detachment of soiling from the composition of the in-

  vention is much greater than that of the witnesses.

EXAMPLE 3 AND 4

  The compositions and controls of Examples 1 and 2, respectively, a nonionic detergent EGE, available from Shell Development Company which identifies it by 23-7P, are substituted for Tergitol 24-L-60N. Tests on fabric pieces similar to those of Examples 1 and 2 show that these detergent compositions are essentially equivalent, as

  the action of aid to the detachment of dirt,

  experimental positions of Examples 1 and 2, respectively

  which proves that Shell's product 23-7P,

  which falls within the description of the deter-

  EGE nonionic gels of the compositions of the present invention, also improves synergistically

  the action of helping to detach the stains of the co-

  PET-POET polymers of the compositions of the invention.

EXAMPLES 5 AND 6

  The compositions and controls of Examples 1 and 2 are prepared, respectively, a non-detergent

  ionic EGE, available from Shell Development Compa-

  which identifies it by 23-7Z, being substituted for the Ter-

  gitol 24-L-60N. Tests on fabric pieces,

  examples of those in Examples 1 and 2 show that these

  detergent compositions are essentially equivalent

  slow, as regards the action to assist the separation of

  cracks, to the experimental compositions of Examples 1 to 4, which proves that Shell product 23-7Z,

  which falls within the description of the deter-

  EGE gels of the composition of the invention also improves, by synergy, the soil-peeling aid action of the PET-POET copolymers of the compositions of the invention. We can get

  similar results using a gamma ethoxylate

  This is the narrow range of the Shell Development Company, designated Neodol 23-6.5 NRE, which is the narrow range ethoxylate that may be Neodol 23-6.5, a product of Shell Chemical Company (this product is an EGL). Similarly, mixtures of the mentioned nonionic EGE substitute detergents can be prepared, and comparable improvements in

detachment of dirt.

EXAMPLE 7

  Various modifications can be made to

  compositions and methods of Examples 1 to 6, without

  frame of the present invention. So for the

  washing operations, the concentration can be varied

  of the detergent composition used in the range of 0.05 to 0.3%, depending on the hardness and temperature of the wash water, the type and model of the washing machine, the type of laundry and the Dirty laundry subject to treatment and washing. We can

  use different detergency builders, polymeric

  PET-POET resins, polyacrylates, fillers, enzymes and

  very additives, as well as various mixtures of them.

  Various mixtures of nonionic detergents of the narrow range ethoxylate type can be used and

  individual proportions of the components of the composi-

  The detergent compositions of the invention may vary from 10% to 20% and up to 30%, provided that they remain

  in the intervals and descriptions mentioned in

  this memoir. Although the compositions of the in-

  do not normally contain detergents

  anionic, their presence within a reasonable limit

  10% of such a composition can be

  times be desirable. Among the anionic detergents,

  the most preferred are (higher alkyl)

  benzene sulphonates, the (fatty alcohols su

  sulphates and the (higher fatty alcohol) poly-

  ethoxy-sulfates, preferably in the form of sodium salts, the alkyl groups and alcohols having from 18 to 18 carbon atoms, preferably 12 to 14 atoms

of carbon.

  When making changes to the formulas

  Examples 1 to 6, as mentioned, the composi-

  resulting procedures and the procedures used to facilitate

  effectively remove the stains from

  synthetic organic polymeric textile

  (especially polyesters) and blends of synthetic and natural fibers. However, it is

  important that the nonionic detergents

  Such compositions which are used in these processes are of the EGE type, as previously described, and are present in proportions

  entering the intervals mentioned.

  Combosants EXAMPLE 8 Percent Nonionic Surfactant EGE Tergitol

24-L-60N * 16.00

  Alkaril QCJ (15% aqueous solution) * 6.67 Fluorescent brightener ** 0.16 (linear dodecyl) sodium benzenesulfonate (52.5% active ingredient, in aqueous solution) 6.67 Mixture of Enzymes (Alcamyl) 0.75 Calcium Chloride Dihydrate 0.17 Sodium Formate 3.00 Sodium Nitrate 0.50

  Blue dye (C.I. Acid Blue 182, so-

  0.38% aqueous solution) 1.00 Ethanol (denatured with methanol) 5.41 Fragrance 0.35 Sodium hydroxide (aqueous solution, m.p.

  38% Na2O) to adjust the pH q.s.

  Citric acid (50% aqueous solution),

to adjust the pH q.s.

  Water (softened) *** 59,32, 00 * A narrow range ethoxylate type nonionic detergent which is a condensation product of a higher fatty alcohol of 12 to 14 carbon atoms with an average of 7 moles of oxide of ethylene per mole, made up of more than 90% ethoxylates

  from 4 to 10 ethoxy groups per molecule.

  Polyethylene terephthalate terephthalate copolymer

  polyoxyethylene phthalate having a molecular weight of

  about 22,000, a molecular weight of the poly-

  oxyethylene of about 3,400, and a molar ratio

  ethylene terephthalate units with terephthalic

  polyoxyethylene late of about 3: 1.

  úXE stilbene fluorescent brighteners (0.11% PhorwiteD RKH and 0.05% Phorwite BHC, both manufactured by Mobay Chemical Co., each of these brighteners can be replaced, but is preferably a stilbene sulfonate or stilbene sulfonic acid). The given percentage relates to compositions to which neither sodium hydroxide nor citric acid (for pH adjustment) has been added. If we use

  one or the other, the percentage of water is decreased

  proportionately. Note that the percentage of water in the final liquid detergent composition is higher

  to that indicated because a certain amount of water

* dresses the various components.

  A liquid detergent having a composition of

  position above by mixing all the components

  with water in any appropriate order, provided that the

  fluorescent brightener is dissolved at the beginning of

  manufacturing process. The solution of hy-

  sodium hydroxide or the citric acid solution to the

  end of the mixing process to adjust the pH, by

  raising or lowering, as required, and the

  fum is normally added after pH adjustment.

  Optionally, the mentioned components, including

  Some may be dissolved in the co-solvent or in aqueous co-solvent, may be mixed with an appropriate fraction of the amount of water of the formula (eg 1/2 or 4/5), and the rest of the water can be added last or shortly before pH adjustment

and / or the addition of the perfume.

  The resulting product is a blue, turbid or translucent liquid having a viscosity of 90 mPa.s at 25 ° C., measured with a Brookfield (RV) viscometer using a rotating N 1 spindle.

  at 20 rpm. The pH of the product is 7.7.

  The liquid detergent composition obtained is stable at room temperature for at least six months

  and often for a year or more without stratification

  cation and component separation, and the soil peeling aid action of the PET-POET copolymer remains after storage, apparently due to the presence of the EGE in the product. Yes

  we replace the EGL with EGL, we notice, after

  storage, a significant decrease in activity

  help in detaching dirt.

  The detergent composition is tested

  liquid of the invention, as to its effect of helping to detach stains, compared to a

  control composition which is identical to the difference

  Tergitol 24-L-60N non-ionic surfactant is replaced by Neodol 25-7. We give below a

  description of the test method, using a

  normal concentration of the detergent compositions

  in the wash water, ie 0.18%.

  In a Tergotometer laboratory washing machine, three rectangular pieces of polyester double knit, each measuring 7.6 x 10.2 cm, are prewashed in one liter of washing water having a hardness of 150 mg / liter, expressed as CaCO 3, for ten minutes at a temperature of 21 C (washing in cold water) or 38 C (washing in hot water), as required. At the end of the washing, the pieces are rinsed by hand for about

  ten seconds and dry them, and after drying,

  reflectance measurements using a reflection of

  tometer (Gardner XL20, for example). The average reflectance value for the three pieces is called Rd (initial). Each of the three pieces is then stained with three drops of dirty engine oil and left to stand overnight. Reflectance measurements are again made and the average is called Rd (stained). The pre-washing process is followed by a washing of the stained parts and again the reflectance measurements are made, the average of which is determined by Rd (washed). The percentage of soil release is calculated as follows: Rd (washed) - Rd (stained) X 100 Rd (initial) - Rd (stained)

  Instead of using the laundering machine-

  laboratory, a domestic washing machine can be used

  classic tick, following the same method at different

  that parts can Dc-Sometimes be in various

  tissue types and generally have larger di-

  mensions, for example 10.2 x 15.2 cm, the volume of

  the washing water being larger, for example 64.3 liters

  the washing machine is set for one cycle

  normal washing time of ten minutes, with the associated cycles

  normal rinsing and spinning conditions. The charge of liquid detergent composition in these tests is 1/2 cup per wash, which represents 0.18% of

washing water.

  The percentage of soil release

  achieved by the composition of the invention having the

  previous mule is 74.2% (21 C) while that

  of a witness, of identical formula except that the surfac-

  Non-ionic tif Tergitol 24-L-60N is replaced by Neodol 25-7, is only 54.4%. The difference is considered very significant and is not justified by any other obvious explanation that the EGE and the PET-POET copolymer act together to

  unexpected and advantageous way to improve the

  soil detachment aid characteristics of the liquid detergent composition, so that

  greasy soils, which may contain

  particulates, for example, motor oil,

  dirty, are much better removed from

  polyester and polyester blends by the composi-

  liquid detergent solution of the invention only by

  similar compositions based on nonionic detergents

  wide range ethoxylate.

  To ensure that the apparent "synergy" does not result from the fact that Tergitol 24-L-60N is itself an agent facilitating soil release, other control experiments are carried out, repeating the experimental and witnesses described

  above, except that Alkaril QCJ is omitted in the formulas

  mules. In these cases, the percentage of soil release for the repeated control (based on Neodol -7) is 7.4% and the percentage soil release for Tergitol 24-L-60N of the formula, without

Alkaril QCJ, is 7.5%.

  The results above show that the

  EGE alone does not facilitate the detachment of

  smears more than the EGL detergent alone, but

  the combination of EGE and the improved PET-POET copolymer

  is substantially the detachment of dirt by the

  copolymer. This improvement is unexpected and

  aunt. The differences in cleaning effects on the parts

  these tissues are obvious to non observers

  experienced and there is no need to use

  sensitive measuring devices to verify these differences.

  ences. When repeating the laboratory test

  in a conventional washing machine, one gets sensi-

  the same results. However, when

  difies the washing temperature from 21 C to 38 C, there is

  There are no appreciable differences from the take-off aid

  This may be due to the fact that at this high temperature of the wash water,

  percentages of soil release are greater than

  90% and therefore close to their maximum

  my. It is considered that in case the tissues are more

  stained so that in the experiment described above, the EGE-QCJ formulas significantly facilitate the removal of soiling more than the formulas

EGL-DCQ.

EXAMPLE 9

  The washing tests are repeated in the laboratory.

  Example 8, but the test pieces are tri-

  Nylon cot and in a 65/35 blend of polyester / cotton.

  In the tests at 21 ° C., the composition of the invention eliminates 56.6% of the soils of the nylon, whereas the

  control composition only eliminates 37.1%. The composition

  tion of the invention eliminates 57.4% of the

  polyester / cotton blend, while the

  less than 49.7%. Differences at 38 C

  are similar, the composition of the invention is

  control composition by eliminating 56.3% of the

  Nylon compared to 47.8% for the control, and eliminating 52.0% of the polyester / cotton blend, compared to 35.9% for the control. Moreover, the

  differences in soil release are apparent.

annuities with the naked eye.

  The example above shows that the improvement

  unexpected release characteristics

  fouling of a composition of the invention,

  to a similar composition based on EGL

  is not limited to polyester fabrics, but

  also applies to nylon fabrics and a mixture of

lyester / cotton.

EXAMPLE 10

  The test procedure of Example 8 is repeated, but using aged and fresh detergent compositions, and washing in a laboratory washing machine with water

  washing at 38 C. Using the compositions

  newly prepared liquid gents, the composition of the invention eliminates 92.4% of the tissue

  polyester, while the control composition in

  mine 90.1%. Thus, the liquid detergent compositions

  practically the same effects of aid to the

  detachment of soiling in these conditions. How-

  after accelerated aging of the composi-

  detergents for one week at 44QC, it appears that

  would be a considerable difference with the product expe-

  rimental which removes 88.6% of the dirt-while the control eliminates only 81.2%. Thus, we see that

  the action of helping to detach the dirt from the

  less deteriorates faster than that of the

  liquid detergent section of the invention.

  The experience described also shows that in order to maintain the activity of helping to detach

  soiling of this type of liquid detergent composition

  of, it is important to use non detergents

  ionic type EGE, rather than detergents of the type

  EGL. It was previously known that copolymers

  PET-POET in the present type of compositions

  liquid (but EGL-based) drugs were destabilized

  triethanolamine, which is used in some liquid detergent compositions for its

  solubilizing effect on fluorescent brighteners

  cent, and it was known that ionizable salts

  tendency to exert such a destabilizing effect.

  Therefore, the triethanolamine (TEA) content

  liquid detergent compositions containing PET-

  -35 POET is reduced to a minimum or TEA is omitted

  totally and the ionizable salt content is limited.

  Generally, for liquid EGE-PET-POET based liquid detergent compositions to exert a good soil detachment effect, the amount of TEA present must be limited to 1%, preferably less than 0.5%. %, and better yet it is zero. As regards ionizable salts, their concentration should normally be limited to 10%, preferably

  at 5%, and more preferably at 1% or less. For the components

  of this memorial and this example, the

  neur ionizable salt is advantageously limited to

  similar way, preferably to 5 or 10% of

  nable (1%, excluding sodium formate and anionic detergent) and 0.1 or 0.2%

  TEA (but it is better to delete it completely-

  is lying). Although the results presented in this example are for a 38 C test, they are considered

  are representative of the results obtained when the

  sai occurs at higher and lower temperatures.

  For example, these results are considered to correspond to results obtained after a shelf life of the liquid detergent composition for six months and for one year, or after

  accelerated aging of one or two months. How-

  after longer periods of storage or

  storage at higher temperatures, the activity

  of soil contamination is further diminished, so that it is important that the products

  to market have the maximum of initial effects

  tials for help in detaching dirt, so that

  that even when these effects are diminished, the perfor-

  maneuvering aid to the separation of dirtying saeitencore

acceptable to the consumer.

EXAMPLE 11

  When modifying the basic formula of the Exem-

  ples 8 to 10 by replacing Tergitol 24-1-60N by comparable EGEs such as 24-L-45N, 24-L-50N and 24-L-75N,

  essentially the same types of revisions can be

  Results. Similarly, other EMTs can be substituted

  23-7P Shell and 23-7Z Shell and obtain

  similar results at least in some of these cases.

  Various modifications can be made to the copolymer

  PET-POET, for example by increasing its molecular weight

  average weight, so that it is in the range of 30 000 to 40 000, and still obtain the

  advantageous effects of aid in detaching dirt.

  Instead of the mentioned anionic detergents, one can

  use others such as sodium lauryl sulphate

  dium, and other alkylarylsulfonates and alkylsulfates

  your comparable. Various enzymes, enzyme stabilizers, copolymer stabilizers, co-solvents, fluorescent brighteners, dyes can be used

  and perfumes, as set forth herein.

  Also, the proportions of the various components of the compositions of these Examples can be varied, based on Example 8, for example + 10%, + 20% and + 30%, provided they are maintained.

  in the previously specified ranges of proportions

  fied. In these cases, the beneficial effects of

are still obtained.

Claims (18)

  i. Detergent composition facilitating the decomposition   stain adhesion with improved properties   help in detaching dirt from the la-   in cold water fabrics containing polyester   which have been soiled by oily soils,   characterized in that it contains a detergent proportion of a non-ionic ethoxylate detergent   narrow range, which is a poly-lipophilic compound   ethoxylated by an average of 5 to 10 oxide groups of   per molecule and of which at least 70% is   ethylene is in polyethoxy groups   4 to 12 ethylene oxide groups, and a proportion   detrimental effect of a polyethylene terephthalate terephthalate copolymer   polyoxyethylene as an agent facilitating   staining, the improved separation of   due to the presence in the composition of the ethylene oxide-type nonionic detergent   narrow and polyethylene terephthalate copolymer   polyoxyethylene terephthalate instead of a wide range ethoxylate nonionic detergent and a polyethylene terephthalate terephthalate copolymer of polyoxyethylene.   2. A detergent composition according to the   cation 1, characterized in that it was in the form   particulate solid, either in liquid form.   3. Detergent composition according to the   cation 2, characterized in that it is in the form   particulate matter and includes a proportion with a   forcing a detergency builder for the deter- nonionic gent.   4. Detergent composition reinforced by   particles according to claim 3, characterized in that   that the nonionic detergent is a product of con-   densification of a higher fatty alcohol and of ethylene oxide   ethylene oxide constituting poly-   ethoxy having an average of 6 to 9 ethylene oxide groups   per molecule and at least 70% of the   which is found in fatty alcohol ethoxylates   with 5 to 10 ethylene oxide groups per molecule, and that the detergency builder   is a mineral detergency adjuvant and the weight   The average molecular weight of the polyethylene terephthalate polyethylene terephthalate copolymer is   in the range of 15,000 to 50,000.   5. Particle detergent composition   according to claim 4, characterized in that   cool fat superior of the nonionic detergent is sa-   and has 12 to 14 carbon atoms, the adju-   of detergency is chosen from the tripolyphos-   sodium pellet, sodium carbonate, bicarbonate   sodium nate, sodium silicate, a zeolite   ion exchanger and their mixtures, the molecular weight   Polyethylene oxide terephthalate   oxyethylene of the polyethylene terephthalate copolymer   lene-polyoxyethylene terephthalate is included   between 1,000 and 10,000, and the composi-   detergent contains a proportion with a stable effect   stabilizer of a copolymer polyacrylate stabilizer   Polyethylene terephthalate terephthalate   oxyethylene, this stabilizing polyacrylate inhibiting the   degradation of the copolymer and the concomitant   an agent for helping soil loosening which would otherwise occur as a result of storage at elevated temperatures in the presence of alkaline substances.   6. Detergent composition according to claim   cation 5, characterized in that more than 85% of the   ethylene oxide of the type 58 nonionic detergent   narrow-range ethoxylate is found in polyethers   xylates of higher C12-C14 fatty alcohol having 4 to 12 ethylene oxide groups per molecule, and in that the nonionic detergent is 10 to 35%   of the composition, the detergency builder constitutes   30 to 75% of the composition, the copolymer   polyethylene terephthalate polyphenylphthalate   ethylene constitutes from 0.5 to 10% of the composition,   the polyacrylate is sodium polyacrylate and   0.1 to 5% of the composition, and the proportion   sodium polyacrylate is 1/6 to 1/2 of the   proportion of the polyethylene terephthalate copolymer   polyoxyethylene terephthalate.   7. A detergent composition according to claim   cation 6, characterized in that more than 85% of the   ethylene oxide present in the nonionic detergent   narrow range ethoxylate of higher fatty alcohol   C12-C14 is in the form of poly-   ethoxy with 5 to 10 ethylene oxide groups   per molecule of this nonionic detergent.   8. Detergent composition reinforced by   particles according to claim 3, characterized in that the percentages of nonionic detergent of the narrow range ethoxylate type, of terephthalate copolymer   of polyethylene terephthalate of polyoxyethylene   reading the detachment of soiling and adjuvant   detergency are included in the intervals   from 10 to 35%, from 0.5 to 10% and from 30 to 75%, and   the detergency consists of 30 to 75% tripoly-   alkali metal phosphate and 0 to 10% hyaline silicate   soluble alkali metal (M) having an M 2 O: SiO 2 ratio in the range of 1: 1.6 to 1: 3, these percentages and the M 2 O: OSiO 2 ratio being expressed as   weight of anhydrous material and on the basis of the composition final decision.   9. Detergent composition according to the claim   7, characterized in that it consists of a   a mixture of spray-dried base particles consisting of sodium tripolyphosphate containing or   not sodium silicate, in which was absorbed   non-ionic detergent of the ethoxylate type   narrow, and particles of a melt and solidified   polyethylene terephthalate copolymer-terephthalate   polyoxyethylene phthalate and stabilized polyacrylate for this copolymer.   10. Particulate detergent composition   a phosphate-free structure according to claim 3,   characterized in that the percentages of non-detergent   narrow range ethoxylate ionic,   polyethylene terephthalate terephthalate   oxyethylene facilitating the detachment of dirt   and detergency builder are included in the   respective amounts of 10 to 35%, 0.5 to 10% and 30 to 3 and the detergency builder consists of 15 to 40% ion exchange zeolite, 10 to 30% sodium carbonate and 5 to 20% of sodium bicarbonate, these   percentages being expressed by weight of anhy-   on the basis of the final composition.   11. A detergent composition according to claim   cation 7, characterized in that it consists of a mixture of spray-dried base particles   consisting of hydrated zeolite A, sodium carbonate   dium and sodium bicarbonate, in which was absorbed the nonionic detergent ethoxylate type gamẻ narrow, and particles of a melt   and solidified polyethylene terephthalate copolymer   lene-polyoxyethylene terephthalate and polyacrylamide stabilizing for this copolymer.   12. Detergent composition according to claim   cation 2, characterized in that it is in the form   liquid and includes water as a vehicle for   nonionic tergent and the terephthalate copolymer of   polyethylene terephthalate of polyoxyethylene.   A liquid detergent composition according to claim 12, characterized in that the narrow range ethoxylate type nonionic detergent is a condensation product of a higher fatty alcohol and ethylene oxide in which the higher fatty alcohol   has 12 to 16 carbon atoms and ethylene oxide   lene is found in polyethoxyethanol groups   having an average of 4 to 10 ethoxy groups per molecule   at least 80% of the nonionic detergent consisting of ethoxylates of higher fatty alcohol with ethoxy content in the range of 4 to 10 ethoxy groups per molecule, the molecular weight   average weight of the polyterephthalate copolymer   ethylene polyoxyethylene terephthalate being included   in the range of 15,000 to 50,000, and the   nonionic detergent, terephthalic   polyethylene glycol polyethylene terephthalate and water in the liquid detergent composition being in the range of 10 to 30%, 0.2 to 3% and 50 to 85%.   14. Liquid detergent composition according to claim 13, characterized in that the nonionic detergent of the narrow range ethoxylate type is a   condensation product of a higher fatty alcohol   from 12 to 15 carbon atoms and from an average of from 5 to 9 moles of ethylene oxide, in polyethoxyethanol groups, per mole of this alcohol.   fat, at least 85% of the non-ionic detergent   that consisting of higher fatty alcohol ethoxylates   ethoxy groups included in the   range from 4 to 10 ethylene oxide groups per molecule,   and the molecular weight of the polyoxyethylene of the tere-   polyoxyethylene phthalate polyoxyethylene polyethylene terephthalate terephthalate copolymer is   in the range of 1,000 to 10,000.   15. Liquid detergent composition according to claim 14, characterized in that it comprises   from 12 to 20% of a nonionic detergent   narrow-range xylat which is a condensate   saturated higher fatty alcohol having 12 to 14 carbon atoms and an average of 6 to 8   moles of ethylene oxide in polyethoxy groups   ethanol, per mole of this higher fatty alcohol, at least 90% of the nonionic detergent consisting of   higher fatty alcohol ethoxylates of group   ethoxy content in the range of 4 to 10 ethylene oxide groups per molecule, 0.5 to 2% of copolymer   polyethylene terephthalate polyoxy terephthalate   ethylene, a brightening ratio, in the range of 0.05 to 2%, of a fluorescent brightening agent, an   the substantivity of the fluorescent brightening agent,   between 1 and 10% of a detergent   sulphate and / or sulphonate anionic, a proportion   enzymatic effect, in the meantime   from 0.1 to 5% of an enzyme, a proportion with a sta-   biliser, in the range of 0.5 to 6%, of a stabilizing agent or stabilizing system for   enzyme, a proportion that helps to dissolve   between 3 and 15% of a co-   polar organic solvent for dissolving non-water soluble components of the detergent composition, 60 to   % water and any possible supplementation of one or more additives.   16. Liquid detergent composition according to claim 15, characterized in that the nonionic detergent of the narrow range ethoxylate type is a   condensation product of a higher fatty alcohol   saturated with 12 to 14 carbon atoms and   with an average of 7 moles of ethylene oxide   per mole of this higher fatty alcohol, the average weight   of the polyethylene terephthalate copolymer   Polyethylene terephthalate is included in the   from 19,000 to 43,000, the fluorescent brightening agent   rescent is a stilbene brightener, the deter-   anionic type of the sulphate and / or sulphonate type   the substantivity of the fluorescent brightener   is a (higher alkyl) benzene metal sulfonate   calin having a higher alkyl group of 12 to 18 carbon atoms, the enzyme is a mixture of proteolytic and amylolytic enzymes, the enzyme stabilizer comprises an alkali metal salt of a carboxylic acid   less than 1 to 3 carbon atoms, the co-   polar organic solvent is a lower alkanol, water is freshwater whose hardness is expressed in   CaCO3 is less than 50 mg / liter, the additives   take a perfume and a coloring matter, and the   proportions of these components in the composition   liquid entanglement are in the respective ranges of 14 to 18%, 0.7 to 1.5%, 0.05 to 0.3%,   2 to 5%, 0.3 to 3%, 0.05 to 0.3%, 2 to 4%, 4 to 10%,   65 to 75% and 0.2 to 2%, the pH of the composition   liquid gente being in the range of 7.3 to 8.1 and its viscosity in the range of 65 to 115   mPa.s at 25QC, and the polyethylene terephthalate copolymer   Polyoxyethylene ethylene terephthalate facilitating   the detachment of dirt being stable at the   WCS. 17. Liquid detergent composition according to claim 12, characterized in that it is   free of triethanolamine and triethanolamine   mine and does not include more than 10% of ionized salts ble.   18. A method of washing clothes and   have properties of aid to the detachment of   sures, characterized in that it consists of washing laundry repeatedly in washing water   containing a proportion of aid to take-off   the soiling of a detergent composition se- according to claim 1.