Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3723—Polyamines or polyalkyleneimines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3719—Polyamides or polyimides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
  • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/395—Bleaching agents

Definitions

• the invention relates to a detergent based on nonionic surfactants or mixtures of nonionic and zwitterionic surfactants containing bleaching compounds and additives for protecting colored textiles from color changes and the use of this detergent for washing and bleaching soiled textiles at the same time.
• Organic active chlorine compounds for example dichloroisocyanurate
• these also have the same disadvantages as inorganic, so that textiles that are bleaching active compounds are sensitive, cannot be washed with detergents without damaging them, they contain bleaches to support the cleaning action. So far it has not been possible to eliminate this disadvantage of detergents of this type without reducing the bleaching effect to an unreasonable extent.
• DE-AS 22 32 353 relates to detergents based on nonionic surfactants and water-soluble vinylpyrrolidone polymers, the detergents being essentially free of anionic surfactants.
• These detergents which can also contain zwitterionic surfactants and bleaching peroxy compounds, improve the inhibitory effect on dye transfer when washing colored and white textiles together, but change the bleach-sensitive dyeings to a large extent.
• the object of the present invention was therefore to provide a detergent containing bleach based on nonionic and / or zwitterionic combinations with improved cleaning action against bleachable soiling, bleach-sensitive textiles being protected.
• detergents containing nonionic surfactants or mixtures of nonionic and zwitterionic surfactants, bleaching compounds and water-soluble polymers which are characterized in that they are synthetic, water-soluble, polymeric amino and / or amido group-containing compounds from the group of Contain polyethyleneimines, polyamines, polyaminamides and polyacrylamides together with active chlorine or active oxygen bleaches, develop good cleaning and bleaching effects, without having any appreciable damaging effect on colored textiles.
• Such polymers which can be used individually or optionally in combination with one another and optionally together with other water-soluble polymeric melamine or urea / formaldehyde compounds in the detergents according to the invention, are known, synthetically produced compounds which are used, for example, in the paper industry as retention agents better separation of paper fiber raw materials and fillers can be used. According to their structural structure, these polymers can be divided into four groups: polyethyleneimines, polyamines, polyaminamides and polyacrylamides, of which the polyethyleneimines, the polyamines and polyamides are particularly preferred.
• Suitable polyethyleneiniines are obtained by acid-catalyzed polymerization of ethyleneimine and can be modified by urea and epichlorohydrin or dichloroethane.
• Polyethyleneimines can contain primary, secondary or tertiary amino groups as well as quaternary ammonium groups.
• Aqueous solutions of polyethyleneimines react basicly. The molecular weight can be up to about 1,000,000.
• Polyamines are addition or conformation products from polyvalent aliphatic amines and substances with several reactive groups, e.g. Epichlorohydrin or alkylene dihalides. They therefore always contain several secondary, tertiary or quaternary nitrogen atoms, and possibly also hydroxyl groups in the molecule. Accordingly, they are hydrophilic, polar compounds that behave like polyelectrolytes and are water-soluble unless they contain large hydrophobic groups in the molecule. The polyamines react basicly in aqueous solution. Suitable compounds are described, for example, in US Pat. No. 2,969,302.
• Polyaminamides simultaneously contain amino and amido groups in the molecule. They are produced, for example, by the condensation of polybasic acids, for example dibasic, saturated, aliphatic C 3 to C 8 acids and polyamines, and also with substances which contain several reactive groups, such as epichlorohydrin. These compounds also react basicly in aqueous solution. Suitable polyaminamides are described, for example, in U.S. Patent No. 2,926,154.
• Suitable polyacrylamides are high molecular weight polymers with molecular weights of several million.
• carboxyl groups which are formed, for example, by partial hydrolysis, in addition to amido groups, anionic polyacrylamides are obtained, while polyacrylamides containing amino groups react in a basic manner in aqueous solution.
• amino groups can be introduced by reaction with alkali and hypobromite or hypochlorite.
• polymers mentioned have in common that they are water-soluble. Such polymers are commercially available products. Particularly suitable as an additive to the detergents according to the invention are the polyethyleneimines and polyamines which react strongly in water. Examples of commercially suitable, particularly suitable polyethyleneimines are “Retaminol E” and for polyamines, “Retaminol K”, from Bayer AG, Leverkusen, Federal Republic of Germany. These polymers can be added either alone or together with water-soluble polymers made from melamine or urea and formaldehyde. Examples of this are the commercial products "Pressal R 50" or "Melan 125" from Henkel, Düsseldorf, Federal Republic of Germany.
• polymers suitable for the detergents according to the invention are, for example, the water-soluble polymers based on alkyleneimine, acrylamide and described in "Encyclopedia of Polymer Science and Technology", John Wiley & Sons, Inc., New York, 1968, Vol. 9, p. 762 Melamine or urea u. Formaldehyde.
• the addition of these polymers to the detergents according to the invention, in combination with the above-mentioned polymers containing amino and / or amido groups, enhances the color-saving effect.
• the concentration of the polymers mentioned in a detergent according to the invention based on nonionic, zwitterionic or amphoteric surfactants is in the range from about 0.5 to 50% by weight.
• the application concentration of the detergent is in the range from 1 to 20 g / l of wash liquor, preferably in the range from 3 to 15 g / l.
• Addition products of 2-40, preferably 2-20, moles of ethylene oxide and 1 mole of fatty alcohol or oxo alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used as nonionic surfactants.
• Nonionic surfactants of the amine oxide or sulfoxide type can also be used.
• the zwitterionic or amphoteric surfactants contain both acidic groups in the molecule, such as, for example, the carboxyl, sulfo, sulfuric acid half-ester, phosphono- or phosphoric acid partial ester groups, and also basic groups, such as amino, imino or ammonium groups.
• Zwitterionic connections with a Quadruple substituted, ie quaternary ammonium group are called betaines if they also have a covalently bound acid group in the molecule and the positive and negative charge is balanced intramolecularly.
• the betaines also include the correspondingly substituted quaternary phosphonium and tertiary sulfonium compounds.
• the surface-active betaines generally have a higher molecular weight aliphatic hydrocarbon radical with a hyarophobic character and two lower alkyl radicals with 1 to 3 carbon atoms, which can be substituted by one or two hydroxyl groups or linked directly or via a hetero atom.
• the water-solubilizing carboxylate, sulfonate or sulfate group is linked to the ammonium nitrogen via the fourth substituent, which usually consists of a short-chain, optionally a double bond or an hydroxyl group-containing aliphatic radical.
• sulfonate betaines in which the anionic, water-solubilizing group is bonded directly to the long-chain, hydrophobic hydrocarbon radical responsible for the capillary activity.
• sulfobetaines can be obtained, for example, from the sultones which can be prepared from C 8 -C 20 - ⁇ -olefins with SO 3 and a tertiary amine with three short-chain aliphatic radicals.
• Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propane sulfonate; 3- (N-tallow alkyl-N, N-dimethylammonio) -2-hy d roxypropanesulfonate; 3- (N-hexadecyl-N, N-bis (2-hydroxyethyl) -ammonio-2-hydroxypropyl sulfate; 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) -ammonio) propane sulfonate; N -Tetraaecyl-N, N-dimethylammonioacetate; N-Hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonium acetate.
• Examples of preferred surfactants of the detergents according to the invention are fatty alcohol mixtures having 12 to 18
• surfactant component of a detergent according to the invention is the following combination of two different nonionic surfactants of the formula:
• This formula encompasses compounds in which R 1 is a straight - chain alkyl group and R 2 is 20 to 75 percent by weight, based on the alcohol on which the alkyl polyglycol ether is based, a C 1 - C 4 alkyl group and the rest is hydrogen, the total number of carbon atoms in R 1 and R 2 is 11 to 15, and n is a value of 5 to 9, and where n is selected so that the ethylene oxide content of the alkyl polyglycol ether is about 50 to 65 percent by weight.
• R 1 is a straight-chain alkyl group and R 2 is either hydrogen or 20 to 75 percent by weight, based on the alcohol on which the alkyl polyglycol ether is based, means a C1-C 4 alkyl group and the rest is hydrogen, the total number the carbon atoms in R 1 and R 2 is 6 to 10 and n is a value of 3 to 8, and where n is selected, the ethylene oxide content of the alkyl polyglycol ether was about 55 to 70 percent by weight.
• the quantitative ratio of the first-mentioned compounds in combination to the last-mentioned compounds is preferably 2: 1 to 1: 2; the total amount of surfactants is 10 to 30 percent by weight of the agent according to the invention.
• the nonionic surfactants of the formula I are fatty alcohol or oxo alcohol ethoxylates with a certain length of the carbon chain and a certain degree of ethoxylation. The surfactants mentioned are described in more detail in DE-OS 28 17 834.
• Addition products of 6 to 12 moles of ethylene oxide onto oxo alcohols or alkylphenols with 8 to 12 carbon atoms in the alkyl group are also useful.
• Mixtures of the nonionic surfactants mentioned with one another or with zwitterionic surfactants can also be used well.
• the active chlorine compounds used as bleaching agents can be inorganic or organic in nature.
• the inorganic active chlorine compounds include alkali hypochlorites, which can be used in particular in the form of their mixed salts or additive compounds on orthophosphates or on condensed phosphates such as, for example, on pyro- and polyphosphates or on alkali silicates.
• the organic active chlorine combinations in particular are the N-chlorine compounds in which one or two chlorine atoms are bonded to a nitrogen atom, the third valence of the nitrogen atoms preferably leading to a negative group, in particular to a CO or SO 2 group.
• These compounds include dichloro- and trichlorocyanuric acid, respectively their salts, chlorinated alkyl guanides or alkyl biguanides, or alkyl biguanides, chlorinated hydantoins and chlorinated melamines.
• H 2 0 2 compounds are sodium perborate tetrahydrate (NaBO 2 .H 2 O 2 • 3 H 2 0) and the monohydrate (NaBO 2 .H 2 0 2) of particular importance.
• H 2 O 2 -lieternde borates for example perborax Na 2 B 4 O 7 ⁇ 4 H 2 0.
• peroxy hydrates such as peroxycarbonates (Na 2 CO 3 .1.5 H 2 O 2 ), peroxypyrophosphates, citrate perhydrates, urea-H 2 O 2 - or melamine-H 2 O 2 -
• peroxycarbonates Na 2 CO 3 .1.5 H 2 O 2
• peroxypyrophosphates citrate perhydrates
• peracidic salts such as, for example, caroates (KHSO 5 ), perbenzoates, perazelainates or perphthalates, are replaced.
• Hydrogen peroxide (H 2 O 2 ) itself is also a suitable bleaching agent.
• water-soluble and / or water-insoluble stabilizers for the peroxy compounds together with these in amounts of 0.25-10 percent by weight.
• suitable stabilizers are alkaline earth metal silicates, such as magnesium silicate, or water-soluble organic complexing agents.
• bleaching components containing activator are preferably incorporated into the preparations.
• certain N-acyl, O-acyl compounds which form H 2 O 2 organic peracid and serve as activators for per compounds which supply H 2 O 2 in water.
• carboxylic acids such as, for example, acetic acid, propionic acid, benzoic acid
• carboxylic acids such as, for example, acetic acid, propionic acid, benzoic acid
• activation can be seen even when amounts of 0.05 mol of activator are used per g-atom of active oxygen. It is preferred to work with 0.1 to 1 mol of activator; however, the amount can be increased to up to 2 moles of activator per g-atom of active oxygen.
• activators are tetraacetylglycoluril and tetraacetylethylenediamine.
• Detergents according to the invention with active chlorine compounds are preferred over agents containing active oxygen.
• the agents according to the invention can be in powder form, liquid or pasty and can be free of builders or contain builders.
• Inorganic and organic compounds can be used as builders.
• the inorganic ones include phosphates, especially sodium tripolyphosphate, and the water-insoluble, finely divided aluminosilicates zeolite A and zeolite X.
• Organic builders are the complex-forming phosphonates, polycarboxylates, aminopolycarboxylates, the salts of polymeric carboxylic acids or of copolymers of maleic vinyl methylene ether and ethylene, ethylene .
• Aminopolycarboxylates are preferably added to liquid agents as heavy metal complexing agents to improve the shelf life.
• the preparations according to the invention may also contain dirt carriers which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying.
• water-soluble colloids of mostly organic nature are suitable, such as the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
• Water-soluble polyamides containing acidic groups are also suitable for this purpose.
• Soluble starch preparations and other starch products than those mentioned above, such as degraded starch, aldehyde starches and so on, can also be used.
• Polyvinyl pyrrolidone is also useful.
• the bestanate parts of the washing and washing aids according to the invention are usually selected so that the preparations react neutral to clearly alkaline, so that the pH of a 1% solution of the preparation is usually in the range of 7-12.
• the weight ratio of polymeric compound to surfactant is 1:10 to 5: 1, preferably 1: 5 to 3: 1 and in particular 2: 1 to 1: 1.
• the usual detergent components which may be present in small amounts are, for example, dirt carriers, heavy metal complexing agents, optical ones Brighteners, for example those for cotton or synthetic fibers, solvents, hydrotropes, especially for liquid, but also for pasty or solid preparations, fabric softeners, dyes, fragrances or preservatives.
• the combination of the water-soluble polymers mentioned and the active chlorine or active oxygen compounds can also be used in color-preserving, bleaching agents for prewashing, soaking or for exclusive bleaching.
• the active chlorine compounds are contained in the agents according to the invention in such a concentration that they lead to a content of 0.02 to 2 g of active chlorine per liter or 0.2 to 10 g of active oxygen per liter in the treatment liquors, the weight ratio of polymeric compounds leading to Active chlorine or active oxygen amount 5: 1 to 1: 5, preferably 2: 1 to 1: 2.
• the invention further relates to a process for washing and bleaching delicate textiles in aqueous liquors, which contain water-soluble polymeric compounds and nonionic surfactants or mixtures of nonionic and zwitterionic surfactants.
• the washing and bleaching process is characterized in that the textiles at 30 to 95 ° C with aqueous liquors containing 1 to 20 g, preferably 3 to 15 g of a detergent containing nonionic or mixtures of nonionic and zwitterionic surfactants and synthetic , water-soluble amino and / or amido group-containing polymers from the group of polyethyleneimines, polyamines, polyaminamides and polyacrylamides together with active chlorine or active oxygen bleaches, treated, the agent or the individual components of the agent being added in such an amount to the aqueous liquor that 0.02 to 2 g of active chlorine or 0.2 to 10 g of active oxygen are contained in the liquor per liter.
• the soiling of tea serves as an indicator of the bleaching effect of the detergents; the green sulfur dye is sensitive to bleaching agents. Little or no lightening of the dye, with good removal of the tea stain, is a measure of the gentle bleaching by the agents according to the invention.
• the reflectance values measured with a spectrophotometer, type: Zeiss Elrepho, filter R 460, were determined before and after the wash (compare Table 1, Example 2 listed following Example 6).
• the textiles to be tested were in a wash liquor containing 5 g / l of this detergent (example 7) and additionally 5 g / l sodium perborate tetrahydrate at 60 ° C. without addition (example 8) and with the addition of the water-soluble polymers mentioned (Example 9) washed.
• the amount of polymers added per liter of wash liquor was:
• test textiles were nettle fabric dyed with sulfur green and gray corduroy fabric made of cotton.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
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• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

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Citations (4)

• 1982
  • 1982-03-29 DE DE19823211532 patent/DE3211532A1/de not_active Withdrawn
• 1983
  • 1983-03-21 EP EP83102771A patent/EP0090310B1/fr not_active Expired
  • 1983-03-21 AT AT83102771T patent/ATE21929T1/de not_active IP Right Cessation
  • 1983-03-21 DE DE8383102771T patent/DE3365791D1/de not_active Expired

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