FR2622204A1 - ANTISTATIC LIQUID DETERGENT COMPOSITION AND METHOD OF USE FOR WASHING LAUNDRY - Google Patents

Abstract

Disclosed is a liquid detergent composition having antistatic and fabric softening properties. This composition contains a nonionic detergent of the narrow range ethoxylate type, which is the condensation product of a higher fatty alcohol of 12 to 16 carbon atoms and an average of 4 to 10 moles of ethylene oxide per. mole of fatty alcohol, at least 80% of the nonionic detergent consisting of ethoxylates having between 4 and 10 ethoxy groups per molecule, a cationic antistatic and fabric softening compound, such as quaternary ammonium halide, and water. Such a composition exerts a better detergency than an identical composition, but containing a broad-range ethoxylate as a nonionic detergent, for the removal of oily stains from the laundry, in particular by washing in warm or cold water. Field of application: laundry detergents.

Description

The present invention relates to composi-

  liquid detergent solutions with anti-

  static and softening of tissues. More particularly

  specifically, it relates to such compositions which comprise a nonionic detergent of the ethoxylate type

  narrow range (EGE), an antistatic cationic compound

  that and softening the tissues, and water.

  The new liquid detergent compositions

  antistatic and fabric softening agents of the present invention, which may be referred to hereinafter as abbreviated, softening detergent products, exert surprisingly better detergency on the

  stains and / or oily stains as composites

  which are identical except that the EGE is replaced by a range ethoxylate detergent

  wide (EGL). This surprisingly advantageous effect is

  particularly pronounced when detergent-

  softeners of the invention are used for washing

  various tissues stained with oily stains / stains

  when washing is carried out at temperatures

  relatively low res, for example 20 C.

  In the prior art, it has been disclosed that cationic compounds can be incorporated into detergent compositions, such as liquid detergent compositions, to soften laundry and the like.

  make it antistatic, which is particularly important

  both when the laundry is dried in an automatic clothes dryer in which electrostatic charges often accumulate on the laundry, resulting in undesirable mutual snagging of the dried washed articles and crackling of these articles and sparking of sparks when the loads electrostatic they wear evacuate. It was also known that cationic compounds, when incorporated

  in detergent compositions, have negative effects

  gatives on detergency. These negative effects are expected in the case of the use of anionic detergents due to the chemical reactions between the anionic and cationic compounds, but it has also been observed that the detergency is decreased when cationic compounds are included in compositions

  based on nonionic detergents.

  With regard to the compositions of the

  the present invention, it has been discovered that these harmful effects

  expected effects of cationic compounds on the deter-

  do not occur if EGEs are used instead of EGLs, and detergency is improved

  compared to similar detergent compositions

  based on EGL. This improved detergency of

  EGE-based positions is not attributable to any better cleaning achieved as EGE

  would be a better detergent than EGL in

  in general, but it relies instead on the associations of EGEs and

  cationic compounds in detergent products-

  softeners. In accordance with the present invention, an antistatic and fabric softening liquid detergent composition, or detergent softener product, comprises a detersive portion of a narrow range ethoxylate (EGE) type nonionic detergent, an antistatic effect and a softening ratio. fabrics of an antistatic cationic compound and

  softening the tissues, and water, this composi-

  A liquid detergent solution which exerts a betterdeterioration on the oily soils of the fabrics to be washed with solutions of the detergent composition in a wash water, compared to similar compositions in which the nonionic detergent component is a nonionic detergent of the ethoxylate type. wide range (EGL). The invention also contemplates methods for washing laundry in wash water in an automatic washing machine, using the

  described compositions or their components.

  A search in the prior art has led

  - to find the U.S. patent N 4 564 463 which

  liquid laundry detergents based on mixed nonionic and anionic detergents, including higher fatty alcohol ethoxylates, and

  alkylbenzene sulfonates. The U.S. Patent

  No. 4,441,881 discloses spray-dried particulate detergent compositions containing those characterized as ethoxylated ethoxylated ethylene oxide alcohols. It is said,

  in this patent, better protection properties

  against soiling may be conferred on

  synthetic fabrics by washing these fabrics with the

detergent section described.

  In addition to the cited patents, it is accepted as a prior art that commercial, antistatic and fabric softening liquid detergents have been made from nonionic and anionic detergents and include cationic compounds.

  to soften the laundry and eliminate static loads

  dried and dried laundry or prevent the development of

i

  oh. such loads on the laundry during drying.

  However, prior to the present invention, as far as the Applicant is aware, no patent or reference in the literature describes or suggests the compositions of the invention and none

  recognizes that a better understanding of

  by liquid detergent compositions containing

  ing an EGE and a cationic compound rather than

  corresponding compositions based on EGL.

  EMTs that are used in products

  detergent-softeners of the invention are

  nonionic tergents in which the hydro-

  phile is a relatively narrow distribution ethylene oxide polymer, which distinguishes these detergents

  those of similar types but in which the

  The ethylene oxide polymer has a wider distribution (EGL). In general, it is advantageous to obtain the best detergency of the compositions of the invention that the ethylene oxide chain (including the terminal ethanol) has a narrow distribution such that at least 80 % of the nonionic detergent have a number of ethylene oxide groups flanking the average number of ethylene oxide groups of the EGE in the range or range of (n-3) to (n + 3), is the average number of ethoxy units in the EGE detergent. In some cases, the framing can be from (n-2) to (n + 2) or from

  t! (n-4) to (n + 2). Usually, the value of n is

  It may be about 6 to 7, but sometimes it may be in the range of from 4 to 12. Preferably, the percentage of nonionic detergent whose ethoxy group content is de (n-3). to (n + 3) or in one or other of the two other ranges above

  at least 85%, and better still, at least 90%.

  Normally, the more weakly ethoxylated nonionic detergents or surfactants, such as those having 1 to 3 ethoxy groups per mole, are limited to a maximum of 1%, preferably less than 2%, and most preferably, less than 1%. %, except when n is less than 7, when such percentages are not applicable to detergents having ethoxy groups.

  in the lower limit range of n-3. In ou-.

  when n is less than 7, the "frame" is preferably n 2 or n-1 to n + 3. It is difficult to completely eliminate the lower ethoxylates because of the manufacturing process which produces a wide range of nonionic detergents with different ethoxy content; however, in EMTs, the curve

  distribution can be considered as being

  awarded ", which results in a more uniform product.

  The corresponding EGLs, even those where n is equal or

  above 7, often contain more than 5% etho-

  xylates with a lower ethoxy content (1 to 3).

  Of course, it is also desirable to limit the proportion of non-ethoxylated lipophilic compound and the EGEs normally contain less than 1% and often less than 0.5%, whereas EGL often contain more than 1% of the compound. lipophilic, for example an alcohol

higher fat.

  Nonionic detergents (EGE) of the pre-

  invention are catalytically produced by

  the reaction of ethylene oxide and a compound or

  ? lipophilic-appropriate. Higher alcohols, usually fatty or linear alcohols from 12 to

  18 carbon atoms, which are usually preferable

  The desired materials react with ethylene oxide to produce the desired nonionic detergents for the compositions of the present invention, but Oxo-type alcohols and (alkyl-middle) phenols, such as nonyl -phenol,

  can also be useful. Preferably, the fragment

  The higher fatty alcohol content is linear and has from 12 to 16 carbon atoms, and more preferably it has from 12 to 14 or 15 carbon atoms, for example alcohol.

  lauryl, myristyl alcohol and mixtures thereof.

  The average ethoxy content of the EGE is in the range of 4 to 10 EtO groups per mole, preferably 5 to 9 and most preferably 6 to 8, eg 6.5 or 7. members of the well-known class of nonionic detergents, such as higher polyethoxyethanol fatty acid esters (also having a narrow range ethoxylate distribution)

  may also be useful in certain composi-

  tions and for particular applications. How-

  In general, a higher fatty alcohol is used as the source of the lipophilic moiety and the product is a nonionic detergent of the ethoxylate type.

  which satisfies the conditions of the preceding EMTs

  listed above, the distribution curve of the

  ethoxy groups preferably reaching a

maximum sharp to the value n.

  EMTs that are currently available

  are preferably manufactured by catalytic reactions

  ticks that favor the production of a range

  polyethoxylates, the distribution curve of which

  Ethoxy group numbers increase from

  top of the page, rather than the wide range of polyethoxylates present in detergents of the type

  alkoxylated lipophilic compound which are generally

  available in the trade. The products obtained by the catalytic route are characterized by a curve of

  normal distribution when the content of ethylene oxide

  lene (abscissa) is plotted against the percentage by weight (ordinate), but the maximum of the "bell-shaped" curve is much higher for

  EGE nonionic detergents than for those of the EGL type.

  It has been suggested that similar products with i

  similar distribution curves, can be obtained

  naked by "quenching" and "equating" EGLs or other EGEs, removing the higher and lower polyethoxylates by solvent extraction, distillation, and other appropriate physical operations, but it is not thought that such-detergents are as useful as those

  mentioned here as being preferred because of the ab-

  likely presence of the same type of "passage through a maximum

  The non-ionic detergents EGL contain

  percentages of a narrow range of desired polyethoxylates, such as those with 4 to 10 EtO groups, often less than 60%, compared to

  more than 80% for EMTs. They often contain

  about 1% of all the individual ethoxylation levels of 1 to 16 or 1 to 20, although it is desirable that the average ethylene oxide content be 6 or 7 moles per mole. On the other hand, EMTs that have an average of 7 moles of EtO per mole

  usually no higher ethylene oxide polymer

  14 or 15, and the proportion of polyoxyethylene in the range of 4 to 10 is significantly increased. This increase, the narrower distribution range

  polyethoxy patterns and its "maximum sharp to no

  In a good sense, the properties of the EGE are incorporated when it is incorporated in a detergent-softening composition of the present invention. The reason of '"

  this difference is not explained at present.

  Of the nonionic detergents EGE preferred

  According to the present invention, the nonionic surfactant Tergitol124-L-60N, which has the formula RO (CH 2 CH 2 O) nH 2 O represents the residue of a mixture of linear C 12 and C 4 alcohols and the

12 14

  mean value of n is about 7.0. This product has a cloud point of 60 ° C for an aqueous solution of g. X

  1%, and it is a narrow range ethoxylate. Its products

  properties are described in a newsletter-

  product published by the manufacturer, Union Carbide Corpora-

  dated April 1987. Other non-ionic surfactants

  Tergitol which can also be used for at least part of the type 24-L-60N include

  types 24-L-45N, 24-L-75N and 26-L-60N, where the names

  45, 75 and 60 indicate the cloud points in

  degrees Celsius. In addition, we can substitute

  similar products, manufactured by Shell Chemical Company, which have been named Shell 23-7P and Shell 23-7Z, although it is considered that the results are not as

  good only for the preferred compositions.

  The cationic compound antistatic and

  pleating the tissues of the present compositions

  liquid gents can be any suitable compound

  with these properties, such as an imidazole salt

  linium or a quaternary ammonium salt. Both of these types of fabric softening agents are described in U.S. Pat. N 4 000 077. Of these two types

  softening agents, ammonium salts quater-

  are preferred and, among these, the halides

  quaternary ammonium compounds, such as ammonium chlorides

  quaternary nium, are more preferred.

  The fabric softening compound of the quaternary ammonium salt type preferably has the formula [R2 R3

R4

  wherein R1 and R2 are lower alkyl groups

  with 1 to 3 carbon atoms, preferably 1 to 2, and more preferably 1, carbon atom, R 3 is a higher alkyl group having 10 to 20 carbon atoms, preferably 12 to 18, and more preferably 16 to t -, 18, carbon atoms, for example an alkyl group of tallow, R is an alkyl group having 1 to 20 carbon atoms (higher, middle or lower alkyl), and X j is a salification anion, preferably chlorine , bromine or the methylsulfate group, and better still,

  chlorine. In these quaternary salts, R1 and R represent

  preferably feel the same lower alkyl group,

  for example methyl, and R and R are preferably

  The same higher alkyl group or one is a higher alkyl group and the other is a methyl group, the most preferred fabric softening agents being trimethyl- (tallow alkyl) ammonium chloride.

  and dimethyl-di (tallow alkyl) ammonium chloride.

  The. quaternary ammonium halides including

  also include those whose higher alkyl group (s)

  are alkyl groups of hydrogenated tallow, coconut alkyl, stearyl, cetyl, myristyl and / or lauryl

  (which may sometimes be ethoxylated) and whose groups

  The lower alkyl groups are methyl and / or ethyl groups. In addition, it is sometimes possible to substitute

  other halogen and methyl group anions

sulfate. -

  The fluorescent brightening compound (s) of the present compositions are products which are substantive to washed laundry and which serve to transform invisible radiation, such as

  ultraviolet light, in visible light, while

  if to appear whiter the surfaces of the linen on the-

  which they were deposited. These brighteners-fluorescers

  These are a class of substances well known in detergent technology, so there is no need to describe them further here. Suffice it to say that they are normally typestilbene and, more particularly, that they are of the acid type

  stilbene sulfonic acid or stilbene sulfonic acid salt.

  Among these brighteners which are used in <; compositions of the present invention is that made by Mobay Chemical Corp. and sold under the trademark Phorwite BBH766 pure, which is the acid

  4,4'-bis (4-anilino-6- [bis (2-hydroxyethyl) amino] -s-

  Triazine-2-yl-amino] -2,2-stilbene-disulfonic acid. Although the above-mentioned fluorescent brightening agent acts very effectively in the present compositions, it is believed that other substantive brighteners

  can be used in its place, such as those

  Example 1, without loss of improvement

  unexpected advantage of the characterization of deter-

  of the compositions of the invention.

  Anionic detergent is also incorporated

  in the preferred embodiments of the present

  liquid detergent product to improve the

  tivity of the fluorescent brightening agent, and also to add its detersive properties to the composition. (Anionic detergents are particularly effective in removing particulate soils from the fabrics). The anionic detergent is preferably sulfate or sulfonate type, normally in the form of a water-soluble salt such as an alkali metal salt,

  for example a sodium salt. These detergents are

  described in various texts, including Surface Active Agents (Their Chemistry and Technology)

  of Schwartz and Perry, and the various annual editions

  the Detergents and Emulsifiers of John W. McCutcheon.

  Although alcohol sulphates may be used

  fat and various other sulphates and sulphates

  It is preferable that the detergent is a (higher alkyl) benzenesulfonate, such as those having an alkyl group of 12 to 18 carbon atoms. More preferably, the alkyl group is linear and has 12 to 16 carbon atoms, such as, for example, C 1 -C 1

  dodecyl or lauryl group, and the cation is sodium.

  Disulfonated anionic detergent salts can also be effective in the compositions of the present invention.

present invention.

  To help solubilize the fluorescent brightener and to buffer the detergent composition

  liquid at a desirable pH, a lower alkanolamine

  may be present in the deter-

  liquid, the lower alkanol group or groups of

  this alkanolamine containing 1 to 3 carbon atoms.

  Preferably, the alkanolamine is a trialkanolamine,

  and better still, it is triethanolamine.

  A hydrotropic compound, such as a benzene

  sulphonate or a (lower alkyl) benzene sulphonate whose alkyl group has 1 to 3 carbon atoms,

  is normally present in the compositions of the in-

  to facilitate the solubilization of certain

  components of compositions which, if not

  should separate from the aqueous medium by settling. Preferably, this hydrotrope is present in the form of an alkali metal salt, usually in the form of a sodium salt, and the hydrotrope is a benzene sulfonate,

  a xylene sulfonate or cumene sulfonate.

  Also to improve the solubility of

  various components of the detergent composition, a co-

  polar organic solvent is usually present and is preferably a lower alkanol, such as ethanol or isopropanol, ethanol (normally

denatured) being preferred.

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

  may be treated water such as water

  of boilers taken from the food system

  boiler plants of the manufacturing plant

  tion. It is normally desirable for this water to be of relatively low hardness, and its hardness should normally be less than 100 mg / liter, expressed as CaCO 3, preferably less than 50 mg / liter, and

better yet, almost nil.

  Various additives can be incorporated into

  compositions of the invention, among which

  fum and dye are the most common additives

t:

  employees. The perfume is normally of a

  pophile, but it is easily solubilized by

  surfactants and solvents of the composition.

  The dye may be a finely divided pigment

  persistant in water, but it is usually preferred

  to use a water-soluble dye or a mixture of: 4 such suitable dyes, although mixtures of

  t! 15 soluble dyes and pigments are also

  : ^ visageables. Another component of the compositions of O! the invention, which can be considered as an additive or adjuvant, is an acidic agent that can be used

  to adjust the pH of the detergent product

  It is useful in cases where triethanolamine and other alkaline substances present have caused the pH to rise.

  j beyond the desired range. Among the acidic agents

  Useful ingredients which can be used, the most preferred are citric acid, which can be a buffer with triethanolamine and other alkaline substances.

of the formula.

  I & J The proportions of the various components of

  i, present liquid detergent compositions are normally

  maintained between the limits of certain inter-

  to obtain a product with the characteristics

  v .; desired, which has better detergency on oily stains deposited on various tissues and È; which also offers an appearance and features

  acceptable physical The major component of

  The liquid detergent compositions of this invention are water J. and its proportion is normally a sufficiently solubilizing effect ratio (together with any cosolvent and hydrotrope that may be present) for the EGE, the cationic compound and the other components of the composition. The water content is in the range of 30 to 70%, preferably 40 to 60%, and more preferably 50 to 60%, most preferably 53.5% or about 55%. The proportion of EGE is a detergent level, which is usually in the range of 10 to 35%, preferably 15 to 30%.

  and more preferably 18 to 25%, better still about 21%.

  The proportion of the cationic compound is a proportion

  with antistatic effects and softening of tissues ,.

  which is usually in the range of 2 to <15%, preferably 3 to 10%, and more preferably 4 to 8%, I

the best being about 6%.

  When a fluorescent brightener is present, its proportion is in the range of 0.1 to 2%, preferably 0.1 to 1%, and more preferably in the vicinity of 0.4%. The intervals of proportions

  for the anionic detergent are 2 to 15%, preferably

  3% to 10%, and more preferably around 6%.

  At best, the molar ratio of the softening agent)

  anionic detergent cationic

  from 0.9: 1 to 1: 1.1, for example 1: 1.

  The intervals for the alkanolamine serving as solubili-

  for the fluorescent brightening agent are 0.3 to 3%, preferably 1 to 2%, and more preferably in the vicinity of 1.5%. The proportion of hydrotrope

  is in the range of 2 to 10%, preferably 3 to 10%.

  7%, and better still around 5%. When a co-j

  solvent is present, its proportion lies in the

* range from 3 to 15%, preferably 4 to 10%, and more preferably in the vicinity of 6%. Any remaining remains may be additives, a normal range for them being 0.1 to 5%. These additives include

  normally a perfume and a dye and their percentage

  respective steps are normally from 0.2 to 2%, preferably from 0.3 to 1% and more preferably from about 4%, on the one hand, and from 0.05 to 1%, preferably from 0.1 to

  0.5% and, better still, about 0.2%, on the other hand.

  However, these proportions depend to some extent on the odor level of the product components and

  of their color. Citric acid or other acidic agent

  The modifier or neutralizer may be considered as another additive, but the proportion employed of this substance is normally only that required to adjust the pH of the liquid detergent composition within the limits of a desired range. This proportion is usually in the range of 0.05 to

0.5%.

  The liquid detergent compositions of the invention are normally clear in appearance, but can be made intentionally cloudy, opaque or pearlescent. The pH of the product is normally in the range of 7 to 8, ideally in the vicinity of 7.5, and the viscosity is normally in the range of 57 to 125 mPa.s at 25 ° C, preferably in the vicinity of

mPa.s.

  The manufacture of the compositions of the invention

  tion is relatively simple, no critical operation is necessary except to be sure that

  the fluorescent brightening agent is dissolved, usually

  in an alcoholic cosolvent. In general, the

  portion of the water specified in the formula, or about one percent of that proportion, is pumped into a mixing vessel or tank, and the various

  components of the detergent compositions are successively

  added and mixed with the aqueous medium, after which the remainder of the water is added. In some cases, ú

  the cosolvent can be added first and, in other

  In many cases, it can be kept for later

  with the rest of the water, at the end or towards the

  end of the mixing operation. In other cases

  core, particular components, such as the agent

  brightening, can be first dissolved in the cosol--

  or sometimes in part of the aqueous environment

  containing the hydrotrope. Although these techniques can

  In order to facilitate faster manufacture of the liquid detergent product in the desired form and appearance, the desired product can generally be obtained without resorting to such process variants (except for the dissolution of the brightening agent). Once all the components have been added and mixed, the rest of the water, if any, can be added,

  stirring, and the pH can be adjusted. After pH adjustment and a viscosity control for

  certify that it falls within the limits of the

  the product can be directly

  vials, or can be filtered and put in vials.

  The use of the compositions of the invention

  is simple and satisfactory from the point of view of

  the user, having little to do, except to measure the desired dose of the liquid detergent composition and add it to the wash water in

  an automatic washing machine. These machines contain

  60 to 70 liters of water, the current capacity being

  67 liters, and 1/2 cup of detergent product

  quide, which corresponds to about 120 grams of it, is used by washing. However, the formula of the composition may be modified so that 1/4 cup or 60 grams introduced into the washing machine perform an effective wash. The laundry (usually about -3 kg) is added to the wash water and the machine is started. The hardness of the wash water is normally not more than 300 mg / liter, expressed as CaCO3, and the water temperature is normally in the range of 10 to

   C. It is recognized that, following American practice,

  caine, the temperature of the wash water approaches only

  rarely, if ever, boiling, but

  of the present invention are made

  at such high temperatures. Preferably, the hardness of the water is not greater than 200 mg / liter, the range of 100 to 200 mg / liter being considered normal. Obviously, it is also possible to use wash water of lower hardness. In the wide range of temperatures mentioned above, a preferred range is from 10 to 50 C and to obtain detergency

  the most markedly improved, compared to the deter-

  the results obtained when using compositions

  EGL, this range is 10 to 25 C,

  for example a temperature of about 20 or 21 C.

  Normally, the wash cycle lasts 5 to 30 minutes, with a rinse cycle of 1 to 5 minutes, and sometimes several rinse cycles, usually 2 or 3, can be used. The drying times are usually between 10 and 60 minutes, with most drying times in the range of 20 to 40 minutes, and drying is usually performed at "normal" drying temperatures for automatic tumble dryers, rather than

  "high temperature. Obviously, the conditions of the-

  drying and drying are determined by the nature of the laundry, soiling and / or stains it bears, and

  characteristics of washing and drying appliances

  used. Top-loading automatic washing machines are usually used, but side-loading machines are also

  acceptable. The weight of linen introduced is normal-

  from 2 to 4 kilograms, for example about 3 kg.

  In the washing process, it is highly preferable to add the liquid detergent composition described in the washing machine, but it is also possible to add its various components, either alone or

  mixed, in the washing machine, so as to obtain

  essentially the same composition of water of

  husbandry. The resulting wash water contains a proportion

  detergent effect of EGE and a proportion with antistatic effect and softening of the cationic compound tissues. These proportions are respectively in the ranges of 0.01 to 0.2% and 0.001 to 0.1%, preferably 0.02 to 0.1% and 0.002 to 0.05% respectively, and more preferably 0, respectively. 03 to 0.06% and

  0.005 to 0.02%, ie for example respectively

  0.04% and about 0.01%. The concentration of

  the fluorescent brightening agent is located in the

  range from 0.0001 to 0.01%, preferably 0.0002 to 0.005%,

  for example, 0.001%. The concentration of

  anionic species is in the range of 0.001 to 0.1%, preferably 0.005 to 0.02%, for example

  about 0.01%. Concentrations of other compounds

  of the liquid detergent composition (with the excep-

  water) in the wash water and their

  the, in percentages on the basis of the washing water, can be obtained by multiplying the concentrations

  example data for the detergent composition

  using 0.0018 to obtain the optimum concentrations

  males in the wash water, and can be calculated

  lower and upper limits of these concentra-

  tions by multiplying the concentrations in the

  sition by 0.0010 (to obtain the lower limit) and 0.0030 (to obtain the upper limit). Thus, it is preferred to use the liquid detergent composition at a concentration in the wash water of about 0.18% but, depending on the nature of the laundry, this concentration may be 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. In these examples and in the preface

  descriptive memory, all parties and

  percentages are by weight unless otherwise indicated

milked.

EXAMPLE 1

  Component% Nonionic Surfactant EGE, Tergitol

24-L-60N * 21.0

Monoalkyl chloride (tallow alkyl)

  trimethyl-ammonium 6.0 (linear dodecyl) sodium benzenesulfonate 6.0 Sodium xylene sulfonate 5.0 Ethanol 6.0 Triethanolamine 1.5 Fluorescent brightener (Phorwite BBH766, pure) ** 0.4 Perfume 0.4 Coloring 0.2

  Citric acid (for pH adjustment) q.s.

  Water (deionized) *** 53.5, 00 * Nonionic detergent of ethoxylate type at range

  which is a condensation product of

  cool fat greater than 12-14 carbon atoms and an average of 7 moles of ethylene oxide per mole, having 4-10 ethoxy groups per molecule

  in a proportion greater than 90%.

  ** Stilbene fluorescent brightening agent (any of these agents may be used

  brightening, preferably stilbene-type

  sulfonate or stilbene sulfonic acid, such as Phorwite and Tinopal products, for example Phorwite HRS, Phorwite BHC or Tinopal 5BM, or mixtures thereof). *** The given percentage is for compositions

  in which citric acid is not included.

  If citric acid is used, the percentage

  water is reduced accordingly.

  A liquid detergent product of the above formula is made by adding and mixing all the

  components in water, in the following order: triethanol-

  amine, brightener, ethanol, hydrotrope (xylene-

  sodium sulphonate), EGE, dodecylbenzene sulphonate

  sodium, quaternary ammonium chloride, citric acid

  that (if necessary to adjust the pH to 7.5) and fragrance.

  Optionally, the fluorescent brightening agent can

  dissolved in aqueous ethanol and other

  mentioned poses can be added and mixed

  half the amount of water specified in the

  mule, the rest of the water being added last.

  The resulting product is a clear liquid. facultative

  Alternatively, a dye, for example about 0.5% of C.I.

  percentage of water being reduced accordingly). The opinion-

  The liquid detergent product has a cosity of approximately mPa.s at 25 ° C. The liquid detergent composition prepared is stable at room temperature for at least six months, without any stratification or deposition of components, and the product remains clear and effective.

  as an antistatic detergent composition and

  softening tissues, improved detergency (compare

  to similar compositions based on EGL)

during this period at least.

  The liquid detergent composition of the invention is tested against a control composition which is identical thereto, except for the replacement

  nonionic surfactant Tergitol with Neodol 25-7.

  The following is a description of the procedure

  test. Before the beginning of the test, we rinse

  thoroughly a Maytag automatic washing machine. We replace

  then folds the machine with 64.3 liters of water

  net and adjust the hardness of the water by adding

  calcium chloride and magnesium sulphate or

  very suitable water-soluble calcium and / or magnesium salts, until its hardness is 150 mg / liter, expressed as CaCO3. We start the agitation

  and add 1/2 cup (120 grams) of the

  liquid detergent to be tested with the wash water, followed by thirteen lots (three in each batch) of

  pieces of soiled test cloth, which were initially

  white before soil debris. These parts

  these include various fabrics used in the confection

  clothing and other articles to be washed, among

  which are simple polyester knit

  ture, double-needle polyester knit, polyester / cotton blend, acetate and nylon. Rooms

  of fabric each measure about 7.6 x 8.9 cm. dif-

  oily stains, such as

  naigrette, liquid foundation, soot in oil, etc., are applied to the fabric pieces, using a Benz Soil Applicator for these applications, resulting in thirteen combinations of stains. / tissues, each in triplicate. We

  sets the washing cycle of the machine for ten minutes

  and the rinse cycle is two minutes. After completion of washing and rinsing, the pieces of fabric are removed and dried for thirty minutes (or until dry) in a Maytag automatic tumble dryer set for "normal" drying. We then submit the soiled pieces of cloth

  to reflectance measurements using a reflectance

  meter for small areas (Gardner XL20).

  The mean values of the measured reflectances (Rd) are calculated for each of the thirteen batches of soiled pieces of cloth, and these averages are added.

  to arrive at a total Rd that denotes the degree of eli-

  oily stains / stains by the composition

  detergent section tested. The piece of fabric is all the more white after washing that the total Rd

  (hereinafter referred to as Rd) is higher.

  - We find that the Rd for the products deter-

  Liquid gels of the formula given above is 781, whereas for the Neodol 25-7 control composition, the Rd is 704. Such a difference of 77 units is very significant, and the differences

  stain removal are apparent to the naked eye.

  When repeating the test, with the sole exception that

  washing water is 38 C instead of 21 C, the Rd to-

  the composition of the invention is 841 and that of the control composition is 789, which is also significant and represents a difference

  observable stain removal. In a repetition

  experience, using a new series of soiled pieces of cloth, the total Rd with

  washing water at 21 C is 800 for the composition

  of the invention and 738 for the witness, these

  figures being in agreement with those given above.

  In this "repetition of experiment", a detergent composition in which a nonionic detergent Neodol 23-6 is also tested is also tested. 5 head was used

  instead of the nonionic surfactant Tergitol 24.L.60N.

  This nonionic detergent is a condensate

  one mole of higher fatty alcohol of 12-13 carbon atoms with 6.5 moles of ethylene oxide, including the higher fatty alcohol and lower alkoxylates;

  (from 1 to 3 ethoxy groups) were removed by distillation.

  lation. The total Rd for the detergent composition containing this nonionic detergent in place of Teritol 24-L-60N or Neodol 25-7 is 753, which is higher than that obtained with the control, but much less than that obtained with the composition of the invention. This result shows that, while eliminating all free fatty alcohol and all

  lower ethoxylate of 1 to 3 ethoxy groups of

  nonionic gent is useful for improving the deter-

  the present compositions, it is more

  to "compress" the ethoxylate distribution curve or make it "sharp", by "eliminating" the higher and lower ethoxylates, outside the range of 4 to 10 ethoxy groups (for nonionic detergents averaging 6 to 8 ethoxy groups per molecule), and this "elimination" is preferably

  a consequence of a catalytic manufacturing process.

  In a new repetition of the tests of

  comparison of the composition of the invention with the com-

  EGL non-ionic detergent control position, the total Rd are found to be 750 and 725 at 21 C,

  and 795 and 747 at 38 C, respectively, for

  experimental and control detergent positions. In these washing experiments, we also test

  products, and it is found that the composi-

  invention is better as to the deter-

  of trade products, both at 21 C and 38 C, although one of the products of commerce is

almost as good at 21 C.

EXAMPLE 2

  In order to make a comparison with the first

  first test described in Example 1, in which the

  Tergitol 24-L-60N non-ionic filler was tested vis-à-

  25-7 Neodol screw in an essay of a composition de-

  EGE-based liquid tergent with respect to such an EGL-based composition as a nonionic detergent component, other non-ionic surfactants are also tested.

  Ionic Tergitol in the same detergent composition.

  These other surfactants are identified by 24-L-35N, 24-L-45N and 24-L-50N. The Rd for 21 C and 38 C washings are 706 and 688, 743 and 745 respectively, and 746 and 743, as compared to 781 and 841, and 704 and 789, for Tergitol 24-L-60N formulations. and Neodol 25-7, respectively. Other simultaneous tests on a commercial product yield Rd's of 654 and 747, respectively. Thus, all 21 C washings with EGE-based compositions give higher Rd than the EGL-based composition and the commercial product. However, results with EGEs Tergitol 24-L-35N, 24-L-45N and 24-L50N are not as good as those obtained with EGE Tergitol 24-L-60N and are not considered as good as those obtained with an EGE Tergitol 24-L-75N. It appears

  these differences in detergency are due to differences

  ferences in the distribution of ethoxylates and / or

  differences in EGE trouble points.

  The ethoxylate distributions of the various EMTs are reported in a Technical Service Bulletin

  Tergitol surfactants published by the division of

  Ethylene Oxide Rivets from Union Carbide Corporation

  and titled "Ethoxylate Distribution of Tergitol 24-L-

  Non-ionic Surfactants by Gas Chromatography The following Table 1 summarizes the distribution of ethoxylates (by gas chromatography) of the two preferred EMTs.

  mentioned above, and comparable EGLs.

TABLE 1

  Percentage in Weight of RO (CH2CH20) nH n Tergitol 24-L-60N Tergitol 24-L-60 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 do I ', ru, C) * a 100% recovery of the sample is not

  because of the retention of higher ethoxylates

in the GC column.

EXAMPLE 3

  Component% EGE (nonionic surfactant Tergitol 24-L-60N) 21.0 (linear dodecyl) sodium benzenesulfonate 3.7 Sodium xylene sulfonate 5.0 Quaternary ammonium chloride mixture

N 87064 * 5.0

  Ethanol 6.0 Triethanolamine 1.5 Fluorescent brightener ** 0.4 Fragrance 0.4 Colorant 0.2

  Citric acid (for pH adjustment) q.s.

  Water (hardness zero) 56.8, 0 * Mixture N 87064, specialty of Akzo Chemie; mixed

  two chlorides of di (higher alkyl) -dimethyl-

  quaternary ammonium and an alkyl chloride

  higher ethoxylated) -trimethylammonium.

  ** Stilbene fluorescent brightening agent, the same

than in Example 1.

  This detergent composition is prepared according to the method of Example 1 and tests it in the same manner.

  way. To facilitate identification and comparisons

  reasons, it is referred to here as Formula 3 (a).

  A Formula 3 (b) is the same as the Formula

  3 (a), except that 6% of (linear dodecyl) is used -

  sodium benzene sulfonate, as well as 6% of the quaternary ammonium halide mixture, so that the percentage of water is reduced by 3.3%. A Formula 3 (c) is the same as Formula 3 (a) except that there is 3.8% of (linear dodecyl) sodium benzenesulfonate, the quaternary ammonium chloride is the mono ( tallow alkyl) -monooctyldimethylammonium, and

  6% of this quaternary salt, so that the percentage

  water is reduced by 1.1%. Control experiments in which Neodol 25-7 is used in place of the nonionic surfactant Tergitol 24-L60N are designated

  as such in the following Table 2.

  The following is a summary of the Ob-

  for the tests with the compositions of the

  (experimental) and with the witnesses after

washes at 21 C and 38 C.

TABLE 2

  Formula N Rd (21 C) 24-L-60N 25-7 (control) 3 (a) 785 737 3 (b) 750 725 3 (c) 765 704 Rd (38 C) 3 (a) 831 771 3 (b) ) 794 748 3 (c) 805 710 It is seen that the Rd's for the compositions of the invention or experimental are substantially higher than those obtained with the controls. In addition, we are testing BOLD liquid and TIDE liquid. The Rd for Liquid Bold are 674 and 712 respectively at

  21 C and 38 C, and the corresponding Rd for TIDE

which are 746 and 758.

  From these results it can be seen that the

  of the invention are superior to controls in detergency (EGEs are better than EGLs). The compositions of the invention are also better, on average, than the detergent products

  commercial liquids subject to testing.

EXAMPLE 4

  In another series of experiments, some of which are parallel to those already described, the composition of the following basic formula, identified as Formula 4 (a), is prepared, as well as compositions of various variants of this formula, and control compositions containing EGL instead of EGE. Component% EGE (nonionic surfactant Tergitol 24-L-60N) 21.0 (Linear Dodecyl) -Sodium benzenesulfonate 6.0, Sodium Xylene Sulfonate 5.0

  Trimethyl mono (tallow) chloride) -

* ammonium 6.0 Ethanol 6.0 Triethanolamine 1.5 Fluorescent brightener * 0.4 Fragrance 0.4 Colorant 0.2

  Citric acid (for pH adjustment) q.s.

  Water (hardness zero) 53.5, 0 * Stilbene type brightener identical to that

of Example 1.

  This detergent composition is prepared

  the method of Example 1 and tested in the same way. Formula 4 (b) is the same as Formula 4 (a), except that the percentage of (linear dodecyl) sodium benzenesulfonate is lowered to 4.4% and the quaternary ammonium chloride is replaced by WA104 of Akzo Chemie (specialty, blend

  two chlorides of (higher alkyl) - (lower alkyl)

  laughing) ammonium). A Formula 4 (c) is the same as Formula 4 (a), except that the percentage of (linear dodecyl) sodium benzenesulfonate is lowered to 3.6% and the quaternary ammonium chloride is dimethyl-di (tallow alkyl) ammonium. A Formula 4 (d) is the same as Formula 4 (a), except that the concentration of (linear dodecyl) benzenesulphonate

  sodium is lowered to 3.9% and that amine chloride is

  quaternary monium is dimethyl mono-

  (tallow alkyl) -monooctyl ammonium. Formula 4 (e) is the same as Formula 4 (a) except that quaternary ammonium chloride is omitted. So, the Formula

  4 (e) is, in fact, a second witness who, like

  the results, reveals that any improvement in detergency of the compositions of the invention is not

  not just because the EMT would be a better

  detergent than EGL in specific compositions.

  liquid substances, and establishes that the presence of

  cationic antistatic fabric softener is needed in these compositions to achieve the comparatively better detergency of which it is made

state here.

  The following is a summary of the Rd

  obtained for the compositions of Formulas 4 (a) to 4 (e).

TABLE 3

  Formula N Rd (21 C) 24-L-60N 25-7 (Controls) 4 (a) 780 725 4 (b) 790 707 4 (c) 776 709 4 (d) 736 671 4 (e) 787 Rd (38C ) 792 Rd (38 C) 4 (a) 850 815 4 (b) 855 802 4 (c) 845 787 4 (d) 803 763 4 (e) 841 831 Based on the above results, it is

  it is obvious that although changes have been made

  with quaternary ammonium halide in the

  Of the compositions of the invention, the improvement in the detergency afforded by the products of the present invention is still apparent compared to the control compositions in which the EGE of the present formula has been replaced by an EGL whose alcohol components fat and medium polyethoxylate are comparable. In addition, when the ammonium halide

  quaternary is omitted from the formulas, there is practically no

  no difference in detergency between

  positions based on EGE and based on EGL. He is responsible

  mark that we consider that the best improvement

  detergency can be achieved when the

  percentages of cationic compound and anionic detergent

  that are equal or nearly equal, and their report does not

  must not be outside the range of 1: 2 to 2: 1.

  Preferably, the molar ratio of the cationic compound

  anionic detergent is about 1: 1.

EXAMPLE 5

  In a series of experiments conducted using EMTs from different trouble points (which

  may correspond to the distribution curve heights

  ethoxylates) and measuring the detergencies

  antistatic liquid detergent compositions / as-

  softening the tissues that contain them as nonionic detergent components, compared to an EGL-based formula, a composition is prepared

  of Formula 5 (a) as well as compositions of various

  its variants of this formula and a control formula.

  Form 5 (a) is the same as Form 4 (a) of

  Example 4 and the control is the same as in this example.

  ple, the nonionic surfactant Tergitol 24-L-60N being also replaced by Neodol 25-7. A Formula 5 (b)

  is the same as Formula 5 (a), except for replacing it

  Tergitol 24-L-60N by Tergitol 24-L-75N, and a Formula 5 (c) is the same as Formula 5 (a), except that

  the alternative detergent is the non-ionic surfactant

  than Tergitol 24-L-50N. The test results are

Table 4.

TABLE 4

Formula N Rd (21 C)

EGE EGL

  (A) 735 669 (b) 717 "(c) 700" Rd (38 C) (a) 777 718 (b) 809 "(c) 718" The tests reported in Table 4 are repeated,

  which gives the following results, focused on the

5.

TABLE 5

Formula N Rd (21 C)

EGE EGL

  (a) 739 677 (b) 745 "5 (c) 697" Rd (38 C) (a) 771 745 (b) 806 "(c) 691"

  According to the results above, it is obvious

  that the incorporation of an EGE detergent improves the

  detergency of the liquid detergent compositions

  EGE-based products compared to comparable compositions

  based on EGL when test pieces are stained with oily soiling

  washed in cold water (21 C). The two EMTs, Ter-

  gitol 24-L-60N and 24-L-75N, more than EGL,

  increase the detergency of detergent-softening

  wrinkles when the test pieces are la-

  at a higher temperature (38 C).

EXAMPLE 6

  In the previous examples, various values

  Examples of EGE and quaternary ammonium halide solutions were given to the various formulas mentioned. In addition to these modifications, the anionic detergent can be replaced by other sulphonates and / or sulphates, such as sodium lauryl sulphate and sodium (tallow alkyl) sulphate or

  hydrogenated tallow) sodium sulphate, and it can be substituted

  hydrotrope with sodium benzenesulfonate or sodium cumenesulphonate. Instead of ethanol, mixtures of ethanol and polyols can be used

  such as glycerol and ethylene glycol.

  Other fluorescent brighteners can be substituted for

  and instead of triethanolamine, mixtures of triethanolamine and other alkanolamines such as isopropanolamine and diethanolamine can be used instead of triethanolamine. In place of citric acid, other weak acids may be used, including

  gluconic acid. Of course, one can also subsist

  storing different dyes and fragrances without affecting

  unfavorably the expected results. In addition to

  of the various components of the compositions, their proportions, for example 10% and 25%, can be varied without departing from the ranges specified herein. The

  described modified compositions possess the properties

  advantageously of the detergent-softener products of the invention and exert better detergency,

  compared to identical compositions in the-

  a non-ionic detergent EGL is used.

  instead of EGE type non-ionic detergent

  longed for. In addition, similar results can be obtained.

  res, corresponding to those of these working examples, when the components of the detergent compositions are added individually to the wash water.

Claims (12)

  1. Antistatic liquid detergent composition   tics, c o m p r e n a n t u n e p r o p o r -   detergent effect of a non-ionic detergent of the narrow range ethoxylate type, an   antistatic and softening tissues of a com   cationic layer, and water, this composition determines   liquid agent exerting better detergency on   oily soiling of fabrics to be washed with   of the detergent composition in a water of   compared to similar compositions in which the nonionic detergent component is a wide range ethoxylate nonionic detergent. 2. Liquid detergent composition according to claim 1, characterized in that the nonionic detergent is a condensation product of an alcohol   fat and ethylene oxide, the fatty alcohol   - lower having 12 to 16 carbon atoms and the oxide   of ethylene being in the form of polyethoxyl groups   ethanol with an average of 4 to 10 ethoxy groups per   at least 80% of the nonionic detergent con-   consisting of ethoxylates of higher fatty alcohol whose ethoxy contents are in the range of 4 to 10 ethoxy groups per molecule, the cationic antistatic compound is a quaternary ammonium salt, and the   proportions of this non-ionic detergent, ammonium salt   quaternary and water are respectively in the ranges of 10 to 35%, 2 to 15% and 30 to 70% by weight.   3. liquid detergent composition according to claim 2, characterized in that it contains, by weight, 15 to 30% of a nonionic detergent of the type   narrow-range ethoxylate which is a condensation product   a saturated higher fatty alcohol having 12 to carbon atoms and an average of 5 to 9 moles   ethylene oxide, in the form of polyethoxy groups   at least 85% of the nonionic detergent   both of higher fatty alcohol ethoxylates having in the range of 4 to 10 ethylene oxide groups per   molecule, 3 to 10% anti-quaternary ammonium salt   static and softening tissues corresponding to the formula: R. R1 - R3 X- _ 2   wherein R1 and R2 are lower alkyl groups   R is a lower alkyl group and R is a lower, middle or higher alkyl group and X is chlorine, bromine or methylsulfate group;   proportion with brightening effect, included in   0.1 to 2% of a fluorescent brightening agent,   an increasing proportion of the substantial   of the fluorescent brightening agent, in the range of 2 to 15%, of a sulfate type anionic detergent   and / or sulfonate, a solubilizing effect   fluorescent brightening agent and buffering the liquid detergent composition, in the meantime   from 0.2 to 3%, a lower alkanolamine, a   portion with hydrotropic effect, in the range of 2   10% of a hydrotropic compound, 3 to 15% of a   polar organic solvent which improves the solubility of the non-aqueous components of the liquid detergent composition in said composition and improves the transparency of said composition, 40 to 60% of water,   and any remainder of one or more additives.   4. Liquid detergent composition according to claim 3, characterized in that it contains, by weight, 18 to 25% of a nonionic detergent of the type   narrow-range ethoxylate which is a condensation product   a saturated higher fatty alcohol having 12 to 14 carbon atoms and an average of 6 to 8 moles   ethylene oxide, in the form of polyethoxy groups   ethanol, per mol of said higher fatty alcohol, at least 90% of the nonionic detergent consisting of ethoxylates of higher fatty alcohol in the range of 4 to 10 ethylene oxide groups per molecule, 4 to 8% of an antistatic quaternary ammonium chloride having the formula: R1 - N - R3 Ci- 1 2   wherein R1 and R2 are lower alkyl groups   each having 1 or 2 carbon atoms, R is   a higher alkyl group of 12 to 18 carbon atoms   and R4 is either a lower alkyl group of 1 or 2 carbon atoms or a higher alkyl group of   12 to 18 carbon atoms, 0.1 to 1% of a   fluorescent derivative derived from stilbene, 3 to 10% of a   tergent type (higher alkyl) benzene sulfonate, 1 to 2% triethanolamine, 3 to 7% of a hydrotrope selected from an alkali metal benzenesulfonate, a   alkali metal xylene sulfonate and a cumene sulfoxide   alkali metal nate, 4 to 10% ethanol, 50 to 60% water, and a remainder of 0.1 to 5% of one or more additives. 5. Liquid detergent composition according to claim 4, characterized in that the antistatic quaternary ammonium chloride is the chloride of   mono (alky) tallow) -trimethylammonium, the avian agent   The fluorescent acid is a stilbene-disulphonic acid, a stilbenedisulfonate, or a mixture thereof, the (higher alkyl) benzene-sulfonate detergent is an alkali metal dodecylbenzene sulfonate, the hydrotrope is a sodium xylene sulfonate. and the   additives include a perfume and a dye.   6. Liquid detergent composition according to   claim 5, characterized in that it is substantially   consisting essentially of about 21% by weight of a narrow range ethoxylate nonionic detergent,   about 6% mono tallow alkyl chloride   trimethylammonium, about 6% of (linear dodecyl) -   sodium benzenesulfonate, about 6% ethanol,   5% sodium xylene sulfonate, about 1.5% triethanolamine, about 0.4% of one or more fluorescent brighteners, about 0.4% perfume, about 0.2% of a or more dyes and about 53.5% water, this liquid detergent composition being clear in appearance and stable in storage and having a pH in the range of 7 to 8 and a viscosity   in the range of 75 to 125 mPa.s at 25 C.   7. Liquid detergent composition according to   claim 6, characterized in that it is constituted   killed, by weight, 21% non-ionic detergent of the narrow-range ethoxylate type, 6% tallow alkyl-trimethyl ammonium chloride, 6% (linear dodecyl) sodium benzenesulfonate, 6% of ethanol, 5% sodium xylene sulfonate, 1.5% triethanolamine, 0.4% one or more fluorescent brighteners, 0.4% perfume, 0.2% of one or more several dyes and 53.5% water, this liquid detergent composition having a pH of about 7.5 and a   viscosity of about 100 mPa.s at 25 C.   8. A method of washing laundry of which   tissues are soiled by oily soiling, which   is used to wash the laundry in a washing water in an automatic washing machine, characterized in that this wash water contains a detergent proportion of a nonionic detergent ethoxylate type g3metroit (E G E) a proportion with antistatic effect   and softening the tissues of a cationic compound   that, this washing makes the linen supple and antistatic   and eliminating oily soils from   better than when the laundry is washed with wash water which is identical except that EGE   is replaced by unedylatàga melage (EGL).   9. The method of claim 8, characterized   in that the nonionic detergent is a condensation product of a higher fatty alcohol and ethylene oxide, the higher fatty alcohol having 12 to 16 carbon atoms and the ethylene oxide being in the form of polyethoxy-ethanol groups having on average 4 to 10 ethoxy groups per molecule, at least 80% of the   nonionic detergent consisting of ethoxylates of   cool, superior fat with ethoxy levels   in the range of 4 to 10 ethoxy groups per molecule   the antistatic compound is a quaternary ammonium salt, and the concentrations of this nonionic detergent and the quaternary ammonium salt in the wash water are respectively in the range of 0.01 to 0.2% and 0.001 to 0.1% by weight, the hardness of the wash water is not more than 300 mg / liter, expressed as CaCO3, and the temperature of the wash water   is in the range of 10 to 900C.   10. The method of claim 9, wherein   in that the nonionic detergent is a   condensation product of a saturated higher fatty alcohol having 12 to 15 carbon atoms and an average of 6 to 8 moles of ethylene oxide, in the form of polyethoxy-ethanol groups, per mole of this fatty alcohol, less than 85% of the nonionic detergent consisting of ethoxylates of higher fatty alcohol with ethoxy contents in the range of 4 to 10 groups   ethylene oxide per molecule, the ammonium salt   ternary antistatic meets the formula: [R 2 + R1 - - R 3 X-   Wherein R) and R are lower alkyl groups, R3 is a higher alkyl group and R is a higher, middle or lower alkyl group and X is chlorine, bromine or methylsulfate group;   washing contains, by weight, 0.02 to 0.1% of the deter-   nonionic gent, 0.002 to 0.05% of ammonium salt   antistatic quaternary, a proportion with an effect of   in the range of 0.0001 to 0.01% of an agent   fluorescent brightening, and an increasing effect ratio   the substantivity of the fluorescent brightening agent, in the range of 0.001 to 0.1%, of an sulfate and / or sulphonate anionic detergent, and the temperature of the wash water is the range from 10 to 50 C.   11. The method of claim 10, wherein   characterized in that the nonionic detergent is a   condensation product of a higher fatty alcohol   from 12 to 14 carbon atoms and from an average of from 6 to 8 moles of ethylene oxide, in the form of polyethoxy ethanol groups, per mole of this higher fatty alcohol, at least 90% of the nonionic detergent   ethoxylates of higher fatty alcohol with   in the range of 4 to 10 ethylene oxide groups   per molecule, the antistatic quaternary ammonium salt that answers to the formula: F R2 + 1 - - R3 Cl- R4   wherein R1 and R2 are lower alkyl groups   each having 1 or 2 carbon atoms, R3 is a lower alkyl group of 12 to 18 carbon atoms and R4 is a lower alkyl group of   1 or 2 carbon atoms, ie a higher alkyl group   12 to 18 carbon atoms, the wash water contains, by weight, 0.03 to 0.06% of the nonionic detergent, 0.005 to 0.02% of the ammonium chloride quater-   antistatic agent, 0.0002 to 0.005% of an avian   fluorescent vage derived from stilbene, and 0.005 to 0.02%   benzene-type (higher alkyl) detergent   sulfonate, the hardness of the wash water is 100 to 200 mg / liter, expressed as CaCO3, and the temperature of the   the wash water is in the range of 10 to 25 C.   12. The method of claim 11, wherein   characterized in that the quaternary ammonium chloride is a mono (tallow alkyl) trimethyl ammonium chloride and the wash water contains, by weight, about 0.04% of the ethoxylate type nonionic detergent.   narrow, about 0.01% monoalkyl chloride   lower) -trimethylammonium, about 0.01% of (dodecyl)   cyl linear) sodium benzenesulfonate and about   0.001% fluorescent brightening agent.