DK145861B - CLEAR NON-GELING POWERFUL LIQUID CLEANER - Google Patents

Description

(19) DENMARK (β I \ Ra

^ 12) SUBMISSION WRITING (id 145861B

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Application No. 3472/73 (51) Int.CI.3 C 11 D 17/08 (22) Filing date 22 Jun. 1973 (24) Race day 22 Jun. 1973 (41) Aim. available Dec 24 1973 (44) Presented 21. March 1983 (86) International Application No. - (86) International Filing Day (85) Continuation Day - (62) Master Application No. -

(30) Priority 23 · Jun. 1972, 265721, US

(71) Applicant COLGATE-PALMOLIVE COMPANY, New York, US.

(72) Inventor Jack Thomas Inamorato, US.

(74) Associate Company Chas. Hude.

(54) Clear non-gelling powerful liquid detergent.

The present invention relates to a clear, non-gelling, powerful liquid cleaning agent containing no phosphate and nitrogen-containing builders useful as a powerful cleaning agent for washing soiled laundry and other clothing and fabrics.

Specifically, the invention relates to such a builder-free clear biodegradable liquid cleaner which acts in a similar manner to conventional industrial heavy duty laundry detergents containing or including phosphate builders or nitrilotriacetate builders.

t

LO

DO In recent years, there has been a growing awareness of potential ^ devastating effects on ecology that accompany the depletion of various pollutants in groundwater, streams and lakes.

^ Particularly undesirable is the large-scale depletion of compounds that 3 persist in the environment and have a detrimental effect on the quality of our waters. As a result of these concerns, manufacturers 2 145861 of detergents attempt to eliminate non-biodegradable synthetic organic detergents, i.e. branched chain alkylbenzene sulfonates as organic surfactants in industrial household laundry detergents. Concurrent with this research, there are extensive efforts to replace the polyphosphate builder components in these cleansers, so that the drained wash water for households and laundries does not cause the accumulation of phosphates in streams and lakes.

The elimination of these polyphosphates from detergents has not been without difficulty, as these materials have highly desirable builder effects, complex binding effects and dirt suspending effects, and the removal of these materials from the detergents results in significant loss of purity. A detergent comprising only active synthetic organic detergents does not provide the same cleaning effect as a combination of these detergents and the polyphosphates.

Currently, the only substitute for the polyphosphates, which seems to be about as good in terms of builder action and soil suspending effect, is the nitrilotriacetic acids and acetates, often referred to as NTA.

From the specification to Danish patent application No. 1908/72, acidifying to Danish, reference no. 14Q.108, there is known a cleaning agent which is composed to avoid the undesirable phosphorus and nitrogen-containing compounds from a pollution point of view. This detergent may contain a mixture of certain anionic and nonionic detergents, but is not formulated so that gelation of the mixture can be avoided.

The present liquid detergent is based on a combination of an ethoxamer sulfate and a nonionic synthetic detergent, both of which are easily biodegraded. However, the use of nonionic synthetic cleaners, although biodegradable, is not without disadvantages. The use of nonionic synthetic cleansers in liquid cleansers must be balanced against the tendency of these materials to gell when left in open contact with the atmosphere. Furthermore, after prolonged contact with the atmosphere, some of these nonionic synthetic cleansers are not readily dispersible in water and gels in contact with water. According to the present invention, it has been found that by using certain special nonionic synthetic cleansers this gelation phenomenon is reduced or completely eliminated, thereby producing nonionic biodegradable synthetic cleansers having cleansing properties similar to the previous ones. known with alkali-based detergents, and this may occur in the absence of polyphosphates and other inorganic builder salts or alkaline materials. Although the agent of the invention may contain a small amount of NTA or the like which acts as a complexing agent for metal to prevent discoloration of the products and the washed clothes, these small amounts of NTA and the like have no builder effect on the overall agent.

In the clear liquid products, various constituents help to solubilize other components so that the product is clear and concentrated, yet easily pourable. Repeated experimental washings further show that the purity of the biodegradable synthetic cleaners is roughly similar to other industrial builder-containing cleansers in terms of cleaning performance against realistic body dirt and in actual laundry in household washing machines against mixed loads, different conditions are encountered.

The detergent according to the invention is characterized in that it consists essentially of: (a) a synthetic detergent mixture of at least one nonionic synthetic detergent and an anionic synthetic detergent in a weight ratio ranging from 15: 1 to 1; which nonionic synthetic detergent is a 1: 0.1 to 1: 1 weight ratio of a C10-C15 fatty alcohol ethoxylate containing from 6 to 11 moles of condensed ethylene oxide, provided the number of moles of condensed ethylene oxide is from 2 / 5 to 8/11 of the average number of carbon atoms in the fatty alcohol and a C14-C20 fatty alcohol ethoxylate containing from 10 to 14 moles of condensed ethylene oxide, the number of moles of ethylene = oxide being 7/10 to 1 times the number of carbon atoms in the fatty alcohol, which is anionically synthetic detergent comprises a sulfated ethoxylated C10-C20 fatty alcohol containing approx. 2 to 6 moles of condensed ethylene oxide; (b) sufficiently much lower alkanol to solubilize the detergent mixture; and (c) water, which liquid cleaner is substantially neutral in water.

In the detergent of the invention, the low molecular weight non-ionic synthetic detergent is a non-ionic substance of the formula RO (C ^H ^O) nH, wherein R is an alkyl group preferably a straight chain alkyl group having 10 to 15 carbon atoms, R in general is in the form of a mixed alkyl and may comprise either a particular chain length or a mixture of up to all six; n is 6 to 11 provided that n is from 2/5 to 8/11 of the average number of carbon atoms in R; and the high molecular weight nonionic synthetic detergent is constituted by a nonionic substance of the formula RO (C2H4O) nH wherein R is an alkyl group preferably a straight chain alkyl group having an average of 14 to 20 carbon atoms and n is a number from 10 to 14, where n is from 7/10 to 1 times the number of carbon atoms in R. The anionic synthetic cleaner is an ethoxamer sulfate, i.e. poly = ethhenoxy sulfate of the formula RO (C 2 H 4 O} nSO 3 M, where R is a fatty alkyl of 10 to 20 carbon atoms, n is from 2 to 6 and preferably from 1/5 to 1/3 of the number of carbon atoms in R, and M is a salt-forming ion which is usually selected from alkali metals, ammonium, lower alkylamino or lower alkanolamino, and the cleaner may also contain a minor amount of a fluorescent clarifying system which is usually at least partially water soluble, the amounts of the nonionic and anionic synthetic cleansers, the fluorescent clarifying system, water and alcohol are such that the insoluble fluorescent clarifier is substantially in soluble form.

The novel liquid non-gelling cleanser containing no phosphate and nitrogen-containing builders according to the invention preferably contains 25 to 75% by weight of the nonionic synthetic cleaner and from 5 to 25% by weight of the anionic synthetic cleaner and 5 to 35 wt.% Water and 5 to 35 wt.% Of a lower alkanol.

The synthetic organic cleaners used according to the invention which give the concentrated clear liquid cleanser of non-gelling nature comprise the low molecular weight non-ionic condensation products of fatty alcohol with ethylene oxide or ethylene glycol optionally containing a small amount of propylene glycol. Normally, this condensation will be with ethylene oxide, which is cheaper and does not require removal of by-product water. Methods for preparing such compounds are well known, and these materials have previously been used in detergents, although their trough has generally been limited to being part of the entire active organic synthetic detergent portion of liquid detergents.

The low molecular weight nonionic substances which give the non-gelling properties of the invention are of formula 110 (O 2) 0, wherein R is an alkyl group preferably having a straight chain of 10 to 15 carbon atoms, and n is from 6 to 11, provided that n is from 2/5 to 8/11 of the average number of carbon atoms in R. Due to the methods of preparation, mixed alkyls are generally used and in order that the agent of the invention may have the desired non-gelling properties, it is preferred to use mixed alkyl chains in which the chain length is on average approx. Furthermore, the ethylene oxide which reacts with these mixed alkyls will also vary somewhat within the above range from 6 to 11. The ethylene oxide content may vary within this range, provided that the amount of ethylene oxide in the final product is within the parameters 2/5 to 8 / 11 of the average number of carbon atoms in the alkyl group. Since it is important to maintain the proper balance between the chain length of the fatty alkyl and the chain length of the ethylene oxide within the above ranges to obtain good cleansing properties along with non-gelling properties and compatibility with other materials, it has been found to be a preferred embodiment of the invention using a nonionic synthetic cleaner of the above formula wherein R is a mixed straight chain alkyl of 10 to 15 carbon atoms, with the average number of carbon atoms being about 12, and n is from 6 to 9, provided that n is from 2/5 to 3/5 of the average number of carbon = atoms in R. Preferred nonionic substances having a minimum of gel properties include "Neodol 25-7 "(R corresponds to mixed alkyls having 12 to 15 carbon atoms, n = 11 in average value) made by Shell Chemical Company.

The nonionic synthetic detergent portion of the highly active liquid detergent of the invention may contain up to 50% of a high molecular weight non-ionic synthetic detergent of the formula R0 (C2H2O) nH where R is a straight chain alkyl of 14 to 20 carbon = atoms, and n is from 10 to 14, provided that n is from .7 / 10 to 1 times the average number of carbon atoms in R. As with the low molecular weight non-ionic substances imparting the agent of the invention 6 145861, non-gelling properties are prepared. these more high molecular weight non-ionic substances also by reacting mixed alkyls with ethylene oxide chains containing different chain lengths in the range of 10 to 14 ethylene oxide radicals. Within this range, as mentioned above, there is a desirable hydrophilic-lipophilic balance which is necessary to obtain good purifying properties along with other desirable properties and compatibility with other detergent ingredients. As a rule, the alkyl group will have from 14 to 16 carbon atoms, and as a rule, the average carbon content in preferred compounds is from 14 to 15, and in the most preferred high molecular weight non-ionic synthetic cleaners for use with low molecular weight non-ionic substances, than 80% have a chain length of 14 to 15 carbon atoms.

Similarly, it is preferable to have from 10 to 12 ethylene = oxide radicals per minute. chain, and in the most preferred embodiment, these will, on average and preferably be equal to approx. 11 ethylene = oxide units per chain. A preferred high molecular weight nonionic substance to use in the agent of the invention is Neodol 45-11 "(R mixed alkyls having 14 to 15 carbon atoms, n = 11 in average value) made by Shell Chemical Company. The desired hydrophilic-lipophilic balance is maintained at to keep n equal to about 7/10 to 1 time R.

In addition to the chain lengths of the hydrophilic-lipophilic moieties of the high-molecular and low-molecular non-ionic synthetic cleaners described above, it is important to obtain the best purity and biodegradability that these moieties have certain configurations. The ethylene oxide chain will necessarily be linear and terminated with a free hydroxyl group. The alkyl groups should preferably be linear, even cm a minor degree of weak branching sawmill. carbon atoms adjacent to or two carbons atoms removed from the terminal carbon atom in a straight chain and away from the ethoxy chain can be tolerated, provided that this branched alkyl portion does not have a length of more than 3 carbon atoms. As a rule, the proportion of carbon atoms present in such a branched configuration will be quite small, rarely more than 20 or 10% of the entire alkyl content of carbon atoms. Although linear alkyls which are ultimately linked to ethylene oxide chains are highly preferred and result in the best purity, biodegradability and other important properties including non-gelling properties, intermediate or secondary bonding to the ethylene oxide in the chain may occur in minor amounts in such alkyls. and generally this amount will be less than 20% and preferably less than 10% thereof. With regard to the content of small amounts of propylene oxide in the ethylene oxide chain, it is preferred that the ethylene oxide chain consists essentially of ethylene oxide in general more than 80% and preferably more than 90% thereof.

The composition of the invention also contains an anionic synthetic detergent. This anionic synthetic detergent is a sulfated ethoxylated higher fatty alcohol of the formula R0 (C2H2O) nSO4M, where R is a fatty alkyl of 10 to 20 carbon atoms, n is from 2 to 6, it may be from 1/5 to 1/3 of the number of carbon atoms in R and M is a solubilizing salt-forming cation such as an alkali metal, ammonium, lower alkylamino or lower alkanolamino. As with the nonionic synthetic detergents, this anionic synthetic detergent is readily degradable and has the best purity when the fatty alkyl is bonded at the end of the polyoxyethylene chain, which is naturally end-linked to the sulfate group. Although slight branching of the alkyl chain can again be tolerated to a maximum of 10% of the carbon atom content, as stated above with respect to the nonionic synthetic detergents, this minor deviation from the linear structure must be particularly avoided in the anionic synthetic detergents. Furthermore, bonding in the center of the alkyl group to the polyoxyethylene = chain must be minimal, less than 10%, even such bonding should preferably be concentrated near the end of the alkyl chain. Among the alkyl = the groups of 10 to 20 carbon atoms are the preferred alkyls, those having 12 to 15 carbon atoms, and the most preferred are mixed alkyls containing 12, 13, 14 and 15 carbon atoms in the chain. The mixture is preferably one containing at least 10% of each chain length, and not more than 50% of a single chain length.

The ethylene oxide content of the anionic synthetic detergent is such that n is from 2 to 6 and preferably from 2 to 4, generally on average about. 3, especially when R is alkyl of mixed chain length from 12 to 15 carbon atoms. To maintain a desired hydrophilic-lipophilic balance when the carbon content of the alkyl chain is in the lower range of 10 to 20, the ethylene oxide content can be reduced, δ 145861 such that n is approx. 2, whereas when R has 16 to 18 carbon atoms, n may be from 4 to 6. The salt-forming cation may be any suitable solubilizing metal or radical, but will most often be alkali metal or ammonium. If alkylamino groups or lower alkanolamines are present, the alkyls and alkanols therein will usually contain from 1 to 4 carbon atoms, and the amines and alkanolamines may be monosubstituted, disubstituted or trisubstituted, and may be e.g. monoethanolamine, diisopropanolamine and trimethylamine.

The importance of using the right anionic synthetic detergent in the present compositions is demonstrated by the fact that similar alcohol sulphates in similar liquid detergents cannot wash as well as the present compositions containing the higher alcohol-ethylene oxide sulphates prescribed. For example, a higher alcohol sulfate in which the alcohol is mixed alcohols having 12 to 15 carbon atoms exhibits e.g. a noticeably lower purity in liquid agents as the agent of the present invention compared to the corresponding ethoxylated sulfate in the same agent. Even within the preferred range of alcohol-ethylene oxide sulfates, an improvement in purity of the agents containing an alcohol-ethylene oxide sulfate of mixed alcohols having 12 to 15 carbon atoms is observed, compared to other higher alcohol-ethylene oxide sulfates, such as an alcohol-ethylene oxide sulfate, wherein the alcohol has 14 to 15 carbon = atoms and having the same ethylene chain length. The preferred synthetic detergent is obtained from Shell Chemical Company and is referred to as "Neodol 25-33Λ which are sodium salts normally sold as a 60% active material containing about 40% aqueous solvents, a minor part of which is ethanol. Although Neodol 25 -3S is the sodium salt, the potassium salt and other suitable soluble salts can also be used in whole or in part in place of the sodium salt.

Examples of the higher alcohol polyethylene oxy sulphates which may be used as the anionic synthetic constituents of the present liquid detergents or in partial replacement thereof include: blended 2 to 15 normal ^ Primary alkyl triethene oxy sulphate, sodium salt; myristyl triethenoxy sulfate, potassium salt; n-decyldiethene oxysulfate, diethanolamine salt; lauryl diethene sulphate, ammonium salt; palmity1 = tetraethenoxy sulfate, sodium salt; mixed normal primary alkyl mixed tri- and tetraethenoxy sulfate, sodium salt; stearyl = pentaethenoxy sulfate, trimethylamine salt, and mixed C- Q Q g normalt usually primarily alkyl triethenoxy sulfate, potassium salt. Smaller amounts of the corresponding branched-chain synthetic cleaners and alkoxylated in the middle of the chain, such as those described above, but modified to have ethoxylation at a carbon atom in the middle of the chain, e.g. one which is four carbon atoms from the end of the chain can be used, but the carbon atom content of the higher alkyl will be the same. Similarly, the bond of a normal alkyl may be at a secondary carbon atom or two carbon atoms from the end of the chain.

In both cases, only the aforementioned smaller quantities will be present.

For most of the highly effective liquid detergents, it will be unnecessary and undesirable to use active detergents in addition to the high molecular weight nonionic and anionic agents described above. Nevertheless, for some applications, smaller amounts of supplementary synthetic cleansers can be used. These will generally be of the nonionic type, although in some compositions other anionic, cationic, amphoteric or ampholytic synthetic cleansers or surfactants of known type may be used. Eg. For example, can be used higher fatty acid esters of polyethylene glycols, block copolymers of ethylene oxide and propylene oxide, higher alkyl di-lower alkyl amine oxides, the sodium salts of sulfuric acid = the derivatives of higher fatty alcohol condensation products with ethylene oxide, triethanolamine lauryl sulphate, ligand chain alkylate , N-higher alkyl, N, N-di-lower alkyl = aminopropane sulfonates, amidosulfobetaines, betaines and amidobetaines. Description of such additional synthetic cleansers is found in the text Synthetic Detergents by Schwartz, Perry and Berch, published 1958 by Interscience Publishers, New York, pages 25 to 145 · It will be recalled that such materials are used only for special purposes and in small quantities compared to the combination of the non-ionic low molecular weight and high molecular weight higher fatty alcohol ethylene oxide and the anionic alkyl ethylene oxide sulfate and will generally be used when a special purifying property thereof is desirable for a given application.

10 145861

The fluorescent or optical brighteners or whitening agents used are important constituents of modern synthetic cleansers that give washed clothes and materials a clear appearance, so that the laundry is not only clean but also clean. Due to the variety of synthetic fibers found in textile materials used in cloths and other items which may act as laundry, and the importance of the substantivity of the detergent to the fibers, many different fluorescent detergents have been produced which can be incorporated into the available cleansers, often in mixtures. Clearing agents suitable for use on cotton, and clearing agents which are stable in the presence of oxidizing bleaching, are of course also important. Therefore, while it is possible to use only a single detergent for a given purpose, it is generally important in the compositions of the invention to use a mixture of detergents having good clarifying effects on cotton, nylon, polyester, and mixtures of such materials. , and which are additionally pale stable. A good description of this type of optical brightener is given in the articles Optical Brighteners and Their Evaluation by Per S. Stensby, a reprint of articles published in Soap and Chemical Specialties in April, May, July, August and September 1967, especially pages 3-5 ·

The cotton clearing agents, often referred to as CC / DAS clearing agents because they are derived from the reaction product of cyanuric acid chloride and the disodium salt of diaminostilbendisulfonic acid in a molar ratio of 1: 2, are bistriazinyl derivatives of 4,4'-diaminostilben-2,2'-disulphide. In most cases, CC / DAS is reacted with two moles of aniline or sulphanilic acid or methanilic acid and the product is further substituted on the triazine rings. Such compounds have the general formula 145861

XI

j? ° 3 Na

x ^ SOnNa I X

J R

where X may be either hydrogen or SO 2 Na and the R's may be those derived from aniline, morpholine, N-methylethanolamine or diethanolamine. Since some powerful laundry detergents are used in combination with bleaching agents, a bleach-stable clarifier will usually be used a benzidine sulfone disulfonic acid, a naphthotriazolylstilbenzulfonic acid or a benzimidazolyl derivative.

These compounds have the formulas SOJTa y

3 SO ^ To A

RNH— <py- “cH === cH— / \ ~ so ^ W '

Q = s__ch ch_c ^ n ~ P

R R

Wherein R may be hydrogen, lower alkyl, lower alkanol, lower aminoalkanol, anilino, morpholino, etc. The polyamide clarifiers which are particularly good for nylons are usually either aminocourmarin or diphenylpyrazoline derivatives. Unfortunately, none of these are particularly stable in the presence of chlorine bleaches. The compounds have the formula set forth below and the groups R and R * may be as previously indicated for substituents on the optical clarifiers, while X and Y may include such substituents as halogens and lower alkyls.

R

R ·· ^ | O-1

The polyester clarifiers, which are more important as polyesters are used to a greater extent in an increasing proportion of the textile materials7, generally have one of the following formulas, where R, X and Y have the previously stated meaning and Z can be selected from the groups of X and Y substituents . These clarifiers usually also serve to whiten polyamides.

r ~ cOc ~ X R »^ H) - ch— ch_ / ~ r \ -N-1” C0 ~ z 13 145861

The clarifiers are used in their acid forms or as salts. The. may be used as solids or in solutions and may be diluted with carrier powder. Although the chemical and physical forms may affect the clearance effects, the clearance activities for the same compounds based on the same active ingredient will be equivalent if the compounds are used in soluble forms. In the present compositions and in the resulting washing water, the detergents are sufficiently soluble to be effective and uniformly substantive to the materials of the laundry being washed.

Among the clarifiers used in the present systems are: "Calcofluor White" ALF (American Cyanamid); ALF-N (American Cyanamid); SOF A-2001 (CIBA); CDW (Hilton-Davis) "Phorwite" RKH (Verona ); CSL, acidic powder (American Cyanamid); FB 766 (Verona); "Blancophor" PD (GAF); UNPA (Geigy); 'tinopal' RBS (Geigy); and RBS 200 (Geigy). The acid forms or nonionic forms of the clarifiers tend to be solubilized by alcohols in the present compositions, while the salts tend to be water soluble.

Thus, a combination of such solvents and the detergent combination serves to keep the fluorescent clarifiers dissolved.

The lower alkanol used is preferably either ethanol or isopropanol, but may be any lower monovalent alcohol. Of the two preferred alcohols, ethanol is the most preferred because of a slightly greater solubility and more pleasant odor. If ethanol is used, it will usually be denatured, and of the denatured alcohols, those called SD40 or 3A are preferred. However, other denatured alcohols may also be used. The alcohols do not have to be anhydrous, and the small amounts of water normally found with them are considered to be part of the water components of the liquid detergents. Part or all of the alcohol may be replaced by divalent or trivalent lower alcohols which, in addition to having solubilizing ability and lowering the flash point of the product, may also act as antifreeze components and may improve the compatibility of the solvent system with particular product components. Among these compounds, the most preferred group includes the lower polyols / 2e $ to 3 carbon atoms, e.g. ethylene glycol, propylene glycol and glycerine, but the lower alkyl ether derivatives of these compounds, called cellosolver, can also generally only be used to a lesser extent.

The water used is preferably deionized so that it has a low content of ions which can form insoluble compounds. However, ordinary tap water can be used, provided that its hardness is sufficiently low so that in the preparation used there is no harmful precipitation of salts upon standing. When complexing agents are found, the hardness is of less importance, in which case even water with hardness can exceed 300 parts per minute. million equivalent of calcium carbonate is accepted. In general, however, the water hardness should be less than 150 parts per minute. million parts and most conveniently less than 50 ppm.

Where a complex binding agent is used, it may be any suitable compound including the aminopolycarboxylic acids and hydroxycarboxylic acids. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, hydroxyalkyl derivatives thereof, wherein the hydroxyalkyl group replaces one or more acetic acid groups, gluconic acid, ascorbic acid, glucono-Δ-lactone (which is converted to gluconic acid), citric acid, metered salts and salts thereof, especially salts, salts and salts thereof, sodium, potassium, etc., ammonium, alkanolamines and amines can be used. Other complexing or water softening agents of the inorganic type such as certain phosphates can be used in very small amounts if desired, but are not present in amounts sufficient to have a builder effect.

Additives may be present in the liquid cleaner to impart the additional properties either functional or aesthetic. Thus, dirt suspending agents or agents for preventing repositioning of dirt can be used, e.g. polyvinylal = carbon, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose, enzymes, e.g. protease amylases, thickeners, e.g. gums, alginates, agar, hydrotropes, e.g. sodium xylol sulfonate, ammonium benzene sulfonate, foam enhancers, diethanolamide of lauric formic acid, antifoaming agents, e.g. silicones, bactericides, e.g. tribromosalicylanilide, hexachlorophen, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet light absorbers, fabric softeners, mother-of-pearl shining agents, cloudiness agents, e.g. behenic acid, polystyrene suspensions and perfumes. Of course, such materials are selected for the properties desired in the finished product and so as to be compatible with the other ingredients of the product.

The pH of the powerful liquid detergent will usually be substantially neutral or only slightly alkaline. The agent according to the invention contains a minimum of alkaline material as such, since the removal of particulate dirt by the specially used nonionic and anionic synthetic cleansers is promoted in approximately neutral solutions. However, for various reasons such as solubilization and neutralization of various used detergents, a small amount of an alkaline material may be added. Suitable alkaline materials include mono-, di- and trialkanol = amines, alkylamines, ammonium hydroxide and alkali hydroxides. The preferred alkali materials are the alkanolamines especially the trialkanolamines and especially triethanolamine. A measurement of the pH of the liquid detergent using a glass electrode and a calomel electrode for reference shows a maximum of approx. 8. However, since the detergent system is essentially not aqueous despite the presence of a small amount of water, the pH reading may be false. A better measurement is obtained by measuring the pH of a 25% solution in water. This should normally be in the interval approx. 6.8 to 8.8. In aqueous objects to be washed, the pH will normally be in the same range.

The amount of the various components of the present powerful liquid detergents is important to achieve a uniform product and an acceptable powerful laundry detergent effect. In the absence of a noticeable builder content, it is very important that the product contains a substantial amount of synthetic cleansers. To promote the solubility of the fluorescent detergents and other constituents and to produce a clearly homogeneous and easily pourable liquid product, from 25 to 75% of the total liquid detergent concentrate must be nonionic fatty alcohol ethylene oxide condensation product in a mixture of from 40 to 50% by weight not low molecular weight ionic substance and from 10 to 50% by weight non-ionic high molecular weight as described above. The preferred range is from 30 to 60% total amount of nonionic substances, and in the most preferred embodiment, approx. 40%. It is preferred that the mixture of non-ionic substances comprise a known portion of low molecular weight non-ionic substance, since the non-gelling property of this material is more effective at higher concentrations. Accordingly, it is preferred to use a nonionic mixture of from 90% to 75% by weight of the low molecular weight nonionic substance and from 10 to 25% by weight of the high molecular weight nonionic substance and it is preferred to use completely low molecular weight non-ionic substances. For the greatest efficiency, the amount of the anionic ethoxamer sulphate must be in the range of approx. 5 to 20% and preferably approx. 1/4 of the total non-ionic content, i.e. preferably 10%. Suitable weight ratios of total amount of nonionic substance to anionic substance range from approx. 15: 1 to 1: 1, with the interval 8: 1 to 2: 1 being preferred, and 5: 1 to 3: 1 being the most preferred.

The concentration of fluorescent or optical brightening or whitening agent in the product will be from approx. 0.5 to 5% calculated on the basis of active ingredient, preferably approx. 1 to 3% and especially about

2%. These amounts are easily soluble in the clear liquid product and contribute significantly to the clearance of fabrics in the laundry. Generally, 25% and preferably at least 50% of the optical brightener will be a cotton brightener. It is preferred to use approx. 51 to 90% of a cotton clearing agent, the rest being one or more polyamide clearing agents, polyester clearing agents and chlorine stable clearing agents.

The lower alcohol will generally be found in a sufficient amount to help stabilize or dissolve the various components of the product such as the clarifiers. The amount used will generally be from 5 to 35%, preferably 5 to 25%. When used without supplemental diol or triol, the amount of alcohol will normally be from 5 to 20%, but when the supplemental polyol is used, the alcohol content can be reduced to from 5 to 15%, preferably approx. 5 to 10%. In such circumstances, the amount of polyol will generally be from 5 to 15%, preferably 10%. The percentage amount of water used will also generally be from 5 to 35%, and a preferred range is from 5 to 25%, with the most preferred range being from 15 to 20%. Similar considerations apply to determining the amount of water to be used as is the case. alcohols.

17 145861

The amount of complexing agent which does not act as a builder, when used, may range from 0.2 to 3%, preferably from 0.5 to 1.5% and especially 0.8%.

Given the many different additives that can be used for very different purposes, the amounts thereof will vary.

In general, however, it can be said that the total amount thereof should not exceed 10% and is preferably kept below 5% and especially less than about 10%. 3%. As a rule, individual components should not exceed 5%, preferably 3%, and most preferably 1% of the product. The use of several of such compounds can often significantly alter the properties of the liquid detergent and must therefore be avoided.

The powerful liquid cleaners according to the invention can be produced by simple fabrication techniques which do not require any complicated equipment or expensive methods. In a typical manufacturing method, the optical brightener can be suspended in the monovalent alcohol or the mixture of monovalent and polyvalent alcohol. If initially slurried in the monovalent alcohol, the polyhydric alcohol, if used, may subsequently be added. Then, water and, if necessary, a small amount of base such as triethanolamine are added, which helps to partially dissolve the previously suspended material but does not provide a clear solution. Addition of the combination of synthetic cleansers dissolves the remainder of the detergent and becomes a clear solution. Then, if used, the complex-binding agent can be added as the acid or salt (preferably sodium, potassium or amine salts) and stirring is continued until the solution becomes clear, which usually takes approx. 5 to 10 minutes. At this point, perfume and dye can be added to give the product its final desired look and smell. All the operations can be performed at room temperature, but suitable temperature ranges from 10 to 80 ° C and can be used if desired. Adding additives can be done at appropriate times in the process, but for the most part these will be added to the finished product. The resulting product will generally have a pH in the range of 6.5 to 8, e.g.

7.0, and a density in the range of 0.9 to 1.1, preferably from 0.95 to 1.05, and most preferably from 0.98 to 1.02. The viscosity of the product at 25 ° C will generally be from 20 to 200 centipoise, preferably from 50 to 150 centipoise, and will be in the higher portion of this range if a polyhydric alcohol is used to replace somewhat lower monovalent alcohol.

Using the available means is very simple and effective. Compared to known powerful laundry detergent powders, much less volume of the present liquids can be used to achieve dirt cleaning. In a typical and preferred composition of the invention containing ca. 40% of the condensate of fatty alcohol and ethylene oxide and 10% of ethoxamer sulfate are required e.g. only approx. 60 g or 1/4 cup of the liquid for a fully automatic washing machine of the type filled above, in which the volume of water can be from 52 to 63 1. The concentration of liquid detergent in the washing water is thus of the order of 0.1%, 1 g per. 1 or 1,000 parts per million.

Generally, the amount used will be from 0.7 to 1.5 g / ml.

1, which corresponds to 0.3 to 0.6 g per liter. 1 of the mixture of fatty alcohol and ethylene oxide condensation products from 0.075 to 0.15 g per liter. 1 of ethoxamer sulfate, from 0.01 to 0.05 g per 1 of the fluorescent or optical brightener, from 0.05 to 0.4 g per 1 of lower monovalent alcohol and from 0.005 to 0.03 g per 1 organic complex binding agent. The amounts of the other constituents of the liquid preparations may vary accordingly. Of course, equivalent results can be obtained by using larger amounts of a more dilute liquid detergent, but the larger quantity required will require additional packaging space and shipping space and will be less convenient for the consumer to use. However, the use of such more diluted products is considered to be within the scope of the invention if the relative amounts of the components are maintained. In other words, the present invention is not circumvented simply by diluting the liquid detergent with water, as the same end result is obtained because the washing water also serves to dilute the detergent down to its use concentration.

Although it is preferable to use wash water with reasonable hardness and at an elevated temperature, the invention is also useful for washing and washing other objects in hard water and in extremely soft water as well as in water at room temperature or below. Water hardnesses can thus range from 0 to 300 parts per year. million as calcium carbonate, and the washing temperatures can be from 10 to 80 ° C. Preferably, the temperatures will be from room temperature, 20 to 25 ° C, to 70 ° C. Although washing is usually carried out in an automatic washing machine, the washing being followed by rinsing and centrifuging or twisting, the cleaning agent can also be used for hand washing clothes. In that case, the concentration in water of the liquid detergent will often increase, and at times it may be of full strength to wash out dirt and discolorations which are otherwise difficult to remove. After completion of washing and centrifugation, it is common practice to dry the clothes in an automatic dryer immediately after, but such a separate drying operation is not necessary.

When the liquid detergent is added to water, whether the water is hot or cold, the detergent immediately dissolves uniformly in the wash water even in the absence of appreciable stirring. Detergents and detergents are brought into contact with all the laundry, and there is no local over-concentration of any of these materials. The washed clothes, when normal methods are followed, are exceptionally clean, and by comparative tests the product has been rated as being just as good as the best in the market being highly effective cleansers. Although it is a low foaming or non-foaming cleanser, and therefore very suitable for side-loading washing machines, excellent washing is also achieved in top-loading machines which normally use foaming cleansers. Repeated testing of soiled and re-soiled laundry items using the present agent and large amounts of commercially available builder-containing cleansers containing phosphate or NTA show that the soiling is repeatedly removed and no harmful buildup of dirt occurs. For the most part, users do not notice any noticeable differences between the washing properties of the present agent and the tested agents. Indeed, an advantage has been given to the present product.

If the low molecular weight non-ionic synthetic cleansers are omitted by the agent and replaced with high molecular weight non-ionic synthetic cleansers with a similar hydrophilic-lipophilic balance, the liquid gels in a short time when exposed to the atmosphere. The liquid detergents without sufficiently low molecular weight non-ionic substance, i.e. Furthermore, at least 50% of the nonionic synthetic cleaners to inhibit or eliminate this gelling are not properly dispersed in water after exposure to the atmosphere. If the liquid detergent gels and does not disperse properly in water, this means that the detergents are concentrated in small areas, resulting in uniform and patchy clearance.

The discovery of the present agents and their exceptionally good properties was unexpected because those skilled in the art did not expect to be able to produce a non-constructed strong-acting laundry detergent without the use of inorganic builder salts or EDTA or NTA to replace such builders. This was particularly surprising given the prior use of the present organic synthetic cleansers only as fine detergents, as their ability to remove dirt from clothing for powerful purposes was not recognized. It was also a contradiction to the conclusion many other researchers have made in this field in the past.

The use of the compositions of the invention without NTA has no detrimental effect on the substantivity of the optical cleaners, whereas complex binding agents of the NTA type or polyphosphate type can interfere with the uniform deposition of cleaners on laundry. Surprisingly, excellent whiteness values are actually obtained by the unique combination of the present nonionic and anionic substances. The detergent does not react with hypochlorite bleaches, whereas the NTA can undergo such reactions. Further, as previously mentioned, the various components of the detergents help to mutually solubilize each other and form a pourable clear liquid. The alcohols and water solubilize the system of detergents, and the detergent condensate helps to produce the best solubility and clear product. The low molecular weight non-ionic substance prevents the liquid synthetic detergent from gelling. Prevention of gel formation means the prevention of discoloration, because otherwise the discoloration of the laundry could occur as a result of deposits of gel which hold the detergent on only part of the laundry. This detergent liquid is easily biodegraded and does not mean that phosphate or NTA builders are added to the wash water.

The agent according to the invention is described in more detail in the following examples, where all parts and percentages are by weight, unless otherwise stated.

21 145861

Example 1.

A clear liquid cleaner of the following composition is prepared by slurrying the optical clarifier mixture in SD-40 alcohol followed by addition of water and triethanolamine with stirring. Then the non-ionic and the anionic synthetic cleanser is added and after a few minutes of stirring at moderate speed the solution becomes clear:

1: 1 mixture of C16-18 + 11E0 and C12-13-6.5 EO

40.00 R0 (C2H40) 3SO3Na (Neodol 25-3S, R = mixed primary alkyls of 12, 13, 14 and 15 carbon atoms) 10.00 SD-40 denatured alcohol 14.00

Triethanolamine 1.5

Optical Clarifier A 1.0

Optical Clarifier B 1.0

Optical Clarifier C *** 0> 17

Optical clarifier D 0.033

Perfume 0.35

Dye 0.002

Water to 100.0 * A = 4,4'-bis [(4-anilino-6-methylamino-5-triazin-2-yl) amino] -2,2'-stilbene disulphonic acid, sodium salt.

= 4,4'-bis [(4-anilino-6- [bis (2-hydroxyethyl) amino] ~ S-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid, sodium salt.

= 4-naphthotriazolyl-2-stilbenzulfonic acid, sodium salt.

= 2- (1,3-isoindazole) -2 '(naphth [1,2-d] oxalol) stilbene.

When the aforementioned detergent composition is tested by the open-glass gel sample, i.e. that the liquid detergent is placed in an uncovered beaker and observed for gelling, it does not gel after exposure to the atmosphere for 18 hours and is easily dispersible in water.

Example 2.

Example 1 is repeated except that the ratio of the constituents is varied from the 1: 1 ratio to the following ratio of high molecular weight non-ionic detergent, i.e. C16-18 + 11 EO, and low molecular weight synthetic detergent, i.e. C12-C13 + 6.5 EO varies as follows: (A) 0.1: 1 (B) 0.25: 1 (C) 0.5: 1 (D) 0.75: 1 When each of the above-mentioned samples are exposed to the gel sample in the opened beaker, do not gel for 18 hours and are easily dispersed by pouring into both hot and cold water.

Example 3

Example 1 is repeated while varying the total amount of nonionic synthetic detergent from 40% to the following with a concomitant increase or decrease in the total amount of water and alcohol: (A) 20% (B) 25% (C) 30% (D 45% (E) 50% (F) 60%

Claims (6)

Each of the aforementioned detergents was cleaned quite well and had excellent cleaning properties, although those with the lower percent non-ionic detergent and those with lower and higher percentages did not purify quite as well as those in which the amount of non-ionic materials was approx. . $ 40. Example 4. Example 1 is repeated except that the following anionic synthetic cleansers are used in place of "Neodol 23-3S": (A) CIO ether sulfate containing 2 moles of condensed ethylene oxide (B) C13 ether sulfate containing 2 moles of condensed ethylene oxide ( C) Cl6 ether sulfate containing 5 moles of condensed ethylene oxide (D) C10 ether sulfate containing 3 moles of condensed ethylene oxide (E) C18 ether sulfate containing 6 moles of condensed ethylene oxide. Each of the aforementioned detergent concentrations also has excellent cleansing properties and does not gel upon standing when tested in the open beaker gel sample. Patent claims. Clear non-gelling, powerful liquid detergent without phosphate and nitrogen-containing builders, characterized in that it consists essentially of: (a) a synthetic detergent mixture of at least one nonionic synthetic detergent and an anionic synthetic detergent in a weight ratio ranging from 15: 1 to 1: 1, which non-ionic synthetic cleaner is a 1: 0.1 to 1: 1 weight ratio of a C10-C15 fatty alcohol ethoxylate containing from 6 to 11 moles of condensed ethylene oxide , provided that the number of moles of condensed ethylene oxide is from 2/5 to 8/11 of the average number of carbon atoms in the fatty alcohol and a C14-C20 fatty alcohol ethoxylate containing from 10 to 14 moles of condensed ethylene oxide, the number of moles of ethylene oxide being 7 / 10 to 1 times the number of carbon atoms in the fatty alcohol, which anionic synthetic purifier comprises a sulfate an ethoxylated C10-C20 fatty alcohol containing about 2 to 6 moles of condensed ethylene oxide; (b) sufficiently much lower alkanol to solubilize the detergent mixture; and (c) water, which liquid cleaner is substantially neutral in water. A detergent according to claim 1, characterized in that the nonionic synthetic detergent comprises a nonionic C10-C15 fatty alcohol ethoxylate containing from 6 to 9 moles of condensed ethylene oxide, the number of moles of ethylene oxide being from 2/5 to 3/5 of the average number of carbon atoms in the fatty alcohol. Cleaner according to claim 1, characterized in that it further contains a cleaning agent. Purifier according to claim 1, characterized in that it further contains a complexing agent for calcium. Purifier according to claim 1, characterized in that the nonionic synthetic detergent comprises from 25 to 75% by weight of the agent; the anionic synthetic detergent comprises from ca. 5 to 25% by weight of the agent; the alcohol comprises from approx. 5 to 35% by weight of the agent, and the water comprises from ca. 5 to 35% by weight of the agent. An agent according to claim 5, characterized in that the total amount of non-ionic synthetic detergent comprises 40% by weight of the agent and the anionic synthetic detergent comprises 10% by weight of the agent.