EP0203486B1 - Detergent with dye and brightener transfer inhibiting additives - Google Patents

Abstract

A detergent for washing mixtures of colored and white or light colored fabrics comprising a mixture of a monionic surfactant, a completely or partially water-soluble polyvinyl pyrrolidone polymeric constituent, a water-soluble cationic compound, a builder salt and other standard detergent ingredients. The detergent is substantially free of anionic-active compounds and strong electrolytes and is effective in preventing the transfer of dyes and optical brighteners between fabrics during washing.

Description

The present invention relates to a detergent based on nonionic surfactants, which contains a combination of polymer components based on polyvinylpyrrolidone and cationic compounds, whereby a dye and brightener transfer from colored or lightened textiles to white or colored or unlightened textiles during the washing together is counteracted. The transfer of dyes, to which the brighteners are also to be counted, when washing colored and white or light-colored textiles together has been a problem which has been known for a long time and for which there have already been some proposed solutions, but not all of which can fully satisfy because they have little effect on a number of dyes or textiles, or they counteract the transfer of either only the dye or only the brightener. A detergent is known from DE-AS 22 32 353, the discoloration-inhibiting addition of which are polymer components based on polyvinylpyrrolidone. According to the teaching of this patent application, the detergents contain about 5 to about 40% by weight of the partially or completely water-soluble polymer component, based on the mixture consisting of nonionic surfactant and the polymer component. DE-OS 29 16 656 describes detergents with an addition of alkylpyridinium salts to prevent the transfer of optical brighteners from laundry items containing brighteners brightener-free items during washing. The detergents according to this patent application contain 0.5 to 10% by weight of an alkyl pyridinium salt, based on the total detergent. From DE-AS 12 24 698 it is known that by treating textiles that have undergone a color shift due to brightener transfer with solutions of tertiary, quaternary or branched-chain organic nitrogen bases or their salts, a color regeneration can be effected.

It has now been found that detergents containing nonionic surfactants, partially or completely water-soluble polymer constituents based on polyvinylpyrrolidone, builders and other customary detergent constituents, the mixture of anionic compounds being practically free, the transfer of both dyes and optical brighteners practically completely prevented if these detergents contain very small amounts of water-soluble cationic compounds and if they are substantially or completely free from strong electrolytes. This observation is surprising because even an extremely small addition of cationic compounds suppresses the transfer of dyes and optical brighteners far more than would have been expected in the prior art from the water-soluble polymer components or the water-soluble cationic compounds alone.

• a) der Formel I
  
  
  
          R¹_m R²_n N^⊕ X^⊖   (I)
  
  
  
  in der R¹ eine Alkyl- oder Alkenyl- oder Acyloxyethyl- oder Benzyl- oder Hydroxyalkylgruppe mit 8 bis 20 Kohlenstoffatomen ist, R² eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen ist, mit der Maßgabe, daß, wenn R¹ 8 bis 12 Kohlenstoffatome hat, m = 1 oder 2 ist und n = 3 oder 2 ist und wenn R¹ 14 bis 20 Kohlenstoffatome hat, m = 1 und n = 3 ist, und X^⊖ ein die Elektroneutralität der quartären Ammoniumverbindung herstellendes Anion ist oder
• b) der Formel II
  
  in der R³ Wasserstoff oder eine gegebenenfalls substituierte Alkylgruppe mit 1 bis 18 Kohlenstoffatomen, R⁴ eine Alkyl- oder Alkenylgruppe mit 10 bis 20 Kohlenstoffatomen oder eine Alkyl- oder Alkenylamidoethylgruppe mit 10 bis 20 Kohlenstoffatomen in der Alkyl- oder Alkenylgruppe und R⁵ eine Alkyl- oder Alkenylgruppe mit 10 bis 20 Kohlenstoffatomen ist und X die oben genannte Bedeutung hat
• c) ein C₁₀- bis C₁₈-Alkylpyridiniumsalz

in Frage.Quaternary ammonium compounds either come as water-soluble cationic compounds

• a) of formula I.
  
  
  
  R¹ _m R² _n N ^⊕ X ^⊖ (I)
  
  
  
  in which R¹ is an alkyl or alkenyl or acyloxyethyl or benzyl or hydroxyalkyl group having 8 to 20 carbon atoms, R² is an alkyl group having 1 to 4 carbon atoms, with the proviso that when R¹ has 8 to 12 carbon atoms, m = Is 1 or 2 and n = 3 or 2 and when R¹ has 14 to 20 carbon atoms, m = 1 and n = 3 and X ^{⊖ is} an anion which makes the quaternary ammonium compound electronically neutral or
• b) of formula II
  
  in which R³ is hydrogen or an optionally substituted alkyl group with 1 to 18 carbon atoms, R⁴ is an alkyl or alkenyl group with 10 to 20 carbon atoms or an alkyl or alkenylamidoethyl group with 10 to 20 carbon atoms in the alkyl or alkenyl group and R⁵ is an alkyl or alkenyl group having 10 to 20 carbon atoms and X has the meaning given above
• c) a C₁₀ to C₁₈ alkyl pyridinium salt

in question.

Partially or completely water-soluble polymer components based on vinylpyrrolidone can be homopolymers and / or copolymers of vinylpyrrolidone with a molecular weight in the range from about 10,000 to about 1,000,000. Particularly suitable Homopolymers have a molecular weight of about 15,000 to about 700,000. In copolymers which are suitable for the detergents according to the invention, the proportion of vinylpyrrolidone is at least about 50% of the copolymer. Suitable comonomers are, for example, vinyl acetate, acrylonitrile and maleic anhydride. The preferred molecular weight of suitable copolymers is in the range of about 20 to about 200,000.

The cationic compounds of the formula (I) used in combination with the polymer constituents based on polyvinylpyrrolidone are quaternary ammonium compounds which have one or two alkyl or alkenyl or acyloxyethyl or benzyl or hydroxyalkyl groups having 8 to 20 carbon atoms and, moreover, alkyl groups Contain 1 to 4 carbon atoms. Quaternary ammonium compounds of the formula (I) which contain an alkyl or alkenyl group having 14 to 20 carbon atoms and, moreover, three alkyl groups having 1 to 4 carbon atoms are also suitable. That is, R¹ is an alkyl or alkenyl or acyloxyethyl or benzyl or hydroxyalkyl group having 8 to 20 carbon atoms, R² is an alkyl group having 1 to 4 carbon atoms, provided that when R¹ has 8 to 12 carbon atoms, m = 1 or = 2 and n = 3 or = 2, and when R¹ has 14 to 20 carbon atoms, then m = 1 and n = 3. X ^⊖ represents an anion which makes the quaternary ammonium compound electroneutral. Examples of suitable ^ones compounds of formula (I) are dioctyl octyldodecyldimethylammonium chloride, hexadecyltrimethylammonium chloride or bromide, hexadecyldimethylbenzylammonium chloride, Methylditalgalkylhydroxypropylammoniumchlorid, Didecylmethylethylammoniumchlorid, Didodecyldimethylammoniumhydrogensulfat, dodecyl or tetradecyl trimethyl ammonium bromide or chloride, Talgalkyltrimethylammoniumchlorid, Octadecyltrimethylammoniumhydrogensulfat. A suitable compound of formula II is methyl 1-oleylamidoethyl-2-oleylimidazolinium methosulfate. The alkyl group can also be used as a water-soluble cationic compound Alkylpyridinium salt contains 10 to 18, especially 12 to 16 carbon atoms in the alkyl group. Suitable anions are, for example, the chloride or the hydrogen sulfate anion.

The polymer component based on polyvinylpyrrolidone is present in the detergents according to the invention in amounts of 0.5 to 8% by weight, based on the detergent as a whole. The proportion of the cationic compound is in the range from 0.01 to 2% by weight, the water-soluble polymer based on polyvinylpyrrolidone always being present in the detergent in a larger amount than the cationic compound. Particularly good results are obtained with detergents which contain 1 to 4% by weight of a polymer based on polyvinylpyrrolidone and 0.01 to 0.5% by weight of alkylpyridinium salt, the weight ratio of polymer to pyridinium salt preferably in the range from 10: 1 to 50: 1, in particular from 30: 1 to 40: 1.

Compounds which are derived from alcohols having 8 to 24 carbon atoms and to which alkylene oxide has been added are particularly suitable as nonionic surfactants. The alcohols can be of natural or synthetic origin, straight-chain or branched and saturated or unsaturated. Oxo alcohols and fatty alcohols, to which 2 to 20 moles of alkylene oxide are added per mole of alcohol, are particularly suitable. In general, the alkylene oxide is ethylene oxide and / or propylene oxide; Ethylene oxide is preferred. Particularly good results are obtained with nonionic surfactants which are derived from fatty alcohols; Coconut fatty alcohol and tallow fatty alcohol are preferred. To achieve particularly balanced properties, it is often advisable to use a combination of fatty alcohol alkoxylates with different degrees of alkoxylation.

In addition to the nonionic surfactants, the polymer based on polyvinylpyrrolidone and the cationic compound, this can Detergents also contain at least one other common constituent of detergents, powdered or granular, liquid or pasty products being present, depending on the composition of the detergents. An essential component of detergents according to the invention are builders, provided they are not strong electrolytes, which are present in particular in amounts of up to 50% by weight, based on the detergent as a whole. In addition to inorganic builders, organic builders, which are often polymers, are also suitable. Examples of such polymers are polyacrylic acid, which is optionally modified with maleic anhydride, and copolymers of vinyl acetate and maleic anhydride. Commercial products are available under the names Sokalan CP 5 ^(R) or Sokalan CP 2 ^(R) , from BASF. Such builders are generally present in amounts of up to 30% by weight, in particular up to 15% by weight. Other common constituents of detergents are, for example, bleaches, bleach activators and bleach stabilizers, heavy metal complexing agents, enzymes, foam regulators, dirt carriers, fragrances, non-anionic dyes, preservatives, fillers, and in particular for liquid or pasty embodiments, hydrotropic agents, opacifiers, viscosity regulators, organic solvents and water. Typical detergents according to the invention therefore have the following composition:

The detergents according to the invention not only have an excellent washing performance against greasy and pigment-like soiling, but they also extremely effectively suppress the transfer of dyes from colored textiles and from optical brighteners from textiles treated with brighteners to non-colored or light-colored textiles or to textiles not treated with brighteners, This means, for example, that mistakes in sorting colored laundry do not lead to unwanted discoloration; washing lightened and unlightened items together does not lead to color-changing brightener transfer. This effect can also be used to advantage in the manufacture of the textiles, for example after printing or dyeing, for textile finishing. Both the suppression of dye transfer and the suppression of brightener transfer in the detergents according to the invention are significantly more pronounced than could be expected from the sum of the amount of water-soluble polymers based on polyvinylpyrrolidone and water-soluble cationic compounds used. Corresponding to the other constituents of the detergents according to the invention, the detergents also have the properties that correspond to the other constituents. They therefore have, for example, good removability of bleachable soiling, of protein or starch soiling and a desired foaming behavior when hand-washed or when washing in the washing machine. What is important for the prevention of dye or brightener transfer in the agents according to the invention is the virtually complete absence of anion-active compounds in the detergents according to the invention, that is to say of anionic surfactants of the sulfate, sulfonate or acylcyanamide type and of alkali metal salts of fatty acids and of anionic dyes and anion-active optical brighteners, since these compounds impair the action of the cationic compounds added according to the invention. It is also important that the detergents according to the invention essentially or are completely free of strong electrolytes. In the context of this invention, “strong electrolytes” are understood to mean the salts of strong bases with strong acids. These are understood to mean, above all, soluble builder salts, for example alkali phosphates, sulfates, sulfonates, but not silicates, carbonates or borates or the alkali alumosilicates of the zeolite A, X, Y or P type known as water-insoluble detergent builders will. Strong electrolytes may be present in the detergent according to the invention to a maximum of about 10% by weight.

In the production of the detergents according to the invention, it is in some cases expedient to add the remaining constituents to a premix comprising part of the detergent constituents in a coordinated sequence.

Examples example 1

A detergent A with the following composition was produced:

This detergent A according to the invention was with a detergent B according to the prior art, in which the C₁₂- to C₁₆-alkylpyridinium chloride had been replaced by soda, with a detergent C, in which the polyvinylpyrrolidone was replaced by soda, and with a detergent D who had replaced the polyvinylpyrrolidone and the alkylpyridinium salt with soda.

In an automatic drum washing machine (Siwamat® 738), the two-eye washing process was carried out at 60 ° C, a water hardness of 16 ° d, each with 140 g detergent for pre-wash and main wash 3.5 kg colored laundry and colored fabric sections stained with naphthol dyes, reactive dyes or non-aftertreated Sirius light dyes and soiled with artificial stains, and then the remission (R values) on white textiles (cotton, polyester / cotton, polyamides, polyacrylonitrile and polyester) ) measured.

The following results were obtained:

The terry towel washed with detergent A according to the invention has the highest R value. The addition of only 0.08% by weight of alkylpyridinium chloride (detergent A) leads to an increase in the R value of 2.1 units compared to detergent B. According to the comparison between the polyvinylpyrrolidone-free detergents C and D, an increase in the R value of at most about 0.5 units would have been expected for an addition of alkylpyridinium chloride of the same size.

The differences in dye transfer prevention characterized by the R values are also clearly visible.

Claims (6)

1. Detergents containing nonionic surfactants, partly or completely water-soluble polymer constituents based on polyvinyl pyrrolidone, builders and other standard detergent ingredients, the detergent being substantially free from anion-active compounds, characterized in that it contains

   (i) 0.5 to 8% by weight and preferably 1 to 4% by weight of a partly or completely water-soluble polymer based on polyvinyl pyrrolidone

   (ii) 0.01 to 2.0% by weight of a cationic compound, preferably 0.01 to 0 5% by weight of a C₁₀₋₁₈ alkyl pyridinium salt,

   with the proviso that constituent (i) is present in a larger quantity than constituent (ii), the ratio by weight of (i) to (ii) preferably being 10:1 to 50:1 and, more preferably, 30:1 to 40:1 and the detergent containing at most 10% by weight strong electrolytes from the group of salts of strong bases with strong acids.
2. A detergent as claimed in claim 1, characterized in that the water-soluble cationic compound is a quaternary ammonium compound corresponding either to

   a) formula I
   
   
   
           R^¹ _mR^² _nN^⊕X^⊖   (I)
   
   
   
   in which R¹ is an alkyl or alkenyl or acyloxyethyl or benzyl or hydroxyalkyl group containing from 8 to 20 carbon atoms, R² is an alkyl group containing from 1 to 4 carbon atoms, with the proviso that, where R¹ contains from 8 to 12 carbon atoms, m = 1 or 2 and n = 3 or 2 and, where R¹ contains from 14 to 20 carbon atoms, m = 1 and n = 3, and X^⊖ is an anion establishing the electroneutrality of the quaternary ammonium compound,
   or

   b) imidazolinium corresponding to formula II

   

   in which R³ is hydrogen or an optionally substituted alkyl group containing from 1 to 18 carbon atoms, R⁴ is an alkyl or alkenyl group containing from 10 to 20 carbon atoms or an alkyl or alkenyl amidoethyl group containing from 10 to 20 carbon atoms in the alkyl or alkenyl group and R⁵ is an alkyl or alkenyl group containing from 10 to 20 carbon atoms and X is as defined above,

   c) a C₁₀₋₁₈ alkyl pyridinium salt.
3. A detergent as claimed in claim 1 or 2, characterized in that the water-soluble cationic compound is a C₁₂₋₁₆ alkyl pyridinium chloride or hydrogen sulfate.
4. A detergent as claimed in any of claims 1 to 3, characterized in that the nonionic surfactants are derived from natural or synthetic, linear or branched, saturated or unsaturated C₈₋₂₄ alcohols, onto which from 2 to 20 mol of alkylene oxide, especially ethylene oxide and/or propylene oxide, preferably ethylene oxide, per mol of alcohol have been added.
5. A detergent as claimed in any of claims 1 to 4, characterized in that the nonionic surfactants are derived from fatty alcohols, more especially coconut oil fatty alcohol and tallow fatty alcohol.
6. A detergent as claimed in any of claims 1 to 5, characterized in that it contains 10 to 20 % by weight tallow fatty alcohol + 5 to 15 mol ethylene oxide, 1 to 4 % by weight polyvinyl pyrrolidone, 0.01 to 0.5% by weight C₁₂₋₁₆ alkyl pyridinium salt, 0.1 to 3 % by weight foam inhibitor, 0.5 to 4 % by weight Na and/or Mg silicate, 10 to 40 % by weight sodium alumosilicate, 10 to 30 % by weight sodium perborate, 0.5 to 2.5% by weight heavy metal complexing agent, 0.5 to 3 % by weight cellulose derivatives, 0.1 to 1 % by weight enzymes 0.01 to 0.5% by weight fragrance, balance water, fillers.