FI86741C - COMPOSER OF A TVAETTMEDEL OCH UPPMJUKANDE MEDEL FOER ANVAENDNING I TVAETTCYKEL - Google Patents

Description

1 86741

The present invention relates to a composition for cleaning and softening textiles in a laundry wash cycle. - This invention relates to a composition for cleaning and softening textiles in a laundry wash cycle. More specifically, the present invention relates to softening compositions suitable for use in a laundry wash cycle, especially when using hot water, and the composition comprises a cationic quaternary ammonium compound as a plasticizer and a nonionic surface tension reducing agent having a cloud point above the washing temperature.

Mixtures that can be used to treat textiles to improve their softness and "feel" properties are known in the art.

When textile softeners are used in household laundry, they are typically added to the rinse water during a rinse cycle lasting only about 2-5 minutes. The user must therefore either monitor the laundry program or take other precautions so that the fabric softener is added at the right time. This requires the consumer to return to the washing machine just before or at the beginning of the rinsing cycle of the washing operation, which is obviously burdensome for the consumer. In addition, special care must be taken to use an appropriate amount of textile softener and · _; avoid overdosing, which may make clothing water: repellent when a greasy film precipitates on the surface of the fabric, - - as well as making the fabrics slightly yellow.

To solve the above problems, it has been known to use fabric softeners that are compatible with conventional laundry detergents so that the fabric softeners can be combined with the detergents in the same package for use during the wash cycle of the washing operation. Examples of such textile softener blends added to a wash cycle are disclosed in U.S. Patents 3,351,438, 3,660,286 and 3,703,480. with the detergents used.

But it is also known that the cationic softeners added to the wash cycle, either as a component of the detergent-softener mixture or as a fabric softener in the wash cycle, interfere with the clarifying performance of the detergent as well as the cleaning performance. As a result, attempts have been made to compensate to some extent for this interfering effect of detergent-softener compositions by using non-ionic surfactants, higher amounts of brighteners, carboxymethylcellulose, anti-yellowing agents, sealants, etc. However, little improvement has been achieved in softeners. a wide variety of detergents are used, most of which are anionic.

But several detergent compositions known in the art have also been reported which contain cationic plasticizers, such as quaternary ammonium compounds as plasticizers and nonionic surfactants. Representative of this technique include U.S. Patents 4,264,457, 4,239,659, 4,259,217, 4,222,905, 3,537,993, 3,583,912, 3,983,079, 4,203,872, 4,264,479, 3,951,879, 3,360. 470, 3,351,483, 3,644,203, etc.

Although many of these prior art recipes provide a satisfactory washing and / or softening effect under a wide variety of conditions, they still suffer from a lack of sufficient softening effect, for example compared to softeners added to the rinse cycle, especially under hot water washing conditions, i. 60 ° C. . temperatures and above; they also form complexes with the cationic compound; less emollient, water-soluble compounds, for example mono-higher alkyl-quaternary-ammonium cationic compounds, must be used; must be limited to liquid mixtures, etc.

I: 3 86741

Today, it is no longer uncommon to use existing laundry detergent mixtures and conventional automatic home washing machines, especially in the United States, to wash / clean dirty textiles using cold or warm washing water, especially in the case of delicate fabrics, so-called. wash-and-use textiles, permanently pressed fabrics, etc., but nevertheless it is considered that more efficient cleaning (removal of dirt stains) requires higher washing temperatures.

In addition, in Europe and other countries, home washing machines operate at temperatures of 60 ° C or higher, even at the boiling point of washing water. Although these temperatures are advantageous for stain removal, they are not equally beneficial for the softening effect.

The present invention is based on the finding that the softening effect is greatly improved in a detergent mixture based on a mixture of a nonionic detergent compound and a cationic quaternary ammonium compound acting as a softener when using a limited class of nonionic compounds known above the washing temperature. In addition, this improvement in the softening effect is achieved without any, or at least without any significant deterioration in the washing (i.e. cleaning) performance.

The relationship between the cleaning power and the same point of the nonionic / cationic detergent composition is known from U.S. Patents 4,222,905 and 4,259,217. More specifically, as shown in column 5, lines 40-61 of U.S. Patent 4,259,217: "Methods which can be used to wash textiles using the compositions of the present invention, which provide better removal of grease and oil stains and which have the advantage of gentle treatment of textiles, are used in these methods at temperature conditions such that the aqueous washing solution is either non-ionic. at or near the cloud point of the / cationic surfactant mixture (i.e., about 20 ° C from the cloud point, which is the temperature at which the phase rich in nonionic surfactant separates the wash solution). This can be advantageously achieved by adjusting 4,86741 of these nonionic / cationic p mixtures of a stress-reducing agent such that their cloud point occurs between about 0-95 ° C, especially between about 10-70 ° C, such as between about 20-70 ° C, most preferably between about 30-50 ° C Between C. During the washing operation, the temperature of the washing solution is kept within this temperature range and 20 ° C from the cloud point temperature. The performance is further improved when the temperature of the aqueous washing solution is about 15 ° C, more preferably about 10 ° C away from the cloud point temperature of the nonionic / cationic surfactant mixture. "

The requirement to work at wash temperatures coinciding with or below the cloud point temperature is apparently based on the fact that the cloud point of the surfactant mixture in the wash water corresponds to the temperature at which the surfactant micelles aggregate to such an extent that these aggregates become so large that come out of solution, resulting in the observed turbidity. If the temperature is further raised, it causes a complete separation of the aqueous phase and the non-ionic surface tension reducing agent, as a result of which their washing power over dirty textiles and other cleaning power is lost.

However, although U.S. Patent 4,259,217 discloses that nonionic / cationic compositions may, depending on the identity and concentration of the cationic component, provide advantages known in the art for such cationic agents. for example ... softens textiles ", however, it is clear that it does not recognize or suggest that the softening effect of cationic substances can be significantly improved by using certain non-ionic substances which themselves have high cloud point temperatures. That is, when U.S. Patents 4,222,905 and 4,259,217 show a relationship between a nonionic / cationic binder mixture, a temperature and a washing power, it has now been found that it is a relationship between a nonionic substance alone (or a nonionic substance); all electrolytes present in the wash water).

between the cloud point and the washing temperature, which affects the softening effect of the water-insoluble cationic quaternary anunonium compound used as a plasticizer 5 86741. In contrast to the requirement of this invention, nonionic compounds having a high cloud point temperature (i.e., above about 60 ° C, especially above about 90 ° C, even more particularly above about 100 ° C) are used in both U.S. Patent 4,222,905 and 4,259,217. non-ionic surface tension lowering agents with relatively low cloud points are preferred. Therefore, the nonionic surface tension reducing compounds used in the compositions described in these patents are ethoxylated fatty alcohols having up to 12 moles of ethylene oxide, preferably up to 9 moles of ethylene oxide, and having hydrophilic-lipophilic equilibrium (HLB) values of about 5-17, preferably about 6-15.

Thus, it was completely unexpected that the softening effect of the cationic softener could be so dramatically improved without reducing the washing performance of the nonionic surfactant by using nonionic surfactants which are higher fatty alcohols ethoxylated with at least 15 ethylene oxide molecules. above.

The present invention has been accomplished based on this finding. The essential features of the invention are set out in the appended claims.

. . It is therefore an object of the present invention to improve the softening effect; ; in detergent compositions containing quasi-· _ _ as plasticizers; ternary ammonium compound and nonionic detergent compounds without significantly adversely affecting the overall performance.

This and other objects of the invention, which will become apparent from the following description, have been accomplished by developing a laundry detergent. a mixture capable of washing soiled textiles in an aqueous washing liquid at an elevated temperature, • · at least from about 60 ° C to about 100 ° C to a boiling point of ... ·, and the mixture contains a non-ionic surface active: -: a substance with a cloud point above this elevated temperature, and a water-insoluble quaternary ammonium compound capable of softening the washed Textile. In a preferred embodiment, the detergent composition comprises at least one detergent additive, such as enhancers, thickeners, anti-fouling agents, anti-corrosion agents, bleaches, enzymes, colorants, sealants, optical brighteners, perfumes.

The non-ionic substances considered are limited only by their water solubility and their cloud point temperature. These criteria are preferably compatible because the high alkylene oxide content promotes both water solubility and high cloud point temperature.

Suitable nonionic surfactants are commercially available and are derived from the condensation of an alkylene oxide or an equivalent reactant and a hydrophobic containing reactive hydrogen. Hydrophobic organic compounds may be aliphatic, aromatic or heterocyclic, although the first two classes of compounds are preferred. Preferred hydrophobic types are higher aliphatic alcohols and alkylphenols, although others may be used, such as carboxylic acids, carboxamides, mercaptans, sulfonamides, etc. Ethylene oxide condensers give higher alkylphenols or higher fatty alcohols. represent the preferred classes of nonionic compounds. The hydrophobic moiety should normally contain. . at least about 6 carbon atoms, and preferably at least about 8 carbon atoms! atoms and may contain as many as about 50 · · · / carbon atoms and above, but the preferred amount is between about 8-22 carbon atoms, especially 10-18 carbon atoms with aliphatic alcohols and 12-20 carbon atoms with higher alkylphenols. The amount of alkylene oxide varies considerably depending on the hydrophobic, but the general guideline and rule is that at least about 15 moles of alkylene oxide per mole of hydrophobic compound should be used up to 30 moles of alkylene oxide per mole of hydrotropic compound to obtain cloud point temperatures. at least about * · "* 60 ° C or above.

7 86741

Preferred nonionic surface tension reducing agents can be represented by the formula RO (CH 2 CH 2 O) n H (I) wherein R is a primary or secondary alkyl chain containing from 8 to 22 carbon atoms and n is on average 15 to 30; or R '(E 2} -O- (CH 2 CH 2 O) m H (II) wherein R' is a primary or secondary alkyl chain of 4 to 12 carbon atoms and m is on average 15 to 30.

Preferred alcohols from which the compounds of formula I are prepared are lauryl, myristyl, cetyl, stearyl and oleyl alcohols and mixtures thereof. Particularly preferred values for R are C 1 -C 4 -C 1 -C 4, and C 1 -C 4 -C 1 alkyls and mixtures thereof are particularly preferred.

Preferred values for R 1 are C 8 -C 12, and C 8 and C 8, such as octyl, isooctyl and nonyl, are particularly preferred.

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

; Other non - ionic compounds which may be used are those obtained from the oxidation of organic acids such as higher fatty acids, rosin acids, tall oil acids, petroleum. : polyoxyalkylene esters of acids, etc. These esters usually contain from about 10 to about 22 carbon atoms in the acid moiety and from about 15 to about 30 moles of ethylene oxide or equivalent.

Other nonionic surface tension reducing agents include alkylene oxide condensates with higher fatty acid amides 8,86741. The fatty acid group usually contains from about 8 to about 22 carbon atoms and this is condensed with about 15 to about 50 moles of ethylene oxide in the preferred example. The corresponding carboxamides and sulfonamides can also be used as suitable equivalents.

The amount of the nonionic agent can be any amount which, when added to the wash water, provides a suitable cleaning effect. Usually amounts of about 6-30%, preferably about 7 to about 20%, and very particularly preferably about 14-16% by weight of the mixture are suitable for use.

The compositions of the present invention are intended for use primarily in household and commercial washing machines operating at high washing temperatures, especially water temperatures above about 60 ° C, especially above 80 ° C, and most preferably near the boiling point of water, i. at or above about 100 ° C. But these blends, which are particularly effective when used at these high washing temperatures, also have an improved softening effect even at lower temperatures below 60 ° C and up to 20 ° C and below.

When the mixtures are formulated for use over a very wide temperature range, for example between 20 ° C and 60 ° C, as well as at higher temperatures, and as suitable as possible for a wide variety of textiles, such as sensitive natural and synthetic fibers and textiles that are less sensitive to temperatures such as cotton, etc., the nonionic material is selected such that its cloud point temperature exceeds the wash water temperature by at least about 20 ° C, such as a nonionic material having a cloud point temperature between 80 ° C and 90 ° C. But where the mixture recipe is intended to be limited to use primarily at temperatures of 60 ° C or above, as is customary in European washing machines, as in industrial washing machines, the non-ionic substance may have significantly higher cloud points, e.g. 9 8 6 7 41 those above the 50 ° C wash temperature. Thus, when the washing temperature is 60 ° C, the nonionic agent should have a cloud point of about 65 ° C, preferably at least about 70 ° C and even up to about 90 ° C, preferably between about 70 ° C and 85 ° C. For wash water temperatures of 100 ° C, the cloud point of the nonionic compound is selected to be about 105 ° C to about 150 ° C, preferably 105 ° C to 120 ° C.

As used herein, the term "cloud point" means the temperature at which a graph representing the intensity of light scattering of a mixture relative to the temperature of a washing solution begins to rise sharply to its maximum value under the following experimental conditions:

The intensity of light decay is measured using a model VM-12397 photogoniodiffusion meter, manufactured by Societe Francaise d'instruments de controle et d'analyses, France (henceforth referred to as SOFICA). The SOFICA sample chamber and its lid are washed with hot acetone and allowed to dry. A mixture of the surface tension reducing agent is made and dissolved in distilled water to a concentration of 1000 ppm. A sample of approximately 15 ml of solution is placed in the sample chamber using a syringe with a 0.2 μm nucleus pore filter. The needle of the syringe pierces the lid of the sample chamber so that the inside of the chamber does not come into contact with atmospheric dust. The sample is left in a variable heat bath and both the bath and the sample are stirred continuously. The bath temperature is heated using a SOFICArn heater and cooled by adding ice (Heating rate = 1 ° C / min); the temperature of the sample is determined from the temperature of the bath. The light scattering intensity (90 ° angle) of the sample at different temperatures is then determined using a green filter without a polarizer in the SOFICA.

In the present invention, turbidity point measurements are made of solutions of nonionic substance (1% by weight) in both distilled water and water containing 10% NaCl, although the latter usually far exceeds the amount of salts and electrolytes actually observed in normal use. Thus, if the cloud point of a nonionic substance measured in a 10% NaCl solution satisfies the cloud point requirement of this invention, no problem should be formulated with 10,86741 mixtures containing very high concentrations of enhancer salts and other electrolytes, up to about 85% of the mixture.

In this regard, it is known that the cloud point temperature of a particular mixture in a wash solution depends on the physical and chemical properties (CMC and solubility) of the cationic, nonionic and other additional components contained in that mixture and can be reduced by increasing the alkyl chain length of the nonionic surfactant, or by reducing the degree of ethoxylation of the nonionic component, or by adding relatively small amounts of electrolytes such as phosphates, polyphosphates, perborates, carbonates, sulfates, and the like (such as about 1 to about 15% of the administered mixture).

Since water-insoluble cations and softening ylides are used in the present invention, the cationic compounds 11a have essentially no effect on the cloud point of the whole mixture. Because the cationic plasticizer compounds used in this invention are insoluble in water, it is very difficult to measure the cloud point temperature of the entire mixture because the mixtures are inherently somewhat turbid. Therefore, the cloud point of the nonionic compound is determined, with or without electrolytes in the absence of the cationic compound, and in this way a sufficiently accurate measurement of the cloud point of the whole mixture containing the cationic compound is obtained.

At washing temperatures of about 60 ° -70 ° C, all the non-ionic surface tension reducing agents described above, and in particular the cloud points above formulas I and III, give above the washing temperature.

However, at higher washing temperatures, 71 ° C-100 ° C, especially 80 ° -100 ° C, it is necessary to use more ethoxylated surface tension reducing agents, for example 25-30 moles of ethylene oxide per mole of hydrophobics. At these higher washing temperatures, the most preferred nonionic surface tension reducing agents are C8-C8 alkyls; 11,86741 phenols ethoxylated with 25-30 moles, especially with 28-30 moles and particularly preferably with about 30 moles of ethylene oxide.

As will be explained in more detail below, it has now been found that alternatively the cloud point of any nonionic compound can be raised up to about 40 ° C, usually about 5-20 ° C by adding an amphoteric surfactant to the mixture, e.g., a carboxyethylated higher fatty alkyl (e.g. coconut) imidazoline, an amphoteric compound, usually in an amount of about 0.5-30% by weight, preferably 1-20%, particularly preferably about 1-10% by weight of the mixture.

In a preferred embodiment of the invention, which is particularly suitable for washing soiled textiles in wash water at an elevated temperature of about 80 ° C to 100 ° C, the detergent mixture therefore comprises a nonionic surfactant of formula I or formula II and a water insoluble compound of formula III or formula IV. In addition to the quaternary ammonium compound according to the above, a sufficient amount of the amphoteric surface tension-lowering compound so that the cloud point of the mixture rises to an elevated temperature of 80 ° C to 100 ° C.

The other main ingredient in the recipes in question is a cationic textile softener. Cationic textile softeners usually contain at least one hydrophilic group with a negative charge and a hydrophobic group containing a quaternary ammonium atom that is positively charged.

In order to provide sufficient softness to the treated textiles, it is important that the cationic compound be insoluble in water. As used herein, a compound is considered to be insoluble in water if it has a solubility in water at a wash temperature of less than 1, preferably less than about 1/2.

It is usually desired that the cationic softener be added to the mixture in a form which ensures good dispersion in the washing liquid and therefore maximum adhesion to the treated textile. Such dispersed particles in the wash liquor are from about <10 to about 50, preferably from about 10 to about 20 for a cationic softener to provide this effect.

Suitable commercially known water-insoluble quaternary ammonium compounds which are textile softeners have the following formula: R1 - '\ X (III) _R2 ^ "^ R4_' + /.Ni r5- ^ X ~ (IV) ^ Xr7 wherein and R2 and R 1 and R 2 each independently represent a long chain aliphatic radical having from 16 to 22 carbon atoms, R 8 and R 4 and R 7 independently represent lower alkyl radicals, or R 1 may be a group -R 9 NHCR 8 where R 8 is long chain an aliphatic radical having 16 to 22 carbon atoms and a divalent alkyl group having 1 to 3 carbon atoms, and X is a water-soluble salt-forming anion such as a halide, for example chloride, bromide, iodine, sulfate, acetate, hydroxide, methosulfate, ethosulfate, or a similar inorganic or organic solubilizing monobasic or dibasic radical, the carbon chain of an aliphatic radical having 16 to 22 carbon atoms, especially 16 to 20 carbon atoms, may be ra or branched, and saturated or unsaturated. Lower alkyl radicals have 1 to 4 carbon atoms and may contain a hydroxy radical. Carbon chains are preferably obtained from long chain fatty acids such as those derived from tallow or soybean oil. The terms "disoyer" and "dithal", etc., as used herein, refer to the source from which the long chain fatty alkyl chain i3 86741 jut is derived. Mixtures of the above, as well as other water-insoluble quaternary ammonium surfactants, may also be used if desired. The preferred ammonium salt is dialkyldimethylammonium chloride in which the alkyl group is derived from hardened tallow or stearic acid, or di-higher alkylimidazolinium chloride. Specific examples of quaternary quaternary ammonium compounds of formula III suitable for use in the composition of the present invention include: cured diethyldimethylammonium chloride, dimethyl-distearyl-ammonium chloride, dimethyl-stearyl-ethyl-ammonium-bromide, dimethyl-dimethyl-dimethyl-ammonium bromide; their corresponding sulfate, methosulfate, ethosulfate, bromide and hydroxide salts, etc.

Examples of emollient quaternary ammonium compounds of formula IV are 1-methyl-1,2-diheptadecylimidazo-1-ynium chloride (bromide, methosulphate), 1,2-di-eicosylalkylamidoethyl-1-methylimidazinium chloride, methosulphate, etc.), 2-hexadecyl-1-methyl-1 - [(2-dodecylamido) ethyl] imidazolinium methyl sulphate, 2-heptadecyl-1-methyl-1 - [(2-stearylamido) ethyl] -imidazolinium methyl sulfate, 2-nonadecyl / henicosyl-1 - [(2-eicosyl / docosylimido) ethyl] -imidazolinium methyl chloride.

Dimethyl-distearylammonium chloride has been considered particularly preferred due to its superior good emollient effect, its dispersion in nature, low water solubility, easy availability and cost.

The amount of cationic fabric softener may usually vary from about 1 to 20%, especially from about 4 to about 16%, and particularly preferably from about 6 to 9% by weight of the mixture.

The weight ratio of nonionic surfactant to cationic fabric softener is between about 1: 1 and 5: 1, preferably about 1.5: 1 to 4.5: 1.

i4 86741 The detergent compositions of this invention are preferably supplied as free-flowing powders, but may also be in liquid form.

The detergent composition of the invention may also contain and usually contains water-soluble enhancing salts. Water-soluble inorganic time-enhancing salts can be used either alone with the detergent compound or in admixture with other enhancers, and are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, and silicates. (Ammonium or substituted ammonium salts may also be used). Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate and sodium monocarbonate, sodium sesquicarbonate. Alkali metal silicates are useful builder salts that also make the mixture corrosion resistant to washing machine parts. Of the sodium silicates, those with Na 2 O / SiO 2 ratios of 1.6 / 1-1 / 3.2, especially about 1/2 to 1 / 2.8, are preferred. Potassium silicates with the same weight ratios can also be used.

Another class of enhancers useful in this context are water-insoluble aluminosilicates, both crystalline and amorphous types. Various crystalline zeolites:. (i.e., aluminosilicates) are described in GB Patent 1,504,168, U.S. Patent 4,409,136, and CA Patents 1,072,835 and 1,087,477, all of which are incorporated herein by reference. An example of amorphous zeolites useful herein is available from BE Patent 835,351, which is also incorporated herein by reference. Zeolites have V ·; usually the formula: '(MO) - (Al-jO,) · (Si0o) · WHo0 2 x 2 3 y 2'z 2 where x is 1, y is 0.8-1.2 and preferably 1, z is 1 , 5-3.5 or higher and preferably 2-3 and W is 0-9, preferably 2.5-6 and: VM is preferably sodium. A typical zeolite is type A * · *: or similar in structure, and type A is particularly

II

is 86741 considered the best. Most preferably, the calcium ion exchange capacity of aluminosilicates is about 200 milliequivalents per gram, or greater, for example 400.

Other substances such as clay grades, especially water-insoluble types, can be used as additives in the compositions of this invention. Bentonite is particularly useful. This substance is mainly montmorillonite, which is a hydrogenated aluminosilicate in which about 1/6 of the aluminum atoms can be replaced by magnesium atoms and with which loosely varying amounts of hydrogen, sodium, potassium, calcium, etc. Bentonite in its purified form (i.e. free from gravel, sand, etc.) can be combined. ), which is suitable for detergents, always contains at least 50% montmorillonite and thus has a cation exchange capacity of at least about 50-75 milliequivalents per 100 g of bentonite. Particularly preferred bentonites are Wyoming or Western US bentonites sold under the name Thixo-Jels 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textiles, as explained in GB Patents 401,413 and 461,221.

Examples of organic temporal sequestering enhancer salts which can be used either alone with the detergent or in admixture with other organic or inorganic excipients are alkali metal, ammonium or substituted ammonium, amino polycarboxylates, for example sodium and potassium methylenediamine tetraacetate, sodium and potassium nitrilotriacetates and triethanolammonium N- (2-hydroxyethyl) nitrilodiacetates. Mixed salts of these polycarboxylates are also suitable.

Other suitable builders of the organic type are carboxymethyl succinates, tartronates and glycollates. Polyacetal carboxylates are of particular value. Polyacetal carboxylates and their use in detergent compositions are described in U.S. Patents 4,144,226, 4,315,092 and 4,146,495.

Other patents for similar enhancers include 4,141,676, 4,169,934, 4,201,858, 4,204,852, 4,224,420, 4,225,685, i6,86741, 4,226,960, 4,233,422, 4,233,423, 4,302,564 and 4,303 777.

European patent applications 0015024, 0021491 and 0063399 also deal with the same.

Several other detergent additives or adjuvants may be present in the detergent product to give it the desired properties, either functional or aesthetic in nature. Thus, minor amounts of dirt suspending or anti-staining agents may be added to the recipe, for example, polyvinyl alcohol, fatty amides, sodium carboxymethylcellulose, hydroxypropylmethylcellulose; optical brighteners, for example, brighteners for cotton, amine and polyester fibers, for example mixtures of stilbene, triazole and benzidine sulfones, especially sulfonated substituted triazinyltilbene, sulfonated naphthotriazolistilbene, benzidine sulfone, etc., are most preferred.

Sealants such as uitramarine blue; enzymes, preferably proteolytic enzymes such as subtilisin, bromelain, papain, trypsin and pepsin, as well as amylase-type enzymes; bactericides for example tetrachlorosalicylanilide, hexachlorophene; fungicides; dyes; pigments (water dispersible) preservatives; ultraviolet light absorbing agents; anti-yellowing agents such as sodium carboxymethyl cellulose, ^ ^ “^^ '^^ ΥΥΐ ^ Ι ^ οΙιοΙϊη 3a C ^ 2-Cyg_alkyl-. sulfate complex; pH regulators and pH buffers; bleaching agents which do not discolour colors, perfumes and anti-foaming agents or anti-foaming agents, for example silicone compounds.

Bleaching agents are generally classified as chlorine bleaches and acid bleaches for convenience. Chlorine bleaches are of the type sodium hypochlorite (NaOCl), potassium chloroisocyanurate (59% free chlorine) and trichloroisocyanuric acid (85% free chlorine). Oxygen bleaches 1 are represented by sodium and potassium perborates and potassium monopersulfate. Oxygen bleaches are preferred. Bleach stabilizing and / or activating agents, such as fetraacetylethylenediamine, may also be used.

The proportions by weight of the components which may be present in the preferred therapeutic compositions as a whole in% by weight (active ingredient) of the total weight of the final product are as follows: nonionic detergent - about 5 1 to about 30%, preferably about 7% - about 20%, especially 14-16%; a quaternary ammonium salt - about 1% to about 20 S, preferably about 4% to about 16%, especially about 6-9%; alkali metal enhancing salts - from about 20% to about 85% and preferably from about 35% to about 80% and especially from about 60 to 75%, and the rest detergent additives, fillers and moisture. Suitable ranges for detergent additives are: enzymes - 0 - 2%, especially 0.7 - 1.3%; corrosion inhibitors - about 0-40%, and preferably 5-30%; antifoams and anti-yellowing agents -0 to 10%, preferably 0.5 to 5%; colorants, perfumes, brighteners and sealants in a total weight of about 2% and preferably 0% to about 1%; pH adjusting agents and pH buffers - 0 to 5%, preferably 0% to 2%; bleaching agents - 0% to about 40% and preferably 0% to about 25%, for example 2 to 20 S; bleach stabilizers and activators 0 to about 15%, preferably 0 to 10%, for example 0.1 to 8%. The choice of additives is made so that they are compatible with the main ingredients of the detergent composition.

Although high cloud point nonionics are preferably the only surfactant compounds used in the compositions of this invention, small amounts of other surfactants may also be used, such as other: nonionic, anionic, amphoteric ion-containing compounds. use up to 5% by weight.

: - Examples of other non-ionic compounds are all of the above with less than 15 moles of alkylene oxide per mole of hydrophobic substance, for example 5-12 - - · moles of ethylene oxide per mole of hydrophobic substance.

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Examples of suitable anionic detergents are water-soluble salts of higher fatty acids, for example sodium, potassium, ammonium, alkylol ammonium salts containing about 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms.

Suitable fatty acids can be obtained from waxes and oils of animal or vegetable origin, for example tallow, coconut oil, tall oil and mixtures thereof. Particularly useful are the sodium and potassium salts of fatty acid mixtures derived from coconut oil and tallow, for example sodium coconut soap and potassium tallow soap.

The anionic class of detergents also includes water-soluble synthetic sulfate and sulfonate detergents having an alkyl radical of 8 to 26 and preferably about 12 to 22 carbon atoms in their molecular structure. (The term alkyl includes the alkyl moiety of higher acyl radicals).

Examples of sulfonated anionic detergents include higher alkyl mononuclear aromatic sulfonates, such as higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the higher alkyl group, either straight or branched chain sulfonate, high alkyl alkyl sulfonate, sodium, potassium and ammonium salts of naphthalene sulphonate. One preferred sulfonate is a straight chain alkylbenzenesulfonate having a high content of 3- (or higher) phenyl isomers and a correspondingly low content of 2- (or lower) phenyl isomers (well below 50%), i.e. the alkyl group is attached to the benzene ring primarily in position 3 or higher (e.g., 4, 5, 6, or 7), and the concentration of isomers in which the benzene ring is attached in position 2 or 1 is correspondingly low. Compounds considered to be particularly good are described in U.S. Patent 3,320,174.

Other suitable anionic detergents include olefin sulfonates such as long chain i9 86741 alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. These olefin sulfonate detergents can be prepared in a known manner by reacting SO 4 with long chain olefins containing 8-25, preferably 12-21 carbon atoms and having the formula RCH-CHR-, wherein R is a higher alkyl group having 6-23 carbons and R 1-4 is an alkyl group having 1-17 carbons or hydrogen to form a mixture of sultones and alkenesulfonic acids, which are then treated to convert the sultones to the sulfonate. Other examples of sulphate or sulphonate detergents are paraffin sulphonates containing about 10 to 20, preferably about 15 to 20 carbon atoms, for example primary paraffin sulphonates made by administering long chain alpha-olefins and bisulphites and paraffin sulphonate groups with sulphonate groups. react with each other as disclosed in U.S. Patents 2,503,280, 2,507,088, 3,260,741, 3,372,188 and DE Patent 735,096 to higher alcohols containing 8 to 18 carbon atoms, sodium and potassium sulfate. sodium lauryl sulfate and sodium tallow alcohol sulfate; sodium and potassium salts of alpha-sulfo-fatty acid esters containing about 10 to 20 carbon atoms in the acyl group, for example methyl alpha-sulfomyristate and methyl-alpha-sulfo-tallowate, mono- and diglycerides of higher (C 1 -C 4) fatty acids ammonium sulfates, for example stearin monoglyceride monosulfate; sodium and alkylol ammonium salts of alkyl polyethyleneoxy ether sulfates prepared by condensing 1 to 5 moles of ethylene oxide with one mole of a higher (C8-C18) alcohol; sodium higher alkyl (C ^ g-C ^ g) -glyseryyli-eetterisulfonaatit; sodium or potassium alkylphenol i.-polyethylene oxy ether sulfates having from about 1 to about 6 oxystethylene groups per molecule and wherein the alkyl radicals contain from about 8 to about 12 carbon atoms.

Suitable Union detergents also include C8-C18-acyl sarcosinates (for example sodium lauroyl sarcosinate), sodium and potassium salts resulting from the reaction of higher fatty acids with 8-18 carbon atoms, in which acids have 8 to 18 carbon atoms. esterified with isethionic acid, sodium and potassium salts of C 8 -C 6 acyl-N-methyl taurides, for example sodium cocoyl methyl taurate and potassium stearoyl methyl taurate.

Amphoteric surface tension reducing agents are commercially known and include derivatives of aliphatic amines containing a long chain of about 8 to 20 carbon atoms and an anionic water-soluble group such as carboxy, sulfo, sulfo, etc. These include, for example, N-long chain alkylaminocurboxylic acids, e.g.

R

1 and R-N-R-COOM; N-long chain alkyl iminodicarboxylic acids of the formula RN (R 2 COOM) J, wherein R is a long chain alkyl group, R is a divalent radical connecting the amino and carboxyl parts of the amino acid (e.g. an alkylene radical or 1-4 carbon atom), M is hydrogen or a salt-forming metal, R is hydrogen or another monovalent substituent (e.g. methyl or other lower alkyl) Examples of specific detergents include N-alkyl-beta-aminopropionic acid; Nodi propi is i acid and N-alkyl). i-N, N-d imetyl-glycine; the alkyl group may be derived, for example, from coconut fatty alcohol, lauryl alcohol, myristyl alcohol (or lauryl-myristyl mixture), hydrogenated tallow fatty alcohol, cetyl or stearyl alcohol, or a mixture of these alcohols. Substituted aminopropionic and iminodipropionic acids are often supplied in the form of a sodium or other salt which can be used in the same manner in the present invention. Specific amphoteric agents include sodium 3-dodecylaminopropionate and sodium 3-dodecylaminopropane sulfonate.

It has also been found that when amphoteric surfactants are added to a recipe with a nonionic surfactant and a water-insoluble cationic softener, the cloud point rises up to about 5 ° -40 ° C depending on the nonionic agent, the amphoteric agent and the two surfactants. relationship.

2i 86741

In particular, when the detergent composition is to be used in wash water at higher temperatures, e.g. 80 ° C-100 ° C, it is often preferred to add an amphoteric surface tension reducing agent and in some cases, with particularly high electrolyte loading, for example, it may be necessary to maintain a cloud point above the wash temperature.

It has also been found that a mixture of a nonionic / amphoteric surface tension reducing agent unexpectedly has a better washing performance when charged in the same amount by weight exclusively of nonionic. For example, when carboxyethylated higher-fatty alkyl imidazoline is used as the amphoteric, about 50-90% of the nonionic surfactant can be replaced with only about 10-40% of the amphoteric surfactant to provide the same or better softening (depending on washing temperature). for better washing performance.

The amount of amphoteric detergent can vary very widely depending on the specific nature and intended use of the recipe, as well as the nature and amounts of other specific ingredients, especially the nonionic surfactant. Usually, however, about 0.5-30%, preferably 2-20% by weight of the total recipe can be used.

As mentioned above, the amphoteric detergent can act synergistically with the nonionic detergent with respect to the washing performance and therefore the total amount of nonionic and amphoteric detergent in the detergent formulation can be significantly reduced, e.g. 1-20%, especially 5-10% of the mixture. The ratio of nonionic to amphoteric is not particularly accurate, but with a given weight of nonionic, the cloud point increases as the amount of amphoteric increases. Usually, the ratios of nonionic to amphoteric agent are about 1: 4 to 6: 1, more preferably 1: 2 to 5: 1, particularly preferably 1: 2 to 4: 1 give an improved washing result, as well as a softening result (where it is necessary to increase the nonionic cloud point of the substance above the washing ... temperature). In addition, within the above-mentioned amounts and ratios of 22,867,741, the nonionic / amphoteric detergent composition is fully compatible with the emollient cationic quaternary ammonium compound.

The so-called in addition to the active ingredients, other important ingredients are the salt or salts of the excipient and moisture. The filler salt helps to improve the mechanical properties of the product, usually by improving the flow rate and preventing the tendency to become sticky. It may also help promote the dissolution of the product in the wash water. Of the useful excipient salts, sodium sulfate is the best, preferably in anhydrous form. But other excipients such as sodium chloride, sodium acetate and alkali metal salts of such acids may also be used, as may starches, talc, silica and various other excipients which have the function of a carrier or support. The proportion of filler or mixture thereof is between 5-50%, preferably 10-30% and most preferably about 20%, especially when the anhydrous sodium sulfate is in the form of a filler salt. Moisture contents are normally 1-15%, preferably 5-12% and most preferably about 8%. When these ratios are used, the result is a product with good flowability, in particulate or functional form, or in granular form, which can be prevented from becoming too dusty by controlling the particle size and moisture content.

Regardless of the form of the laundry detergent, its use in the washing process is essentially the same. The mixture in particulate form is usually added to the washing water in an automatic washing machine so that its concentration in the washing water can be between about 0.05-1.5%, usually 0.1-1.2%. The water to which it is added is preferably of medium or low hardness, for example 30 to 120 ppm hardness, as calcium carbonate, but both softer and harder waters may be used. The temperature of the water may be 20 ° C to 100 ° C and is preferably 60 to 100 ° C in cases where the text. brick or laundry can withstand high temperatures without being ruined or colors fading. When it is desired to wash the laundry at a low temperature, the temperature is maintained between 20 ° -40 ° C and under these conditions good cleaning and softening also results. although the garment may not be 23 86741 as clean as when washed at higher temperatures. In said concentrations of detergent mixtures, the pH of the wash water is usually 7-11, preferably 8-10. At these ρΗ values, the mixture is effective as a detergent, and is not unsuitable for the material to be washed or for human skin, and washes effectively and softens. The weight ratio of laundry: wash water is usually about 1: 4 to 1:30, or 1:10 to 1:30.

The compositions of the present invention provide a significantly improved softening result at wash temperatures of at least 60 ° C compared to, for example, identical recipes with a cloud point of a non-ionic detergent below 60 ° C, e.g., a straight chain higher fat (e.g. C ^) alcohol having 7-13 ethylene oxide units. This effect could not have been predicted from the prior art because the correlation between the cloud point and the softening effect of the nonionic surface tension reducing agent is not known.

Turbidity values (° C) for various nonionic surfactants at 1% w / w concentrations were measured in distilled water and 10% NaCl.

Non-ionic surface tension lowering agent 10 Distilled water NaCl_ C12-C ^ 5 fatty alcohol EO 7: 1 43 + 2 <25 C ^ 2 ~ c ^ 5 ~ fatty alcohol EO 11: 1 85 + 2 59 + 2 C 1-4 C 1-4 fatty alcohol EO 15: 1> 100> 60

Iso-octylphenol EO 30: 1> 100> 60

Nonylphenol EO 20: 1> 100 72

Nonylphenol EO 15: 1 91 70

Nonylphenol EO 8: 1 45> 30

The following is a recipe for a typical fine powder detergent-softener mixture according to the invention, in which all parts and percentages are by weight: 24 86741

Relationship Δ

Iso-octylphenol EO 30: 1 (70% Al) 21.6

Sodium metasilicate 8.0

Sodium tripolyphosphate 28.0

Sodium pyrophosphate · 10 (^ O 24.0

Sodium orthophosphate 0.5

Nitrile triacetate (NTA) 8.0

Dimethyl distearyl ammonium chloride (93% Al) 8.0

Various inferior ingredients (eg perfume, optical brighteners, moisture, etc.)

The soiled textiles are washed at 60 ° C in about 20 liters of water containing 0,1 g of hardness ions per liter using about 100 g of mixture A.

Of the washed textiles, the softness was judged by a panel of four expert judges in a number of repetitions after cumulative washes. For comparison, an identical mixture is prepared except that instead of iso-octylphenol EO 30: 1, the same amount of iso-octylphenol EO 8: 1, C12-Cl5 fat is used in mixture A or C12-Cl5-fat-E0 ^ 0 ^ EO 7: 1, and each of these blends is evaluated in the same manner as Blend A. Each blend is rated on a scale of 1-10, with "10" being the highest rating and representing the same detergent blend (without cationic softener) and softener added to the rinse cycle (dimethyldistearyl ammonium chloride). On this scale, mixture A achieved a grade of 5-6. Each reference mixture scored only 2-3.

When isooctylphenyl EO 30: 1 is replaced by the same amount of nonylphenol EO 15: 1, nonylphenol EO 20: 1 or C 12 -C 15 fatty alcohol 20: 1, a score of 5-6 is also obtained.

Similar good results are obtained by replacing dimethyldiearearammonium chloride with dimethylhydrogenated dithalammonium chloride, diethyldisoylammonium chloride, dimethylstearylcetylammonium chloride or 2-hexadecyl-1-methyl-1 - [(2-dodecylamido) ethyl] ethyl] ethyl -methyl- 25 867 41 sulfone and their corresponding bromide, sulfate and hydroxide salts.

Methods for preparing the compositions described herein are well known in the art, and reference is made in particular to U.S. Patent 4,269,722, which discloses the preparation of relatively high density, enhanced nonionic powders from spray-dried spheres sprayed on the surface with a nonionic detergent. (which may contain minor amounts of other conventional additives such as colorant, perfume, brightener, bleach, etc.). This entire patent specification is incorporated herein by reference.

Claims (7)

26 86741 A laundry detergent composition capable of washing and softening soiled textiles in an aqueous washing liquid at an elevated washing temperature of at least about 60 ° C, characterized in that said composition comprises by weight (A) a surfactant detergent comprising substantially about 5-30% high cloud point a water-soluble nonionic surfactant having a cloud point of at least above about 60 ° C, said nonionic surfactant being at least one compound selected from the group consisting of 15 to 30 moles of alkylene oxide per mole of condensation product reactive compound, having from about 8 to about 50 carbon atoms, said compound (hydrophobic) being selected from the group consisting of aliphatic alcohols, alkylphenols, carboxylic acids, carboxamides, mercaptans and sulfonamides, and up to 5% of a second surfactant compound selected from the group consisting of (i) low cloud point own nonionic surfactants which are 5 to 12 moles of alkylene oxide condensation products per mole of hydrophobic, (ii) anionic surfactants selected from the group consisting of water-soluble salts of higher fatty acids containing about 8 to 8 moles. 20 carbon atoms, mononuclear aromatic C8-C26 alkyl sulfonates, long chain C8-C25 alkene sulphonates, long chain C8-C25 hydroxyalkanesulphonates, C1-C20-Paraffin sulphonates / C8-C20 alpha-sulphates fatty acid esters, mono- or diglycerides of C 10 -C 18 fatty acid sulphates, C 1 -C 6 alkyl (mono-pentaethyloxy) ether sulphates, C 1 -C 6 alkylglyceryl ether sulphonates, C 1 -C 6 alkylH-phenol (monohexaethane) (iii) amphoteric surfactants selected from the group consisting of long chain N-alkylaminocarboxylic acids, long chain N-alkyl iminodicarboxylic acids and carboxyethylated higher fatty alkyl over-imidazoline, 27,36741 wherein the long chain alkyl contains from 8 to 20 carbon atoms, and (iv) mixtures thereof; and (B) about 4 to about 16% of a water-insoluble cationic quaternary ammonium compound capable of softening the washed Textile selected from the group consisting of compounds of the following formulas: - "R 1. R 3 + ^ Isr X '(III) r 2 X Xr 4 and < - η _ ^ N] r5-C X- (iv) / \ r6 r7 wherein R1, R2, R5 and R8 independently represent a C15-C22 long chain aliphatic radical, R3, R4 and Ry each independently represent , or lower alkyl radicals, or Rg may be a group -RgNHCRg, wherein O Rg is a long chain aliphatic radical having 16 to 22 carbon atoms, and Rg is a divalent alkyl radical having 1 to 3 carbon atoms, and X is a salt-forming anion; the weight ratio of nonionic surfactant to cationic compound is between 1: 1 and 5: 1. Mixture according to Claim 1, characterized in that the non-ionic surfactant having a high cloud point is at least one compound selected from the group consisting of compounds of the following formula R 0 (CH 2 CH 2 O) n H (I) 28 86741 wherein R is a primary or secondary alkyl chain having about 8 to 22 carbon atoms and n averaging 15 to 30; and O- (CH 2 CH 2 O) m H (II) wherein R 1 is a primary or secondary alkyl chain having 4 to 12 carbon atoms and m averaging 15 to 30. Mixture according to Claim 2, characterized in that R is alkyl of 12 to 15 carbon atoms and R 1 is alkyl of 8 to 9 carbon atoms. Mixture according to Claim 3, characterized in that the cationic compound is dimethyldistearylammonium chloride. Mixture according to Claim 1, characterized in that the cationic compound is dimethyldistearylammonium chloride. The composition of claim 1, further comprising at least one detergent additive selected from the group consisting of inorganic detergent builder salts, organic detergent builder salts, stain suspending agents, anti-fouling agents, fatty amides, foaming agents. and antifoams, optical brighteners, dyes, pigments, sealants, anti-yellowing agents, enzymes, anti-corrosion agents, pH adjusting agents, pH buffers, bactericidal agents, fungicides, preservatives bleaches, bleach stabilizers, bleach activators, perfumes and water. A composition according to claim 1, characterized in that said high cloud point nonionic surfactant is at least one compound selected from the group consisting of compounds of formula 29 8 6 7 41 R0 (CH2CH2O) nH (I) ΚΗ ^ Ο ^ - ° - (ch2ch2 °) mH (Π) wherein R is a primary or secondary alkyl chain having about 8-22 carbon atoms, R1 is a primary or secondary alkyl chain having about 4-12 carbon atoms and n and m are each averaging 15-30; and wherein said second surfactant compound is an amphoteric surfactant selected from the group consisting of long chain N-alkylaminocarboxylic acids, long chain N-alkyl iminodicarboxylic acids and carboxyethylated higher fatty alkyl imidazetoline wherein ; said amphoteric surfactant being present in an amount such that the cloud point of the mixture is above 80 ° C; and the weight ratio of said high cloud point nonionic surfactant to said amphoteric surfactant is from 1: 1 to 6: 1.