EP0086423B1 - Means and process for the aftertreatment of washed linen - Google Patents

Abstract

1. A liquid after-wash treatment preparation having fabric softening, souring and anti-chlorinating properties and containing a fabric-softening quaternary ammonium compound, an inorganic or organic acid or acidic salts as the acidic compound, hydrogen peroxide or organic percarboxylic acid as reducing agents for chlorine end chlorine compounds of positive valency and, in addition, a stabilizer for peroxy compounds, characterized in that the stabilizer is 1-hydroxy-ethane-1,1-diphosphonic acid and/or hydroxy ethylenediamine triacetic acid or an alkali salt thereof, with the proviso that the quantity of the acidic compound is selected so that the pH value of the preparation is at most 4.

Description

In commercial laundries, very alkaline detergents are usually used. Bleaching is usually done with hypochlorite. Detergent and bleach residues that adhere to the washed laundry after the last rinsing process cannot be removed economically by rinsing alone. The removal of these residues is necessary, for example, to avoid skin irritation and to remove an unpleasant smell of chlorine originating from hypochlorite. Hypochlorite or chlorine residues also damage the textile fibers.

For this reason, agents with acidic and / or reducing constituents, by means of which disruptive detergent and bleach residues are converted into non-disruptive compounds, are added to the last rinsing bath. In many cases it is also desirable that washed laundry has a pleasantly soft feel after drying; this is especially true for laundry that lies on the skin and for terry towels. Occasionally, bacteriostatic finishing of the textiles, e.g. B. roll towels required.

For this reason, a treatment with a fabric softening agent and / or with antibacterial agents in aqueous liquor or in the subsequent drying cycle in an automatic tumble dryer is often followed in the last rinsing bath.

The laundry treatment generally requires several operations for "acidifying" (neutralizing) and "antichlorinating" (reducing) as well as softening or antibacterial treatment. Agents and processes with which acidification and antichlorination of freshly washed laundry as well as post-treatment with textile softeners or antibacterial agents can be carried out in one operation, therefore represent a considerable simplification of post-washing treatment for commercial laundries.

The agents and methods known from US Pat. Nos. 3,193,505, 3,676,353, 3,925,230,984,335.4,053,423,483,489,476,215,281 and DE-A-29 04 876 meet the requirement for an equally good softening or antibacterial treatment, acidification and antichlorination in one operation, or only incompletely, or the agents are difficult to dose automatically because they are in the form of a powder. The work with liquid aftertreatment agents, which is desirable because of the metering devices for liquid agents usually present on commercial washing machines, and which could be produced, for example, by dissolving powdery agents into a stock solution, usually fails because of the poor solubility or the insufficient stability of the solution or dispersion of the known aftertreatment agents intended for use in commercial laundries. Known liquid agents do not have acidifying, antichlorinating and softening properties at the same time.

The agents known from US 4,166,794 contain EDTA as a stabilizer for per compounds. Another disadvantage of many known agents is e.g. B. also in the deposition of salt-like components of these agents on the textiles, whereby the wearing properties and durability of the textiles are impaired. In addition, these deposits, if they get into the trough of a lack of laundry, can lead to faults there.

The object of this invention is therefore to provide a liquid laundry aftertreatment agent with fabric softening, acidifying and antichlorizing properties, comprising a fabric softening quaternary ammonium compound, an acidic compound and a reducing agent.

This object is achieved according to the invention by a liquid laundry treatment agent with fabric softening, acidifying and. antichlorinating properties, containing a quaternary ammonium compound which softens the textile, an inorganic or organic acid or acid salts, hydrogen peroxide or organic percarboxylic acids as reducing agent for chlorine and chlorine compounds with positive valency and additionally a stabilizer for peroxy compounds, which is characterized in that the stabilizer 1-Hydroxyethane-1,1-diphosphonic acid and / or hydroxyethylenediaminetriacetic acid or its alkali metal salts, with the proviso that the amount of the acidic compound is selected so that the pH of the agent is at most 4.

In addition, the agent can contain antibacterial agents. Furthermore, conventional additives such as. B. dispersants, foam regulators, colors and fragrances may be included in the agent. Water can be used as the liquid carrier, possibly with the addition of small amounts of organic solvents.

By using the agent according to the invention for post-treating washed laundry, it is possible at the same time to neutralize alkaline detergent residues that adhere to the laundry after the washing and rinsing process, to reduce hypochlorite bleach residues, to give the laundry items a pleasantly soft feel and antistatic behavior after drying confer and if necessary to make them antibacterial, while at the same time the formation of deposits on the textiles is reduced. The agent according to the invention can also be conveniently and precisely dosed automatically.

The quaternary ammonium compounds with preferably two long-chain, preferably saturated aliphatic radicals each having 14-26, preferably 16-20, carbon atoms and at least one quaternary nitrogen atom in the molecule are suitable as fabric softening agents. The long-chain aliphatic radicals can be straight-chain or branched and can accordingly be derived from fatty acids or from fatty amines, Guerbetamines, or from the alkylamines obtainable by reduction of nitroparaffins. These quaternary ammonium compounds are, in particular, derivatives of ammonia, ie the quaternary salts obtainable by alkylation of long-chain secondary amines, such as, for. B. the compounds distearyldimethylammonium chloride or ditallow alkyldimethylammonium chloride, or the by reacting 1 mol of an aminoalkylethylenediamine or hydroxyalkylethylenediamine with 2 mol of a long-chain C12-C26 fatty acid or its ester, obtainable imidazoline compounds which are subsequently converted into the quaternary imidazolinium compounds by alkylation. In these quaternary ammonium compounds, the anion generally consists of the acid residue which has arisen from the alkylating agent used in the quaternization. For example, chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluenesulfonate are suitable as anions. In addition to these quaternary ammonium compounds, the condensation products of 1-3 moles of fatty acid alkyl ester or 1/3-1 mole of fatty acid triglyceride with 1 mole of a hydroxyalkyl polyamine, for example hydroxyethyl ethylene diamine or hydroxyethyl diethylene triamine, are also suitable as textile softeners. The product obtained by reacting 1 mol of a fatty acid triglyceride, in particular hardened tallow, with 1 mol of hydroxyethylethylenediamine at 90-150 ° C. is particularly suitable. A quaternary ammonium compound of the ammonia type with 2 C, ₆ -C ₂₀ alkyl or alkenyl groups and 2 methyl groups in the molecule and with the chloride, bromide or methyl sulfate anion, in particular the distearyldimethylammonium chloride or ditalgalkyldimethylammonium chloride, is preferably used as the textile softener. In the treated textiles, these active ingredients lead to a uniform, striking improvement in the grip and, at the same time, an antistatic finish without staining.

Acidic compounds include inorganic acids, such as, in particular, orthophosphoric acid, acidic salts of orthophosphoric acid, such as, for. As sodium dihydrogen phosphate, non-surfactant organic acids with 1-8 carbon atoms, such as. B. Amidosulfonic acid, urea compounds of orthophosphoric acid, boric acid, oxalic acid, lactic acid, glycolic acid, citric acid, tartaric acid, benzoic acid, phthalic acid, gluconic acid, formic acid, acetic acid and propionic acid as well as sulfobenzoic acids or optionally acidic alkali salts of these acids or mixtures thereof. Glycolic acid, citric acid, formic acid, acetic acid, lactic acid, tartaric acid are preferred organic acids because of their easy accessibility and non-toxicity. A mixture consisting of adipic acid, glutaric acid and succinic acid can also be used as an acidic additive. The particularly preferred orthophosphoric acid (H ₃ P0 ₄ ) can also be used together with sodium dihydrogen phosphate as an acidifying agent. The agent according to the invention contains so much acidic additives that the pH of the agent is at most 4. Depending on the desired acidification effect, the agent contains different amounts of acidic substances, so that the pH is also significantly lower, e.g. B. may be 1 or below.

Laundry that has been treated with a hypochlorite-based bleach often has a slight smell of chlorine. To remove this chlorine smell from the laundry, the agent according to the invention preferably contains hydrogen peroxide (H ₂ 0 ₂ ) as an antichlorinating component. The H ₂ 0 ₂ acts as a reducing agent compared to the stronger oxidizing agent hypochlorite. Instead of H ₂ 0 ₂ , organic percarboxylic acids such as. B. diperazelaic acid or diperisophthalic acid can be used.

The hydrogen peroxide is preferred because of its easy accessibility and because it is converted to the water which is present anyway upon reduction. Another advantage of the H ₂ 0 ₂ is that it cannot form solid deposits.

To stabilize the agent according to the invention against heavy metal, in particular copper and / or iron ions, the agent contains 1-hydroxyethane-1,1-diphosphonic acid and / or hydroxyethylene diamine triacetic acid or its alkali metal salts as a stabilizer.

Antimicrobial active ingredients which the agent according to the invention can contain are understood here to mean compounds having a bactericidal or bacteriostatic or fungicidal or fungistatic action. These active ingredients are said to be water-soluble either as such or in the form of their salts. The antimicrobial agents suitable as additives are e.g. For example, such quaternary ammonium compounds which, in addition to a long-chain aliphatic and two short-chain aliphatic hydrocarbon radicals, contain an aromatic radical linked via an aliphatic carbon atom to the nitrogen atom, or an aliphatic organic radical having double bonds in the molecule. Examples of such antimicrobial quaternary ammonium compounds are the following: dimethylbenzyldodecylammonium chloride, dimethylbenzyltetradecylammonium chloride, dimethyl (ethylbenzyl) dodecylammonium chloride, dimethylbenzyldecylammonium bromide, diethylbenzyldodecylammonium chloride Dibutylallyl, methyl-ethyl-benzyl, ethyl-cyclohexyl-allyl, ethyl-crotyldiethylaminoethyl-dodecyl-ammonium chloride and in particular coconut alkyl dimethyl benzyl ammonium chloride. Dimethyldidecylammonium chloride is also effective.

In addition, other antimicrobial agents can also be used, provided they are stable in the presence of per compounds in an acidic medium. These include, for example, betaines, such as. B. Dodecyl di (aminoethyl) glycine. Other useful antimicrobial agents are e.g. B. hexamethylene bis - (chlorophenyl) biguanide digluconate or dihydrochloride and dodecylglycine.

The nonionic surfactants ("nonionics") are particularly suitable as dispersants, as they can be contained in the liquid textile aftertreatment agents according to the invention. These include products that owe their hydrophilic properties to the presence of polyether chains, amine oxide, sulfoxide or phosphine oxide groups, alkylolamide groups or, in general, an accumulation of hydroxyl groups. Such nonionics contain at least one hydrophobic radical with 8 to 26, preferably 10 to 20 and in particular 12 to 18 carbon atoms in the molecule, and at least one nonionic, water-solubilizing group. The preferably saturated hydrophobic residue is usually aliphatic, possibly also alicyclic in nature; it can be with the water-solubilizing groups directly or via Intermediate links. As intermediate links come z. B. benzene rings, carboxylic acid ester or carbonamide groups, ether or ester-bonded residues of polyhydric alcohols, such as. B. that of ethylene glycol, propylene glycol, glycerol or corresponding polyether radicals in question. Typical nonionics preferred as dispersants are e.g. B. the adducts of about 9 moles of ethylene oxide with nonylphenol or with dodecyl alcohol, polyethylene glycols with up to 50-ethoxy units or polyethoxypolypropoxy-glycols with up to 20 ethoxy or propoxy units.

• a) 1 - 20 Gew.-% textilweichmachende quartäre Ammoniumverbindungen
• b) 1 - 50 Gew.-% saure Verbundungen
• c) 1 - 25 Gew.-% Wasserstoffperoxid oder organische Percarbonsäuren
• d) 0,1 -10 Gew.-% Stabilisator
• e) 0 -15 Gew.-% antimikrobiell wirksame Substanzen

The content of the inventive constituents of the constituents essential to the invention, depending on the focus of the application, that is to say depending on whether the detergents should have particularly pronounced textile softening or acidifying or antichlorizing (= hypochlorite reducing) properties or particularly pronounced combinations of these properties, are in the range below Amounts:

• a) 1 - 20 wt .-% textile softening quaternary ammonium compounds
• b) 1 - 50 wt .-% acidic compounds
• c) 1-25% by weight of hydrogen peroxide or organic percarboxylic acids
• d) 0.1-10% by weight stabilizer
• e) 0 -15% by weight of antimicrobial substances

Remainder water, and optionally small amounts of dispersants, foam regulators or other conventional additives.

• a) 2 - 7 Gew.-% einer textilweichmachenden qartären Ammoniumverbindung
• b) 2 - -40 Gew.-% saure Verbindungen
• c) 1 - -15 Gew.-% Wasserstoffperoxid oder organische Percarbonsäuren
• d) 0,2 - 3 Gew.-% Stabilisator
• e) 0,5 - 7 Gew.-% eines antibakteriellen Wirkstoffs
• Rest Wasser, sowie ggf. Dispergator in geringen Mengen

The agents according to the invention preferably have the following composition:

• a) 2-7% by weight of a textile softening quaternary ammonium compound
• b) 2 - -40 wt .-% acidic compounds
• c) 1 - -15 wt .-% hydrogen peroxide or organic percarboxylic acids
• d) 0.2-3% by weight stabilizer
• e) 0.5-7% by weight of an antibacterial agent
• Remainder of water, as well as small amounts of dispersant, if applicable

The quaternary ammonium compound which softens the textile is preferably in particular the compounds Dimethylditalgalkylammoniumchlorid or Dimethyldistearylammoniumchlorid used on a large scale, of which Dimethyldistearylammoniumchlorid is particularly preferred. Quaternary ammonium compounds are preferred as antibacterial active substances, in particular coconut alkyldimethylbenzylammonium chloride. Hydrogen peroxide, which has sufficient stability in the presence of heavy metal complexing agents, is used in particular for the antichlorination. Suitable stabilizers by which both the hydrogen peroxide is stabilized and a discoloration of the laundry is counteracted by the use of washing water and rinsing water with a content of heavy metal ions which is disruptive are hydroxyethylene diaminotriacetic acid and / or 1-hydroxyethanl, 1-diphosphonic acid or the like Alkali salts. Agents according to the invention advantageously contain small amounts, for example 0.5-5% by weight, of nonionic surfactants as dispersants, if larger amounts of textile-softening quaternary ammonium compounds are used to achieve a pronounced softening effect.

• a) 2 - 7 Gew.-% Dimethyldistearylammoniumchlorid
• b) 2 -40 Gew.-% Orthophosphorsäure
• c) 1 - -15 Gew.-% Wasserstoffperoxid
• d) 0,2 - 3 Gew.-% 1-Hydroxyethan-1,1-diphosphonsäure
• e) 0,5 - 7 Gew.-% Kokosalkyldimethylbenzylammoniumchlorid
• Rest Wasser, sowie nichtionische Tenside als Dispergator in geringen Mengen

Agents with the following composition have particularly balanced properties:

• a) 2-7% by weight of dimethyldistearylammonium chloride
• b) 2 -40 wt .-% orthophosphoric acid
• c) 1 - -15 wt .-% hydrogen peroxide
• d) 0.2-3% by weight of 1-hydroxyethane-1,1-diphosphonic acid
• e) 0.5-7% by weight cocoalkyldimethylbenzylammonium chloride
• Rest of water, as well as non-ionic surfactants as dispersants in small quantities

The invention further relates to a method for simultaneous softening, for removing active chlorine and for neutralizing alkaline detergent residues and optionally for antibacterial finishing of freshly washed laundry. The process is characterized in that the washing in the last rinse cycle with 0.5 to 20 g per liter of an agent of the composition described above, which is added to the rinsing bath, for 0.5 to 5 minutes with constant movement at about 10 to 30 ° C treated. The treatment liquor is then separated off, for example by squeezing or centrifuging, to a residual moisture content of about 10 to about 100% by weight, based on the dry weight of the laundry. The laundry is then dried in a tumble dryer, for example, and ironed if necessary. It has a soft handle after drying. It is free from alkaline detergent residues. A smell of chlorine is no longer detectable. The acidic aftertreatment also reduces the incrustation, which is expressed in the decrease in ash-forming constituents adhering to the fiber. The laundry treated in this way also shows extremely antibacterial properties.

EXAMPLES example 1

• a) 3 Gew.-% Dimethyldistearylammoniumchlorid
• b) 15 Gew.-% Orthophosphorsäure
• c) 1 Gew.-% Wasserstoffperoxid
• d) 1 Gew.-% Hydroxyethylethylendiamintriessigsäure
• Rest Wasser
• miteinander vermischt. Es bildete sich eine stabile, nahezu klare Flüssigkeit mit einem pH-Wert von 1. Von dieser Flüssigkeit setzte man dem letzten Spülbad einer gewerblichen Waschmaschine 5 g pro Liter Spülwasser von ca. 25°C zu und behandelte damit die gewaschene und mit Hypochlorit gebleichte Wäsche ca. 2 Minuten lang. Nach dem Abschleudern dieser Behandlungsflotte konnte man durch pH-Wert-Messung der anhaftenden Feuchtigkeit feststellen, daß alkalische Waschmittelreste auf der Wäsche neutralisiert waren; die Wäsche wies keinen Chlorgeruch mehr auf. Nach dem Trocknen hatte sie einen weichen vollen Griff.

In a vessel were using an intensive mixer

• a) 3% by weight of dimethyldistearylammonium chloride
• b) 15% by weight of orthophosphoric acid
• c) 1% by weight of hydrogen peroxide
• d) 1% by weight of hydroxyethylethylenediamine triacetic acid
• Rest of water
• mixed together. A stable, almost clear liquid with a pH of 1 was formed. 5 g of this liquid was added to the last rinsing bath of a commercial washing machine per liter of rinsing water at approx. 25 ° C., and the laundry washed and bleached with hypochlorite was treated with it for about 2 minutes. After spinning off this treatment liquor, it was possible to determine by measuring the pH of the adhering moisture that alkaline detergent residues on the laundry had been neutralized; the laundry no longer smelled of chlorine. After drying, it had a soft full grip.

Similar results were obtained if the phosphoric acid was replaced by an amount of NaH ₂ P0 ₄ equivalent in terms of acidity.

Examples 2 to 5

Die hiermit behandelte Wäsche wies nach dem Abschleudern der Behandlungsflotte und dem Trocknen in einem automatischen Wäschetrockner die gleichen vorteilhaften Eigenschaften, wie in Beispiel 1 beschrieben, auf. Dabei zeichneten sich die Rezepturen 3 und 5 durch besondere Lagerstabilität aus, wenn sie zusätzlich 1,5 Gew.-% (Beispiel 3) bzw. 5 Gew.-% (Beispiel 5) Nonylphenol, an das ca. 9 Mol Ethylenoxid angelagert waren, als Dispergator enthielten.Agents according to the invention of the following composition were produced and tested in the same way:

The laundry treated with this had the same advantageous properties as described in Example 1 after the spin-off of the treatment liquor and drying in an automatic laundry dryer. Recipes 3 and 5 were distinguished by special storage stability if they additionally had 1.5% by weight (Example 3) or 5% by weight (Example 5) of nonylphenol, to which approx. 9 moles of ethylene oxide had been attached, contained as a dispersant.

Comparable results were obtained if, instead of orthophosphoric acid, the agents contained equivalent amounts of glycolic acid, formic acid, acetic acid, citric acid, lactic acid or tartaric acid.

The replacement of the hydrogen peroxide with amounts of diperazelaic acid or diperisophthalic acid equivalent in terms of peroxygen in the aforementioned formulations led to similar properties of the tissues treated therewith.

The aforementioned agents contained small amounts of an antimicrobial compound such as. B. 2 wt .-% Kokosalkyldimethylbenzylammoniumchlorid, the laundry treated with it also had antimicrobial properties against a number of test germs, eg. B. Trichophyton mentagrophytes, Microsporum gypseum, Trichophyton rubrum, Staphylococcus aureus.

Claims (8)

1. A liquid after-wash treatment preparation having fabric softening, souring and anti-chlorinating properties and containing a fabric-softening quaternary ammonium compound, an inorganic or organic acid or acidic salts as the acidic compound, hydrogen peroxide or organic percarboxylic acide as reducing agents for chlorine end chlorine compounds of positive valency and, in addition, a stabilizer for peroxy compounds, characterized in that the stabilizer is 1-hydroxy-ethane-1,1-diphosphonic acid and/or hydroxy ethylenediamine triacetic acid or an alkali salt thereof, with the proviso that the quantity of the acidic compound is selected so that the pH value of the preparation is at most 4.

2. A preparation as claimed in Claim 1, characterized in that it contains

a) from 1 to 20% by weight fabric-softening quaternary ammonium compounds,

b) from 1 to 50 % by weight acidic compounds,

c) from 1 to 25 % by weight hydrogen peroxide or organic percarboxylic acids,

d) from 0.1 to 10 % by weight stabilizer,

e) from 0 to 15 % by weight antimicrobial agents,

balance water and, optionally, small quantities of dispersants, foam regulators or other standard additives.

3. A Preparation as claimed in Claims 1 and 2, characterized in that it contains

a) from 2 to 7 ⁰J₀ by weight of a fabric-softening quaternary ammonium compound,

b) from 2 to 40 % by weight acidic compounds,

c) from 1 to 15 % by weight hydrogen peroxide or organic percarboxylic acids,

d) from 0.2 to 3 % by weight of a stabilizer,

e) from 0,5 to 7 % by weight of a antibacterial agent,

balance water and, optionally, a dispersant in small quantities.

4. A preparation as claimed in Claims 1 to 3, characterized in that the fabric softening quaternary ammonium compound is in particular dimethyl ditallowalkyl ammonium chloride or dimethyl distearyl ammonium chloride.

5. A preparation as claimed in Claims 1 to 4, characterized in that the antibacterial agent is a quaternary ammonium compound, prefabebly cocosalkyl dimethyl benzyl ammonium chloride.

6. A preparation as claimed in Claims 1 to 5, characterized in that it contains small quantities of nonionic surfactants as dispersant.

7. A preparation as claimed in Claims 1 to 6, charactarized in that it contains

a) from 2 to 7 by weight dimethyl distearyl ammonnum chloride,

b) from 2 to 40% by weight orthophosphoric acid,

c) from 1 to 15% by weight hydrogen peroxide,

d) from 0.23% by weight 1-hydroxyethane-1,1-diphosphonic acid,

e) from 0,5 to 7 % by weight cocosalkyl dimethyl benzyl ammonium chloride,

balance water and small quantities of non-ionic surfactant as dispersant.

8. A process for simultaneously softening, neutralizing alkaline detergent residues, removing active chlorine and, optionally, antimicrobially finishing freshly washed laundry in an aqueous liquor, characterized in that the laundry is treated for 0,5 to 5 minutes at around 10 to around 30°C in the final rinse with a preparation as clamed in Claims 1 to 7 added to the rinse liquor in quantities of from 0.5 to 20 g per liter, the laundry circulating continuously during the treatment, after which the aftertreatment liquor is removed from the laundry by wringing or spinning to a residual moisture content of from about 10 to 100% by weight, based on the dry weight of the laundry.