RU2404315C2 - Method for chemical cleaning of textile materials - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method of cleaning textile articles involves treatment of the textile articles using a compound of formula (I)

,

where A denotes (CH₂)_a, R¹, R², R³ and R⁴, which can be identical or different, denote (C₁-C₄)alkyl, and a equals 0, as an organic cleaning agent and solvent.

EFFECT: method improves working conditions owing to an improved environment and toxicology with good quality of cleaning textile materials from stains.

8 cl, 10 tbl, 4 ex

Description

Washing with water and washing detergents at home or industrial conditions and laundries is not the only important cleaning method applicable to textiles. Dry cleaning is used for water-sensitive textiles, as well as in cases of persistent contamination, especially oil and greasy stains.

As means for dry cleaning, halogenated hydrocarbons are still used. These include chlorine-containing hydrocarbons trichloroethane, 1,1,1-trichloroethane and dichloromethane, which are no longer allowed for use, for example, in Germany. Similarly, chlorofluorinated hydrocarbons (CFCs), which have been widely used for dry cleaning, are no longer allowed for such applications in many countries.

The solvent, which is still widely used, is tetrachloroethane (perchlorethylene, perchlorethylene, perc, PER). Tetrachloroethane is a volatile chlorinated hydrocarbon, which, due to its ability to dissolve fats, has found wide application in industry, including dry cleaning, as a solvent / cleaner.

The disadvantages of PER are, in particular, its possible carcinogenic effect on humans, its high volatility, its easy solubility in fat-containing foods and its strong properties, which pose a danger to water.

PER is classified as a hazardous substance on the EU's Black List and according to Germany's Haz Chem.

Solvents for dry cleaning, in particular perchlorethylene, are dangerous if released into the environment. Potential emission sources are a cleaning machine, drying air, contacting water and sludge from distillation, a textile product if it is improperly dried and / or retaining solvent, as well as accidents.

The control of the emission paths of organic solvents in the dry cleaning sector is located in various countries according to their environmental laws and the extent to which their laws are respected and controlled.

In Germany, dry cleaners and machine manufacturers must comply with many requirements for limiting perchlorethylene emissions, such as the maximum permissible values for PER emissions in the exhaust gas, in the storage area and in adjacent rooms, which entail substantial technical obligations.

However, regardless of the extent to which PER emissions are controlled in dry cleaners, significant amounts of PER can be held in the most important textile foundations (wool, polyester fiber), so that solvent release by textiles is also important. In the case of PER, this can result in exposure to the consumer far from the dry cleaning facility due to air pollution.

The chlorofluorinated hydrocarbons (CFCs) indicated at the beginning of the description, which are now not allowed for use in dry cleaning in most countries, make the cleaning temperatures extremely low and, due to their high volatility, also reduce drying time and therefore reduce possible mechanical stress on textile products.

In this way, irreversible damage to textiles with the precautionary symbol "F" can be avoided.

For some time, halogen-free hydrocarbon solvents (HCS) have been used as a technical alternative to the prohibited CFC, as well as the widely used PER. Initially, HCS solvents were only considered as a replacement for CFC with respect to the cleaning of particularly sensitive textiles.

HCS solvents are linear aliphatic hydrocarbons or mixtures of linear, branched and cyclic aliphatic hydrocarbons with 10-14 carbon atoms. A higher range of their boiling points from about 180 to 210 ° C distinguishes them from the petroleum fractions also used previously for dry cleaning, or from perchlorethylene, which has a boiling point of only 121 ° C. HCS solvents are widely used for dry cleaning in the USA and Japan. However, the disadvantage of using HCS is that, as a consequence of the low vapor pressure, drying temperatures increase and / or drying time increases significantly. This leads to noticeably greater thermal and mechanical stress for sensitive textiles, which shortens the period of their use by the consumer.

In addition, the energy requirements for the distillation and recycling of HCS are significantly higher compared to PER.

Accordingly, there is still a need for organic solvents that not only have good cleaning ability, but can also be considered superior to the current level of technology, according to toxicologists and ecologists, and due to their physicochemical properties.

In addition, they should be substantially applicable to cleaning methods in which perchlorethylene (PER) and hydrocarbon solvents (HCS) are used in the art.

The cleaning method with PER includes three stages:

1) the actual cleaning operation in the solvent bath, which also contains some water and cleaning enhancers (including surfactants, cosolvents and other components);

2) drying with hot air and solvent extraction by condensation and adsorption;

3) solvent regeneration by filtration and distillation or desorption.

Cleaning with HCS basically involves the same steps as the cleaning method with PER. Cleaning methods offer various procedures that differ in the separation of the stages of cleaning and drying (reloading method), and cleaning and drying are combined in one machine (closed loop), and also by inertization during cleaning and drying (nitrogen, a combination of fresh air and circulating air or vacuum )

Organic solvents, considered an alternative to perchlorethylene and / or hydrocarbon solvents, must satisfy at least essentially the following requirements: good cleaning ability in general and good ability to separate water-soluble or water-wettable contaminants and pigment contaminants, if combined with water-soluble surfactants -active substances (cleaning enhancers); very good dissolving power in relation to fats and oils; good dispersing ability and sufficient dispersion stability against pigmented contaminants in order to avoid graying; very little, if any, effect on fibers, dyes and finishes, i.e. only a very limited swelling of the fibers, the absence of harmful effects in the form of shrinkage of the wool, minor changes in the thermomechanical properties of the fibers, the absence of peeling of dyes, finishes, melting of adhesives, etc. (and in the process of drying); very little fiber-based retention; lack of smell of solvent in the cleaned textile products; high volatility to facilitate drying and removal; sufficiently high flash point; slight, if any, corrosive activity in relation to metals and other materials of machines for cleaning and drying, even in the presence of water; only minimal, if any, decomposition under conditions of purification and distillation, i.e. in the presence of contaminants and at higher temperatures; low viscosity to facilitate separation of contaminants and for better mechanical solvent removal by centrifugation; low solubility in water, but still some dissolving ability in relation to water (if surfactants and other solubilizers are added); solubility with respect to so-called cleaning enhancers (containing, for example, nonionic, anionic, cationogenic, amphoteric surfactants, other solvents, for example (2-methoxymethylethoxy) propanol, certain salts, bleaches, disinfectants, antistatic agents and other additives) ; the formation of stable emulsions of water - surface-active substances in a solvent; compliance with the maximum processing indicators provided by the care leaflet; and low toxicity to humans and the environment.

The aim of the present invention are organic solvents that satisfy the requirements of dry cleaning better than solvents of the prior art, and which have a better toxicological and environmental profile.

Surprisingly, it has been found that the compounds of formula (1) have an excellent cleansing or dissolving ability with respect to fats and oils and an excellent ability to suspend impurities and therefore form less gray, and are considered both toxicologically and ecologically to be substantially more favorable than perchlorethylene and hydrocarbon solvents, and, in addition, also satisfy the above requirements and, thus, are quite applicable as a means for dry cleaning.

Accordingly, the present invention relates to the use as an organic cleaning agent and solvent for dry cleaning textiles of compounds of the formula (1)

Where

A represents (CH ₂ ) _a or phenylene,

R ¹ , R ² , R ³ and R ^{4 are the} same or different and are (C ₁ -C ₂₂ ) -H- and / or isoalkyl, C ₅ - or C ₆ -picloalkyl, phenyl- (C ₁ -C ₄ ) - alkyl, (C ₁ -C ₉ ) -alkylphenyl or phenyl,

and a is an integer from 0 to 6.

Preferably, R ¹ , R ² , R ³ and R ^{4 are the} same or different and are (C ₁ -C ₁₃ ) -H- and / or isoalkyl, C ₅ - or C ₆ -cycloalkyl, phenyl- (C ₁ -C ₂ ) -alkyl, (C ₁ -C ₉ ) -alkylphenyl or phenyl, and a is an integer from 0 to 2.

More preferably, R ¹ , R ² , R ³ and R ^{4 are the} same or different and are (C ₁ -C ₈ ) -H - and / or isoalkyl, cyclohexyl, benzyl or phenyl, and a is 0 or 1.

Most preferably, R ¹ , R ² , R ³ and R ^{4 are the} same or different and are (C ₁ -C ₃ ) n and / or isoalkyl, and a is 0.

Examples of R ¹ -R ⁴ radicals are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, isoamyl, tert-amyl, neopentyl, cyclopentyl, n -hexyl, isohexyl, cyclohexyl, octyl, decyl, isotridecyl, phenyl, benzyl, phenylethyl, nonylphenyl.

Compounds of general formula (1) are acetals. Acetals are typically prepared by reacting aldehydes with 2 mol of alcohol per carbonyl group in the presence of catalysts, such as, for example, dry hydrogen chloride.

Dialdehydes should be used for the synthesis of compounds of formula (1). Preferred dialdehydes for the synthesis of compounds of formula (1) are glyoxal, malonic aldehyde (1,3-propanedial, 1,3-propanedialdehyde), 1,4-butanedial and terephthalic aldehyde. A particularly preferred dialdehyde is glyoxal, which results in compounds of formula (1), where a = 0.

A particularly preferred compound for the described purpose is tetramethoxyethane (2) from Clariant

and a similar compound tetraethoxyethane.

The compounds of formula (1) can be used at various stages of the dry cleaning process both in industry and in dry cleaning at home. They allow, in particular, the use as a solvent and cleaning agent in the main cleaning operation. In this case, the compounds of formula (1) can completely replace detergents perchlorethylene, hydrocarbons, as well as other solvents.

The use of solvents of formula (1) can be carried out according to existing methods in the so-called PER machines or in HSC machines (for example, from Satec).

Typical processing conditions for the use of compounds of formula (1) are indicated below as the conditions described for processing in PER and HSC machines.

Method parameter Per machine HSC machine Speeds: cleaning 35 rpm 30-40 rpm centrifugation 380 rpm 700-800 rpm g-factor (centrifugation) 77 330 Loading 18 kg 18 kg Solution ratio low level 1: 1.7 kg / l 1: 3.9 kg / l high level 1: 3.9 kg / l 1: 6.7 kg / l whirlpool bath --- 1: 6.7 kg / l Filter Centrifugal filters Cartridges Drying temperature 60 ° C 70 ° C Drying method Completion of the drying process in a PER drum, content <2 g / m ³ at a product temperature of at least 35 ° C Inertization with nitrogen, heating is turned off when the oxygen content <9% Solvent distillation At atmospheric pressure max. - 70 cm Hg

Modifications of processes or modifications of machines for cleaning may be required, depending on the physicochemical properties of certain compounds of formula (1). For example, different boiling points due to different radicals R ¹ -R ⁴ and / or differences in magnitude can inevitably lead to different drying temperatures and, for example, a change in the distillation conditions for solvent extraction (pressure, temperature).

Ignition temperatures other than HCS solvents used may also require changes in safety measures, for example, in the type of inertization (residual oxygen content).

In particular, the organic radicals R in the solvents of the formula (1) can be changed to regulate the dissolving ability with respect to non-polar substances (other solvents, fats, oils), as well as for polar substances and solvents (including water).

Different retention rates and viscosities may also, for example, necessitate different g-factors to remove the solvent by centrifugation. In commercial practice, HCS machines use higher g-factors than PER machines.

Other factors that can be mentioned / optimized in connection with the use of solvents of formula (1) include, for example, brushing time, mortar ratio, reversal rhythm, load level, identity and number of amplifiers used, use of a vortex bath through an air-solvent mixture for delicate cleaning sensitive textiles.

All such modifications of conventional dry cleaning methods that result from the use of new solvents of formula (1) are readily determined by one skilled in the art through preliminary tests.

Dry cleaning methods are also divided into a single bath method and a two bath method. The standard treatment, as a rule, is the cleaning method in two baths using a small solution in the first bath and a larger solution in the second bath. The first bath is used to separate the main contaminants. Solvents of the formula (1) can be used both in the single bath method and in the two bath method.

But, in principle, it is also possible to combine cleaning agents of formula (1) with perchlorethylene, hydrocarbons or other solvents and, thus, a partial replacement of traditional solvents.

Just as when used as the “main cleaning agent” (for the main cleaning operation), the compounds of formula (1) can also be used in stain removers, cleaning activators or cleaning enhancers. Stain removers are used to remove stains in textile cleaning technology. There are groups of stain removers listed below.

1) Brush cleaners are used to pre-stain large contaminated areas of textiles. They are used pure with a soft brush or sprayed onto heavily soiled areas before the main cleaning operation.

2) Special stain removers are used to treat intense specific stains on textiles. They are applied directly to the stain and left to act before the main cleaning operation.

3) The post-stain treatment products are used after the main cleaning operation to remove any remaining stains.

Cleaning activators are used to remove stains, and they may also contain, for example, odor adsorbents. They are used in the bath for pre-treatment and, since they are solvents of contaminants in order to avoid any brushing.

Cleaning enhancers, when added to an organic solvent used as a cleaning agent, are intended to enhance cleaning performance and, more specifically, also to remove water-soluble or water-swellable contaminants that only slightly dissolve, if not dissolve, in the organic solvent. Examples of such water-soluble compounds include a salt in the form of fine particles (high purity NaCl or also mixed with CaCl ₂ or MgCl ₂ sols), used in winter to combat icing on sidewalks and streets. They will also remove insoluble pigmented contaminants and detect the ability to disperse pigments and thus inhibit the back deposition of separated dirt particles. They also serve to avoid pilling and improve the texture of the fabric. Cleaning enhancers usually contain surfactants (in particular, anionic, nonionic, amphoteric surfactants and also cationic surfactants), solvents, antistatic agents, softeners or softeners, and, as appropriate, special additives, such as disinfectants and bleaches. In addition, a cleaning booster can be used to introduce small amounts of water into the cleaning bath, which form emulsions in organic solvents with surfactants.

A bathtub with a cleaning agent, i.e. the solvent of formula (1) used for the main cleaning operation, stain removers, cleaning activators and cleaning enhancers containing the solvent of formula (1) may also contain the pollution separation enhancers listed below.

Surfactants

Surfactants that can be used to add to or in cleaning agents of formula (1), for example tetramethoxyethane (2), are as follows.

Anionic Surfactants

Suitable anionic surfactants include sulfates, sulfonates, carboxylates, phosphates, and mixtures thereof. Suitable cations are alkali metals, for example sodium or potassium, or alkaline earth metals, for example calcium, including mono-, di- or triethanolammonium cation, and mixtures thereof.

Particularly preferred are the following types of anionic surfactants:

alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkylbenzenesulfonates, alkanesulfonates and soaps described below.

Alkyl ester sulfonates include linear esters of (C ₈ -C ₂₂ ) carboxylic acids (i.e. fatty acids) that sulfonate with gaseous SO ₃ . Suitable starting materials are natural fats, such as, for example, lard, coconut oil and palm oil. But carboxylic acids can also be synthetic in nature. Preferred alkyl ester sulfonates are compounds of the formula

where R ¹ represents a (C ₈ -C ₂₀ ) -hydrocarbon radical, preferably alkyl, and R represents a (C ₁ -C ₆ ) -hydrocarbon radical, preferably alkyl. M represents a cation that forms a water soluble salt with an alkyl ether sulfonate. Suitable cations are sodium, potassium, lithium or ammonium cations, or such as monoethanolamine, diethanolamine and triethanolamine. Preferably, R ¹ is (C ₁₀ -C ₁₆ ) -alkyl, and R is methyl, ethyl or isopropyl. Particular preference is given to methyl ester sulfonates, where R ¹ is (C ₁₀ -C ₁₆ ) -alkyl.

Alkyl sulfates are salts or acids of the formula ROSO ₃ M, where R is a (C ₁₀ -C ₂₄ ) hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with a (C ₁₀ -C ₂₀ ) alkyl component, more preferably a (C ₁₂ -C ₁₈ -alkyl or hydroxyalkyl.

M represents hydrogen or a cation, for example, an alkali metal cation (sodium, potassium, lithium being examples) or ammonium or a substituted ammonium cation, for example methyl, dimethyl and trimethyl ammonium cations, and quaternary ammonium cations such as tetramethyl ammonium and dimethyl piperidinium cations, and quaternary ammonium cations formed from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof.

Alkyl ether sulfates are salts or acids of the formula RO (A) _m SO ₃ M, where R is an unsubstituted (C ₁₀ -C ₂₄ ) alkyl or hydroxyalkyl radical, preferably a (C ₁₂ -C ₂₀ ) alkyl or hydroxyalkyl radical more preferably a (C ₁₂ -C ₁₈ alkyl or hydroxyalkyl radical. A is an ethoxy or propoxy unit, m is greater than 0, preferably from about 0.5 to about 6, and more preferably from about 0.5 to about 3, and M represents a hydrogen atom or a cation, for example, a cation of sodium, potassium, lithium, calcium, ma Nia, ammonium or substituted ammonium.

Specific examples of substituted ammonium cations are methyl, dimethyl and trimethylammonium cations, and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations, as well as cations formed from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof. Examples that can be mentioned are ether sulfates (C ₁₂ -C ₁₈ fatty alcohols, where the EO content is 1, 2, 2.5, 3 or 4 mol per mol of fatty alcohol ether sulfate, and where M is sodium or potassium.

The alkyl group in the secondary alkanesulfonates may be either saturated or unsaturated, branched or linear, and optionally hydroxy substituted. The sulfo group can be located at any position of the carbon chain, although the primary methyl groups at either end of the chain do not contain any sulfonate groups.

Preferred secondary alkanesulfonates contain linear alkyl chains with about 9-25 carbon atoms, preferably about 10 to about 20 carbon atoms, and more preferably about 13-17 carbon atoms. The cation is, for example, a cation of sodium, potassium, ammonium, mono-, di- or trimethylammonium, calcium, or magnesium, or mixtures thereof. Sodium cation is preferred.

Secondary alkanesulfonates can be obtained under the trade name Hostapur SAS (from Clariant).

As well as secondary alkanesulfonates, primary alkanesulfonates can be used in a similar manner in the detergent compositions of the present invention. Preferred alkyl chains and cations are the same as for secondary alkanesulfonates.

Suitable anionic surfactants include alkenyl or alkylbenzenesulfonates. The alkenyl or alkyl group may be branched or linear and optionally hydroxy substituted. Preferred alkylbenzenesulfonates contain linear alkyl chains with about 9-25 carbon atoms, and preferably contain from about 10 to about 13 carbon atoms; the cation is a sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium cation, or a mixture thereof.

Magnesium cation is preferred for systems with mild surfactants, while sodium cation is preferred for standard applications. The same applies to alkenylbenzenesulfonates.

The term "anionic surfactants" also includes olefin sulfonates, which are obtained by sulfonation of (C ₈ -C ₂₄ ) olefins, and preferably (C ₁₄ -C ₁₆ -α-olefins, sulfur trioxide and subsequent neutralization. This production method is as follows that the obtained olefin sulfonates may contain minor amounts of hydroxyalkanesulfonates and alkanedisulfonates.

Preferred anionic surfactants also include carboxylates, with examples of fatty acid soaps and comparable surfactants. Soaps may be saturated or unsaturated and may contain various substituents, such as hydroxyl groups or α-sulfonate groups. Preference is given to linear saturated or unsaturated hydrocarbon radicals as hydrophobic groups containing from about 6 to about 30, and preferably from 10 to about 18 carbon atoms.

Suitable anionic surfactants also include salts of acylaminocarboxylic acids, acyl sarcosinates obtained by reacting fatty acid chlorides with sodium sarcosinate in an alkaline environment; condensation products of fatty acids and proteins obtained by the interaction of fatty acid chlorides with oligopeptides; salts of alkyl sulfamidocarboxylic acids; salts of alkyl and aryl ethers of carboxylic acids; sulfonated polycarboxylic acids; alkyl and alkenilglitserilsulfaty such as oleilglitserilsulfaty, alkylphenol ether sulfates, alkyl phosphates, alkyl ether phosphates, isethionates such as the acyl isethionates, N-acyl taurides, isethionates, sulphosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated monoesters of C ₁₂ -C ₁₈₎ and sulfosuccinate diesters (in particular C ₁₂ -C ₁₈ saturated and unsaturated diesters), acyl sarcosinates, alkyl polysaccharide sulfates such as alkyl polyglycoside sulfates, branched primary alkyl sulfates and alkyl fields ethoxycarboxylates, such as compounds of the formula RO (CH ₂ CH ₂ ) _k CH ₂ COO ^- M ⁺ , where R is (C ₈ -C ₂₂ ) -alkyl, k is a number from 0 to 10, and M is a cation.

Nonionic Surfactants

Condensation products of aliphatic alcohols with from about 1 to about 25 mol of ethylene oxide.

The alkyl chain of aliphatic alcohols may be linear or branched, primary or secondary and contains, in general, from about 8 to about 22 carbon atoms. Particular preference is given to C ₁₀ -C ₂₂ s alcohol condensation products from about 2 to about 18 mol of ethylene oxide per alcohol molecule. The alkyl chain may be saturated or unsaturated. Alcohol ethoxylates may contain ethylene oxide with a narrow homologous distribution ("narrow ethoxylate range") or a wide homologous distribution ("wide ethoxylate range"). This class of products includes, for example, Genapol® products (from Clariant).

Condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol

The hydrophobic part of such compounds preferably has a molecular weight of from about 1500 to about 1800. The addition of ethylene oxide to such a hydrophobic part leads to improved solubility in water. The product is a liquid until the polyoxyethylene content is about 50% of the total mass of the condensation product, which corresponds to condensation with up to about 40 mol of ethylene oxide. Commercially available examples of this class of products are Genapol PF® brand products (from Clariant).

Condensation products of ethylene oxide with the reaction product of propylene oxide and ethylene diamine

The hydrophobic unit of such compounds consists of the reaction product of ethylene diamine with an excess of propylene oxide and, as a rule, has a molecular weight in the range of about 2500-3000. Ethylene oxide is attached to such a hydrophobic unit to a level of from about 40 wt.% To about 80 wt.% Polyoxyethylene and a molecular weight of about 5000-11000. Commercially available examples of this class of compounds are Tetronic® grades from BASF and Genapol PN® grades from Clariant GmbH.

Semipolar nonionic surfactants

The category of nonionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides, each type of compound containing an alkyl radical with from about 10 to about 18 carbon atoms. Semipolar nonionic surfactants also include amine oxides of the formula

where R represents an alkyl, hydroxyalkyl or alkyl phenol group with a chain length of from about 8 to about 22 carbon atoms, R ² represents an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms, or mixtures thereof, each radical R ¹ represents an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide units, and x is from 0 to about 10. Groups R ¹ mo ut connected together through an oxygen or nitrogen atom and thus form a cycle. Amino oxides of this type are, in particular, (C ₁₀ -C ₁₈ ) -alkyl dimethyl amine oxides and (C ₈ -C ₁₂ -alkoxyethyl dihydroxyethyl amine oxides.

Fatty acid amides

Fatty acid amides have the formula

where R represents an alkyl group containing from about 7 to about 21, and preferably from about 9 to about 17 carbon atoms, and each radical R ¹ represents a hydrogen atom, (C ₁ -C ₄ ) -alkyl, (C ₁ —C ₄ ) hydroxyalkyl or (C ₂ H ₄ O) _x H, where x ranges from about 1 to about 3. Preferred are (C ₈ -C ₂₀ ) amides, monoethanolamides, diethanolamides and isopropanolamides.

Suitable nonionic surfactants also include alkyl and alkenyl oligoglycosides and also polyglycol fatty acid esters or polyglycol fatty amine ethers, which all contain 8-20, and preferably 12-18 carbon atoms in the fatty alkyl portion, alkoxylated triglycamides, mixed ethers or mixed formyls, alkyl oligoglycosides, alkenyl oligoglycosides, fatty acid N-alkyl glucamides, phosphine oxides, dialkyl sulfoxides and protein hydrolysates.

Polyethylene, polypropylene and polybutylene alkyl phenol condensates

Such compounds include condensation products of alkyl phenols with a (C ₆ -C ₂₀ ) -alkyl group, which may be either linear or branched, with alkylene oxides. Preference is given to compounds containing from about 5 to about 25 moles of alkylene oxide per mole of alkyl phenol. Commercially available surfactants of this type are, for example, Arkopal N® brand products (from Clariant). Such surfactants are referred to as alkyl phenol alkoxylates, an example of which are alkyl phenol ethoxylates.

Zwitterionic Surfactants

Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkylamide betaines, aminopropionates, aminoglycinates or amphoteric imidazolinium compounds of the formula

where R ¹ is (C ₈ -C ₂₂ ) -alkyl or alkenyl, R ² is hydrogen or CH ₂ CO ₂ M, R ³ is CH ₂ CH ₂ OH or CH ₂ CH ₂ OCH ₂ CH ₂ CO ₂ M, R ⁴ is hydrogen, CH ₂ CH ₂ OH or CH ₂ CH ₂ COOM, Z is CO ₂ M or CH ₂ CO ₂ M, n is 2 or 3, preferably 2, M is hydrogen or a cation, such as an alkali metal cation, alkaline earth metal, ammonium or alkanolammonium.

Preferred amphoteric surfactants of this formula are monocarboxylates and dicarboxylates. Examples thereof are cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate (also called cocoamphodiacetate) and cocoamphoacetate.

Preferred amphoteric surfactants also include alkyl dimethyl betaines (Genagen LAB / ® Clariant GmbH) and alkyl dipolyethoxy betaines with an alkyl radical of from about 8 to about 22 carbon atoms, which may be linear or branched, preferably with 8-18 carbon atoms, and more preferably containing from about 12 to about 18 carbon atoms.

Suitable cationic surfactants include substituted or unsubstituted linear or branched chain Quaternary ammonium salts of the type R ¹ N (CH ₃ ) ₃ ⁺ X ^- , R ^l R ² N (CH ₃ ) ₂ ⁺ X ^- , R ¹ R ² R ³ N (CH ₃ ) ⁺ X ^- or R ¹ R ² R ³ R ⁴ N ⁺ X ^- . The radicals R ¹ , R ² , R ³ and R ⁴ can, preferably independently, represent unsubstituted alkyl with a chain length of 8-24 carbon atoms, and in particular 10-18 carbon atoms, hydroxyalkyl containing from about 1 to about 4 carbon atoms, phenyl, (C ₂ -C ₁₈ ) alkenyl, for example, fatty alkenyl or oleyl, (C ₇ -C ₂₄ ) aralkyl, (C ₂ H ₄ O) _x H, where x is from about 1 to about 3, or alkyl radicals containing one or more ester groups, or cyclic quaternary ammonium salts. X represents a suitable anion.

Along with surfactants, other materials may also be present, such as

odor absorbers, deodorants, flavorings, antistatic agents, antimicrobial agents such as bactericides and fungicides, preservatives, solubilizers, agents, regenerating fibers, finishes, emulsifiers, enzymes, impregnating substances, and also water in small quantities.

Examples

The studies described herein below are carried out using tetramethoxyethane (TME) of formula (2) as an example of a solvent of formula (1).

As standard solvents use

tetrachlorethylene (= perchlorethylene, = PER) and

C _10-13 -isoalkanes (= hydrocarbon solvent = HCS).

Example 1

The ability to remove a liquid paraffin stain from various tissues is examined for standard tests at the Waschereiforschunganstalt Krefeld Laundry Research Institute.

The fabrics used for testing are

cotton wfk 10A, polyester cotton wfk 20A, polyester wfk 30A, polyamide wfk 40A, acrylic wfk 50A, woolen wfk 60A and silk wfk 70A.

Each of these tissues is contaminated with paraffin oil stained with Sudan Red, a fat-soluble dye. The reflection coefficient (degree of whiteness) of the contaminated tissues is measured.

The test fabrics are then washed with tetramethoxyethane and standard solvents at room temperature in a Linitest laboratory washing machine. For each type of fabric, washing includes unpainted white fabric of the same type so that the transfer / reprecipitation of dirt can be investigated. After washing, the test fabrics are dried and evaluated as described below.

The amount of separated dirt, the reflection coefficient (degree of whiteness) of clean tissues are determined, and the difference with the values measured for contaminated tissues is calculated.

The higher the dR values of reflection coefficients, the better the removal of experimental contamination. In order to determine the re-deposition of dirt, compare the values of L, a, b of adjacent white fabrics before and after washing and calculate the color difference dE.

The smaller the color difference dE, the less tissue samples are stained due to the transfer of dirt (reprecipitation).

Table 1 Parametric oil removal with tetramethoxyethane compared to PER and HSC Test fabric dR whiteness (%) after cleaning ... tetramethoxyethane Per Hsc wfk 10A 47.1 45.8 38.6 wfk 20A 41.9 41,4 37.1 wfk 30A 38,2 36.8 36,4 wfk 40A 21.7 21.5 20.1 wfk 50A 40.9 39.5 39.6 wfk 60A 35.0 34.0 34.2 wfk 70A 28.0 26.3 27.6 General (all fabrics) 252.8 245.3 233.6

table 2 dE staining of white tissues due to reprecipitation of dirt Test fabric dE staining of white fabrics by re-deposition of dirt in ... tetramethoxyethane Per Hsc wfk 10A 1.7 2.0 4.6 wfk 20A 1.7 2.1 2.6 wfk 30A 0.7 0.9 1,0 wfk 40A 2.2 2.2 3.2 wfk 50A 0.8 2.5 1,2 wfk 60A 3.0 3,5 1,0 wfk 70A 0.7 2.6 0.5 General (all fabrics) 10.8 15.8 14.1

Example 2

Investigate the ability to remove stain of vegetable oil from various tissues for standard tests of the Laundry Research Institute Waschereiforschunganstalt Krefeld. The vegetable oil used for testing is sunflower oil, also dyed with Sudan red.

The analysis procedure is similar to the procedure in example 1.

Table 3 Removal of sunflower oil with tetramethoxyethane compared to PER and HSC Test fabric dR whiteness (%) after cleaning ... tetramethoxyethane Per Hsc wfk 10A 46.0 42.9 36,2 wfk 20A 43.3 41.3 38.3 wfk 30A 36.5 34.7 35.3 wfk 40A 21.1 19.8 19.9 wfk 50A 24.8 23.3 22.1 wfk 60A 17.0 17.1 17.6 wfk 70A 15.9 15,2 15.8 General (all fabrics) 204.6 194.3 185.2

Table 4 dE staining of white tissues due to reprecipitation of dirt Test fabric dE staining of white fabrics by re-deposition of dirt in ... tetramethoxyethane Per Hsc wfk 10A 1.8 2,4 4.0 wfk 20A 1.8 2.0 2,8 wfk 30A 0.8 1,2 1,0 wfk 40A 2.2 2,3 3.2 wfk 50A 0.7 1.8 1.4 wfk 60A 3,5 3.6 1,0 wfk 70A 0.6 1,6 0.8 General (all fabrics) 11,4 14.9 14.2

Example 3

The cleaning ability of tetramethoxyethane is compared with PER and HSC on various contaminated standardized fabrics from the Waschereiforschunganstalt Krefeld Laundry Research Institute. The following test fabrics are used: cotton-polyester wfk 20C (fabric mixed with greasy pigment stain) and cotton-polyester wfk 20D (fabric mixed with stained synthetic skin fat). Test tissues are washed in a Linitest laboratory washing machine at room temperature. The wash includes an uncontaminated wfk 20A white fabric so that the transfer of dirt from the contaminated fabric to the white fabric can be investigated.

Quantitative determination of tissue cleansing and cleaning efficiency, based on measurements, and the transfer of dirt / graying is carried out as described in example 1.

Table 5 Cleaning standard contaminated tetramethoxyethane test fabrics compared to PER and HSC Test fabric Increase in dR (%) of the brightness after brushing ... tetramethoxyethane Per Hsc wfk 20C 17.9 13.7 17,2 wfk 20D 17.6 9.5 11.5 General (all fabrics) 35.5 23,2 28.7

Table 6 dE staining of white tissues due to reprecipitation of dirt White fabric washed in the presence of ... dE staining of white fabrics by re-deposition of dirt in ... tetramethoxyethane Per Hsc wfk 20C 4.3 9.2 5.9 wfk 20A 6.5 7.2 5.1 General (all fabrics) 10.8 16,4 11.0

Example 4. The stability of dyeing textile products

The dyeing stability of textiles is tested on various commercially available dyed fabrics. Dyed fabrics are

1) 100% polyamide, turquoise,

2) 100% polyester, pure bright blue,

3) 100% polyester, yellow,

4) 100% silk, burgundy,

5) 100% silk, dark green,

6) 100% viscose, burgundy,

7) 100% viscose, black,

8) 100% wool, brownish yellow.

Two samples of the dyed fabric were simultaneously washed along with 4 samples of the white wfk 20A tetramethoxyethane test fabric and standard solvents in a Linitest washing machine at room temperature.

One stained sample and two white samples are removed after 10 minutes. The second stained swatch and the remaining two white swatches are erased for another 50 minutes.

After drying, dyed fabrics and white fabrics are evaluated as follows.

The color difference dE with unwashed stained tissues is determined in order to quantify the color retention of stained tissues. The lower the color differences dE, the less the detergent affects the color.

The possible transfer of contamination due to dye separation is quantified by measuring the color difference dE of the erased white samples relative to the non-washed white samples. The lower the dE value, the less white tissue stains with stained tissues.

Ideally, the values of dE are equal to zero both in the case of color preservation and in the case of color transfer.

Table 7 Preservation of color of various dyed textiles after washing with tetramethoxyethane for 10 min in comparison with PER and HCS Dyed fabric Color differences dE after a 10-minute wash in ... Tme Per HCS 100% Polyamide, Turquoise 0.6 2.1 2.1 100% polyester, pure bright blue 0.2 0.4 0.2 100% polyester, yellow 0.9 1.4 1,0 100% silk, Bordeaux 1,0 0.1 0.6 100% silk, dark green 0.4 0.2 0.3 100% viscose, Bordeaux 1,0 0.9 1,1 100% viscose, black 0.6 1,1 0.8 100% Wool, Brownish Yellow 0.4 0.6 1,0 General (all fabrics) 5.1 5.8 7.1

Table 8 Preservation of color of various dyed textiles after washing with tetramethoxyethane for 60 min in comparison with PER and HCS Dyed fabric Color differences dE after a 60-minute wash in ... Tme Per HCS 100% Polyamide, Turquoise 1,0 2.7 2,4 100% polyester, pure bright blue 0.4 0.4 0.3 100% polyester, yellow 1,2 1,5 1,5 100% silk, Bordeaux 1.8 0.8 1.4 100% silk, dark green 0.6 1.3 0.4 100% viscose, Bordeaux 2.6 0.9 2,3 100% viscose, black 0.7 1,1 1,2 100% Wool, Brownish Yellow 0.9 1,2 1,2 General (all fabrics) 9.2 9.9 10.7

Table 9 Transfer of dye to white fabric when washing with dyed fabrics in tetramethoxyethane for 10 min in comparison with PER and HCS White fabric, washed in the presence of dyed fabric ... dE staining after 10 min washing in ... Tme Per HCS 100% turquoise polyamide 4.4 4,5 3,5 100% Polyester Pure Bright Blue 2.6 3.0 3.2 100% Polyester Yellow 2.1 2.1 2.0 100% Bordeaux silk 2,8 3.0 2.9 100% dark green silk 2,8 3.4 2.6 100% Viscose Bordeaux 2,4 2,8 2.6 100% viscose black 2,3 2.5 2,4 100% Wool Brown 2.5 2.9 2,8 General (all fabrics) 21.9 24.2 22.0

Table 10 Transfer of dye to white fabric when washing with dyed fabrics in tetramethoxyethane for 60 min in comparison with PER and HCS White fabric, washed in the presence of dyed fabric ... dE staining after 60 min washing in ... Tme Per HCS 100% turquoise polyamide 4.9 4.7 4.6 100% Polyester Pure Bright Blue 2.6 3.0 3.2 100% Polyester Yellow 2.1 2.1 2.2 100% Bordeaux silk 3.2 3.2 2.9 100% dark green silk 2.9 3.6 2,8 100% Viscose Bordeaux 3.0 3.4 2.7 100% viscose black 2,4 2.7 2.7 100% Wool Brown 2.7 3.0 2.9 General (all fabrics) 23.8 25.7 24.0

Claims (8)

1. A method of cleaning a textile product, comprising processing a textile product using a compound of formula (I)

where a represents (CH ₂ ) _a ,
R ¹ , R ² , R ³ and R ⁴ are the same or different are (C ₁ -C ₄ ) -alkyl, and
a is 0. 2. The method according to claim 1, where the compound of formula (1) is used for the basic cleaning operation. 3. The method according to claim 1, where the compound of formula (1) is used as a component for removing stains, a cleaning enhancer or a cleaning activator. 4. The method according to claim 1, where the textile product is treated with a compound of the formula (1), where R ¹ , R ² , R ³ and R ⁴ are methyl and / or ethyl, and a is 0. 5. The method according to claim 1, where the method of dry cleaning of textile products is carried out in an industrial environment. 6. The method according to claim 1, where the method of dry cleaning textile products is carried out at home. 7. The method according to claim 1, in which the compounds of formula (I) are used, where R ¹ , R ² , R ³ and R ⁴ contain different numbers of carbon atoms. 8. The method according to claim 1, in which two or more compounds of the formula (1) are used, which differ in the number of carbon atoms in their composition.