FR2620728A1 - Detergent and softening article for fabrics, detergent composition, process for its manufacture and washing process - Google Patents

Abstract

A detergent and softening article 11 for fabrics, in the form of a flexible sachet made of nonwoven material, is permeable to a detergent composition having a softening effect contained in the latter and makes it possible for it to pass into the washing water in an automatic washing machine. The presence of a relatively low proportion of anionic surfactant in the detergent composition having a softening effect facilitates passage of the composition through the walls of the sachet, so that a low or zero amount of residue remains in the latter once the washing operation is complete, even when the washing water is cold, for example at approximately 20 DEG C. The invention also comprises a liquid detergent composition which can be used in the present articles, a process for the manufacture of the articles of the invention and washing processes in which these articles are used.

Description

 The present invention relates to a detergent and fabric softener article. More particularly, it relates to an article of this type comprising a particulate detergent composition for softening fabrics, in a water-insoluble, water-permeable container, such as a flexible sachet made of a fabric made of fibers or filaments of material. synthetic organic polymer plastic. The constituents of such a composition can pass into the washing water by passing through the walls of the sachet during the washing of laundry in an automatic washing machine, when this article is used for such a purpose, so that the sachet is emptied or practically emptied during this use, retaining only a small or zero amount of residue. The invention also relates to liquid detergent compositions comprising a nonionic detergent and an anionic surfactant, useful in the preparation of the low residue compositions of the present articles. In addition, it comprises a method for manufacturing the articles described, as well as a method for washing and softening linen using these articles.

 Before the present invention, the packaging of detergents in water-permeable or water-soluble containers was known for direct additions to washing water in automatic washing machines. By using such articles containing quantities of detergent compositions measured beforehand, there was no need for the consumer to measure detergent powder from a can. The sachet or envelope of detergent composition, correctly dosed beforehand normal use in an automatic washing machine for household use, could conveniently be removed from a cardboard box containing several of these sachets, and could easily be introduced into a washing machine, without the need for the consumer to pour a powder of a detergent composition taken from a box, with the concomitant risk that the powder will spread, make dust or be inhaled. In addition, the introduction of a preset dose of detergent composition eliminates dosing errors, so that the most effective washing and most effective fabric softening can easily be achieved when a fabric softener is also present. .However, certain drawbacks are linked to the use of sachets and other soluble and permeable containers which open in the washing water, and other "transparent" containers for detergent compositions, in particular for compositions which also include a Cationic fabric softener.

 Water-soluble containers are frequently susceptible to rupture during handling, and may lose their contents before use, as can sachets made of water-insoluble materials, which are intended for s open when added to washing water in an automatic washing machine. In addition, sachets made of water-insoluble materials, which can retain considerable softeners after washing operations, can allow for this softener to come into contact in relatively large quantities with the laundry which is dried in a hot air dryer, so that deposits of quaternary products ("quat-spotting") can occur, that is to say localized deposits of cationic softener, causing the appearance of greasy stains on the laundry and frequently causing the yellowing of the laundry in these places. When permeable sachets are used which allow a more gradual passage l of the constituents of the composition in the washing water, the composition is sometimes not entirely discharged from the bag during the normal operation of the washing machine, and this problem is frequently encountered when the washing machine is set for a slow agitation and when the wash water temperature is low.

Residue problems are also more serious when the detergent composition is a detergency builder or heavy duty nonionic detergent composition, such as a composition in which the detergency builders include carbonate and in which the detergent fabric softener is a softener of the quaternary ammonium halide type, like that of the distearyl-dialkyl (lower) -ammonium halide type.

 The residue problem mentioned above has manifested itself in the use of non-ionic detergent compositions with detergency builder, in water-insoluble, water-permeable containers, such as heat-sealed non-woven polyester bags and the like. synthetic organic polymer fibers, when a proportion of cationic fabric softener was present in the sachet, and the residue was greater and even less acceptable when the detergent was nonionic and the detergency builder (s) included sodium carbonate. In various attempts to use such detergent articles with a softening effect in a washing machine, in particular when the delicate washing cycle of the washing machine has been used and the temperature of the washing water has been relatively low, for example around 200C, we have found inadmissible percentages, for example greater than 10%, of detergent composition with drowsy effect smoothing in the sachet once the washing is finished. Efforts to overcome the residue problem by redesigning the sachet or the envelope have been made by others, but the authors of the present invention have tried to approach this problem differently by modifying the composition intended to be released. by the article. Thus, while others have suggested the use of a polyvinyl alcohol-based seal for the sachet (which would open in the washing water), or of particles soluble in the water, dispersed in the surface material of the bag, to create passages through the walls of the bag when the article was introduced into the washing water, the present invention avoids problems of production and premature opening of such seals before use, and uses a more traditional (and more reproducible) material for sachets which does not allow its contents to escape prematurely.

 The surprisingly effective solution of the invention to the residue problem comprises the incorporation into the detergent composition of a relatively small or minimal proportion of an anionic surfactant (surfactant), such as triethanolammonium dodecylbenzenesulfonate ( hereinafter designated by its more common name of triethanolamine dodecylbenzenesulfonate, English initials TEALDBS). This product apparently facilitates the evacuation of the contents of the sachet and produces a more effective washing and softening of the linen, and increases the consumer satisfaction with the product.

 The reason why the presence of the anionic surfactant in the composition contained in the permeable sachet facilitates the transport of the content through the walls of the sachet is not completely understood.

It has been theorized that the anionic surfactant reacts preferentially with the cationic softener, thereby preventing the reaction of the softener with the alkaline detergency builder salt, which could produce an objectionable residue and could prohibit a high proportion of the softener reach the wash water and soften the laundry. One would have expected such transport to be inhibited by the formation of the lipophilic reaction product of the anionic and cationic substances, but apparently such a reaction product does not significantly interfere with dissolution, emulsification or the dispersion of the contents of the sachet. The action promoting the transport manifested by the anionic surfactant must be more than a simple action of wetting or of decreasing the surface tension, since a much higher proportion of anionic detergent, also having wetting properties, is also present in the composition. detergent. A theory which has been advanced to explain the action of the non-ionic surfactant in the present articles is applicable to detergent compositions free from phosphate, in which the detergency builder systems include carbo-type detergency builders
v nate, bicarbonate and zeolite. During the production of the detergent composition according to the invention, to be used in the present articles, the nonionic and anionic detergents, which are applied in common solution to base grains, penetrate into the base grain pores, which inhibits the premature reaction of anionic and cationic surfactants. However, the combination of anionic and nonionic surfactants is easily extracted from the grains of detergency builder by the washing water which enters the sachet, whereby a preferential reaction of the anionic surfactant with the softener can take place, preventing the softener from reacting with the detergency builder, which would give a residue in the form of aggregates which would remain in the sachet. Such a theory does not explain why the articles of the present invention, which include sodium tripolyphosphate as a detergency builder, may also include an anionic surfactant in the form of powder or flakes, added subsequently to the base grains, as the softener powder is added subsequently, without taking place a premature reaction or a residue remains in the sachet, and without there being a noticeable reduction in the detergent and softening action, but this detergency builder of the tripolyphosphate type It is not as reactive as carbonate with the cationic softener and is found to be more readily soluble in wash water when released from water permeable packets or sachets.

 According to the present invention, a detergent and fabric softener article for use in washing and softening laundry in an automatic washing machine is a particulate detergent composition with detergency builder and softening effect, in a permeable container in water, insoluble in water, through a permeable wall from which the components of the particulate detergent composition with softening effect, in the form of an aqueous solution, emulsion and / or dispersion, can pass into the washing water in the automatic washing machine during a washing cycle of such a machine, so that the laundry present in the washing water can be washed and softened by these components, and in which article the detergent composition with softening effect comprises a detergent proportion of non-ionic detergent, an additional proportion of detergency of an adjuvant for the non-ionic detergent, a proportion with softening effect of a comp daring cationic softener, and a proportion of anionic surfactant (surfactant) promoting transport, which proportion of anionic surfactant is less than the proportions of the nonionic detergent and of the cationic softening compound, and which anionic surfactant solubilizes, emulsifies or disperses the component (s) of the detergent composition with softening effect, comprising the cationic softener compound, in the permeable container, so that practically all of this composition and of this compound leaves the container and passes into the washing water while washing laundry in the washing machine.

The state of the art relating to this subject and known to applicants includes patents relating to disposable packages of detergent composition and bleaching products, such as US-A-4,220,153, 4,286,016, 4 348-293, 4,374,747, 4,410,441 and 4,567,675; GB-A-1 578 951 and 1 587 650, and
EP-A-0 184 261. Detergent compositions with softening effect have been described in numerous patents
US, among which there may be mentioned US-A-4,582,615, 4,609,473 and 4,659,496. Detergent compositions comprising anionic and cationic surfactants are described in US-A-4,000,077, and permeable sachets containing complexes anionic and cationic surfactants are described and claimed in French patent application NO 87.23682 filed on October 2, 1987. However, these descriptions, separately or in combination, do not anticipate the present invention or make it obvious because they do not contain any indication that a minimal proportion of an anionic surfactant such as triethanolamine dodecylbenzenesulfonate would significantly improve the removal of the softening detergent composition of the present invention from the permeable bag during machine washing, which improved evacuation leads to improved cleaning, brightening and softening of the linen, prevents the deposition of quaternary products and avoids atti negative studies of the consumer towards the product (because it is not fully used).

 The detergent and softener article of the present invention comprises two main components: a permeable dispenser container and a composition contained therein. Although detergent builder detergent compositions containing an anionic detergent and a nonionic detergent are known and have been described in the technical literature, and envelopes or packages for detergents made of synthetic and natural polymeric fibrous materials are known and have been described before the present invention, there was no article of this type, in which a small proportion of anionic detergent or surfactant clearly improves the evacuation, from its dispensing container, of a contained detergent composition, with softening effect , during use.This improved effect depends on the described composition which is present in the permeable container, insoluble in water, and the unexpected advantageous effect which is obtained makes it possible to establish that the new articles of the present The invention is not obvious from the state of the art.

The invention can easily be understood from the present description, together with the attached drawings, in which
Figure 1 is a top view of an actual item of the present invention;
FIG. 2 is a top view of a sachet of the present invention sealed on three sides and open on one side, before being filled with the detergent composition with softening effect;
Figure 3 is a perspective view of an article of the present invention, which is introduced into the tub of an automatic washing machine; and
Figure 4 is a perspective view of the empty sachet of the present invention, which is introduced into the dryer after washing of the laundry.

 In FIG. 1, the pre-weighed detergent and softener article 11, suitable for introduction into an automatic washing machine for washing an average load of laundry therein, comprises two sheets of non-woven polyester, namely a top sheet 13 and a bottom sheet (not visible) which are heat sealed to each other on their four sides, which is designated by the number 15. The polyester material 13 has a diamond texture, as shown (highlighted) in 17, which design extends over the two surfaces of the sheet but is flattened by heat-sealing along its sides at 15. A particulate detergent composition with softening effect (not visible) is contained in the bag 18, this number designating the permeable envelope of article 11 surrounding its particulate content.

 Item 11 has a flat cushion shape, the thickness of which is normally 0.01 to 0.2 times the width of the part of the sachet containing the particulate detergent (the "inside" part of the heat-sealed sides of the 'article). The ends of the bag are represented by the shaded part designated by the number 19 and by the clear part 21, which parts, as shown, indicate the thickness of the article.

 In FIG. 2, an open sachet 18 ′ is represented, comprising three heat-sealed sides designated by the number 15 ′ and an open end 23. A particular detergent composition with softening effect can be introduced into this sachet by the open end 23, at the after which this end can be heat sealed to give the article 21 (shown in Figure 1).

 FIG. 3 shows the article 11 of the present invention which is introduced into washing water (not shown) contained in the tub 25 of a top-loading washing machine 27. This introduction is made before that clothes and other items to be washed in the wash water.

 In FIG. 4, the empty sachet or spent detergent article, designated by 11 ′, is represented when it is introduced into the drum 29 of the automatic side-loading dryer 31. At this stage, the sachet contains little or no longer contains of its initial content, due to the effectiveness of the anionic surfactant in promoting the transport of this content through the permeable walls of the sachet and their passage through the washing water. Thus, the exhausted article can be disposed of once the washing and softening of the laundry is completed in the automatic washing machine 27, or it can be dried with the laundry in the automatic dryer 31 and then be disposed of. the remains of the article will be dried with the laundry, as they impose only a small drying load on the dryer, it is desirable to have to separate the wet sachet from the washed linen, and a sachet dry is more convenient to dispose of than a wet sachet. In cases where a detergent composition with a softening effect is used other than that of the present invention, which does not completely escape from its dispensing container during the washing cycle, any cationic softener remaining in the sachet can melt under the effect of the heat of the dryer and, in the liquid state, can flow out of the sachet and be deposited on the laundry during drying. Although in the dryer, such transport through the wall of the sachet can improve the softening of fabrics (because only part of this desired effect was obtained in the washing machine), it can also lead to a deposit of quaternary products ("quat-spotting") on the laundry being drying, with deposit of greasy spots of cationic softener on the laundry. Such spots, in addition to being inadmissible due to their greasy nature, also tend to yellow or cause other variations in color, and therefore should be avoided as much as possible. It goes without saying that such a deposit of cationic products is minimized when the articles of the present invention are used according to the methods described.

 The detergent composition with softening effect of the invention comprises a detergent proportion of a nonionic detergent, a complementary detergency proportion of a detergency builder for the nonionic detergent, a proportion with softening effect of a cationic softening compound, and a proportion of an anionic surfactant promoting transport, which proportion of anionic surfactant is less than the proportions of the nonionic detergent and the cationic softening compound. Such an anionic surfactant promotes the transport of the cationic softening compound and other components of the composition, in particular of alkaline detergency builders normally soluble in water, such as sodium carbonate and other alkaline detergency builders mentioned herein, through a water-permeable, water-insoluble wall, or several of these container walls, which is preferably made of a flexible material, such as non-woven polyester, fi nylon or rayon bres (which can be mixed together or with other natural or synthetic fibers). The anionic surfactant is considered to aid the dissolution, emulsification and / or dispersion of components of the present compositions, but it is admits that its main function is to promote the transport of these through the container wall (s), which can be obtained by avoiding a disadvantageous insolubilization of part or all of these components (which in effect promotes their dissolution, emulsification and / or dispersion).

The nonionic detergent of the present compositions is any suitable nonionic detergent, belonging to a group well known in the art, many representatives of which are described in the various annual publications of "Detergents and
Emulsifiers "(Detergents and emulsifiers) by
John W. McCutcheon, for example publication of the year 1973. These volumes give the chemical formulas and trade names of virtually all non-ionic detergents sold in the United States, and virtually all of these detergents can be used in the present compositions . However, it is highly preferred that this non-ionic detergent is a condensation product of ethylene oxide and higher fatty alcohol (although instead of higher fatty alcohol, alkylphenols and higher fatty acids may also be used. The higher fatty acid fragments, such as the alcohol of these condensation products, will normally be linear and will have from 10 to 18 carbon atoms, preferably from 10 to 16 carbon atoms, even better from 12 to 15 carbon atoms. carbon and sometimes at best 12 to 14 carbon atoms.

Since these fatty acids are normally only commercially available as mixtures, the numbers of carbon atoms given are necessarily average numbers, but in some cases the ranges of number of carbon atoms may be limits. actual for the alcohols used and for the corresponding alkyl radicals.

The ethylene oxide (EO) content of the nonionic detergent will normally be in the range of 3 to 15 moles of EO per mole of higher fatty alcohol, although sometimes there may be as high as 20 moles of dfOE . Preferably, this proportion will be from 3 to 10 moles, and even better from 6 to 7 moles, for example 6.5 or 7 moles per mole of higher fatty alcohol (and per mole of nonionic detergent). As in the case of higher fatty alcohol, the limits given for the polyoxyethylated product are also the limits of the means of the numbers of the OE groups present in the condensation product. Wide range oxyethylated products and narrow range oxyethylated products can be used ("BRE" and "NRE", English initials for "broad range ethoxylate" and "narrow range ethoxylate"), the difference between these residing in " spreading "the numbers of the ethylene oxide groups, the average of which is within the ranges shown. For example, the NREs which have on average 5 to 10 EO groups per mole in the nonionic detergent will have at least 70% of the EO in polyethoxy groups comprising from 4 to 12 moles of EO and will preferably have more than 85% of the OE groups in such a range. Non-ionic detergents of the type
BRE have a wider range of ethoxy group contents than NREs, frequently with a spread of 1 to 15 moles of EO when the EO content is in the range of 5 to 10 (on average). As examples of nonionic detergents of BRE type, mention may be made of those sold by Shell Chemical Company under the trade name of Neodol Q comprising Neodol 25-7,
Neodol 23-6.5 and Neodol 25-3. NRE type non-ionic detergents are available from Shell
Development Company, which designates these products by 23-7P and 23-7Z, and from Union Carbide Corporation which gives such a product the name Tergitol 24-L-60N. The corresponding NRE and BRE "are described in the application of Patent No. 88.10698 filed August 8, 1988, which describes the advantages of
NRE.

 The detergency builder for the nonionic detergent may be any suitable detergency builder, water soluble or insoluble, organic or inorganic, provided that it is useful as a detergency builder for the detergent particulate nonionic or the mixture of particulate nonionic detergents which may be used.These detergency builders are well known to those skilled in the art and include alkali metal phosphates, such as polyphosphates and alkali metal pyrophosphates, including metal tripolyphosphates alkali, alkali metal silicates1 including those having a Na2O: SiO2 ratio in the range of 1: 1.6 to 1: 3.0, preferably 1: 2.0 to 1: 2.8, and more preferably equal at 1: 2.35 or 1: 2.4; an alkali metal carbonate, an alkali metal bicarbonate; an alkali metal sesquicarbonate (which can be considered as a mixture of alkali metal carbonate and alkali metal bicarbonate); an alkali metal borate such as borax; an alkali metal citrate; an alkali metal gluconate; an alkali metal nitrilotriacetate; zeolites, preferably hydrated zeolites such as zeolite A, zeolite X and zeolite Y hydrated; and mixtures of individual detergency builders belonging to these and other types of detergency builders. Preferably, the detergency builders will be the sodium salts and will also be inorganic. A composition of detergency builders, water soluble, which is particularly preferred, based primarily on detergency builders of the phosphate type, comprises detergency builders of the tripolyphosphate and silicate type, the silicate being in small proportion. Among the non-phosphate type detergency builder systems, the one comprising a carbonate, a bicarbonate and a zeolite is preferred.

 The various detergency builders do not require a more detailed description, with the possible exception of zeolite. This detergency builder is insoluble in water and is preferably hydrated, for example with from 4 to 36%, preferably from 5 to 30%, even better from 10 or 15 to 25%, and in particular from 17 to 22%, for example about 20% water of hydration. The zeolite is normally in a finely divided state, with particle sizes normally ranging from 0.15 to 0.04 mm, preferably from 0.104 to 0.044 mm, but it can also be agglomerated to the grain size of adjuvant. The diameter of its elementary particles will be in the range of 0.01 to 20 µm, in particular 0.01 to 15 µm, for example 3 to 12 µm, and at best 0.01 to 8 µm ( average particle size), for example from 3 to 7 µm if it is crystalline and from 0.01 to 0.1 µm if it is amorphous.

The cationic softening compound can be any suitable compound of this type, such as an imidazolinium salt or a quaternary ammonium salt. These two types of softeners are described in
US-A-4 000 077. Among the two types of softeners, quaternary ammonium salts are preferred, and among these, in particular quaternary ammonium halides such as quaternary ammonium chlorides.

dans laquelle R1 et R2 sont des groupes alkyle infé
3 rieurs ayant de 1 à 3 atomes de carbone, R3 est un groupe alkyle supérieur ayant de 10 à 20 atomes de carbone, R4 est un groupe alkyle ayant de 1 à 20 atomes de carbone, et X est un anion salifiant, de préférence chlorure ou bromure, et en particulier chlorure. Dans ces sels quaternaires, R1 er R2 représentent de préférence le même groupe alkyle inférieur, et R3 et R4 représentent de préférence le même groupe alkyle supérieur, l'assouplisseur particulièrement préféré étant le chlorure de diméthyl-distéarylammonium.Les halogé nures d'ammonium quaternaire utilisables comprennent ceux dans lesquels les groupes alkyle supérieurs sont des groupes alkyl de suif ou alkyle de suif hydrogéné, cétyle, myristyle et/ou lauryle, et dans lesquels les groupes alkyle inférieurs sont le groupe méthyle et/ou éthyle.The softening compound of the quaternary ammonium salt type is preferably of formula

in which R1 and R2 are lower alkyl groups
3 laughers having from 1 to 3 carbon atoms, R3 is a higher alkyl group having from 10 to 20 carbon atoms, R4 is an alkyl group having from 1 to 20 carbon atoms, and X is a salifying anion, preferably chloride or bromide, and in particular chloride. In these quaternary salts, R1 and R2 preferably represent the same lower alkyl group, and R3 and R4 preferably represent the same upper alkyl group, the particularly preferred softener being dimethyl-distearyl ammonium chloride. The quaternary ammonium halides usable include those in which the higher alkyl groups are tallow alkyl or hydrogenated tallow alkyl, cetyl, myristyl and / or lauryl, and in which the lower alkyl groups are methyl and / or ethyl.

The anionic surfactant which promotes transport can be any suitable surfactant of this type, such as those described in the abovementioned publications by McCutcheon, but among these, those which are preferred are the alkali metal or alkanolamine salts, water soluble, (higher) alkyl benzenesulfonate, higher fatty alcohol sulfate or higher fatty alcohol polyethoxysulfate or mixtures thereof. These salts are preferably sodium or triethanolammonium (triethanolamine) salts, and among these, the triethanolamine salts are particularly preferred. Among the triethanolamine salts and other suitable salts, particular preference is given to those of (higher) alkyl-benzenesulfonic acid, for example triethanolamine n-dodecylbenzenesulfonate. The corresponding alkali metal salts and mixtures of alkali metal salts (preferably sodium) and alkanolamine (preferably triethanolamine) can also be used, as well as mixtures of dialcanolamine or monoalkanolamine salts and trialkanolamine. As regards the preferred lipohile groups of the anionic surfactants, the upper alkyl radical will have from 12 to 16 carbon atoms, the higher fatty alcohol moiety will have from 12 to 18 carbon atoms, the polyoxyethylated product will have from 3 to 15 ethoxy groups and the alkanolamine will be a lower mono-, di- or trialkanolamine having from 1 to 4 carbon atoms, the latter preferably being an ethanolamine, for example triethanolamine.
Particularly preferred anionic moiety is a triethanolamine alkyl (higher) benzenesulfonate in which the upper alkyl group has 12 to 14 carbon atoms, such as the n-dodecyl group.

 Various other components may be present in the detergent composition in order to improve its properties and in some cases act as diluents or fillers. Among the suitable fillers, that which is particularly preferred is sodium sulfate. Among the additives, agents facilitating the release of soils can be listed, such as the polyethylene terephthalate-polyoxyethylene terephthalate (PET-POET) copolymers facilitating the release of soils, having molecular weights ranging from 19,000 to 43,000, molecular weight of the polyoxyethylene moiety being in the range of about 2,500 to 5,000 and the molar ratio of the PET units to the POET units being in the range of 2: 1 to 6: 1, and the proportion of ethylene oxide to the moiety phthalic in the copolymer being in the range of 20: 1 to 30: 1. Enzymes may be present to facilitate the removal from the laundry of stains which are difficult to remove. Among the enzymes most useful in washing operations are the proteolytic and amylolytic enzymes, preferably in admixture. Polyacrylates such as sodium polyacrylate, with molecular weights ranging from 1000 to 3000, are useful for their dispersing properties and also function as stabilizers for the PET-POET copolymer, which stabilizing action is important for obtaining the most effective way of removing dirt from the laundry, especially washing items made of polyester fabrics. Flow-promoting agents, such as hydrated calcium silicate, often marketed under the trade name of Microcel C, can be used, in relatively small proportions, for their mentioned functions. Additional components of the detergent composition with softening effect include optical brighteners, such as optical brighteners of the stilbene type; perfumes; dyes, comprising coloring substances and water-dispersible pigments; and water.

 The water-permeable container, insoluble in water, for the particulate detergent composition with softening effect of the present invention, can be any suitable container of this type which allows the penetration of water and the passage of the composition contained. , through its permeable walls, in the washing water. However, although it is envisaged that containers retaining their shape, such as those resembling bottles of perforated polyethylene or polypropylene, or polyurethane sponges, may also be used, the particularly preferred form of the container is a flexible sachet in thin material, preferably in fabric and even better in non-woven fabric. Such a fabric can be made of fibers or filaments of various natural or synthetic materials, but it is preferred that it is wholly or essentially made of synthetic organic polymer fibers. Among these fibers, particular preference is given to those of polyesters, nylon and rayon, polyester fibers being considered to be the best. Such fibrous materials can easily be provided with the desired permeability, by modifying the manufacturing methods, the size of the fibers and the weight of the fabric.

 Preferred nonwoven sheets, used for making the pouches for the present articles, will normally have a thickness in the range of 0.1 to 1 mm, a weight in the range of 35 to 45 g / kg and a air permeability ranging from 1 to 3 i / min / cm2. Air permeability is related to the fluid permeability of a material that is used, and is also related to the ease of transport of the contents d 'a sachet through this material. One of the other variables which affects the permeability and integrity of the sachet before use (no passage of the content through the walls thereof) and the thickness of the fibers or filaments. preferred fibers have been found to be 2 to 4 denier fibers, for example about 3 denier. The preferred bag material is that produced by Kendall Corporation, which also manufactures and refills the bags to produce the desired items. The materials that are used by this company for sachets are designated by their references, including 149-026, SP 284, SP 284.1, SP 289 and SP 289.1.

 The detergent and softener article described above will be of a size, weight, sachet material, composition and particle size of the composition suitable for satisfactory washing of laundry in washing machines. automatic washing and for the evacuation of practically all, more than 90%, preferably more than 95%, even better more than 99% and at best 100% of the detergent composition with softening effect out of the permeable container , through the permeable walls thereof, and its release into the washing water in an automatic washing machine. Desirably, the amount of detergent composition carried in the wash water will be the amount of cleaning and softening satisfactorily a washing machine load of dirty laundry. However, the size and / or weight of the laundry can be adjusted. The article of the invention so that several of these articles provide the required amount of such a detergent composition. Ideally, about 50 g of detergent composition will be present in the article of the invention, but, depending on the proportions of the components in this composition, this weight can range from 10 to 200 g, and it is preferably in the range of 30 to 100 g.

 The concentration of the detergent composition in the washing water, after complete evacuation of the detergent composition with softening effect from the article, will theoretically be approximately 0.075%, with a corresponding wide range and preferred range of 0.015 to 0.3 % and 0.045-0.15%, respectively (assuming that the volume of wash water in the tub of an automatic washing machine is approximately 64 liters. Ideally, the concentration of non-ionic detergent in the the washing water will be 0.012%, the ideal concentration of the softening compound will be 0.006% and the proportion of the detergency builder salt will be approximately 0.04% both for the formulations containing phosphate and for the formulations without phosphate. anionic detergent promoting transport will ideally be about 0.003%. The concentration ranges of these components can be calculated from the concentration ranges of the total composition, based on the concentrations s individual favorites given above.

 The size of the article of the invention will be that allowing it to be conveniently handled by hand.

It has been determined that an article square and measuring approximately 10 cm x 10 cm (by measuring the external surfaces through which, after heat-sealing, the components of the composition can pass into the washing water) is ideal, but other sizes and shapes can also be used. Thus, the total surface area of the permeable surface, measured externally, can be in the range of 100 to 500 cH and will ideally be around 200 cS (2 x 10 cm x 10 cm). For such a product, the thickness of the article, after filling the sachet, will be approximately 1 cm, but thicknesses ranging from 0.5 to 4 cm, preferably from 0.8 to 2 cm are possible, frequently with corresponding adjustments of the bulk density of the composition and the permeability characteristics of the sachet material. This bulk density will normally be relatively high, such as for example from 0.4 to 0.8 g / cry., preferably from 0, 5 to 0.7 g / cry ?.

 With regard to the permeability of the sachet, the weave of the fabrics and the deposition of fibrous material of the nonwovens will be sufficiently tight to avoid undesirable losses of the particulate material out of the article before use, and should however be sufficiently loose to allow the passage of liquids and undissolved fine particles of the composition contained, through the permeable material of the wall of the sachet or container. it has been found that with the preferred materials for sachets of the present invention, using the preferred compositions and containing an anionic surfactant promoting transport, the sachet is almost completely emptied in normal washing in a water washing machine cold (210C), even with slow agitation, and a minimum escape through the sachet results, even with vigorous shaking, before the introduction of the article into the washing water. Thus, during such a shaking, less than 0.1% of the composition is lost, and no quantity of the composition escapes from the sachet before use, during normal packaging, transport and storage. However, if the anionic surfactant of the composition contained is omitted, more than 20% of the composition will frequently remain in the sachet at the end of a delicate washing cycle in an automatic washing machine, at 210C. In order to obtain these desirable results with the articles of the invention, it is considered that the openings in the material of the sachet must be kept less than 0.1 mm in width or diameter, and must be wide enough to allow passage through those - aqueous liquids and finely divided particles, such as the particles of insoluble components of the detergent composition contained, for example zeolites, the extreme sizes of which have been mentioned above.

 Desirably, the material of the sachet is flexible, as are almost invariably woven and non-woven fabrics, because during the operation of the washing machine, flexible containers or sachets, frequently changing shape, can help facilitate the passage of fluids through their walls, which facilitates the evacuation from these containers of the composition contained. Experimental work has shown that the more intense the agitation, the more the emptying of the sachet will be complete during an operation of washing, and the use of a flexible sachet, with a detergent composition containing an anionic surfactant as an agent promoting transport, promotes complete evacuation and total transport through the walls of the sachet of the composition contained, during washing, even under stirring conditions which are less than the optimum (normal or delicate washing cycle, at low temperatures and with a heavier load of laundry than it is desirable).

 The proportions of the various components of the present compositions which are important with regard to the effectiveness of the invention will be chosen to give the desired result, good detergency, good softening, practically complete emptying of the sachet, the absence of deposit of quaternary products or of yellowing of the linen, and the absence of significant harmful effects of the softener of the quaternary ammonium halide type on any optical brightener which may also be present in the compositions. The non-ionic detergent content of the detergent composition will normally be in the range of 8 to 40%, preferably 12 to 25%, more preferably 14 to 20% and in particular 16% or about 16%. The content of detergency builder (s) will normally be in the range of 30 to 70%, preferably 40 to 65%. When the detergency builder is a "phosphate type detergency builder system", the proportion of sodium tripolyphosphate contained therein will preferably be in the range of 40 to 60%, and the proportion of sodium silicate will be in the range of 3 to 8%. These proportions will be even better around 48% and 5% respectively. When the detergency builder system is not based on phosphate, the proportions of sodium carbonate, sodium bicarbonate and hydrated zeolite (expressed as anhydride) will be respectively in the ranges of 15 to 35%, from 5 to 20 % and from 10 to 35%, and even better of or around 24%, 10% and 23% respectively. In the phosphate-based detergent composition, the weight of the phosphate or tripolyphosphate will represent from 5 to 20 times the weight of the silicate, and in the phosphate-free detergent composition, the weight of sodium carbonate will represent from 0.7 to 1.5 times the weight of the zeolite (expressed as anhydride), and the weight of sodium bicarbonate will represent 0.3 at 0.7 times the weight of sodium carbonate.

 The cationic softening compound will normally constitute from 0.5 to 15%, preferably from 7 to 10%, and even better 8.5% or approximately 8.5% of the detergent composition with softening effect. The transport promoting anionic surfactant will usually be present in the detergent composition in an amount in the range of 1 to 8% thereof, this amount preferably being 3 to 6% and more preferably of or about 4%. The moisture contents of the detergent compositions can vary, depending on whether the composition is a phosphate-based formulation or a phosphate-free formulation. Phosphate-containing compositions are designed to contain 8-14%, preferably 9-12%, and most preferably about 11% moisture, while phosphate-free formulations will usually contain 5-10%, preferably 6 to 9%, and even better about 7.7 or 8% humidity. The rest of the detergent compositions will normally consist of additives and / or fillers, the most important of which have already been mentioned. The content of PET-POET copolymer promoting soil release will normally be in the range of 1 to 5%, preferably 2 to 4%, and more preferably around 3%, and the proportion of the sodium polyacrylate stabilizer for the The PET-POET copolymer will normally be in the range of 0.25 to 1.25%, which is preferably 0.5 to 1%, and more preferably about 0.7 or 0.75%. The enzyme content of the detergent composition will normally be in the range of 0.3 to 3%, preferably 0.5 to 2%, and more preferably about 1%, and the content of flow promoting powder, of the type Microcel C or hydrated synthetic calcium silicate will be 0.3 to 3%, preferably 0.2 to 2%, and more preferably about 8%. The ranges of optical brightener and fragrance contents normally range from 0.2 to 2%, preferably from 0.3 to 1% and even better from approximately 0.5%, and from 0.3 to 2%, preferably from 0.3 to 1% and even better about 0.4%. The percentages and ranges of percentages given above are all relative to a final product "as is", with the exception of the zeolite, as already indicated.

When, in the present description, components of the composition, such as nonionic detergent, nonionic surfactant, softener compound and detergency builder, are mentioned individually but not specifically identified, it should be understood that this description encompasses more than one of these components, and the percentages given relate both to these components and to mixtures thereof.

 In the production of the softening detergent compositions used for the manufacture of the articles of the present invention, essentially conventional spray drying methods can be followed, with certain modifications. Thus, base grains, usually of inorganic detergency builder, are prepared by mixing an aqueous mixture of this detergency builder or a mixture of detergency builders, usually at a solid content within the range from 40 or 50 to 75%, at a temperature in the range of 40 to 750C, then spray drying in a conventional atomization column, at a temperature of the drying gas in the range of 250 to 4500C, to obtain practically spherical grains having particle sizes of 2.0 to 0.15 mm, preferably 2.0 to 0.25 mm. Optical brighteners, such as a stilbene-based brightener, and all other additives and fillers heat stable, can be incorporated into the mixture to be dried with the adjuvant or detergency builders.

If such spray drying also results in the production of larger particles and smaller particles, they can be screened or sorted by pneumatic classification to the desired range or to another range considered acceptable to projected purposes. The liquid detergent is then made to absorb by these dried grains, after cooling, by spraying with the desired nonionic liquid detergent, either a BRE detergent or an NRE detergent, on the surface of the moving grains. An advantage of using the NREs for the process is that they liquefy at a temperature closer to room temperature than the BREs, and therefore require less heating for liquefaction. at a given temperature, they penetrate better inside the spray-dried base grains, which can improve processing and lead to a better flowing product. In a preferred aspect of the manufacturing process used in the production of the compositions of the present invention, instead of spraying only the nonionic detergent, in liquid state, on the base grains, a solution is also sprayed on these grains. , at relatively low temperature, anionic surfactant facilitating transport, in the nonionic detergent. While the liquid detergent solution may be at a higher temperature, for example up to 45, 50 or 600C, in some cases it is preferred keep its temperature as low as possible, normally in the range of 30 to 400C, for example around 320C, the temperature at which the anionic surfactant and the nonionic detergent will frequently be mutually soluble, especially when it is NRE and in the presence of an appropriate co-solvent. In such a solution, the ratio of anionic surfactant to nonionic detergent will be in the range of 1: 6 to 1: 2, preferably 1: 5 to 1: 3, and more preferably about 1: 4. Among the co-solvents which can be used, water is preferred. In the final detergent composition with detergency builder, there will usually be 3 to 6 parts of anionic surfactant for 12 to 25 parts of nonionic detergent. Ideally, in such a solution, the proportions of nonionic detergent, anionic surfactant and water will be approximately 16 parts of nonionic detergent, 4 parts of anionic surfactant and 2.7 parts of water, in percentages and compared to the final products. Normally, such solutions will include 60 to 80 parts of nonionic detergent, 10 to 25 parts of anionic surfactant, and 5 to 20 parts of water, based on the solution. The water can be replaced by other solvents, when considered desirable, and in some cases the water can be omitted while retaining the relative proportions of the nonionic detergent and the anionic surfactant. Conveniently, the anionic surfactant will sometimes be provided in the form of an aqueous solution or a paste which can be used as it is. The solution of the detergent and the surfactant is preferably sprayed on the moving basic grains in a mixing apparatus. suitable, such as an inclined drum, the temperature of the solution being at best about 320C. After application of the solution to the base grains, it is likewise possible to spray them with a perfume and, in certain cases, this spraying can take place approximately at the same time (but usually on surfaces distinct from the moving grains).

 The described application of nonionic detergent and anionic surfactant (at best triethanolamine dodecylbenzenesulfonate) to the base grains is an important process step in the production of the described detergent compositions, phosphate free, of the present articles. Although this process can also be used in the production of compositions containing a phosphate-type detergency builder, it has been found that such compositions frequently work in the present articles and are removed from them during washing in a machine. to be washed automatically, even when the anionic surfactant is subsequently applied, even in the solid state as a sodium salt (in the form of flakes or powder), on the detergent composition already containing the nonionic detergent absorbed in the grains of In these compositions, it appears that the problems of transport and residue are not as serious and, therefore, the particular effects of the anionic surfactant and non-ionic detergent coabsorbed, as regards the inhibition of an undesirable reaction of l alkaline detergency builder and cationic softener may frequently not be necessary (although such action may still be beneficial e).

 After absorption of the anionic surfactant, the co-solvent of non-ionic detergent (if there is one) and the perfume by the base grains, this resulting particulate sub-composition is then mixed, an enzyme composition, an agent promoting the release of soiling. , and a cationic softening compound, all in powder form. The particle sizes of these powdery components will be such that they do not pass unacceptably through the "pores" of the sachet or container, and usually these powders will have a particle size of 0.074 mm or more, if possible. finer powders, such as those with particle sizes less than 0.074 mm, are used, their adhesion to larger grains can prevent these powders from spreading into dust and escaping, and can also improve flow characteristics of the composition, which can facilitate rapid filling of the sachets (which is carried out by automatic machines).

The PET-POET copolymer promoting the release of dirt will be added and mixed with the grains of the detergent composition in a mixture prepared beforehand with sodium polyacrylate, in desired proportions of these components in the composition, as indicated above. The softening compound can be mixed with the other components alone or, as it is preferable, in a mixture previously prepared with Microcel C and an emulsifier or wetting agent (preferably a polyoxyethylated higher fatty alcohol having 12 to 18 carbon atoms in the higher fatty alcohol fragment and approximately 20 moles of ethylene oxide per mole). In the mixture consisting of softener, flow-improving agent and emulsifier, the proportions of these will ideally be approximately 8.5%. , 0.1% and 0.8%, based on the final product, which corresponds to approximately 90%, 1% and 9% of the mixture, respectively. Usable ranges of these components are 80 to 95%, 0.2 to 5% and 4 to 15%, respectively. In addition to Microcel C which is added jointly with the softener and the emulsifier, 0.3 to 2% (ideally about 0.7%) is also added, relative to the final product, to the scented detergent powder, mixture of enzymes, mixture of PET polyacrylate
POET and fabric softener composition, due to its flow improving properties. Improving product flow is important in the automated production of detergent articles, particularly in the filling of sachets, where flow reliable composition in the pocket formed by the bag material is required. The antiagglutination properties of hydrated synthetic calcium silicate are also of certain importance, since they are considered to facilitate the evacuation of the sachet when the article of the invention is added to the washing water in an automatic washing machine. .

 Although it is much preferred that the base grains of the compositions of the present invention are spray dried, since spray dried grains tend to be more porous, and therefore more able to absorb liquid detergent, under certain circumstances granular components or agglomerates can be used, provided they are sufficiently absorbent. For the production of the phosphate-type detergency builder detergent composition, it is preferred to use hydrated or humidified pentasodium tripolyphosphate as the phosphate-type starting material, but this is not essential.

 In the final mixing step, when the various powders are mixed with the intermediate composition of particulate detergent, the powders will tend to coat these intermediate particles, but that does not mean that all of these applied powders actually form coatings on the intermediate particles. Some do, but others can form independent particles or can agglomerate with other additives. However, the coating of the intermediate particles actually appears to occur to a desired degree, whereby the flowability is increased and the separation and exhaust are reduced.The resulting product, although it may contain certain powders added in finely divided form, have essentially or to a large extent particle sizes in the range of 2.00 to 0.15 mm, preferably 2.00 to 0.25 mm.

 In the manufacture of the detergent articles with softening effect of the invention, once the production of the detergent composition with softening effect has been completed, this composition is sent to a conventional packaging machine which automatically fills and hot seals the composition in formed cavities. between strips of the woven or non-woven fabrics described, to give the flat cushion-shaped articles described here. After this filling, the various packages are separated by cutting, if desired, out of the formed strip, and are packed in boxes, larger envelopes, cartons or other suitable containers.

 In using the articles of the invention, the consumer fills the washing machine with water, which may have any hardness, but preferably has a hardness in the range of 25 to 150 ppm (expressed as carbonate of calcium). The wash water, at a temperature in the range of 15 to 700C, usually 20 to 40 "C, is normally in a volume ranging from 50 to 75 liters per wash, and one of the articles is added to this wash water of the invention for lightly or normally soiled laundry and two packs for more heavily soiled laundry. The laundry to be washed is then introduced into the washing machine, the load weight usually being in the range of 2 to 4 kg, The washing cycle normally takes 10 minutes to 1 hour, preferably 15 to 30 minutes, and after washing the laundry is usually rinsed twice, automatically. It is then spun and then removed to its original state. of the washing machine, at the same time as the detergent and softening effect (s), and with these is placed in an automatic dryer or it is subjected to drying with normal or moderately hot air, depending on the type of fabric. After drying, carried out on the laundry will show that it is satisfactorily cleaned, flexible as it is desirable and does not contain deposits of quaternary products or yellow stains due to the quaternary softener, and that it is satisfactorily brightened by the stilbene-type optical brightener of the composition. Examination of the article of the invention, once removed from the dried linen, normally shows that it has been completely emptied of the particles of detergent composition with softening effect which it contained initially. In poor solubilization conditions, such as when the wash water is cool or cold, and when minimal or slow agitation is used, a small proportion of detergency builder salt, usually less than 5% and often less than 1% , may sometimes be present in the package. However, when the article of the invention is removed from the washing machine and not placed in the dryer, it is usually found that the contents of this article have been completely expelled or that only a very small proportion, less than 1% of it, which shows that during the washing cycle (and probably also during the rinsing cycles), the cationic softener is passed through the permeable sachet to end up in the washing or rinsing medium, in which it acted to soften the laundry.

 The present invention is illustrated with the aid of the descriptive and nonlimiting examples below. Unless otherwise indicated, all parts are given by weight and all temperatures in OC.

Example 1
To 0.45 parts of tap water, in a conventional detergent mixer (or soap mixer), 0.422 part of optical brightener (Tinopal UNPA, produced by CIBA-GEIGY Corp;), 8.658 parts of an aqueous solution is added. of sodium silicate (Na2O: SiO2 = 1: 2.4) at 47.5%, and 40.669 parts of pentasodium tripolyphosphate (humidified) to obtain a mixture of 45% solids, at a temperature of about 600C. The malange is then pumped to a conventional spray drying column, where it is dried in hot drying gas at a temperature of about 4000C, to give 52.001 parts of spray dried base grains, having sizes in the range from 2.00 to 0.15 mm and a moisture content equal to 13.5%. After cooling, 72.594 parts of these basic grains are sprayed onto the moving surfaces 19,000 parts of Neodol 25-7 (condensation product a higher fatty alcohol having on average from 12 to 15 carbon atoms and approximately 7 moles of ethylene oxide per mole, marketed by Shell Chemical Company) and 7.935 parts of an aqueous solution of triethanolamine n-dodecylbenzenesulfonate ( TEALDBS) at 60%. The TEALDBS solution comprises 4.761 parts of TEALDBS and 3.174 parts of water. The common solution of nonionic detergent, anionic surfactant and water (cosolvent), at a temperature of 320C, is sprayed on the moving surfaces of the basic grains, is absorbed by these grains and penetrates inside them, while also coating these grains. In addition, 0.471 parts of perfume are also sprayed on these moving grains. The moisture content of the 100,000 parts of resulting intermediate product is approximately 12.6%.

This intermediate particulate product is then mixed with the other powdery or particulate components of the final formulation of the detergent composition with softening effect. In this final mixing, which also takes place in a mixer suitable for particulate products, such as an inclined drum, 84,970 parts of the intermediate detergent product described above are mixed with: 1,060 parts of a mixture of proteolytic and amylolytic enzymes (Maxatase MP 37500); 3,700 parts of an 80:20 mixture of PET-POET copolymer (Alkaril QCF, having a weight average molecular weight of approximately 22,000, the molecular weight of polyoxyethylene being approximately 3,400 and the molar ratio of PET units to POET patterns being approximately 3: 1 (produced by
Alkaril Chemicals Inc.) and Alcosperse 107D (sodium polyacrylate with a molecular weight of approximately 2,000; 9,600 parts of softener-based pre-mix; and 0,670 parts of Microcel C. The d-based pre-mix softener comprises 8.448 parts of dimethyl-distearyl ammonium chloride, 0.768 parts of a condensation product of higher fatty alcohol and ethylene oxide (surfactant and emulsifier) in which the higher fatty alcohol has on average 12 to 18 atoms of carbon and is condensed with about 20 moles of ethylene oxide per mole, and 0.096 part of hydrated synthetic calcium silicate (Microcel C). The rest (0.288 part) of the softener pre-mix is essentially moisture, which may be present in the cationic softener component of the pre-mix. Add the additional 0.670 part of
Microcel C to improve the flowability of the final product. A certain amount of Microcel C is also present in the softener pre-mix to improve the flowability of the softener, and the surfactant non-ionic is present therein to facilitate easy wetting of the softener, its dispersion in the aqueous medium which is present in the sachet after addition of the article to the washing water, and the transport of the softener through the walls of the bag.

 The formulation of the final detergent composition obtained, with softening effect, which is contained in the articles according to the invention of this example, is given below.

Component Parts (by weight)
Phosphate-based solids (from
sodium tripolyphosphate) 48,000
Silicate-based solids (from
sodium silicate (Na2O: SiO2 = 1: 2.4 4.878
Polyoxyethylated higher fatty alcohol
(Neodol 25-7) 16.144
TEALDBS 4,045
Alkaril QCF 2,960
Alcosperse 107D 0.740
Dimethyl-distearyl ammonium chloride 8,448
Polyoxyethylated higher fatty alcohol
(condensation product of an alcohol
higher fat having 12 to 18 atoms
car :: ne with 20 moles of oxide
ethylene per mole) 0.768
Microcel C 0.766
Enzyme mixture 1.060
Optical brightener 0.500
Perfume 0.400
Water 11,291
100,000
The final detergent composition with softening effect, described above, consists of particles having sizes ranging essentially from 2.0 to 0.15 mm, more than 90% by weight of the particles being in this range, and often more than 95 % of these falling within these limits. Ideally, all particles are in sizes from 2.0 to 0.25 mm, with smaller particles frequently adhering to larger particles, so that the actual particle sizes fall within these limits. products, the most finely sprayed components, such as those added to the final mixture, which can have particle sizes as small as 0.074 mm, coat the larger particles of the base grains containing detergents and perfume. The detergent composition with softening effect described is capable of flowing satisfactorily freely, flowing in a narrowed orifice at a speed corresponding to approximately 70% of that of dry sand, which satisfactorily meets a standard d flowability for spray dried detergent compositions.

Once prepared, the particulate detergent composition with softening effect can be aged, for example overnight, before being introduced into sachets or packages permeable to water, but in some cases it can be introduced directly. The filling is preferably carried out pa. automatic packaging machine, in the operation of which strips of woven or non-woven fabric are brought in parallel, the particulate composition is brought between them, in a pocket created by the machine, the edges of the strips are heat welded or joined together in another way, and the individual packages or sachets are separated from the strip, such as by automatic cutting. Instead of an automatic machine, a semi machine can be used
Ju automatic, and in some cases packages can be filled manually using measured amounts of composition, after which the package or bag is sealed, usually at one unsealed end. The filled sachets, which constitute the softening detergent articles of the present example, are then put in boxes or in cartons and are packed in polyethylene bags or other suitable containers, in which. they are intended to be marketed.

 Although it is possible to use various types of continuous web material, that described in this example is a 100% non-woven polyester material, manufactured by kendall Company, designated by SP 284.1, which is made of polyester fibers of 3 deniers. Such a material weighs approximately 14 g / d and has an air permeability of approximately 2 i / min / cm2.

 The article produced is essentially square, the volume filled (excluding the heat-welded edges) measuring approximately 10 cm x 10 cm x 1 cm. it contains 50 g of composition, the apparent density of which is approximately 0.5 g / ci.

 In the practical use test, this article is added to 64 liters of tap water (hardness: 150 ppm, expressed as CaCO3), at 210C, in an automatic top-loading washing machine, following which adds 2.7 kg of assorted linen, mostly polyester, cotton-polyester blends and cotton, to the wash water. We set the washing machine for normal washing, the washing period for 20 minutes, and then rinse the laundry twice (rinse with cold water), then spin. It is then placed, along with the wet sachet which is practically empty (more than 99% expelled), in an automatic dryer, and they are dried for 40 minutes at medium heat. The laundry is removed from the dryer and the bag is examined. The sachet does not contain any residue and it is removed. The linen is examined by a jury of examiners who are well versed in the detergents and linen flexibility ratings. These examiners find that the various items washed are clean and flexible, and practically free of static electricity. Thus, the articles of the invention satisfactorily release into the washing water a detergent composition with softening effect, and this composition satisfactorily cleans and softens the laundry, without leaving deposits of quaternary products on the laundry, and does not do not yellow or harm the optical brightener present.

 In addition to the importance of evacuating the composition from the bag, so that no residue remains in it, it is also important that the composition leaves the bag in the first stages of the washing operation. , say in the first five minutes of it, so that the laundry to be washed and softened is in contact with the detergent components and softening effect, for a sufficiently long time that these compounds can essentially exert their full effects.

When, during the washing operation, the sachet is removed from the washing water after five minutes of washing, it is found that it is practically <at a rate of more than 95%) emptied of its content initial, which shows that the transport of the detergent composition with softening effect, through the walls of the sachet, to the washing water, is not only total but also rapid.

In the example above, the Neodol 25-7 used is a non-ionic BRE detergent. When replacing the
Neodol 25-7 by a non-ionic detergent NRE, Tergitol 24-L-60N, the transport of the composition through the walls of the sachet is also complete and rapid, and the cleaning and softening of the linen are just as effective. In addition, as revealed by the French patent application ET cl. 10698 filed on August 8, 1988, the RNE detergent composition synergistically improves the effect of improving the release of dirt which is exerted by the polymer
PET-POET, which improves subsequent cleaning. Similar advantageous results are obtained by replacing Neodol 25-7 with non-ionic detergents of type NRE 23-7P and 23-7Z from Shell Development Company.

When control articles not containing an anionic surfactant (TEALDBS) are produced in the formulation of the composition, this constituting the only modification compared to the BRE formulations and
NRE of the present example, as described above, the articles do not wash the laundry as well and do not soften it as well as those described above. The reason for this is obvious, since significantly greater amounts of particulate composition remain after washing in the control bags. In some cases, this proportion remaining in the sachet exceeds 20% of the initial composition.

The residue appears to be a reaction product of the cationic softener compound and the builder or builders. However, when sodium n-dodecylbenzenesulfonate is present in place of TEALDBS, even when it is mixed separately with the particulate product after absorption of only the nonionic detergent in the liquid state by the spray-dried base grains, the The residue in the sachet after washing is likewise remarkably reduced, an amount as low as 0.1%, or zero, of residue being frequently observed.

 The determinations of the amounts of residue which are mentioned above are in accordance with the results obtained in laboratory tests carried out on various articles such as those of the present invention, under "difficult expulsion conditions", such as low temperature. water, gentle agitation, short wash times, and placement of the item in the laboratory washing machine in a location with relatively little agitation. In such laboratory tests, it is confirmed that the presence of the anionic surfactant in the particulate composition contained in the sachet effectively promotes the transport of the content through the walls of the sachet and its passage through the washing water, and reduces the residue, frequently until it is void.

Example 2
To 39,841 parts of tap water in a conventional detergent mixer, 0.460 parts of Tinopal UNPA optical brightener, 16,483 parts of sodium bicarbonate, 16,922 parts of sodium carbonate (natural anhydrous sodium carbonate) and 26,294 parts of hydrated zeolite 4A (expressed in anhydrous form), to obtain a mixture having a content of 54.9% in solids, which is at a temperature of approximately 600C. In order to improve the mixing and the absorption capacity of the spray-dried grains, with acceptable mechanical strength of the grains, the mixture is prepared by first adding the optical brightener to the water in the mixer, then the bicarbonate. , carbonate and zeolite. These additions are carried out while the water or the aqueous mixture is stirred, and the carbonate is added in two stages, adding 80% of it first, with maximum stirring, after which stirring is continued for approximately 3 minutes, then the remainder of the carbonate is added while stirring is continued for another 1 minute, and then the zeolite is added (this mixing technique is not the invention of the authors of the present invention, but was the result of the work of a colleague, working for their transferee corporation. The resulting mixture (100,000 parts) is then pumped to a conventional spray drying column, where it is dried in a drying gas hot, at a temperature of about 4000C, to give 56.766 parts of spray dried base grains, having sizes ranging from 2.0 to 0.15 mm, and a moisture content equal to 8.2%. During the spray drying operation, part of the bicarbonate is converted into carbonate, with the release of water and carbon dioxide.

After the base grains have cooled to room temperature, 19,000 parts of
Neodol 25-7, 4.761 parts of TEALDBS and 3.174 parts of water on the moving surfaces of 72.594 parts of these basic grains, keeping the grains in motion in a suitable mixer, for example an inclined drum mixer. Water normally accompanies TEALDBS as supplied, in an aqueous solution of 60% solids. Non-ionic detergent, anionic surfactant and water, in common solution, at a temperature of 320C, are sprayed on the moving surfaces of the base grains. The solution is absorbed by these grains and penetrates inside them, while coating them or at least partially coating them. In addition, 0.471 parts of perfume are also sprayed onto the moving grains. The moisture content of the 100,000 parts of the resulting intermediate product is approximately 8.7%.

This intermediate particulate product is then mixed with the other particulate or sprayed components of the final formulation of the detergent composition with softening effect. In this final mixing, which also takes place in a suitable mixer for particulate materials, such as an inclined drum, 84.970 parts of the particulate intermediate product described are mixed with 1.060 parts of
Maxatase MP 37500; 3,700 parts of an 80:20 mixture of Alkaril QCF and Alcosperse 107D; 9,600 parts of fabric softener premix and 0.670 parts of Microcel C. The fabric softener pre-mix includes 8.448 parts of dimethyl distearyl ammonium chloride, 0.768 parts of condensation product of higher fatty alcohol and ethylene oxide (an emulsifier / surfactant in which the higher fatty alcohol has on average 12 to 18 carbon atoms and is condensed with approximately 20 moles of ethylene oxide per mole), and 0.096 part of
Microcel C. The rest (0.288 part) of the fabric softener pre-mix consists essentially of moisture which can accompany the cationic fabric softener of the pre-mix, as supplied. The additional 0.670 part of
Microcel C is added to improve the flowability of the final product, and this additional quantity accelerates machine filling of the sachets with this product. Microcel C is also present in the softener pre-mix to improve its flowability. Non-ionic surfactant is present in the softener pre-mix to facilitate wetting of the softener, its dispersion in the aqueous medium which is formed in the sachet after addition of the article to the washing water, and the transport of the softener through the walls of the sachet.

 We give below the formulation of the final detergent composition with softening effect, that is to say the content of the sachets, described below.

Component Parts (by weight)
Sodium carbonate 23.569
Sodium bicarbonate 9,699
Zeolite (expressed in anhydrous form) 22,857
Neodol 25-7 16,144
TEALDBS 4,045
Alkaril QCF 2,960
Alcosperse 107D 0.740
Dimethyl-distearyl ammonium chloride 8,448
Fatty alcohol condensation product
higher having an average of 12 to
18 carbon atoms, with 20 moles
ethylene oxide per mole 0.768
Microcel C 0.766
Mixture of enzymes (mixture of enzymes
proteolytics and amylolytics) 1,060
Optical brightener (stilbene type) 0.500
Perfume 0.400
Water 8,044
100,000
The detergent composition with softening effect of this example is composed of particles which have a size essentially in the range of 2.0 to 0.15 mm, more than 90% by weight of the particles falling within this range and frequently more than 95% of these correspond to these sizes. Particles of larger or smaller sizes can be removed by sieving or other classification operation. It is preferred that all of the particles be between 2.0 and 0.25 mm in size, with the smaller particles frequently adhering to the larger particles, so that their actual particle size is larger and within these limits. Thus, it can be considered that the finely sprayed components of these products, such as those mixed in the final mixing, which can sometimes have particle sizes as small as 0.074 mm, can deposit and form a coating on the larger particles of the basic grains. These larger particles contain detergents and perfume, which can help fix the smaller particles.

 The described softening detergent composition flows satisfactorily freely and can pass through a narrowed orifice or outlet pipe of a container at a speed representing approximately 70% of the dry sand, thus meeting a standard of good suitability for the flow of spray dried detergent compositions.

 After production, the particulate composition can be aged (which is frequently preferred), before being introduced into water-permeable sachets, but in some cases it can be introduced directly without any intermediate aging. This filling is preferably carried out by an automatic packaging machine, in the operation of which strips of fabric or nonwoven are brought in parallel, the particulate composition is brought between them in a pocket created by the machine, the edges of the strips are heat sealed or otherwise joined together, and individual packages or sachets are separated from the strip, such as by automatic sectioning operations. The filled sachets are then packed in cardboard boxes for storage, transport and sale.

 The continuous web material which is used to feed the automatic packaging and filling machine is a 100% non-woven polyester material, Kendall SP 284.1, which is made of 3 denier polyester fibers. Such material weighs approximately 40 g / d and has an air permeability of approximately 2 i / min / cm2. The article produced is essentially square, the volume filled, excluding the heat-sealed edges, measuring approximately 10 cm x 10 cm x 1 cm. it contains 50 g of composition, the apparent density of which is approximately 0.5 or 0.6 g / cm3.

 Tests of practical use, such as those described for the articles of Example 1, give essentially the same results, and these are confirmed by laboratory tests in which the washing conditions, including agitation, are controlled and kept constant for experimental and control tests. Thus, although the composition of the present articles comprises a significant percentage of water-insoluble substances (zeolite) and although the carbonate, which is more alkaline, is more likely to react with the cationic softener than the polyphosphate of the articles of Example 1, an evacuation of the sachet is obtained by the detergent composition, which can be attributed to the presence of the anionic surfactant in the detergent composition with softening effect.

 When preparing control articles which do not contain an anionic surfactant in the formulation of the composition, this being the only modification compared to the formulation of the preceding composition of this example, clearly greater quantities of the particulate composition remain in the sachets after washing, which leads to a much worse cleaning of the laundry and a less effective softening thereof. In such cases, the proportion of this composition remaining in the sachet after washing can exceed 10% of the initial composition. Such a residue is a reaction product of the cationic softener compound and a detergency builder, apparently the carbonate type detergency builder. When using sodium n-dodecylbenzenesulfonate instead of TEALDBS, but in mixing it with the intermediate detergent particles (instead of spraying it on the basic grains in common solution with the nonionic detergent), no improvement in the transport of the composition is obtained through the walls of the sachet. In fact, the amount of residue is greater and the softening action is even less good.

 In this example, as in Example 1, the non-ionic detergent BRE Neodol 25-7 used can be replaced by a non-ionic detergent NRE, and such replacement is generally preferable.

Thus, by replacing the Neodol 25-7 with Tergitol 24-L-60N (or by Neodol 23-7P or Neodol 23-7Z), the desired cleaning and softening of the linen is obtained, as with the article containing the composition based on nonionic detergent of BRE type, but the composition based on detergent of NRE type also synergistically improves the effect promoting the release of dirt which is exerted by the copolymer
Alkaril QCF, and therefore improves subsequent cleanings.

Example 3
(Additional modifications of the invention)
Other detergent compositions with a softening effect can be prepared, comprising other components described above, and they can be used in the sachets of the preceding examples, to obtain articles which will satisfactorily expel the compositions contained and will clean and soften
v the laundry satisfactorily. Thus, in addition to particulate non-ionic detergents of the BRE and
RNE indicated in the examples mentioned, or at least as a partial replacement for them, other nonionic detergents, such as Neodol 23-6.5, Igepal CO-630 and Pluronic F-68 or equivalent, and detergents can be used corresponding non-ionic NREs, and detergency builders can be changed as described, and other cationic softeners can be used, including other quaternary ammonium compounds, such as cetyl bromide trimethylammonium, dimethyldi-tallow-alkylammonium chloride and imidazolinium salts, for example 2-heptadecyl-1-methyl methyl sulfate 1 - [(2-stearoylamido) ethyl] imidazolinium. TEALDBS can be replaced by other anionic surfactants, preferably triethanolamine salts, such as triethanolamine lauryl sulfate, but the corresponding sodium and potassium salts can also be replaced in appropriate cases (the sodium salts being preferably limited to use in detergent compositions with a phosphate-type detergency builder. The various additives present in the compositions of the examples may be varied, or some or all of them may be omitted (except that a certain amount humidity is normally present).

 In addition to replacing the components of the preceding examples with others (these other components being mentioned in the present description), the proportions of the components as indicated in the examples can be modified, for example + 108 and + 25% , provided that these proportions are maintained within the limits indicated in the present description.

 Instead of using a polyester nonwoven fabric sachet, these sachets can be made of other materials, including a polyester-cotton blend, e.g. 50:50 polyester-cotton, rayon, Nylon, blends of these plastics and mixtures thereof with natural fibers, such as blends with cotton. The fabrics may be woven or nonwoven, and the fibers may have different denier numbers (although they preferably have the same denier number), different weights and permeabilities, provided that satisfactory expulsion of the composition out of the sachet (or other permeable container) during the washing of laundry in an automatic washing machine, but normally the number of deniers, the weight of the fabric and its permeability will fall within the preferred ranges given in the description.

 Although the bags for the articles of the invention are preferably produced automatically by a packaging and filling machine, they can also be produced by hand, and instead of the edges being heat-sealed, they can be sealed using an adhesive, solvent, by melting the polymeric material, by stitching or stapling. The size, shape, weight of the contents and density of the contents of the bag can be varied, and these bags can be replaced with permeable containers of constant size and shape, such as tubes with closed ends.

 In the production of the detergent composition, instead of spraying the common solution of nonionic detergent, anionic surfactant and solvent on the base grains, the nonionic and anionic components can be absorbed separately by these grains, and it is preferred to apply them under form of the single solution described, to save an additional operation and to facilitate penetration into the pores of the grains. The temperature of the application can be modified to adopt any other suitable temperature at which the mixture is in the liquid state, but it will normally be maintained in the range of 30 to 400C. In some cases, instead of spraying the liquid on the moving base grains, this application can be done by running the liquid on the grains or by applying it on them as a stream or a "film". In such cases, the miantian of the grain bed will be used with sufficient agitation so that the liquid is distributed over the surface of these grains.

In washing laundry with an article or articles of the present invention, the consumer is always assured of having the exact amount of detergent composition in the washing water for a normal washing load, and pouring and measuring the powder detergents are avoided. The hardness of the wash water will normally be less than 300 ppm, expressed in
CaCO3, but harder waters can be used. Washing temperatures will usually be less than 700C, but higher temperatures may be used, and sometimes the use of higher temperature washing water may be more desirable, since heat facilitates the solubilization of the contained composition and, therefore, facilitates the transport thereof through the permeable walls of the container. The washed linen will usually contain a certain amount of synthetic fabrics or mixed natural-synthetic fabrics, but the invention works with linen made exclusively of fibrous materials. natural, such as cotton linen.

After washing in the washing machine (which is normally automatic), the laundry is usually dried in the machine, but one can also note an improved softening wise, compared to a control, of laundry articles which are dried on the thread, although the improvements in their softening are not as marked.

 The molecular weights and / or number of carbon atoms of the compounds given in the above description can be considered to apply to average molecular weights, as well as to actual molecular weights.

 it should be understood that the foregoing description has been given by way of illustration and not limitation, and that any variations or modifications may be made thereto without departing from the general scope of the present invention as defined in claims appended hereto.

Claims (25)

 1. A detergent and fabric softener article for use in washing and softening laundry in an automatic washing machine, which article is a particulate detergent composition with a detergency builder and softening effect, in a permeable container water, insoluble in water, through a permeable wall from which the components of the particulate detergent composition with softening effect, in the form of solution, emulsion and / or aqueous dispersion, can pass into the washing water in the machine automatic washing during a washing cycle of such a machine, so that the laundry present in the washing water can be washed and softened by these components, and in which article the detergent composition with softening effect comprises a detergent proportion of non-ionic detergent, an additional proportion of detergency of an adjuvant for the non-ionic detergent, a proportion with softening effect of a cationic compound fabric softener, and a proportion of anionic surfactant (surfactant) promoting transport, which proportion of anionic surfactant is less than the proportions of the nonionic detergent and the cationic softener compound, and which anionic surfactant solubilizes, emulsifies and / or disperses the component (s) of the detergent composition with softening effect, comprising the cationic softener compound, in the permeable container, so that practically all of this composition and of this compound leaves the container and passes into the washing water while washing laundry in the washing machine.  2. Detergent and fabric softener article according to claim 1, characterized in that the insoluble and water permeable container is a permeable sachet made of thin material, the proportion of nonionic detergent in the detergent composition is in the range from 8 to 40 *, the proportion of the detergency builder therein is in the range of 30 to 70%, the proportion of the cationic softening compound therein is in the range of 0.5 to 15%, and the proportion of anionic surfactant therein is in the range of 1 to 8%.  3. Detergent and softener article according to claim 2, characterized in that the permeable sachet is made of non-woven synthetic organic polymer material, the nonionic detergent is a condensation product of ethylene oxide and higher fatty alcohol, in wherein the fatty alcohol greater than on average from 10 to 18 carbon atoms and the ethylene oxide content of the nonionic detergent is on average from 3 to 15 moles of ethylene oxide per mole of higher fatty alcohol; the detergency builder salt is chosen from an alkali metal tripolyphosphate, an alkali metal silicate, an alkali metal carbonate, an alkali metal bicarbonate, an alkali metal borate, an alkali metal citrate, an alkali metal gluconate, nitrilotriacetate (NTA), zeolite and mixtures thereof; the cationic softening compound has the formula

 in which R1 and R2 are lower alkyl groups  3 laughers having from 1 to 3 carbon atoms, R3 is a higher alkyl group having from 10 to 20 carbon atoms, R4 is an alkyl group having from 1 to 20 carbon atoms and X is chlorine or bromine; and the anionic surfactant is a detergent which is a higher alkyl (benzenesulfonate of alkali metal or alkanolamine, a higher fatty alcohol-sulfate of alkali metal or alkanolamine, or a higher fatty alcohol-polyethoxysulfate of alkali metal or d alkanolamine, or a mixture thereof, the upper alkyl radical having from 12 to 16 carbon atoms, the higher fatty alcohol having from 12 to 18 carbon atoms, the polyethoxy moiety consisting of 3 to 15 ethoxy groups and the alkanolamine being a lower mono-, di- or trialkanolamine having from 1 to 3 carbon atoms.  4. Article according to claim 3, characterized in that the sachet is made of non-woven polyester, nylon or rayon fibers, or in any mixture thereof, the non-ionic detergent is a condensation product of oxide of ethylene and higher fatty alcohol, wherein the higher fatty alcohol has on average 10 to 16 carbon atoms and the ethylene oxide content of the nonionic detergent is on average 3 to 10 moles of ethylene oxide per mole; the detergency builder is a mixture of sodium tripolyphosphate and sodium silicate; the weight of the tripolyphosphate representing from 5 to 20 times the weight of the silicate; the quaternary ammonium salt is a dialkyl (lower) -dialkyl (upper) -ammonium chloride in which the lower alkyl groups have 1 or 2 carbon atoms and the higher alkyl groups have from 12 to 20 carbon atoms; and the anionic detergent is a triethanolamine alkyl (higher) benzenesulfonate in which the upper alkyl group has 12 to 14 carbon atoms.  5. Article according to claim 4, characterized in that the proportion of the non-ionic detergent in the detergent composition is from 12 to 25%, the proportion of the mixture of detergency builder salts therein is from 40 to 65%, the proportions of sodium tripolyphosphate and silicate being 40 to 60% and 3 to 8% respectively, the proportion of the quaternary ammonium salt in this composition is 7 to 10%, and the proportion of the anionic detergent in that- ci is 3 to 6%, and the sachet is heat-sealed and has a size suitable for being easily taken in hand, the total surface area of the permeable surface, through which water and one or more solution (s) can pass, emulsion (s) and / or dispersion (s) of constituents of the detergent composition, being in the range of 100 to 500 cS, measured externally, and the weight of the detergent composition in the permeable sachet being in the range of 30 to 100 g.  6. Article according to claim 1, characterized in that the particulate detergent composition with detergency builder and softening effect consists of grains of spray-dried detergency builder, in which the non-ionic detergent and the surfactant are absorbed anionic, and a particulate cationic softener being mixed with these nonionic detergent-anionic detergent detergent builder particles.  7. Article according to claim 5, characterized in that the higher fatty alcohol of the nonionic detergent is a mixture of higher fatty alcohols having on average 12 to 15 carbon atoms in their molecule, the content of ethylene oxide non-ionic detergent is on average 6 to 7 moles per mole of higher fatty alcohol, the concentration of non-ionic detergent in the detergent composition is approximately 16%, the mixture of adjuvant detergency minerals soluble in water is constituted about 48% of pentasodium tripolyphosphate and about 5% of sodium silicate having a Na2O: SiO2 ratio of about 1 :: 2.4, the quaternary ammonium salt is dimethyl distearylammonium chloride and the proportion of it in the detergent composition is about 8.5%, and the anionic detergent or surfactant is triethanolamine n-dodecylbenzenesulfonate, and the proportion thereof in the detergent composition is about 4%, all percentages and all l es proportions being relative to the weight of the final product.  8. Article according to claim 7, characterized in that the particulate detergent composition of detergent with detergency builder and softening effect consists of grains of detergency builder, spray-dried, which contain both pentasodium tripolyphosphate and sodium silicate, and have particle sizes in the range of 2.0 to 0.15 mm, in which are absorbed the nonionic detergent which is a condensation product of a higher fatty alcohol and ethylene oxide , and the anionic detergent n-dodecylbenzenesulfonate of triethanolamine, and dimethyl-distearyl ammonium chloride softener being mixed with, adhering to and coating these particles of detergency builder-nonionic detergent-detergent or anionic surfactant.  9. Article according to claim 8, characterized in that the detergent composition with a softening effect also comprises approximately 3% of copolymer promoting the release of soiling, of the polyethylene terephthalate-polyoxyethylene terephthalate (PET-POET) type having a molecular mass in the range 19,000 to 43,000, the molecular weight of the polyoxyethylene moiety thereof in the range of 2,700 to 5,000, the molar ratio of PET units to units POET being in the range of 2: 1 to 6: 1, and the ratio of the ethylene oxide moiety to the phthalic moiety in the copolymer being in the range of 20: 1 to 30: 1; about 1% of a mixture of proteolytic-amylolytic enzymes; about 0.7% sodium polyacrylate having a molecular weight in the range of 1,000 to 3,000, about 0.8% calcium silicate as a flow-promoting agent; about 0.5% optical brightener; about 0.4% perfume; and about 11% water; and in that the sachet is made of polyester filaments having from 2 to 4 denier, in the form of a nonwoven sheet having a thickness in the range of 0.1 to 1 mm and an air permeability ranging from 10 to 15 ri? / Min, is essentially square, is heat-sealed on several of its sides and has a total permeable surface area of approximately 200 cm., Measured externally, and the weight of the detergent composition with softening effect in the sachet permeable is approximately 50 g.  10. Article according to claim 6, characterized in that the nonionic detergent is a narrow range oxyethylated product (NRE), which is a polyoxyethylated lipophilic product, oxyethylated with on average 5 to 10 ethylene oxide groups per mole, and at least 70% of the ethylene oxide groups present in polyethoxy groups comprising from 4 to 12 ethylene oxide units.  11. Article according to claim 8, characterized in that the nonionic detergent is a narrow range oxyethylated product (NRE), in which the higher fatty alcohol fragment is saturated and has on average from 12 to 14 carbon atoms, and more 85% of the ethylene oxide present in this NRE are present in the form of polyethoxy groups comprising from 5 to 10 moles of ethylene oxide.  12. Article according to claim 3, characterized in that the sachet is made of polyester fibers, Nonwoven nylon or rayon, or a mixture of any of these, the nonionic detergent is a condensation product of ethylene oxide and higher fatty alcohol, in which the higher fatty alcohol has on average 10 to 16 carbon atoms and the ethylene oxide content of the nonionic detergent is on average 3 to 10 moles of ethylene oxide per mole; the detergency builder is a mixture of sodium carbonate, sodium bicarbonate and hydrated zeolite, the weight of sodium carbonate representing from 0.7 to 1.5 times the weight of the zeolite (expressed in anhydrous form), and the weight of sodium bicarbonate representing from 0.3 to 0.7 times the weight of sodium carbonate; the quaternary ammonium salt is a dialkyl (lower) -dialkyl (upper) -ammonium chloride, in which the lower alkyl groups have 1 or 2 carbon atoms and the higher alkyl groups have from 12 to 20 carbon atoms, and the anionic detergent is a triethanolamine alkyl (higher) benzenesulfonate in which the upper alkyl group has 12 to 14 carbon atoms.  13. Article according to claim 12, characterized in that the proportion of nonionic detergent in the detergent composition is from 12 to 25%, the proportion of the mixture of detergency builder salts therein is from 40 to 65%, the proportions of sodium carbonate, sodium bicarbonate and hydrated zeolite, expressed in anhydrous form, being from 15 to 35%, from 5 to 20% and from 10 to 35% respectively, the proportion of the quaternary ammonium salt is from 7 to 10%, and the proportion of the anionic detergent is 3 to 6%, and the sachet is heat sealed is of a size allowing it to be easily taken in hand, and has a total surface area of the permeable surface, through which can pass water and one or more solution (s), emulsion (s) and / or dispersion (s) of constituents of the detergent composition, in the range of 100 to 500 cS, measured externally, and the weight of the composition detergent in the permeable sachet being in the range of 30 to 100 g.  14. Article according to claim 13, characterized in that the higher fatty alcohol of the nonionic detergent is a mixture of higher fatty alcohols having on average 12 to 15 carbon atoms in their molecule, the content of ethylene oxide non-ionic detergent is on average 6 to 7 moles per mole of higher fatty alcohol, the concentration of non-ionic detergent in the detergent composition is approximately 16%, the proportion of the mixture of detergency adjuvant mineral salts is approximately 24% of sodium carbonate, approximately 10% sodium bicarbonate and approximately 23% sodium hydrated zeolite (expressed in anhydrous form), the quaternary ammonium salt is dimethyl-distearyl ammonium chloride and the proportion thereof in the detergent composition is approximately 8.5%, and the anionic detergent is triethanolamine n-dodecylbenzenesulfonate and the proportion thereof in the detergent composition is approximately 4%, all percentages and all proportions being given relative to the weight of the final product, except the percentage of the zeolite which is a percentage of anhydrous zeolite (with elimination of the water of hydration) relative to this final product.  15. Article according to claim 14, characterized in that the particulate detergent composition with detergency builder and softening effect consists of grains of detergency builder, spray-dried, which contain sodium carbonate, sodium bicarbonate and hydrated zeolite, and have particle sizes in the range of 2.0 to 0.15 mm, in which the non-ionic detergent, of the condensation product type, is absorbed  vv of higher fatty alcohol and ethylene oxide, and the anionic detergent which is triethanolamine n-dodecylbenzenesulfonate, and of dimethyl-distearyl ammonium chloride softener particulate being mixed with, adhering to and coating these particles of detergency builder nonionic detergent anionic detergent.  16. Article according to claim 15, characterized in that the detergent composition with softening effect also comprises approximately 3% of copolymer promoting: the release of soiling, of polyethylene type. terephthalate-polyoxyethylene terephthalate (PET-POET) having a molecular weight in the range of 19,000 to 43,000, the molecular weight of the polyoxyethylene moiety thereof being in the range of about 2,500 to 5,000, the molar ratio of PET units with POET units being in the range of 2: 1 to 6: 1 and the proportion of ethylene oxide relative to the phthalic moiety in the copolymer being in the range of 20: 1 to 30: 1; about 1% of a mixture of proteolytic-amylolytic enzymes; about 0.7% of a sodium polyacrylate having a molecular weight in the range of 1,000 to 3,000; about 0.8% calcium silicate as a flow promoting agent; about 0.5% optical brightener; approximately 0.4% of perfume and approximately 8% of water, and in that the sachet is made of polyester filaments having from 2 to 4 denier, in the form of a nonwoven sheet having a thickness in the range of 1, 0 to 1.2 mm and air permeability in the range of 1 to 3 n? / Min / cn ?, is essentially square, is heat sealed on several of its sides and has a total permeable surface area of approximately 200 cri ?, measured externally, and the weight of the detergent composition with softening effect in the permeable sachet is approximately 50 g.  17. Article according to claim 12, characterized in that the nonionic detergent is a narrow range oxyethylation product (NRE) which is a polyoxyethylated lipophilic product, oxyethylated with on average 5 to 10 ethylene oxide groups per mole, and at least 70% of the ethylene oxide are in polyethoxy groups comprising from 4 to 12 moles of ethylene oxide.  18. Article according to claim 14, characterized in that the nonionic detergent is a narrow range oxyethylation product (NRE), in which the higher fatty alcohol fragment is saturated and has from 12 to 14 carbon atoms, and more 85% of the ethylene oxide present in the polyoethoxy fragment of this NRE are present in the form of polyethoxy groups comprising from 5 to 10 moles of ethylene oxide.  19. Liquid detergent composition, usable for application in the liquid state, at a temperature in the range of 30 to 400C, on grains of inorganic detergency builder spray-dried, and for absorption by these grains, to provide synthetic organic particulate detergent builder compositions to which a particulate cationic softener compound can be applied to provide a particulate detergent builder and softener composition comprising a mutual solution of 3 to 6 parts of a anionic detergent selected from (higher) alkyl-benzenesulfonates of alkali metals and alkanolamines, higher fatty alcohols-sulfates of alkali metals and alkanolamines, and higher fatty alcohols-polyethoxysulfates of alkali metals and alkanolamines or mixtures of these, the higher alkyl group having 12 to 16 carbon atoms, the higher fatty alcohol having 12 to 18 carbon atoms arbone, the polyethoxy moiety comprising from 3 to 15 ethoxy groups, and from 12 to 25 parts of a nonionic detergent which is a condensation product of ethylene oxide and higher fatty alcohol, in which the fatty alcohol has an average of 10 to 16 carbon atoms and the ethylene oxide content is on average 3 to 10 moles of ethylene oxide per mole, the ratio of this anionic detergent to this nonionic detergent being in the range from 1: 5 to 1: 3.  20. Liquid detergent composition according to claim 19, characterized in that the anionic detergent is triethanolamine n-dodecylbenzenesulfonate, the nonionic detergent is a product of polyoxyethylation of a higher fatty alcohol, in which the higher fatty alcohol has average of 12 to 15 carbon atoms per molecule and the polyethoxy fragment comprises on average of 6 to 7 ethylene oxide groups, the proportion of this alkyl (linear superior) -benzenesulfonate of triethanolamine in the liquid detergent composition is approximately 4 parts, the proportion of the condensation product of higher fatty alcohol and ethylene oxide is approximately 16 parts, the liquid detergent composition also comprises approximately 2.7 parts of water, as a co-solvent, and the temperature of the liquid detergent composition at which temperature the components are mutually soluble and at which the composition can be applied by spraying onto adjuvant base grains ant inorganic detergency, spray dried, is around 320C.  21. Process for the production of a detergent composition with softening effect, suitable for being released into the washing water in an automatic washing machine from a container which is insoluble in water, permeable to water, through a permeable wall thereof, which comprises spray-drying an aqueous mixture of detergency builder (s) for the production of porous base grains, preparing a liquid solution of detergents consisting of 3 to 6 parts of an anionic detergent chosen from alkyl (higher) -benzenesulfonates of alkali metals and alkanolamines, higher fatty alcohols-sulfates of alkali metals and alkanolamines, and higher fatty alcohols-polyethoxysulfates of alkali metals and d alkanolamines and mixtures thereof, the higher alkyl group having 12 to 16 carbon atoms, the higher fatty alcohol having 12 to 18 carbon atoms and the polyethoxy moiety having 3 to 15 ethoxy groups, in 12 to 25 part s of a condensation product of ethylene oxide and higher fatty alcohol, in which the nonionic detergent the fatty alcohol fragment has on average from 10 to 16 carbon atoms and the ethylene oxide content is on average from 3 to 10 moles of ethylene oxide per mole, the ratio of this anionic detergent to this nonionic detergent being in the range from 1: 5 to 1:: 3, at a temperature in the range from 30 to 400C, spraying this anionic detergent-nonionic detergent solution onto spray-dried porous detergency builder grains, by which it is absorbed, and applying a particulate cationic softener compound to these detergency builder grains -anionic detergent-nonionic detergent, which adheres to these grains and coats them.  22. The method of claim 21, characterized in that the aqueous mixture has a content of 50 to 75% in solid matter, which solid matter comprises sodium tripolyphosphate and sodium silicate, the weight of the tripolyphosphate representing from 5 to 20 times the weight of the silicate, or include detergency builders such as sodium carbonate, sodium bicarbonate and zeolite, the weight of sodium carbonate representing 0.7 to 1.5 times the weight of the zeolite (expressed as anhydrous) and the weight of sodium bicarbonate being 0.3 to 0.7 times the weight of sodium carbonate (relative to spray dried grains), the spray dried grains have particle sizes in the range of 2 0.0-0.15 mm, the nonionic detergent is a polyoxyethylation product of a higher fatty alcohol in which the higher fatty alcohol has on average 12 to 15 carbon atoms per molecule and the polyethoxy moiety is formed on average from 6 to 7 moles per mole, the anionic detergent is triethanolamine n-dodecylbenzenesulfonate, the temperature of the liquid detergent is approximately 320C, the liquid detergent comprises approximately 4 parts of said anionic detergent, approximately 16 parts of said nonionic detergent and approximately 2.7 parts of water, and the cationic compound with a softening effect on tissues is distearyl dimethylammonium chloride, which is applied to the particles of detergency builder-anionic detergent nonionic detergent in a powder, which powder comprises about 8.5 % of this softening cationic compound, approximately 0.8% of emulsifier of product type of polyoxyethylation of higher fatty alcohol, and approximately 0.1% of hydrated synthetic calcium silicate, as agent facilitating the flow.  23. A method of washing and softening laundry, which comprises adding to the washing water, at a temperature in the range of 15 to 70 "C, in an automatic washing machine, an article according to the claim 1, and washing the laundry in said wash water using a normal wash cycle for a washing machine of this type.  24. The method of claim 23, characterized in that the container of the article is a sachet insoluble in water, permeable to water, in a nonwoven fabric, consisting of synthetic organic polymer fibers, and the composition in this sachet contains from 8 to 40% of a nonionic detergent which is a condensation product of ethylene oxide and higher fatty alcohol, in which the higher fatty alcohol has on average from 10 to 16 carbon atoms and the ethylene oxide content is on average 3 to 10 moles of ethylene oxide per mole; from 30 to 70% of a detergency builder which is a mixture of sodium tripolyphosphate and sodium silicate, the weight of the tripolyphosphate representing from 5 to 20 times the weight of the silicate; from 0.5 to 15% of a cationic softening compound which is a dialkyl (lower) -dialkyl (upper) -ammonium chloride in which the lower alkyl groups have 1 or 2 carbon atoms and the higher alkyl groups have from 12 to 20 carbon atoms; and from 1 to 8% of an anionic detergent which is a triethanolamine alkyl (higher) benzenesulfonate, in which the upper alkyl group has from 12 to 14 carbon atoms.  25. The method of claim 23, characterized in that the container of the article is a sachet insoluble in water, permeable to water, in nonwoven fabric, consisting of synthetic organic polymer fibers, and the composition in this sachet comprises from 8 to 40% of a nonionic detergent which is a condensation product of ethylene oxide and higher fatty alcohol, in which the higher fatty alcohol has on average from 10 to 16 carbon atoms and the ethylene oxide content is on average from 3 to 10 moles of ethylene oxide per mole; from 30 to 70% of a detergency builder which is a mixture of sodium carbonate, sodium bicarbonate and hydrated zeolite, the weight of sodium carbonate representing from 0.7 to 1.5 times the weight of the zeolite (expressed in anhydrous form) and the weight of sodium bicarbonate representing from 0.3 to 0.7 times the weight of sodium carbonate; from 0.5 to 15% of a cationic softening compound which is a dialkyl (lower) -dialkyl (upper) ammonium chloride in which the lower alkyl groups have 1 or 2 carbon atoms and the higher alkyl groups have from 12 to 20 carbon atoms; and from 1 to 8% of an anionic detergent which is a triethanolamine (higher) benzenesulfonate alkyl, in which the upper alkyl group has from 12 to 14 carbon atoms.