NO165685B - TOYSY WASHING AND SOFTING AGENT. - Google Patents

Description

The invention relates to a means for

to clean and soften textiles during the wash cycle of a laundry operation. More specifically, the invention relates to softening agents which are suitable for use during the wash cycle of a laundry operation using hot water,

wherein the agent includes non-ionic surfactant,

a fabric softener consisting of a cationic, quaternary ammonium compound, and a multi-functional additive to increase the attachment of the softener.

Mixtures useful for treating textiles

to improve the textiles' softness and grip, are well known in the relevant art.

When used for home laundry,

the fabric softeners are typically added to the rinse water during the rinse cycle, which lasts only 2-5 minutes. The consumer must therefore monitor the laundry operation or

take other precautions so that the fabric softener becomes

set at the correct time. This makes it necessary that consumer

it returns to the washing machine just before or at the beginning of the washing operation's rinse cycle, which is of course a burden for the consumer. In addition, special care must be taken so that the correct amount of the fabric softener is used to avoid overdosing which can make the clothes water-repellent due to the deposition of a greasy film on the fabric surface, as well as the fact that an overdosing can cause the clothes to acquire a certain yellowness. To solve the above problems, it has been known to use fabric softeners which are compatible with ordinary laundry detergents, so that the softeners can be combined with the detergents in a single package for use during the wash cycle of the laundry operation. Examples of such fabric softening detergents that are added during the wash cycle are given in US patents 3351438, 3660286 and 3703480. The fabric softening detergents for addition to the wash cycle generally contain a cationic, quaternary ammonium textile softener and additional ingredients that make the softening compounds compatible with the commonly used surfactants for washing clothes.

However, it is also known that the cationic softening compounds that are added to the wash cycle, either as a component of a detergent-softener preparation or as a softener for the wash cycle, adversely affect the whitening effect as well as the cleaning effect of the detergent. As a result, it has been attempted to some extent

to counteract this adverse effect in detergent softeners by using non-ionic surfactants, higher concentration of whiteners, carboxymethyl cellulose, anti-yellowing compounds and bluing agents etc. However, little progress has been achieved in softening preparations for use during the wash cycle and in which a number of surfactants are used, most of which are anionic.

However, there have also been a number of prior art disclosures relating to laundry detergents containing cationic fabric softeners, including the softeners of quaternary ammonium compounds, and non-ionic surface-active compounds, as well as other surface-active compounds, e.g. anionic, zwitterionic and amphoteric. As representative of this state of the art can be mentioned

US Patents 4264457, 4239659, 4259217, 4222905, 3537993, 3583912, 3983079, 4203872, 4264479, 3951879, 3360470, 3351483 and 3644203, etc.

In the following patents, detergents and/or shampoos containing a non-ionic surfactant are described: US patents 3313734 (shampoo - quaternary ammonium - containing polymers) 3351557 (ethylene/maleic anhydride copolymers - emulsion stabilizers), 3509059 (polymer containing acidic group, eg polyacrylic acid,

formed in situ, i.e. in the presence of nonionic surfactant), 3703480 (aminopolyureylene resins - to make a cationic fabric softener compatible with an anionic surfactant) 3723322 (carboxylated polysaccharide - as surfactant builder), 3962418 (cationic cellulose ether - thickener and hair conditioner ), 4213960 (polyaminoamides and quaternary ammonium homopolymers and copolymers - hair treatment agent), 4371517 (cationic polymers and anionic polymers). The use of poly-cationic materials, polyamines and polyamides to produce

in

the better softening achieved by using the classic fabric-softening quaternary compounds in fabric softeners for the rinse cycle is known, for example, from US patent 4237016, British patents 1576326 and 2041025A, Belgian patent 844122, European patent 13780 and West German patent 2925859A1.

Although a number of these known materials provide satisfactory cleaning and/or softening under a variety of different conditions, they still suffer from shortcomings in that they must be added to the rinse cycle, in that they do not provide sufficient softening - e.g. compared to softeners added during the rinse cycle - especially in washing conditions with hot water, i.e. at a temperature of 60°C and above, in that they require the formation of complexes of the cationic compound, in that water-soluble ones are used, e.g. mono higher alkyl, cationic quaternary ammonium compounds, and in that they are limited to liquid materials etc.

Although it is not unusual for the currently used laundry detergents and for common automatic household washing machines, especially in the USA, to be able to effect the washing/cleaning of soiled clothes using cold or warm washing water, especially delicate clothes, clothes to be worn in such as washed condition, or clothes of the type with permanent pressure etc., it is nevertheless recognized that a more effective cleaning (dirt removal) requires higher washing temperatures. Moreover, in Europe and in other countries, household washing machines are used at high temperatures of 60°C or above, up to the boiling temperature of the washing water. Although these high temperatures are favorable for the removal of dirt, an equally large advantage is not obtained in terms of the softening result.

The present invention is based on the recognition that the softening result obtained with a surfactant system based on a mixture of a non-ionic surfactant compound and a cationic, quaternary ammonium compound as softener is significantly improved by the use of a limited group of multifunctional compounds that increase the water-insoluble , cationic fabric softener's adhesion to the fabric being treated, thereby increasing the softening result. It has also been shown that the softening result is improved by using as the non-ionic surfactant one that has a fading point, alone or together with an amphoteric surfactant, which is at least 5° higher than the washing temperature which is at least 60°C. This improvement of the softening result is moreover achieved without any, or at least without any significant, deterioration of the washing result (ie the cleaning result).

A relationship between the cleaning result and the fading point for a mixture of non-ionic/cationic surfactant is known from US patents 4222905 and 4259217. More specifically, it is stated in column 5, lines 40-61, of US patent 4259217: "Methods for washing clothes with the detergents according to the present invention, which provides superior removal of grease and oily dirt and benefits for the treatment of the laundry, is described here. In these processes, the laundry detergents are used under such temperature conditions that the aqueous laundry detergent solution is at or close to (i.e. within approx. 20 °C of) the flash point (i.e. the temperature at which a phase rich in non-ionic surfactant separates from the laundry solution) of the non-ionic/cationic surfactant mixture. This can preferably be achieved by making these mixtures of non- ionic/cationic surfactant such that their flash point falls between about 0 and 95°C, especially from about 10 to 70°C, especially between m approx. 20 and 70°C, and more particularly from approx. 30 to approx. 50°C. During the washing operation, the temperature of the laundry solution is kept within this temperature range and within 20°C of the bleaching point temperature. The result is further improved if the temperature of the aqueous laundry solution is within approx. 15°C, more preferably within approx. 10°C, of the flash point temperature of the mixture of nonionic/cationic surfactant."

The need to work at wash temperatures at or below the flash point temperature is apparently based on the assumption that the flash point of the mixture of surfactants in the wash water corresponds to the temperature at which micelles of the surfactant aggregate to such an extent that these aggregates become so large and concentrated thought that they fall out of the solution, and therefore the observed opacity. Moreover, temperature increase will lead to complete phase separation of the water and the non-ionic surfactant, and as a result, their cleaning effect on the soiled laundry and the overall cleaning power will be lost.

Although, however, it is stated in US patent 4259217 that the mixtures of nonionic/cationic surfactant can "depending on the identity Qg concentration of the cationic component provide the advantages known in the art for such cationic compounds, e.g. .. softening effects for textiles", it is nevertheless clear that there was no recognition or suggestion that the softening effect of the cationic compounds can be significantly improved by using certain non-ionic compounds which, as such, have high flash point temperatures. This means that while in the two above-mentioned US patents a teaching has been put forward regarding the relationship between the fading point of the mixture of non-ionic/cationic compound, washing temperature and cleaning result, it has now been shown that it is the relationship between the fading point of the non-ionic compound alone (or the non-ionic compound, amphoteric compound and any electrolytes present in the wash water) and the wash temperature that effect the softening performance of the water-insoluble, fabric softening, cationic, quaternary ammonium compounds. In contrast to the requirement made according to the present invention to use non-ionic compounds with a high flash point temperature (ie above 60°C, especially above 90°C, and especially preferably above 100°C), it is preferred according to each of the two above-mentioned US patents to use non-ionic surfactants and combinations of non-ionic and cationic surfactants with relatively low flash points.

It was therefore completely unexpected that the softening action of the cationic softener could be dramatically improved, especially under hot water washing conditions, without reducing the nonionic surfactant. medium cleaning effect, by preparing the washing softener so that it has a bleaching point that is higher than the washing temperature.

The use of non-ionic surfactants with flash points of at least 60°C and higher than the wash water temperature is described in the simultaneously filed Norwegian patent application 853465. The use of amphoteric surfactants to increase the flash point of the non-ionic surfactant compounds to above the wash temperature is also described in the aforementioned Norwegian patent application and in more detail in connection with the non-ionic surfactants with a low flash point as referred to in Norwegian patent application 853426.

The present invention is based on the recognition that the softening effect of fabric softening, water-insoluble, cationic, quaternary ammonium compounds can be further improved by incorporating in the mixture of the non-ionic surfactant and cationic fabric softener a multifunctional additive that increases the adhesion of the cationic fabric softener to the textiles which is processed. Moreover, the cleaning effect of the non-ionic surfactant can also be improved at the same time.

It was on the basis of this realization that the present invention was developed.

The invention therefore aims to improve the softening effect of detergents containing fabric softeners of water-insoluble, cationic, quaternary ammonium compounds and non-ionic surfactant compounds,

without adversely affecting, and in some cases improving, the overall cleaning effect.

These and other objects of the invention which will

can be seen from the following description, is achieved by providing a laundry detergent and softener for washing and softening soiled textiles in an aqueous washing liquid at an elevated temperature of 60°C-100°C, the laundry detergent

and the plasticizer is characterized by the features specified in the characterizing part of claim 1.

According to a preferred embodiment of the invention, a laundry detergent and softener is provided which

is distinctive in that it includes

(a) 1-15% by weight of the nonionic surfactant, (b) 2-20% by weight of the fabric softening, water-soluble, cationic, quaternary ammonium compound, (c) 0.5-10% by weight of the multifunctional additive, wherein the amount of (b) + (c) is 5-22% by weight and the ratio between (b) and (c) is 10:1-1:3, (d) 0-10% by weight of the amphoteric surfactant, ( e) 25-80% by weight of at least one surfactant builder,

(f) 0-40% by weight of a bleaching agent,

(g) 0-7% by weight of a bleach activator,

(h) 0-4% by weight of each of dirt suspending agents, antigen deposition agents and thickening agents,

(i) 0-5% by weight anti-corrosion agents,

(j) 0-1% by weight organic chelating agents,

(k) 0-2% by weight of dyes, dyes, pigments, bluing agents and optical brighteners,

(1) 0-2 wt% enzymes,

(m) 0-0.5% by weight perfume,

(n) 0-10% by weight pH modifiers and buffers,

(o) 0-50% by weight inert fillers, flowability promoting agents and carriers, and

(p) 2-20% by weight of water.

According to a preferred embodiment of the laundry detergent and softener according to the invention, this includes 25-50% by weight surfactant builders, 0-5% by weight corrosion inhibitor, 0-1% by weight organic chelating agent, 0-40% by weight oxygen bleach, 0-7 % bleach activator, 0-4% by weight thickener and antigen depositing agent,

0.2 - 0.5% by weight optical brightener,

0.7-1.3 wt% enzyme, 0-0.5 wt% perfume and the rest up to 20 wt% moisture.

Although the reason for this is not fully understood, according to the invention, it has been shown that the best softening results from cationic textile softeners are achieved when the softener is very finely divided in the wash water (with a diameter from a few microns to less than 1 micron) and insoluble in water. The finely divided particles must of course be evenly, albeit arbitrarily, dispersed in the washing bath in order to uniformly come into contact with all items of clothing, towels, linen and other items being washed. Apparently, the softener particles are effectively captured by the textile fibers and adhere to them due to a combination of electrical, chemical and physical attraction. According to the present invention, the adhesion to the treated textiles is further improved and the softening effect of the cationic fabric softener is proportionally increased by adding a multi-functional additive to the fabric softener. Although these multi-functional additives as such contribute to the treated textiles becoming soft due to the affinity of the additives towards textiles, which is known from the above-mentioned state of the art, their mechanism of action in the washing-softening agents according to the invention for addition during the washing cycle does not appear primarily to include some direct softening action, but it is apparently based on one or both of the following factors: (1) their ability to stabilize the dispersion of the textile softening quaternary compound and (2) their ability to improve the contact between the quaternary compound and textile the material. Regardless of the mechanism by which the multifunctional additives function to improve softness, it is a distinctive feature of the invention that the softness of textile materials treated during the wash cycle is essentially equivalent to textile materials which have been treated in the usual way by adding a textile softener during the rinse cycle'. It is also possible to achieve a significant improvement in the cleaning effect when the preferred detergent softeners according to the invention are used.

The essential ingredients in the detergent softeners according to the invention are therefore the non-ionic surface-active agent, the textile softener of a water-insoluble cationic compound and the multifunctional additive. The use of an amphoteric surfactant in addition to the above-mentioned essential ingredients is strongly preferred, especially if the flash point of the non-ionic surfactant is the same as or lower than the wash water temperature.

Although the detergent softeners according to the invention can provide a good softening and cleaning effect in cold washing water, e.g. 20-30°C, or in warm washing water, e.g. 30-40°C or higher, the best results are obtained when the agents according to the invention are used in washing water with elevated temperatures of 60-100°C (boiling temperature).

The non-ionic surfactant compounds for the laundry detergent and softener according to the invention can be represented by the formula

in which R is a primary or secondary alkyl chain of 8-22 carbon atoms and n averages 3-30, or by the formula

wherein R^" is a primary or secondary alkyl chain of 7-12 carbon atoms and m averages 3-30.

The preferred alcohols from which the compounds of formula I are prepared include lauryl, myristyl, cetyl, stearyl or oleyl alcohol or mixtures thereof. Particularly preferred carbon atom numbers for R are C^-C-^g, with C^2<-C>15~ alkyl chains and mixtures thereof being particularly preferred.

The preferred carbon numbers for R 1 are C 8 and C 8 , including octyl, isooctyl and nonyl.

A typical example of a nonionic compound

with the formula I, lauryl alcohol is condensed with 15 mol of ethylene oxide. A typical example of a non-ionic compound of formula II is isooctylphenol condensed with 30 mol of ethylene oxide.

The amount of ethylene oxide will vary considerably depending on the hydrophobic compound, but as a general guide and rule, at least 15 mol of ethylene oxide and up to 30 mol of ethylene oxide per moles of hydrophobic compound are used to achieve flash point temperatures of at least 60 C or higher.

According to the invention, it is also aimed at

completely or partially replacing the above-described non-ionic surfactants with a high boiling point with the corresponding non-ionic surfactants with a low boiling point, i.e. with the same hydrophobic group, but condensed with only 3-14 mol of ethylene oxide. However, when the non-ionic surfactants with a low flash point temperature are used, it is also of significant importance

to include one of the amphoteric surfactants, as described in more detail below, to ensure that the mixture has a sufficiently high flash point. Preferably, not more than 50% by weight, especially not more than 30% by weight, and most preferably not more than 20% by weight, of the total content of nonionic surfactant is a compound with a low flash point.

The amount of the non-ionic surfactant will generally be the minimum amount which, when added to the washing water with or without the amphoteric surfactant, will provide a sufficient cleaning effect. In general, amounts of 1-20, preferably 3-10, and particularly preferably 4-9, % by weight of the mixture give a good cleaning effect.

As used herein, "fading point" means the temperature at which a curve of the light scattering intensity of the material plotted against the temperature of the washing solution sharply begins to increase to its maximum value, under the following test conditions:

The light scattering intensity is measured using

a "Model VM-12397 Photogoniodiffusometer manufactured by Societe Francaise d'instruments de controle et d<1>analyses, France (the instrument will hereafter be referred to as (SOFICA). The SOFICA sample cell and its lid are washed with hot

acetone and allow to dry. The surfactant mixture is prepared and dissolved in distilled water at a concentration of 1000 ppm. About. 15 ml of a sample of the solution is placed in the sample cell using a syringe with a 0.2 µm nucleopore filter. The syringe needle passes through the lid of the sample cell, so that the inside of the cell is not exposed to atmospheric dust. The sample is left in a bath with a variable temperature, and both the bath and the sample are subjected to constant stirring. The bath temperature is heated by turning the SOFICA heater and cooled by adding ice (heating rate = 1°C/min.). The temperature of the sample is determined by the temperature of the bath. The ice scattering (90° angle) intensity of the sample is then determined at different temperatures using a green filter and no polarizer in the SOFICA used.

According to the present invention, clouding point measurements are made for both solutions of the nonionic surfactant (at a concentration of 1% by weight) in distilled water and in water containing 10% NaCl although the latter concentration generally far exceeds the amount of salts and electrolytes actually encountered in normal use. If the melting point of the non-ionic surfactant measured in a 10% NaCl solution satisfies the melting point requirement according to the invention, there will therefore be no problem in preparing mixtures containing very high concentrations of building salts and other electrolytes, for example up to 85% by weight of the mixture, as well as the multifunctional additive.

It is known in this regard that the flash point temperature of a given material in the washing solution is dependent on the physical and chemical properties (such as CMC and solubility of the cationic, non-ionic and additional components contained in this material) and that it can be lowered by increasing the alkyl chain lengths of the nonionic surfactant compound and the amphoteric surfactant compound, by reducing the degree of ethoxylation of the nonionic component or by adding electrolytes, such as phosphates, polyphosphates, perborates, carbonates or sulfates, etc., especially in relatively small amounts (as eg from 1 to 15% by weight of a given material).

Due to the fact that water-insoluble, cationic softening compounds are used in the detergent softeners according to the invention, the cationic compounds will essentially have no effect on the bleaching point of the overall material. Due to the fact that the softening cationic compounds used according to the invention are water insoluble, in reality the flash point temperature of the overall mixture will be very difficult to measure because the mixtures are of course somewhat cloudy. The flash point of the non-ionic component, with or without the addition of electrolytes, is therefore determined in the absence of the cationic compound, and this gives a sufficiently accurate measure of the flash point of the overall mixture, including the cationic component.

For washing temperatures of 60-70°C, even in a mixture in which the multi-functional additive component is present, all of the above-described EO 15-30 non-ionic surfactants with formulas I and II should have flash points that are higher than the washing temperature.

However, for higher washing temperatures of 71-100°C, especially 80-100°C, it is necessary to use the stronger ethoxylated surfactants, for example with 25-30 mol of ethylene oxide per moles of hydrophobic compound. For these more elevated washing temperatures, the most preferred non-ionic surfactants are the C 8 -C 8 alkylphenols which are ethoxylated with 25-30, especially 28-30, moles, and especially preferably approx. 30 moles, ethylene oxide.

Alternatively and as discussed in more detail in the above-mentioned patent application 853465, it has now also been shown that for any of the non-ionic surfactants the flash point can be increased by as much as 40°C, generally by 5-20°C, by adding to the mixture an amphoteric surfactant compound, for example an amphoteric carboxyethylated higher fatty alkyl (eg coconut)-imidazoline compound, generally in an amount of 0.5-10, preferably 1-4, and particularly preferably 1-3 , wt% of the mixture.

According to a preferred embodiment of the invention which is particularly useful when washing soiled textiles in an aqueous wash bath at an elevated temperature of 80-100°C, the detergent therefore comprises in addition to (a) the non-ionic surfactant of the formula I or the formula II, (b) the water-insoluble, quaternary ammonium compound of formula III indicated below-

for, and (c) the multifunctional additive, (d)

an amphoteric surfactant in an amount sufficient to raise the flash point of the mixture above the elevated temperature of 80-100°C.

The other essential component in the present mixtures is the cationic fabric softener.

In order for the treated textiles to have sufficient softness, it is of essential importance that the cationic compound is water insoluble. As used herein, a compound is considered water-insoluble if its solubility in water at the washing temperature is below 1%, preferably below 0.5%. •-

It is generally desirable that the cationic softening compound is incorporated into the mixture in such a form that strong dispersibility in the washing liquid is ensured and therefore maximum adhesion to the treated laundry. Such dispersed particles in the washing liquid have sizes varying from less than 10 to 50 µm, and preferably particles with a size from less than 10 to 20 µm can be used for the cationic softening compound to achieve this effect.

Suitable fabric softening, water-insoluble quaternary ammonium compounds available commercially can be represented by the following formula:

wherein and R 2 , independently of each other, is a long-chain aliphatic radical of 16-22 carbon atoms, and R 3 and R 4 , independently of each other, are lower alkyl radicals, and X is a water-soluble salt-forming anion, such as a halide, i.e., chloride, bromide or iodide, a sulfate, acetate, hydroxide, methosulfate, ethosulfate or a similar inorganic or organic solubilizing mono- or dibasic radical. The carbon chain of the aliphatic radical containing 16-22, especially 16-20, carbon atoms may be straight or branched and saturated or unsaturated. The lower alkyl radicals have 1-4 carbon atoms and may contain a hydroxy radical.

The carbon chains are preferably obtained from long-chain fatty acids, such as those obtained from tallow and soybean oil. The terms "di-soya" and "di-tallow" etc. used here denote the starting material from which the long-chain fatty alkyl chains are formed. Mixtures of the above quaternary ammonium agents can also be used if this is desired. The preferred ammonium salt is a dialkyldimethylammonium chloride in which the alkyl group is derived from hydrogenated tallow or stearic acid. Specific examples of quaternary ammonium softeners of the formula III which are suitable for use in the detergent softeners according to the invention include the following: hydrogenated dietary algal dimethylammonium chloride, dimethyldistearylammonium chloride, dimethylstearylcetylammonium bromide, dimethyldicetylammonium chloride, disoyadimethylammonium chloride or the corresponding sulfate, methosulfate, ethosulfate, bromide or hydroxy salts thereof etc.

Dimethyldistearylammonium chloride is particularly preferred because of its superior softening action, bio-chemical degradability, low water solubility, availability and cost.

The amount of cationic fabric softener can vary from 2 to 20, preferably from 3 to 16, and especially from 6 to 15,% by weight of the mixture.

The weight ratio between the non-ionic surfactant and the cationic fabric softener will lie within the range 1:10-5:1, preferably 1:5-4:1, and particularly preferably 1:2-3.5:1.

The multifunctional additives used to increase the fabric softening, water-insoluble, cationic, quaternary ammonium compound adhesion to textiles include

(i) diquaternary ammonium compounds and

(ii) polymers of dimethyldiallylammonium chloride.

The diquaternary ammonium compounds are particularly preferred and are N-mono-higher-alkyl-penta-lower-alkyl-lower-alkane diammonium salts as represented by the following formula

wherein Rg denotes a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon group of 12-22, preferably 14-20, carbon atoms, Rg denotes a divalent alkyl group of 2-4 carbon atoms, and each of R-^q» and R^0 are the same or different and denote a lower alkyl group of 1-4 carbon atoms, and X is a salt-forming anion, such as chloride, bromide, iodide, sulfate, methyl sulfate, ethyl sulfate, or nitrate, etc. As a specific example, mention may be made of the compound sold under the trademark " Adogen 477"

which is N-tallow pentamethylpropanediammonium chloride.

The polymers of dimethyldiallylammonium chloride include both homopolymers and copolymers. The comonomers in the copolymers include acrylamide and methacrylamide. Acrylamide is particularly preferred.

The polymerization can be carried out using standard methods which are well known in the relevant art. The degree of polymerization is not particularly critical, and satisfactory results are obtained with polymers with molecular weights of from 500 to 10 7 . These polymers are commercially available.

The amount of the multifunctional additive will vary from 0.5 to 10, preferably from 2 to 8,% by weight of the total mixture. It is also preferred that the cationic fabric softener (b) and the multi-functional additive (c) are used within the amounts described above in a weight ratio between (b) and (c) of 10:1-1:3, preferably 6:1-1 :2, especially 4:1-1:1.

. As mentioned above, according to the preferred embodiment of the invention, the detergent softener further includes (d) at least one amphoteric surfactant. These do not

(1) alkyliminopropionate surfactants of the formula

(2) alkyliminodipropionate surfactants of the formula (3) alkyliminodipropionate surfactants with an ether bridge and of the formula (4) carboxyethylated higher fatty alkylimidazoline-based amphoteric surfactants of the formula

Mixtures of any of the amphoteric surfactants with each other indicated above can also be used.

In the above formulas (1) - (4), R is a straight or branched, saturated or unsaturated aliphatic radical with 7-20, preferably 8-18, especially preferably 10-14, carbon atoms, and R2 denotes a divalent lower alkyl radical with 1-4 carbon atoms.

A particularly preferred group of amphoteric compounds are the carboxyethoxylated higher fatty alkylimidazoline compounds of the formula (4) in which R^ is a straight or branched, saturated or unsaturated aliphatic radical with 7-20, preferably 8-18, particularly preferably 10-14, carbon atoms , and R 2 is a divalent lower alkyl radical with 1-4 carbon atoms, preferably 1 or 2 carbon atoms. Preferred groups R 1 include coco, tallow, heptadecyl, oleyl, decyl, especially coco (ie derived from coke fatty acid). The preferred group R 2 is ethyl (-Cf^Cl^-). The compound carboxyethylated cocoimidazoline is commercially available under the trademark "Rexoteric CSF" on a 100% active ingredient basis or as a 45% active ingredient solution.

The open-chain carboxyethylated higher fatty alkylamine derivatives are another effective group of amphoteric compounds. These include the above groups (1), (2) and (3), i.e. alkyliminopropionate surfactants and ether-bridged alkyliminopropionate surfactants. Carboxyethylated octylamine available under the trade name "Rexoteric "OASF" is a particularly preferred member of this group.

Although there are no fixed guidelines for the selection of combinations of nonionic surfactants and amphoteric surfactants or of the correct amounts of each to achieve the necessary bleach point temperature above the wash temperature to promote the softening effect of the cationic fabric softener, it is sufficient to use the amphoteric surfactant, together with the amount of nonionic surfactant specified above, in an amount of 0.1-10, preferably 0.5-4, particularly preferably 1-3, wt% of the total weight of the mixture. Generally, ratios of nonionic to amphoteric surfactant in the range of 1:5-10:1, preferably 1:3-6:1, especially 1:2-4:1, will give the desired high flash point and improved softening action, especially in combination with the multifunctional connection.

The detergents according to the invention are preferably provided in the form of free-flowing powders or granules, but they can also be available in liquid form.

The detergent according to the invention can also, and generally does, • include water-soluble building salts. Water-soluble, inorganic, alkaline builder salts that can be used alone together with the surfactant compound or in a mixture with other builders are alkali metal carbonates, borates, phosphates; polyphosphates, bicarbonates and silicates. (Ammonium or substituted ammonium salts can also be used). Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexamethaphosphate, sodium sesquicarbonate, sodium mono- and diorthophosphate and sodium bicarbonate. "The alkali metal silicates are useful building salts which also act so that the mixture becomes anti-corrosive to washing machine parts. Sodium silicates with a Na20:SiO2 ratio of 1.6:1-1:3.2, especially 1:2-1:2.8,

are preferred. Potassium silicates with the same conditions can also be used.

Another group of builders which are useful for the detergent-bleaching agents according to the invention are the water-insoluble aluminosilicates, . both of the crystalline and the amorphous type. Various crystalline zeolites (ie aluminosilicates) are described in British patent 1504168, US patent 4409136 and Canadian patents 1072835 and 1087477. An example of amorphous zeolites which are used

according to the present invention only, is found in Belgian patent 835351. The zeolites generally have the formula

wherein x is 1, y is 0.8-1.2, preferably 1, z is 1.5-3.5 or more, preferably 2-3, and w is 0-9, preferably 2.5-6, and N is preferably sodium. A typical zeolite is of type A or of a similar structure, with type 4A being particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of 200 milliequivalents per g or above, e.g. 400.

Other materials, such as clays, especially of the water-insoluble types, can be beneficial additives for the detergent softeners according to the invention. Bentonite is particularly beneficial. This material is primarily montmorillonite which is a hydrated aluminum silicate in which approx. 1/6 of the aluminum atoms may be replaced by magnesium atoms, and with which varying amounts of hydrogen, sodium, potassium or calcium etc. may be loosely combined. The bentonite in its more purified form (ie free of any grain or sand etc.) suitable for detergents invariably contains at least 50% montmorillonite, and its cation exchange capacity is therefore 50-75 meq. per 100 g bentonite. Particularly preferred bentonites are the Wyoming or "Western. U.S." bentonites sold under the trade name "Thixo-jels" with quality designations 1, 2, 3 or 4. These bentonites are known to soften textiles, as described in British Patents 401413 and 461221 .

Examples of organic, alkaline, sequestering builder salts that can be used alone with surfactants or in a mixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium aminopolycarboxylates, e.g. sodium or potassium ethylenediamine tetra-acetate, sodium or potassium nitrile triacetate or triethanol-ammonium-N-(2-hydroxyethyl)-nitrile diacetate. Mixed salts of these polycarboxylates are also suitable.

Other suitable builders of the organic type include carboxymethyl succinates, tartronates and glycolates. The polyacetal carboxylates are particularly valuable. The polyacetal carbox songs and applications in detergents are described in US Patents 4144226, 4315092 and 4146495. Other patents relating to similar builders, including US Patents 4141676, 416993, 420111111. 4303777. Also European patent applications 0015024, 0021491 and 0063399 are relevant. Various other detergent additives or auxiliary additives may be present in the detergent to give it additional desired properties which may be of a functional or aesthetic nature. Small amounts of dirt suspending agents or dirt re-depositing agents can thus be included in the mixture, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose or hydroxypropyl methyl cellulose, or optical brighteners, e.g. cotton, amine or polyester whiteners, for example stilbene, triazole or benzidine sulfone materials, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene or benzidine sulfone etc., stilbene or triazole combinations being most preferred.

Bleaching agents, such as ultramarine blue, enzymes, preferably proteolytic enzymes such as subtilisin, bromelain, papain, trypsin or pepsin, as well as enzymes of the amylase type, bactericides, e.g. tetrachlorosalicylanilide or hexachlorophene, fungicides, dyes, pigments (dispersible in water), preservatives, ultraviolet absorbers, anti-yellowing agents such as sodium carboxymethylcellulose or a complex of C^ 2~ C22~ a^^^ a^ 0^ 10^' me^ C^2~C-^g-alkyl sulphate, pH modifiers and pH buffers, colourfast bleaches, perfumes or antifoams or suds suppressants, e.g. silicon compounds, can also be used.

For the sake of simplicity, the bleaches are generally classified as chlorine bleaches and oxygen bleaches. Chlorine bleaches can be represented by sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine) and trichloroisocyanuric acid (85% available chlorine). Oxygen bleaches can be represented by sodium or potassium perborates or potassium monopersulfate. The oxygen bleaches are preferred. Bleach stabilizers and/or activators, such as tetraacetylethylenediamine, may also be incorporated.

The amounts of components which may be present in the preferred aggregate detergents are, based on weight % (of active ingredient) based on the aggregate weight of the final product, as follows: (a) nonionic surfactant - 1-20, preferably 3-10, especially preferred 4-9, %, (b) quaternary ammonium textile softener - 2-20, preferably 3-16, especially preferred 6-15, %, (c) multifunctional additive — 0.5-10, preferably 3-8.%, (d) amphoteric surfactant - 0-10, preferably 0.1-5, particularly preferred 0.5-4, and most particularly preferred 1-3.%,

(e) alkali metal builder salts - 25-80, preferably 25-70,

and particularly preferred 25-50%, the rest being made up of detergent additives, fillers and moisture. Suitable areas for the detergent additives are: enzymes

- 0-2, especially 0.7-1.3, %, corrosion inhibitors - 0-5, preferably 0.1-2, %, anti-foaming agents and foam-suppressing agents - 0-4, preferably 0-3, for example 0.1 -3.%, dirt-suspending agents or dirt-repeating agents-

coloring agents and anti-yellowing agents - 0-4, preferably 0.5-3.%, dyes, perfumes, whitening agents and bluing agents in a total weight of 0-2, preferably 0-1.%, pH modifiers and pH buffers - 0-5, preferably 0-2.%, bleach - 0-40, preferably 0-25, for example 2-20.%, and bleach stabilizers and bleach activators 0-15, preferably 0-10, for example 0.1-8 , %. When choosing auxiliary additives, this will be done so that these are compatible with the main ingredients in the detergent.

Although the non-ionic surfactants with a high flash point are preferably the only surface-active cleaning compounds used in the detergents according to the invention, smaller amounts of other surface-active compounds, including for example anionic and zwitterionic compounds, can also be used, preferably in amounts of up to 20, especially up to 10, and especially preferred up to 5, weight%.

Examples of suitable anionic cleansing compounds include the water-soluble salts, e.g. the sodium, potassium, ammonium or alkylolammonium salts of higher fatty acids containing 8-20, preferably 10-18, carbon atoms.

Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, e.g. tallow, shortening, coconut oil, tallow oil or mixtures thereof. Particularly advantageous are the sodium and potassium salts of the fatty acid mixtures obtained from coconut oil and tallow, e.g. sodium coconut soap or potassium tallow soap.

The anionic group of cleaning compounds also includes the water-soluble sulphated and sulphonated synthetic surfactants with an alkyl radical of 8-26, preferably 12-22, carbon atoms in its molecular structure (the term alkyl includes the alkyl part of the higher acyl radicals).

Examples of the sulphonated, anionic surfactants are

the mononuclear aromatic higher alkylsulfonates, such as the higher alkylbenzenesulfonates containing 10-16 carbon atoms in the higher alkyl group in a straight or branched chain, e.g. the sodium, potassium or ammonium salts of

higher alkyl benzene sulfonates, higher alkyl toluene sulfonates, higher alkyl phenol sulfonates or higher naphthalene sulfonate. A preferred sulfonate is linear alkylbenzenesulfonate with a high content of 3 (or higher)-phenyl isomers and with a correspondingly low content (well below 50%) of 2 (or lower)-phenyl isomers, i.e. in which the benzene ring is preferably for a large part bound to the alkyl group's 3- or higher (e.g. 4, 5, 6 or 7) position and the content of isomers in which the benzene ring is bound to the 2- or 1-position is correspondingly low. Particularly preferred materials are disclosed in US patent 3320174.

Other suitable anionic surfactants are the olefin sulfonates, including long-chain alkenesulfonates, long-chain hydroxyalkanesulfonates or mixtures of alkenesulfonates and hydroxyalkanesulfonates. These olefin sulfonate surfactants can be prepared in a known manner by reacting SO^ with long-chain olefins containing 8-25, preferably 12-21, carbon atoms and having the formula RCH-CHR^, in which R is a higher alkyl group of 6-23 carbon atoms and R^ is an alkyl group of 1-17 carbon atoms or hydrogen, forming a mixture of sultones and alkenesulphonic acids which are then treated to convert the sultones to sulphonates. Other examples of sulfate or sulfonate surfactants are the paraffin sulfonates containing 10-20, preferably 15-20, carbon atoms, e.g. the primary paraffin sulfonates prepared by reacting long-chain α-blefins and bisulfites, and paraffin sulfonates with the sulfonate groups distributed far along the paraffin chain, as described in US patents 2503280, 2507088, 3260741 and 3372188 and West German patent. 735096, sodium or potassium sulfates of higher alcohols containing 8-18 carbon atoms, for example sodium lauryl sulfate or sodium tallow alcohol— sulfate, sodium or potassium salts of α-sulfofatty acid esters containing 10-20 carbon atoms in the acyl group, for example methyl α-sulfomyristate or methyl-α-sulfotalgate, or ammonium sulfates of mono- or diglycerides of higher (C10-Clg) fatty acids, e.g. stearin monoglyceride monosulfate, sodium and alkylolammonium salts of alkylethenoxyether sulfates prepared by condensing 1-5 mol of ethylene oxide with 1 mol of higher (C8~ci8^ alcohol, sodium higher (c1o~C18^~ alkylglyceryl ether sulfonates and sodium or potassium alkylphenolpolyethenoxyether sulfates with 1- 6 oxyethylene groups per molecule and in which the alkyl radicals contain 8-12 carbon atoms.

The suitable anionic surfactants also include the cg~Clo acylsarcosinates (e.g. sodium lauroyl sarcosinate), the sodium and potassium salts of the reaction product of higher fatty acids containing 8-18 carbon atoms in the molecule and esterified with isethionic acid, and the sodium and potassium salts of Cg-C^ the g-acyl-N-methyltaurides, e.g. sodium cocosylmethyltaurate or potassium stearoylmethyltaurate.

Examples of zwitterionic surfactants include the derivatives of quaternary ammonium compounds containing an aliphatic straight chain group of 14-18 carbon atoms and an anionic solubilizing sulfate or sulfonate group. Specific examples include 3-(N,N-dimethyl-N-hexadecylammonium)-2-hydroxypropane-1-sulfonate, 3-(N,N-dimethyl-N-tallowylammonium)-2-hydroxypropane-1-sulfonate and 6-N /N-(dimethyl-N-hexadecylammonium)-hexanoate.

Regardless of the form in which the laundry detergent is present, its use during the washing process is essentially the same. A particulate detergent is usually added to the wash water in an automatic washing machine, so that the concentration of this in the wash water will be 0.05-1.5,

as a rule 0.1-1.2%. The water to which it is added will preferably have medium or low hardness, e.g. 30-120 parts hardness per million, calculated as calcium carbonate, but both softer and harder water can be used with good results. The water temperature is 60-100°C. At the mentioned concentrations of

detergents, the pH of the wash water will usually be 7-11, preferably 8-10. At such pH values, the detergent works effectively as a cleaning agent and is not too aggressive towards the material being washed or towards the skin and will provide effective cleansing and softening. The weight ratio between laundry and washing water will usually be 1:4-1:30 or 1:10-1:30.

The detergents according to the invention provide significantly improved softening results at washing temperatures of at least 60°C compared to, for example, identical detergents, except that the non-ionic surfactant has a flash point below 60°C, for example a straight chain higher, e.g. . <~' i2~ <^ 15' fatty alcohol with 7-13 ethylene oxide units. This effect could not have been predicted from a knowledge of the state of the art because there was no known correlation between the flash point of the non-ionic surfactant and the softening result.

The procedures for the production of the detergent softeners described here are generally well known in the relevant art, and reference can be made in particular to US patent 4269722 according to which structured non-ionic powders with a relatively high density are produced from spray-dried base beads which are showered with non-ionic surfactant (which may contain other less common additives, such as colourant, perfume, whitener or bleach etc.).

Flash point values (°C) for various nonionic surfactants at a concentration of 1 wt% and for mixtures of nonionic/amphoteric surfactants at a concentration of 1 wt% were measured in distilled water and in 10% NaCl and are reproduced below.

The invention will now be described using the following illustrative examples. Unless otherwise stated, all parts and percentages are based on weight.

Example 1

Using 100 g of each of the mixtures A,

B and C, bath towels and hardened cotton terry cloth are washed for approx. 20 1 water at 60°C.

The softness of the washed textiles is judged by a panel of 4 experts for several repetitions after cumulative washing. Each of the detergent softeners is given a score according to a scale from 1 to 10, of which 10 is the highest score and represents the degree of softness achieved with a softener (dimethyldistearylammonium chloride) added during the rinse cycle. According to this scale, both fabric softener A and fabric softener B received a score of 8-10. The fabric softener C received a score of 4-5.

In addition, detergents A and B are evaluated to determine their overall removal of dirt and stains on 10 different types of soiled textiles and are found to provide comparably excellent cleaning results.

Example 2

Each of the detergent softeners below is compared to determine their softening effect under the same conditions as described in Example 1.

The following results are reported for the softening effect on bath towels and hardened cotton terry cloth:

E significantly better than D

G significantly better than D

F directionally better than D

E is directionally better than G

G directionally better than F

D is not according to the invention.

Example 3

A preferred recipe for a built powder or granular full detergent according to the invention is reproduced below together with wide concentration ranges:

Claims (6)

1, Fabric washing and softening agent for washing and softening soiled textiles in an aqueous washing liquid at an elevated temperature of 60-100°C, characterized in that it comprises on a weight basis (a) 1-20% of at least one water-soluble, non-ionic over- surfactant compound of the formula I or II wherein R is a primary or secondary alkyl chain of 8-22 carbon atoms, R<1> is a primary or secondary alkyl chain of 7-12 carbon atoms, and n and m both average 3-30, (b) 2-20% of at least one water insoluble, cationic, quaternary ammonium compound of the formula III wherein R^ and independently of each other are long-chain aliphatic C18-C22~<r>a<licals, and R^ and R4, independently of each other, are lower alkyl radicals, and X is a salt-forming anion, (c) 0.5- 10% of a multifunctional additive selected from the group consisting of diquaternary ammonium compounds of the formula wherein Rg is a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon group of 12-22 carbon atoms, Rg denotes a divalent alkyl group of 2-4 carbon atoms, each of the groups R1Q, R and R12 are the same or different and are lower alkyl of 1- 4 carbon atoms, and X is a salt-forming anion, and homopolymers of dimethyldiallylammonium chloride or copolymers of dimethyldiallylammonium chloride with acrylamide or methacrylamide, (d) at least one amphoteric surfactant in an amount of 0-10% selected from the group consisting of alkyliminopropionate surfactants of the formula alkyliminodipropionate surfactants of the formula alkyliminodipropionate surfactants with an ether bridge and with the formula and carboxyethylated higher fatty alkylimidazoline-based amphoteric surfactants of the formula and mixtures thereof, in which R denotes an aliphatic radical with 7-20 carbon atoms and R 2 denotes a divalent lower alkyl radical with 1-4 carbon atoms, with the proviso that the non-ionic surfactant (a) alone or that the combination of the non-ionic surfactant (a) and the amphoteric surfactant (d) causes the fabric softener when added to wash water at a concentration of 1% by weight, has a flash point that is higher than the washing temperature, and (e) the rest surfactant builders, auxiliaries for detergents, inert materials and water. 2. Fabric washing and softening agent according to claim 1, characterized in that it comprises on a weight basis (a) 1-15% of the non-ionic surfactant, (b) 2-20% of the water-insoluble, fabric-softening, cationic, quaternary ammonium compound, (c) 0.5-10% of the multifunctional additive, the amount of (b) + (c) being within the range 5-22% and the ratio between (b) and (c) within the range 10:1-1:3 , (d) 0-10% of the amphoteric surfactant, (e) 25-80% of at least one surfactant builder, (f) 0-40% of a bleaching agent, (g) 0-7% of a bleaching agent activator, (h ) 0-4% of each of dirt suspending agents, antigen deposition agents and thickeners, (i) 0-5% anti-corrosion agents, (j) 0-1% organic chelating agents, (k) 0-2% dyes, dyes, pigments, bluing agents and optical whitening agents, (1) 0-2% enzymes, (m) 0-0.5% perfume, (n) 0-10% pH modifying agents and buffers, (o) 0-50% inert fillers,, flowability enhancing agents and carriers and (p) 2-20% water. 3. Fabric washing and softening agent according to claim 1, characterized in that (e) comprises 25-50% ■ surfactant builders, 0-5% corrosion inhibitor, 0-1% organic chelating agent, 0-40% oxygen bleach, 0-7% bleach activator, 0-4% thickener and antigen depositing agent, 0.2-0.5% optical brightener, 0.7-1.3% enzyme, 0-0.5% perfume and the rest up to 20% moisture. 4. Fabric washing and softening agent according to claims 1-3, characterized in that R is alkyl with 12-15 carbon atoms, R"<*>" is alkyl with 8-9 carbon atoms, and m and n are both on average 15-30. 5. Fabric washing and softening agent according to claims 1-4, characterized in that the cationic compound (b) is dimethyldistearylammonium chloride. 6. Fabric washing and softening agent according to claims 1-5, characterized in that, on a weight basis, it includes at least 0.1% of the amphoteric surfactant (d).