FR2565246A1 - ANTISTATIC SYNTHETIC ORGANIC DETERGENT COMPOSITION, MANUFACTURING METHOD THEREOF, AND WASHING METHOD - Google Patents

Abstract

ANTISTATIC LOADED ANIONIC SYNTHETIC ORGANIC DETERGENT COMPOSITIONS WHICH ARE PARTICULARLY USEFUL FOR ELIMINATING A LARGE VARIETY OF DIRTY AND COMMON TASKS THAT ARE DIFFICULT TO REMOVE FROM DIFFERENT FIBROUS MATERIALS, SUCH AS COTTON AND THOSE, OF NYLON , COMPRISING AN ANIONIC SYNTHETIC ORGANIC DETERGENT OR A MIXTURE OF SUCH DETERGENTS, A POLYACETAL-CARBOXYLATE AND A CATIONIC ANTISTATIC AGENT. PROCESSES FOR THE WASHING OF SUCH FIBROUS MATERIALS DIRTY AND STAINED BY PERSISTENT STAINS AND DIRTS ARE ALSO DESCRIBED, TO ELIMINATE THEM AND AT THE SAME TIME TO PREVENT "STATIC" ADHESION TO OTHER WASHED MATERIALS.

Description

The present invention relates to compositions for

  tergentes. More particularly, it relates to composites

  detergent solutions comprising a synthetic organic detergent

  as anionic or a mixture of such detergents, a detergency builder for this (these) detergent (s) consisting of polyacetalcarboxylate and a cationic antistatic agent. The invention also includes a method for washing fibrous materials

  that have been soiled and / or stained, to remove such dirt

  safe and / or stained and to prevent static "adhesion"

materials.

  The need to remove dirt and stains

  of fibrous material is secular and a multitude of components

  sitions have been described to achieve this result. So

  that soap used to be the universal detergent, today

  almost all detergent compositions today

  domestic are based on one or more organic detergents

  synthetic nicks. Among such detergents, detergents

  anionic and nonionic are the most effective and the

  anionic tergents are the most used. These ampholytic or amphoteric detergents and cationic detergents can also be used. Cationic compounds which

  have detergent activity are often also germic-

  and act as anti-static agents ("anti-static

  that ") which is particularly important because they decrease the static adhesion of articles washed from synthetic organic polymer plastics, for example,

  Nylon, acrylic and polyester materials. The compounds ca-

  also have softening properties for fabrics. However, a disadvantage of cationic detergents is their reactivity towards anionic substances such

  than anionic detergents, which can be the cause of

  your decreases in detergent action. These last years,

  cationic detergents such as ammonium halides

  quaternary nium have been used in compositions

  tergents to give softening and anti-aging properties

  static to washed fabrics or linen made of ma-

  third synthetic organic polymer plastics, without having a serious unfavorable effect on the detergent activities of the compositions. Also recently, detergency builders

  polyacetal-carboxylate type have been used in compounds

  detergent solutions instead of polyphosphate type detergency builders because they do not contain phosphorus

  and therefore were not intended to promote eutro-

  phisation of river waters. Another advantage of such a detergency builder is that they are easily degradable in

  normally acidic waste water.

  Although the main components of these

  detergent compositions have been used in other com-

  positions like this, the present compositions are new

  old, not obvious and useful, and they have surprising

  good stain and soil removal properties.

  Particularly important is the highly improved capacity

  ree that have the present compositions, in particular the

  compositions not containing phosphate, to remove various

  its stains and soiling of synthetic textile materials and to give softening and antistatic properties to such materials during conventional machine washing, which antistatic properties prevent the materials

  washed to remain adhered to each other after drying

automatic laundry.

  According to the present invention, a composition

  tergente antistatique includes a detergent proportion of a

  synthetic organic detergent or a mixture of such

  tergents, a proportion reinforcing the detergency of an adju-

  of detergency of the polyacetal-carboxylate type suitable

  for this (these) detergent (s) or a proportion reinforcing the

  tergence of a mixture of a polyacetalcarboxylate type detergency builder and a zeolite type detergency builder, and a proportion a n t i s t a t i q u e of a

  cationic antistatic component. Such compositions pre-

  fairies comprise about 5 to 30% of linear linear sodium alkylbenzene sulfonate in which the upper alkyl radical has 12 to 14 carbon atoms, about 5% of a polyacetal-carboxylate detergency builder

  sodium with a weighted average molecular weight calculated

  from 3,500 to 10,000, or a mixture of such a de

  tergency and a detergency builder of the Zeolite A type, approximately 2 to 10% of distearyl dimethyl ammonium chloride,

  about 2 to 20% humidity, the rest being char-

  inert ge (s) and / or other detergency builder (s) and / or other additive (s). The invention also includes a

  O10 process for the removal of stains and mixed dirt

  of fibrous materials, particularly acetate

  lulose, which includes washing of ta- fibrous materials

  chopped and soiled in washing water which contains a compound

  detergent solution comprising a detergent proportion of a synthetic organic detergent or a mixture of such detergents

  tergents, a proportion reinforcing the detergency of an adju-

  amount of detergency of the polyacetal-carboxylate type suitable for this detergent and an antistatic proportion of a product

  cationic antistatic, at a concentration of such a

  detergent position in the washing water from 0.05 to 0.5%.

  The invention further comprises a method for manufacturing

of the compositions described.

  Anionic synthetic organic detergent according to

  the present invention normally consists of

  this (s) lipophilic (s) sulfate (s) and / or sulfone (s) having an alkyl chain of 8 to 20, preferably 10 to 18 and more preferably 12 to 16 carbon atoms. Although various

  water soluble salt-forming cations can be used

  to form sulfated detergents and soluble sulfones

  desired, including ammonium and lower alkanolamines

  res (such as triethanolamine), and magnesium, we use

  usually an alkali metal such as sodium or po-

  potassium, and most preferably one such cation is sodium.

  Among the various anionic detergents that can be used

  in the practice of this invention, the alkylbenzene-

  linear higher sulfonates whose alkyl chain consists of 10 to 18, preferably 12 to 16 and very preferably about 12 to 14 carbon atoms, are considered very suitable. Also usable, among others, are the sulfates of monoglycerides, the sulfates of higher fatty alcohols, the higher polyethoxylated alkanols

  fat, such alkanols which may be synthetic or natural

  real, containing 3 to 20 or 30 ethoxy groups per mole, paraffinsulfonates and olefin sulfonates, the alkyl group present in all these compounds containing from 10 to 18

  carbon atoms. Some of these alkyl groups may be

  be slightly branched, but they always have a length

  carbon chain in the range described.

  Cationic antistatic products that can

  be used, usually in limited proportion, i.e.

  say no more than 20% and preferably only up to 15%, are preferably upper dialkyl halides, lower dialkylammonium, in which the higher alkyl radicals have from 10 to 18, preferably from 16 to 18 atoms

  carbon, lower alkyl radicals have 1 to 3 ato-

  carbon mes, preferably 1 carbon atom, and the ha-

  logenes are chromium or bromine. Among such products, mention may be made of distearyl dimethyl ammonium chloride, tallow dedi-dimethyl ammonium chloride (in which the radical

  alkyl comes from animal fats) and di bromide (tallow-

  hydrogenated) -dimethyl-ammonium. However, various other pro-

  such cationic products - including N ethosulfate

  cetyl-ethyl-morpholinium, which often also have properties

  deodorant and germicidal tees can also be used.

  Descriptions of various anionic and cationic detergents

  what are appropriate are given in various annual publications-

  titled McCutcheon's Detergents and Emulsifiers,

  for example, in the one published in 1969. Such products

  also form a well-known category and they are

  described in detail in the literature (as are the

  anionic tergents) and therefore it is not necessary

  let them be discussed in more detail here. In addition, de-

  nonionic and amphoteric tergents, also described in McCutcheon texts, may be present with the detergent

  anionic and the cationic antistatic product, usual-

  in lower proportions than the anionic detergent, and usually also in lower proportions

  lower than those of the cationic antistatic product present.

  The polyacetal-carboxylate can be considered as

  me being that described in US Patent 4,144,226 and it can be prepared by the method mentioned therein. A characteristic product of this kind corresponds to the formula: R1 - (CHO) n - R2 1) n R2 COOM

  in which M is chosen from alkali metals, ammonium

  nium, alkyl groups having 1 to 4 carbon atoms, tetraalkylammonium groups and alkanolamine groups both having 1 to 4 carbon atoms in alkyl radicals; n averages at least 4; and Ri and R2 are any chemically stable groups which

  stabilize the polymer against rapid depolymerization

  tion in alkaline solution. Preferably, the polyacetal-car-

  boxylate is one in which M is an alkali metal, the so-

  dium for example; n is between 20 and 100: R1 is

CH3CH20 MOOC

,,

HCO- or H3C-CO-

H C MOOC

or a mixture thereof; R2 is

OCH2CH3

-CH CH3

  and n is on average between 20 and 100, more preferable-

  between 30 and 80. The average molecular weights are

  calculated derivative of polymers are normally 2,000 to

  000, preferably from 3,500 to 10,000 and more preferable-

  from 5,000 to 9,000, for example being about 8,000.

  Although the preferred polyacetal carboxylates

  have been described above, it should be understood that they may

  may be totally or partially replaced by others

  polyacetal-carboxylates or by adjuvant salts of deter-

  Related organic gence described in a number of Monsanto patents dealing with such compounds, processes for their manufacture and compositions in which they are used. Similarly, the terminal groups of the chains described

  in the Monsanto patents cited, in particular in the patent

  vet US 4,144,226, can be used provided that they have the desired stabilization properties which allow- '

  try the detergency builders mentioned to be depolymerized

  rised in acidic environments, which facilitates their biodegradation in waste water courses, but ensures their stability

  in alkaline environments such as washing solutions.

  The component of zeolite usually has the form

  mule (Na20) x. (Al203) y. (SiO2) .wH20, in which x is 1; y is between 0.8 and 1.2, preferably being equal to 1; z is between 1.5 and 3.5, preferably between 2 and 3

  or is equal to about 2; and w is between 0 and 9, pre-

  roughly between 2.5 and 6. Such zeolites are

  cation changers and they have a capacity for exchange

  for the calcium ion about 200 to 400 mg equivalent of du-

  calcium carbonate by g or more. They are preferably hydrated to a degree of 5 to 30%, preferably from 10 to 25% of humidity, for example to a degree of humidity

  20%. Zeolite A is preferred (X and Y are also used

  sands) and in this type of zeolite, 4A is particularly

  favorite. Corresponding particle sizes of zeolite (s)

  usually lay at 149 to 37 µm, preferably 110 or 74 to 44 µm, but their ultimate sizes are less than one micron. The various zeolites are described in detail in the text Zeolite Molecular Sieves by Donald W. Breck, published

  by John Wiley & Sons, in particular at pages 747-749.

  In the compositions of the invention, other ad-

  detergency builders that polyacetal-carboxylate can

  also be present although they are not necessary.

  It is often desirable to avoid the presence of phosphorus in the detergent composition; so polyphosphates,

  which have been the detergency adjuvants of choice in the do-

  main detergents for many years (in part

  especially pentasodium tripolyphosphate), are preferably omitted from the present formulations. They can be however

  present in some cases, if kept in pro-

  relatively small portions, for example up to 5 or 10%.

  Among detergency builders other than polyphospha-

  such as sodium tripolyphosphate and tyrophosphate

  trasodium, those which it may be desirable to incorporate

  to the present compositions to complete the reinforcing action

  of the polyacetal carboxylate include the carbonate of

  sodium, sodium bicarbonate, sodium sesquicarbonate

  dium, sodium silicate, zeolites, Zeolite A for example, NTA, sodium citrate, sodium gluconate,

  borax, other borates and other detergent builders

  those known in the detergent field. Inert fillers may be present, such as sodium sulfate and

  sodium chloride, to give volume to the product when

  that it is considered desirable. Among the adjuvants of

  tergence, we consider that zeolites are particularly

  effective in these compositions, as indicated previously

  cédemment and, among the inert fillers, one usually prefers-

sodium sulfate.

  Among the various additives that can be used

  are dyes such as dyes and pigments

  elements, fragrances, enzymes, stabilizers, ac-

  stains, fluorescent optical brighteners, buffers, fungicides, germicides and fluidizers. Also included among additives, detergency builders and inert fillers, unless they are in other categories listed, are various other components or

  additional impurities that accompany other ingredients.

  For example, it is recognized that sodium carbonate and water frequently accompany polyacetal-carboxylate in

  Builder U, the product is the present source of polyac-

  tal-carboxylate. Moisture is usually present in

  compositions according to the invention, either as liquid moisture

  bre, either in one or more hydrates. Although moisture is not an essential component of the present compositions

  detergents, it is normally present due to the utility

  water in manufacturing and it can help solu-

  bind components of the composition and bind them.

  The proportions of components of the compositions are

  lon the invention given below are those for products

  into particles which usually have part dimensions

  cules in the range of 2.38 or 1.68 mm to 0.149 or 0.110 mm.

  However, such proportions also apply to others.

  very solid forms such as bars or breads, to powders

  more finely divided or with larger grains, to compounds

  granular and agglomerates. They can also

  apply to liquid preparations. However, because

  their relatively low stability (due to interactions

  between anionic and cationic components) of

  aqueous liquid preparations should be used relatively

  quickly after preparation. Likewise, although the relationships between pairs of components, except water,

  can be roughly the same in single preparations

  liquids or pastes only in solids, liquid products

  are often much more diluted, so that the proportion

  water or other solvent or a mixture of pre-

  smells can be much higher. In certain aspects of the invention, the components can be added directly

  with washing water, in which case it can be considered that the

  detergent position is the wash water containing the various

active and other components.

  In solid detergent compositions particularly

  laires and other solid detergent compositions of this invention, the total proportion of detergent present is normally 5 to 40%, preferably 5 to 30%, more

  preferably from 10 to 25%, particularly pre-

  fairy from 13 to 23%, for example about 19%. Such a detergent is normally an anionic detergent and among these are

  higher alkylbenzene sulfonates are preferred, e.g.

  ple, linear sodium tridecylbenzene sulfonate. Any-

  times, it may be present with other anionic detergents or it may be replaced wholly or in part by one or more of these other anionic products. The

  proportion of polyacetal-carbon detergency builder

  xylate is usually 5 to 50%, preferably 5 to

  %, more preferably from 15 to 30% and, in particular

  most preferred, from 17 to 23%, for example, about 19%, when it is the only detergency builder present or when up to 50% of other detergency builder (s) than the zeolite is / are also present. When zeolite

  is present, the sum of the polyacetal carboxylate and the zeo-

  lite is in the proportions given above for the polyacetalcarboxylate alone and, if zeolite is present,

  the polyacetal-carboxylate represents at least 5% of the com-

  detergent position. Likewise, the ratio between polyacetal-

  carboxylate and zeolite is in the range of

  1: 3 to 3: 1, preferably from 2: 3 to 2: 1 and more preferable-

  about 3: 4 to 7: 4, for example, about 1: 1 to 3: 2.

  The cationic compound that acts as an antistatic (and

  which also has softening properties) is pre-

  feels in an antistatic proportion in the compositions according to the invention, at least with regard to certain

  materials. It has been found that the present compositions

  tergents were particularly effective in dimi-

  nution of electrical charges (and static adhesion

  resulting) on acetate materials, but they are also

  so effective against other types of synthetic fabrics such as acrylic and polyester fabrics. The proportion of cationic antistatic product is usually within

  the range from 2 to 10%, preferably from 3 to 8% and more pre-

  roughly 4 to 6%, for example, about 4 or 5%. The

  humidity percentage is normally 2 to 20%, prior to

  3 to 15%, and more preferably 5 to 12%, for example, about 6 or 8%. Such percentages include moisture in the form of hydrate which is released during the

  heating for 2 hours at 105 C (the standard method of ana-

  humidity lyser). The proportions of other components such as inert fillers are normally limited to 50% and they are often in the range of 5 to 35%. Likewise, contents of non-phosphate detergency builders other than

  polyacetal-carboxylate are limited, being in general

  less than 40%, such as 3 to 30% or 5 to 25%, but

  such additional detergency builders were not born

  dealers. However, the presence of other adjuvant deter-

  gence and inert loads is often desirable. So the

* sodium carbonate is a non-phos detergency builder

  preferred phaté, as is sodium silicate. Silica-

  your favorites are the sodium salts in which the Na2O: SiO2 ratio is from 1: 1.6 to 1: 3.0, preferably from 1: 2.0 to 1: 2.6, for example from 1: 2, 4 The proportions of carbonate and

  silicate, if they exist, can range from 3 to 25%, pre-

  preferably from 8 to 18%, and more preferably from 10 to 15%,

  and from 2 to 15%, preferably from 5 to 10%, and more preferably

  6% to 9%, respectively. The proportion of inert filler, if present, is usually 5 to 35%, preferably 20 to 35%, and more preferably 22 to%.

  The total content of additives does not exceed usual-

  Lely not 10 or 20%, and it is preferably less than%, the separate contents of usual additives generally not exceeding 3 or 5%, and often being preferably

  less than 1 or 2 Z. For example, carboxymethyl-cellu-

  lose sodium, which is a desired anti-redeposition agent

  table is usually present in the range of ll 0.3 to 3%, preferably 0.5 to 2%, for example, 1%

  composition, when included.

  In preferred embodiments of the invention

  tion, particulate solid compositions of particle size such as those described above, it

  is often preferred to spray dry as much as possible.

  ble of the formulation in order to obtain spherical particles

  of practically constant shapes. As the product an-

  cationic tistatic can react with anio-

  nics such as with anionic detergent it is normal-

  later added to the rest of the composition. To avoid segregation during transport and storage of the final product, it is desirable that all components added later, such as the cationic compound, the

  polyacetal-carboxylate and the enzyme, be of form, of di-

  particle and bulk density mensions similar to those of the rest of the composition. However, even when

  this is not the case and when the materials added later

  laughingly are in finely divided form, such as di-

  particle sizes in the range of 95 to 44 µm, and

  higher bulk density, they can be added ul-

  after spray-dried pearls or other

  very particles of the basic detergent composition which has

  larger particle size, and they adhere

  only to such particles to provide a product

  siré of dimensions in the range from 1.68 to 0.149 mm.

  The polyacetal carboxylate can sometimes be spray dried

  sation with the detergent composition, provided that

  take care to prevent it from being decomposed by heat.

  In a variant of the manufacturing process, the various

  posers in finely divided form can be simply

  mixed together. Also, when the part dimensions

  of the various components or some of them are less than those desired, for example in the

  range from 110 to 44 Dm, their particles can be agglomerated

  to the desired size, sometimes with the aid of ag-

  glomerants such as dilute aqueous silicate solution

  sodium, and other times with only water to make

cilitate the agglomeration

  The anionic detergent or the mixture of such detergents

  tergents, which is / are the main detergent (s) of the desired composition, can / can be spray-dried with inert fillers such as sulphate

  sodium, detergency builders as so carbonate

  dium, sodium bicarbonate, borax and silicate

  sodim, and additives such as fluorescent optical brighteners

  rescents, pigments and dyes, in a normal way,

  using a combined spray drying column

  rant or conventional counter-current, with drying air

  ge entering around 200 to 600 C (Preferably 300 to 350 C when polyacetal-carboxylate is

  present). Polyacetal-carboxylate and antistatic product

  tick can be mixed then by adding them either one

  after the other either simultaneously, or else the anti-

  static and polyacetal-carboxylate can be mixed

  beforehand and then mixed with the pearls dried by ato-

  bet. When a relatively small proportion of

  non-ionic detergent must be present with the detergent

  anionic, it can be spray dried with this deter-

  anionic gent, inert charges, etc, and other sub-

  stable tances which must be present can also be

  be incorporated in the "mixer" and then be dried

  by atomization with the anionic detergent. However, when

  that more than about 4 or 5% (sometimes more than 2%) of

  gent nonionic are present in the formula, any pro-

  additional portion is usually added later

  such as by spraying on particles of moving detergent beads. Polyacetal-carboxylate and

  antistatic product can then be added later-

  is lying. In some cases, the polyacetal carboxylate can be dispersed and / or dissolved in the nonionic detergent which is heated so as to be in the liquid state (or which can be dissolved in a solvent) and the combination of detergent

  non-ionic and polyacetal-carboxylate can be sprayed

  placed on detergent beads or base beads,

  which is followed by the addition of the anti-static product

  tionic. It is desirable that the particulate material prepared be of particle sizes in the range of 2.38 to 0.120 mm or 1.68 to 0.149 mm and the manufacturing process is designed accordingly. However, we can

  use sieving to remove excessively small particles

  your or too large sizes which can be reworked, crushed, agglomerated or treated otherwise to arrive at

  desired dimensions (sometimes corresponding to 2.38 to

0.177 mm).

  To produce the present products in the form of bars, breads or bricks, the compositions can be extruded, compressed or molded to the desired shapes according to the

  known methods. To convert them into liquid preparations

  components can be dissolved and / or dispersed

  in liquid media such as water and / or one or more sol-

  suitable materials such as ethanol, glycerol and isopropanol.

  To put into practice the methods of removing stains and stains of the invention, which result in non-adherent and clean (and also soft) washed articles, one of the compositions described can be added to a water of

  washing or else you can add the different components.

  Normally, the concentration of the compositions used is from 0.05 or 0.1 to 0.4 or 0.5%, preferably from 0.1 to 0.35%, and more preferably from 0.15 to 0.25 or 0, 35 Z. Higher concentrations such as 0.25 to 0.45 e or more (and less washing water) are often used in machine washes following European practice which

  normally uses higher temperature wash water

  ture. In American practice, lower concentrations

  The compositions are used, such as from 0.05 to 0.25%, often preferably around 0.1 to 0.2%. Usually the washing temperature in America is at 55 ° C, preferably 35 to 55 C, compared to 99 C, often 70 to 9 C or 95 C in Europe. However, it is considered that the compositions of the present invention can be used to remove stains and stains from laundry from different types of fabrics and materials, and to result in such laundry free of static charges and

  soft, whatever the washing method used.

  In the implementation of the present invention, sufficient detergent composition according to the invention is added to washing water in a conventional household washing machine (industrial machines can also be used) in the desired proportion in given limits, for example, 0.2% (-130 g per 65 liters

  wash water), wash water at room temperature

  normal value, for example, 49 C, and normal hardness (around 50 to 250 or 300 ppm, expressed as calcium carbonate). The laundry is then added, the normal loading weight ranging from 2.7 to 4.5 kg, for example 3.6 kg. Washing of the laundry is carried out in a normal cycle lasting from 2 to 30 minutes, for example from 5 to 20 minutes, as desired, usually depending on the dirtiness of the laundry. Surprisingly,

  the compositions of this invention have, in water relatively

  very soft and in water of medium hardness, hardness

  about 50 to 150 ppm, roughly the same properties of

  removal of stains and soiling as compositions

  witnesses in which the polyacetal carboxylate is replaced

  created by an equal (even greater) proportion of tripoly-

  sodium phosphate, but they are clearly better than these at higher hardnesses (250ppm). Also,

  terry cloth towels washed with either a

  tion according to the invention either with a control composition (the

  composition according to the invention contains polyacetal-carbon

  xylate and zeolite and in the control composition these

  these are replaced by an equal weight of sodium tripolyphosphate) appear to have roughly the same flexibility and the same overall electrostatic charges. However,

  such compositions according to the invention are clearly superior to

  laughs at the witness regarding the decrease in char-

  electrostatic age (and the decrease in the adhesion of the

sus) for acetate fabrics.

  The invention is illustrated by the following examples

  which are not limiting. Unless otherwise indicated, all parts represent weights and all temperatures are given in C, in these examples, in

  the rest of the specification and in the claims.

EXAMPLE 1

  Component Percent linear tridecylbenzene-sulfonate of sodium 19.0 Builder U (79.7% sodium polyacetal-carboxylate, supplied by Monsanto Co (lot N 2538422, of molecular weight as calculated weighted average of 8,034) 23.8 Carbonate sodium (anhydrous) 12.4 Sodium silicate (Na20: SiO2 = 1: 2.4) 7.6 Sodium sulfate (anhydrous) 26.7 Water 5.7 De-distearyl dimethyl ammonium chloride (Arosurf TA- 100, about 90% active, supplied by Sherex Chemical Company) 4,8,0 A particulate detergent in the form of spray-dried beads consists of all of the above components except the cationic compound by preparing an aqueous mixture of "mixer" (concentration of substances

  solids = 55%) consisting of the components listed at a time

  temperature of around 55 ° C. and by spray-drying such a "mixer" mixture. The drying column used

  is a counter-current column operating under conditions

  soft, with drying air at an inlet temperature of around 300 C and taking other measures to prevent the beads from smearing and decaying

  sodium polyacetal carboxylate (by preventing the formation

  tion of deposits on the walls of the column, using cooling air and controlled spraying to avoid contact of the pulverized material with the walls

  column). The resulting product has part dimensions

  sheets in the range of 1.68 to 0.149 mm, to a specific mass

  apparent form of about 0.3 g / ml and has a moisture content of about 8%. Mix with 20 parts of the composition

  detergent thus prepared part of the product Sherex Che-

  mical Co describes. It is desirable that such a product have

  particle sizes similar to those of the compound

  lO basic detergent sition, but even when it is in finer powder, with particle sizes from 149 to 44 pim,

  the antistatic product is well distributed within the compound

  detergent sition and it adheres to the particles thereof,

  providing a product which is always in the range of di-

  mensions from 1.68 to 0.149 mm and which still has a specific mass

  apparent fique of about 0.3 g / ml. The prepared product is examined from the point of view of removing stains and soiling, using a Tergotometer laboratory type test washing machine in which standardized batches of various materials, stained and soiled in a standardized manner , are washed in washing water at a composition concentration of 0.21%, at a washing temperature of 49 ° C.,

  and for a washing time of 10 minutes, with the agitator

  tor rotating at 100 revolutions / minute. The hardness of the water used

  are hardnesses of calcium and magnesium in the

  Ca: Mg ratio of 3: 2, has hardnesses of 50, 150 and 250 ppm.

  Readings of the reflectance of the washed and dried batches are taken and indices indicative of the weighted sums of the reflectances are calculated, which indices, based on experience, have been shown to be representative of the

  ability to remove stains and soiling from a

  detergent position examined (the higher the index, the better

  their is detergency). At hardness levels of 50,

  and 250 ppm, the experimental product of this example pre-

  described above gives indices of 256, 242 and 234 respectively. When the same composition is prepared with sodium tripolyphosphate replacing Builder U in the

  formula (which gives a product with an adjuvant content

  with higher active detergency than that of the experimental formula) the indices are 254, 240 and 222 respectively. It can therefore be seen that the efficiency of stain removal and cleaning of the composition according to the invention in water duration (250 ppm hardness) is greater than that of a

  control composition which contains tripolyphosphate penta-

  sodium, the most powerful commercial detergency builder

  success in this area, even when more

  lyphosphate is used in the control composition.

EXAMPLE 2

  When we replace in the formula of Example 1 half of Builder U with Zeolite 4A (hydrated to

  20%), which is added to the "mixer" in the form of a

  finely divided dre having a particle size in the range of 149 to 44 µm, and the quaternary ammonium halide is mixed with the spray dried beads

  as described in example 1, the detergent composition

  The resultant antistatic has essentially the same pro-

  cleaning properties (as measured by the same

  stain and soil removal index) than a compound

  control sition based on three-way detergency builder

  sodium lyphosphate in place of Builder U and zeolite.

  Likewise, when viewed from the point of view of the load

  electrostatic, revealing of "adhesion" of materials la-

  vés, the product according to the invention, containing Builder U and zeolite, gives essentially the same improvement

  that gives the "witness", in comparison to comparisons de-

  tergents which do not contain the cationic compound. We

  notes the superiority in the reduction of electro- charge

  static for acetate fabrics with the experimental formula

  compared to a witness containing as adjutant

  of detergency of sodium tripolyphosphate and the compo-

  is cationic mentioned (but not Builder U or zeolite).

  Thus, after washing with the compositions subjected to the com-

  parison and drying in an automatic dryer, the batch

  of acetate has an electrostatic charge of 5.5 kV after the

  vage with the control, and 1.6 kV after washing with the pro-

  experimental product according to the invention, and similar drying.

  When looking at their softening properties, the

  control composition mentioned and the experimental composition

  the mentioned rank roughly the same in a test in which six people have stored, from the softest and roughest, series of terry towels washed with either composition. The conditions of the test are the same as those described above for the examination of the detergency, except that small washing loads are used (approximately 0.5 kg of loading for 65 1 of washing water) and that the concentration of the detergent composition be reduced to 0.15 Z (100 g in 65 l of washing water).

  In another modification of this example, we have

  do the proportions of Builder U and zeolite at 3: 2. The in-

  the stain and dirt removal dices obtained are essentially the same as those of the control which contains

  instead as a detergency builder for polyphosphate.

  From the above experiments, it appears that the experimental compositions of these examples are equal or superior from the point of view of stain removal and

  heavy soiling, reduced electrical load

  trostatic and softening properties, comparative-

  ment to a control composition in which tripolyphos-

  sodium dip is used in place of Builder U or

  instead of a mixture of Builder U and zeolite.

  It is considered that such results can also

  be obtained when changes are made to the

  experimental model and / or when changes are made

  killed in the manufacturing and / or washing processes. So,

  the anti-static product mentioned can be replaced by -

  other similar substances, such as di (hydrogenated tallow) -dimethylammonium chloride, the corresponding quaternary ammonium bromides and other antistatic agents

  known. Similarly, when the tridecylbenzene sulfonate of so-

  dium is replaced by other higher alkylbenzene sulfonates

  water-soluble laughers such as dodecylbenzene-sulfo-

  sodium nate or mixtures of tridecylbenzene-sulfonate

  linear of sodium and sodium lauryl sulfate (in par-

  equal parts) or by other anionic detergents as described above, satisfactory products in the

  part of the invention can thus be obtained. The polyaceous-

  particular sodium tal-carboxylate may be replaced by other similar products of different molecular weights, for example, by that having a molecular weight of 5,250

  (Monsanto, lot N 2547321) or by other similar compounds

  res within the given molecular weight ranges and having the end groups described, and useful antistatic detergents are obtained. Likewise, detergency builders, inert fillers and additives can be changed, such as

  it is described here. For example, the Zeolite 4A can be changed

  gee for other A zeolites or for X and / or Y zeolites. In addition, the proportions of the various components can also be changed, usually by 10 or 25%, without losing

  the advantages of the present invention, as long as the propor-

  tions remain in the above ranges.

  In modifications to the manufacturing process,

  the compositions described are prepared by subsequent addition

  of Builder U powder, in particles having the di-

  mension of spray dried pearls or more finely

  divided (149 to 44 pm), spray-dried pearls

  tion, before, after or at the same time as particles of antistatic product of similar dimensions or in powder

  finely divided. The polyacetal-carboxylate can be mixed

  managed beforehand with the antistatic product to be

  immediately mixed with the spray dried product. In certain aspects of the invention, the separate components can be

  mixtures with each other without spray drying

  of most of them. In some cases, the various components can be added to the wash water as individual charges. In a preferred method, the polyacetalcarboxylate is added

  later rather than spray dried with different

  other components of the final product, in order to better maintain

  maintain all its effectiveness in detergent loading and

  nution of electrostatic charge (avoiding subjecting such a detergency builder to heat which may be excessive and thereby causing its degradation). When such a change is made in the manufacturing process described, the product obtained is equal to or greater than the point of

  view of the characteristics described compared to those indicated

  previously mentioned here. In the methods described, the pro-

  duits obtained have an apparent specific gravity of 0.25 to 0.5 g / ml, like the spray-dried pearls, both have particle sizes in the range

  from 1.68 to 0.149 mm, while the poly-detergency builder

  carboxylate acetal and the antistatic product consisting of distearyl dimethyl ammonium chloride usually have a higher apparent specific mass (from 0.6 to 0.9 g / ml)

  and have smaller particle sizes (149 to 44 µm).

  However, in the final compositions, the smaller particles adhere satisfactorily to the larger ones,

to provide the desired product.

  The washing method in this example can also be

  be changed, as by the use of water of various durations

  mixed calcium / magnesium tees from 50 to 250 ppm and even

  more, sometimes up to 300 ppm or more, and washing can be

  be carried out in the temperature range from 10 to 55 ° C., and at concentrations of the detergent composition of 0.05

  at 0.5%, and satisfactory antistatic effects are obtained

  health without excessive loss of detergency, and products may be equal to or greater than "controls" containing

  sodium tripolyphosphate in place of polyacetal-carbon-

  xylate or in place of a combination of this adjuvant

detergency and zeolite.

EXAMPLE 3

  15 parts of dodecylbenzene sulfonate are mixed

  linear sodium and 25 parts of sodium polyphosphate

  dium to 4.5 parts of Arosurf TA-100 (distearyl chloride-

  dimethyl ammonium active at 90%), all components being

  in the form of finely divided powder, with dimensions of

* tiles in the range of 149 to 74 pm. We use such a pro-

  duit, the witness, for washing terry cloth towels,

  using essentially the same method as that

  described in examples 1 and 2. The towels are then evaluated by an expert and they receive a grade of 9 for softness on a standardized scale ranging from 1 to 10, 10 corresponding to the softest. In another control experiment, 3 parts of the Arosurf TA-100 are used with the 15 and 25 parts of the other constituents, and a similar examination of the softness is carried out. Washed towels are assessed

to 8 on this scale of sweetness.

  When instead of the 25 parts of tripolyphos-

  sodium phate is incorporated into such a composition 25 per-

  ties of Builder U (lot 2538422), and that the examination is repeated, the degree of sweetness obtained is 10 and such a degree is also obtained when the content of Arosurf TA-100 is reduced in

  the formula mentioned in 3 parts.

  The compositions described according to the invention are all satisfactory detergents and they have

  good antistatic and softening properties.

  Instead of dry mixing of the different ingredients

  other compositions of this example can be produced

  picks by spray drying and other operations

  described in Example 1 and in the specification which

  give in. Also, the compositions mentioned can be

  used for washing stained and soiled linen and for

  crease, and to reduce the static adhesion that results nor-

  improperly, after washing such a linen, drying it in

  an automatic dryer. Instead of using dodecyl-

  linear sodium benzene sulfonate, you can use

  linear sodium tridecyl benzene sulfonate, lauryl-

  sodium sulfate and polyalkoxy sulfates of alcohols

  higher fats, and Zeolite A or Zeolite X may

  Can be used to replace half of the Builder U. Similarly, other agents among the antistatic agents mentioned can be used in place of the Arosurf TA-100, and the various proportions can be varied.

  as previously described, leading to de-

  satisfactory tergents with good antistatic properties

ticks and softeners.

  The invention has been described in relation to various illustrations and embodiments thereof, but should not be limited to these because it must be obvious that a specialist, in view of the present specification, will

  suitable for using equivalents or substitute products

  without departing from the scope of the invention.

Claims (12)

R E V E N D I C A T I 0 N S   1 - Particulate detergent composition, reinforced by anti-static detergency additives, comprising   a detergent proportion of an anionic organic detergent   than synthetic, a proportion enhancing the detergency of a polyacetal-carboxylate detergency builder   suitable for this detergent (s) or a higher proportion   drying detergency of a mixture of a detergency builder   polyacetal-carboxylate type and a deter   lO gence zeolite type, and an antistatic proportion of a cationic antistatic compound.   2 - detergent composition according to claim l, wherein the cationic antistatic compound is a quaternary ammonium compound.   3 - detergent composition according to claim 2, which is essentially free of phosphate, and wherein the synthetic anionic organic detergent is a sulfated or sulfone detergent, the detergency builder of polyacetal-carboxylate type has a weighted average molecular weight calculated from 3,500 to 10,000, the zeolite-type detergency builder is a hydrated zeolite of   type A, type X or type Y, and the ammonium salt qua-   ternary is a higher dialkyl halide - dialkyl   lower - ammonium, in which the upper alkyl radical   laughing has 10 to 18 carbon atoms and the radical   lower alkyl has 1 to 3 carbon atoms.   4 - Detergent composition according to claim   3, in which the anionic organic detergent synthesized   tick is a higher alkylbenzene sulfonate in which the alkyl radical contains from 10 to 18 carbon atoms, the polyacetal-carboxylate is a polyacetal-carboxylate in which the carboxylate is sodium carboxylate, the zeolite is a type A zeolite (Na20) x '(Al203) y' (Si02) z.wH20 in which x is l, y is between 0.8 and 1.2,   preferably equal to about l, z is 1.5 to 3.5, pre-   roughly from 2 to 3 or equal to about 2, and w is 0   to 9, preferably 2.5 to 6, and the ammonium salt qua-   ternary is an upper dialkyl-dimethyl halide   ammonium in which the higher alkyl radical contains from 10 to 18 carbon atoms.   - Detergent composition according to claim 4, which comprises approximately 5 to 30% of linear sodium higher alkylbenzene sulfonate in which the higher alkyl radical has from 12 to 14 carbon atoms, from 5 to 40% of detergency builder polyacetal-carboxylate type or   of a mixture of such alkaline filler and zeo- filler   lite, 2 to 10% distearyl dimethyl ammo- chloride   nium, from 2 to 20% humidity and the rest, if any, consists of inert filler (s) and / or other adjuvant (s) (s) and / or additive (s).   6 - detergent composition according to claim, which comprises from 10 to 25% of linear sodium tridecylbenzene sulfonate, from 15 to 30% of detergency builder of polyacetal-carboxylate type with a molecular weight on a weighted average calculated from 5,000 to 9000 or a mixture of such a detergency builder and a detergency builder   zeolite type, at least 5% of the composition being   polyacetal-carboxy-type detergency builder   late, from 3 to 8% of distearyl dimethyl ammonium chloride, from 3 to 15% of humidity, from 8 to 18% of sodium carbonate, from 5 to 10% of sodium silicate with Na20: SiO2 ratio of   1: 1.6 to 1: 3.0, and 20 to 35% sodium sulfate.   7 - detergent composition according to claim 6,   comprising from 13 to 23% of tridecylbenzene sulfonate li-   sodium, from 17 to 23% of detergency builder of the polyacetal-sodium carboxylate type with a calculated weighted average molecular weight of approximately 8,000, from 4 to 6% of distearldimethyl ammonium chloride, of 5 at 12% humidity, 10 to 15% sodium carbonate, 6 to 9% sodium silicate with a Na20: SiO2 ratio of 1: 2.0 to 1: 2.6,   and 22 to 30% sodium sulfate.   8 - Detergent composition according to claim 6, comprising from 13 to 23% of linear sodium tridecylbenzene-sulfonate, from 17 to 23% of a mixture of detergency builder of polyacetal-sodium carboxylate type   a calculated weighted average molecular weight of approxi-   ron 8000, and type A zeolite in which x is 1, y is 1, z is 2 to 3, and w is 2.5 to 6, in which mixes the ratio between the type detergency builder polyacetal-carboxylate and the charge of zeolite is 2: 3   2: 1, 4 to 6% distearyl dimethyl ammo- chloride   nium, 5 to 12% moisture, 10 to 15% sodium carbonate, 6 to 9% sodium silicate with Na20 ratio:   SiO2 from 1: 2.0 to 1: 2.6, and from 22 to 30% sodium sulfate.   9 - Process for the manufacture of a composition   antistatic particulate detergent reinforced by ad-   detergency builder, which includes a deter-   synthetic anionic organic detergent, a pro-   portion enhancing the detergency of a detergency builder   gence of polyacetal-carboxylate type suitable for this (these) detergent (s) or a proportion enhancing the detergency   of a mixture of a polyacetal type detergency builder-   carboxylate and a zeolite-type detergency builder,   and an antistatic proportion of an ammonium salt qua-   antistatic ternary, which includes spray drying   sation of an aqueous suspension of synthetic anionic organic detergent, inert filler and / or detergency builder suitable for this detergent and water, to arrive at essentially spherical beads having particle sizes in the range of 1, 68 to 0.149 mm, and the mixture with such beads dried by spraying with a detergency builder of the polyacetal-carboxylate type   and an antistatic proportion of ammonium salt quater- antistatic.   10 - Process according to claim 9, wherein   the synthetic anionic organic detergent is an alkyl-   sodium linear higher benzene sulfonate in which the higher alkyl radical contains from 12 to 14 atoms   carbon, the polyacetal-carbon detergency builder   xylate is a sodium polyacetal carboxylate with a weighted average molecular weight calculated from 5,000 to 9,000, the detergency builder in the "mixer" mixture comprises a hydrated zeolite A, sodium silicate having a Na20 ratio : SiO2 from 1: 2.0 to 1: 2.6, sodium carbonate and sodium sulfate, the detergency builder of polyacetal-carboxylate type and the antistatic quaternary ammonium halide are mixed beforehand and are   added to the spray dried beads, and the composition   The resulting detergency comprises from 13 to 23% tri-   sodium decylbenzene sulfonate, from 17 to 23%   a total of polyacetal type detergency builder-   weighted average molecular weight carboxylate   abutment of about 8,000, and a zeolite A type detergency builder, the ratio of the polyacetal carboxylate to the zeolite being 2: 3 to 2: 1, 4 to 6% of distearyl dimethyl chloride ammonium, 5 to 12% moisture, 10 to 15% sodium carbonate, 6 to 9% sodium silicate with Na20: SiO2 ratio of 1: 2.0 to 1: 2.6, and 22 to % sodium sulfate.   ll - Process according to claim 10, in the-   which the apparent specific mass of the spray-dried pearls is 0.25 to 0.5 g / ml, the specific mass   apparent mixture of poly- type detergency builder   sodium acetal carboxylate and distearyl chloride   antistatic dimethyl ammonium being greater than the apparent specific mass of the spray-dried pearls, and such a mixture having particle sizes in the range of 149 to 44 pm.   12 - Process for removing dirt and   difficult to remove stains from fibrous materials, which   takes washing of such stained and soiled materials in water of mixed hardness of calci: um and magnesium of 50   at 250 ppm, expressed as calcium carbonate, at a temperature   rature in the range of 10 to 55 C, and at a concentration   tion from 0.05 to 0.5%, with a composition comprising a detergent proportion of anionic detergent, a proportion enhancing the detergency of a detergency builder of polyacetal-carboxylate type suitable for this detergent (s) or a proportion enhancing the detergency of a mixture of a polyacetal-carboxylate detergency builder   and a zeolite-type detergency builder, and a pro-   anti-static portion of an anti-static cationic compound.   13 - Process according to claim 12, in the-   what the washing water temperature is in the interval   the 35 to 55 C, the concentration of the deter-   gente in the wash water is 0.1 to 0.35%, and the com-   detergent position includes 13 to 23% tridecyl-ben-   linear sodium zene sulfonate from 17 to 23% of a mixture   polyacetal-carboxylate-type detergency builder   sodium with a weighted average cal-   abutment of approximately 8,000, and type A zeolite, in which   x is 1, y is 1, z is 2 to 3 and w is 2.5 to 6,   in which mixes the ratio of the detergent builder   this polyacetal-carboxylate type and the adjuvant of deter-   zeolite type gence is 2: 3 to 2: 1, 4 to 6% of chlorine   distearyl dimethyl ammonium rure, 5 to 12% moisture   dity, from 10 to 15% of sodium carbonate, from 6 to 9% of sodium silicate with Na20: SiO2 ratio of 1: 2.0 to 1: 2.6,   and 22 to 30% sodium sulfate.   14 - Process according to claim 13, in the-   which the washed materials are made of acetate 1 ulose.