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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium 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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/001—Softening compositions
  • C11D3/0015—Softening compositions liquid
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/46—Compounds containing quaternary nitrogen atoms

Definitions

• R and R are selected from the group consisting of alkyl and alkenyl having from 10 to 24 carbon atoms, R is alkyl having 1 to 4 carbon atoms, A is selected from the group consisting of alkenyl and alkenylene having from 2 to 5 carbon atoms, X is an anion selected from the group consisting of halide and the anion of an organic, non-surface-active acid and n is an integer of 1 or 2.
• Liquid compositions containing from 1 to 25% by wegiht of said carboxylic acid esters and the process of softening washed textiles are also disclosed.
• liquid softening rinsing agents for laundry on the market which contain as active ingredient difattyalkyldimethylammonium salts, generally in the form of halides, in an aqueous dispersion. It is known, however, that such cationic softening rinsing agents, even in a strict adherence to the application directions, effect adversely the absorptivity of the treated laundry.
• R and R are selected from the group consisting of alkyl and alkenyl having from to 24 carbon atoms, R is alkyl having 1 to 4 carbon atoms, A is selected 3,729,416 Patented Apr. 24:, 1973 from the group consisting of alkenyl and alkenylene having from 2 to 5 carbon atoms, X is an anion selected from the group consisting of halide and the anion of an organic, non-surface-active acid and n is an integer of 1 or 2.
• a further object of the present invention is the obtention of liquid softening rinsing agent compositions consisting essentially of (A) From 1% to 25% by weight of an unsaturated carboxylic acid ester of the formula wherein R and R are selected from the group consisting of alkyl and alkenyl having from 10 to 24 carbon atoms, R is alkyl having 1 to 4 carbon atoms, A is selected from the group consisting of alkenyl and alkenylene having from 2 to 5 carbon atoms, X is an anion selected from the group consisting of halide and the anion of an organic, non-surface-active acid and n is an integer of 1 or 2.
• a yet further object of the invention is the development of a process for the softening of washed textiles which consists of rinsing said washed textiles with a rinse liquid containing from 0.1 to 2.0 gm./l. of an unsaturated carboxylic acid ester of the formula wherein R and R are selected from the group consisting of alkyl and alkenyl having from 10 to 24 carbon atoms, R is alkyl having 1 to 4 carbon atoms, A is selected from the group consisting of alkenyl and alkenylene having from 2 to 5 carbon atoms, X is an anion selected from the group consisting of halide and the anion of an organic, non-surface-active acid and n is an integer of 1 or 2, drying said textiles and recovering said softened, washed textiles.
• rinsing bath which substances are usable for the after-treatment of washed laundry, such as optical brighteners, anti-microbial active agents, souring agents, sequestering agents, perfumes and dyes, etc. At least part of these substances should be acidic, and the amount of the acidic substances, particularly of the souring and sequestering agents is selected so that the rinsing bath has a neutral to weakly acidic pH range.
• the alkyl radicals R and R may be straight-chain or branched, and can be, for instance, lauryl, myristyl, cetyl, oleyl, stearyl, arachidyl, behenyl, lignoceryl, etc.
• alkyl radicals R and R which are derived from natural fatty acids, particularly from hardened tallow fatty acids or coconut fatty acids.
• A is an alkenyl
• it can be, for instance, vinyl, allyl, isopropenyl, l-propenyl, Z-butenyl, 1,3-butadienyl, etc.
• a is an alkenylene it can be, for instance, vinylene, methylvinylene, 1,4 butz.dienylene-( 1,3), etc.
• the radical A may be present both in the cis and in the trans form.
• the particularly preferred compounds of the Formula I are the esters of acrylic, methacrylic and crotonic acids, 3-butene carboxylic acid and 3-methyl-3-butene carboxylic acid, as well as of maleic, fumaric, itaconic, mesaconic, methylenemalonic, citraconic, muconic acids, etc.
• the active softening ingredients of Formula I used according to the invention, can be prepared in a known, not claimed herein, manner.
• the compounds of Formula I may be obtained by the reaction of the alkali salts of the unsaturated carboxylic acids with 3-chloro-2-hydroxypropyltrialkyl-ammonium halide or by the reaction of the unsaturated carboxylic acid with glycidyl-trialkylammonium halide.
• the compounds may be obtained from the unsaturated carboxylic acid, an epihalohydrin, for instance, epichlorohydrin, and a tertiary amine by reaction in an inert solvent.
• the object of the invention is a liquid softening rinsing agent for laundry consisting of dispersions or solutions of esters of unsaturated carboxylic acids of the above-defined Formula I and, optionally, of other conventional ingredients of softening rinsing agents for laundry in water and/or water soluble organic solvents.
• compositions are liquid softening rinsing agent compositions consistin essentially of (A) From 1% to 25% by weight of an unsaturated carboxylic acid ester of the formula wherein R and R are selected from the group consisting of alkyl and alkenyl having from 10 to 24 carbon atoms, R is alkyl having 1 to 4 carbon atoms, A is selected from the group consisting of alkenyl and alkenylene having from 2 to 5 carbon atoms, X is an anion selected from the group consisting of halide and the anion of an organic, non-surface-active acid and n is an integer of l or 2,
• ingredients of softening rinsing agents for laundry are, for instance, considered optical brighteners, antimicrobial active ingredients, souring and sequestering agents, perfumes and dyes, etc.
• the carboxylic esters of the Formula I are mostly present as oily, pasty or waxy substances. Their consistency depends widely upon the length and degree of saturation of the radicals R and R also whether the radicals R and R possess a homogenous chain length or if they are present as technical mixtures of homologs.
• Such liquid softening rinsing agents for laundry contain the carboxylic acid esters, serving as textile softeners, of the Formula I in amounts of from 1-25% by weight. If the liquid agents contain additionally nonionic dispersing agents, the latter are present in amounts of up to 8.0% by weight, preferably in amounts of from 0.2-6.0% by weight; water soluble organic solvents may be present in amounts up to 30.0% by weight, preferably in amounts of from 02-30% by weight. Water represents the balance of the compositions.
• composition of particularly interesting liquid softening rinsing agents for laundry can lie within the following recipe:
• Residue water.
• the active substances, used according to the invention show an excellent softening effect on fabric hardened by washing, particularly cotton terry cloth.
• Particularly advantageous, in comparison to known cationic softeners, is the practically insignificant effect on the absorptivity of these fabrics.
• the softening rinsing agents for washed textiles of the invention render, therefore, the fabric hardened by washing, particularly cotton terry cloth, again agreeably soft and nappy.
• an undesirable static charging of the textiles, particularly those of synthetic fibers is largely prevented.
• the compounds of the Formula I are obtained, as already mentioned, in the preparation generally as halides, particularly as chlorides and bromides.
• the compounds of the Formula I are also incorporated into the agents of the invention as halides.
• at least part of the halide anions may be replaced by other acid radicals which are generally admixed into the preparations of the invention as alkali metal salts and present in this form, conventional ingredients of the softening rinsing agents for washed textiles.
• carboxylic acid ester of the Formula I for instance, the following may be used:
• ingredients contained in the softening rinsing agents for washed textiles of the invention are described more particularly by their various classes.
• nonionic surface-active agents are particularly suited, here designated in the following as nonionics. These are products which owe their hydrophilic properties to the presence of polyether chains, amineoxide, sulfoxide or phosphine oxide groups, alkylolamide groups as well quite generally to an excess of hydroxyl groups.
• nonionics contain in the molecule at least one hydrophobic radical of 8 to 26, preferably 10 to and particularly 12 to 18 carbon atoms and at least one nonionic water-solubilizing group.
• the preferably saturated hydrophobic radical is mostly of an aliphatic, optionally also alicyclic nature.
• connecting member for instance, benzene rings, carboxylic acid ester or carbonamide groups, ether-like or ester-like bound radicals of polyhydric alcohols, such as those of the ethylene glycol, the propylene glycol, the glycerine or of corresponding polyether radicals, are of interest.
• ethylene oxide and/or glycide to fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid or sulfonic acid amides having the above hydrophobic radicals.
• These nonionics may contain from 4 to 1 00, preferably 6 to 40 and particularly 8 to 20 ether groups, above all ethylene glycolether groups, per molecule.
• propylene or butyleneglycolether groups or polyether chains may be present.
• nonionics further belong the products, known under the trade name Pluronics or Tetronics. They are obtained from water-insoluble polyoxypropylene glycols or from water-insoluble propoxylated lower aliphatic alcohols, containing 1 to 8, preferably 3 to 6 carbon atoms, or from water-insoluble propoxylated alkylene diamines. These water-insoluble (that is hydrophobic) propylene oxide derivatives are transformed by ethoxylation to give water-solubility and come under the named nonionics. Finally, as nonionics, *Ucon-Fluid which are partly still water-soluble reaction products of the above-named aliphatic alcohols with propylene oxide, are useable.
• fatty acid or sulfonic acid alkylolamides which are derived, for instance, from mono or diethanolamine, from dihydroxypropylamine or other polyhydroxyalkylamines, for insance the glycamines are in the class of useable nonionics. They can be replaced by amides of higher primary or secondary alkylamines and polyhydroxy carboxylic acids.
• the surface-active amine oxides belong, for instance, the products derived from higher tertiary amines containing one hydrophobic alkyl radical and two shorter alkyl and/ or alkylol radicals with up to 4 carbon atoms.
• nonionic dispersing agents optionally suitable are also non-surface-active, water-soluble or water-emulsifiable or dispersible compounds, such as partial fatty acid glycerides as well as such compounds which contain no hydrophobic radicals in the sense of the above-described nonionic surface-active agents, such as solid or liquid polyethylene glycols, ethylene oxide adducts of glycerine and other polyalcohols, etc.
• water-soluble organic solvents of interest are watersoluble lower alcohols, etheralcohols, glycolethers or ketones with 1 to 6 carbon atoms, such as water-soluble alkanols, for example, metanol, ethanol, propanol, isopropanol; water-soluble alkanediols and alkoxyalkanediols, for example, ethylene and diethylene glycol; and their mono or dimethyl or ethyl ethers; alkanones, such as acetone and methylethylketone, etc. Isopropanol is particularly of practical interest.
• Inorganic and non-surface-active organic acids innocuous to the fibers to be treated, with 1 to 8 carbon atoms, optionally in the form of their slightly acidic to slightly alkaline water-soluble salts are suitable as souring and sequestering agents, such as amidosulfonic acid, urea compounds of orthophosphoric acid, oxalic acid, lactic acid, glycolic acid, citric acid, tartaric acid, benzoic acid, phthalic acid, gluconic acid, acetic acid and propionic acid as well as benzene, toluene or xylene sulfonic acids, sulfoacetic acid or sulfobenzoic acids.
• amidosulfonic acid such as amidosulfonic acid, urea compounds of orthophosphoric acid, oxalic acid, lactic acid, glycolic acid, citric acid, tartaric acid, benzoic acid, phthalic acid, gluconic acid, acetic acid and propionic acid as well as
• the usable brighteners are mostly, if not exclusively, derivatives of diaminostilbene-sulfonic acid, diarylpyrazolines and of the amino-coumarins.
• Examples for brighteners from the class of the derivatives of the diaminostilbene sulfonic acid are compounds according to Formula II:
• R and R signify halogen atoms, alkoxy groups, amino groups or residues of aliphatic, aromatic or heterocyclic, primary or secondary amines, or residues of aminosulfonic acids, while aliphatic residues present in the above groups preferably contain 1 to 4 and especially to 4 carbon atoms, and in the heterocyclic ring systems, fiveor six-membered rings are usually of interest.
• Aniline, anthranilic acid or anilinesulfonic acid residues are preferred as the aromatic amines.
• Brighteners derived from diaminostilbenesulfonic acid are mostly used as cotton brighteners.
• the following products derived from the above Formula II in which R represents the residue -NHC H and R may represent the following residues, are at present on the market.
• Some of these brighteners are to be regarded as transitional types to the cotton brighteners as regards their affinity (for the fiber, for example the brightener in which R equals -NHC H
• the compound 4,4'-bis(4-phenylvicinal-triazolyl-2-)-stilbenedisulfonic acid-2,2 also belongs to the cotton brighteners of the diaminostilbenesulfonic acid type.
• Diarylpyrazolines of Formulas III and IV belong to the polyamide brighteners, of which again a few have a certain affinity for cotton fibers:
• R and R represent hydrogen atoms, or alkyl or aryl residues possibly substituted by carboxyl, carbonarnide or ester groups.
• R and R represent hydrogen or short-chain alkyl residues.
• Ar and Ar represent aryl residues such as phenyl, diphenyl or naphthyl, which may carry further substituents such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, carboxylic acid ester, sulfonic acid, sulfonamide and sulfone groups or halogen atoms.
• 9-cyano-anthracene is also on the market as a polyamide brightener.
• polyamide brighteners for example 4-methyl-7-dimethylaminoor 4-methyl-7-diethyl amino-coumarin.
• polyamide brighteners are the compounds l-(benzimidazolyl-Z)-2-(N-hydroxyethylbenzimidazolyl-Z')-ethylene and 1-N-ethy1-3-phenyl-7-diethylamino-carbostyril.
• Suitable brighteners for polyester and polamide fibers are the compounds 2,5-di-(benzoxazolyl-2)-thiophene and 1,2-di-(5'-methyl-benzoxazolyl- 2' -ethylene.
• Anti-microbial active substances are here understood as bactericidal or bacteristatic or fungicidal or fungistatic acting compounds. These active substance should be water-soluble as such, or in the form of their salts.
• the anti-microbial active substances, usable according to the invention are mostly quaternary ammonium compounds, particularly those which contain, in addition to a long chain aliphatic and two short-chain aliphatic hydrocarbon radicals, an organic radical in the molecule, either aromatic residue connected over an aliphatic carbon atom to the nitrogen atom or an aliphatic residue with double bonds. Examples for such anti-microbial quaternary ammonium compounds are the (following:
• Other usable antimicrobial active substances are the lower alcohols or diols, substituted both by bromine and nitro groups, with 3 to 5 carbon atoms, such as the compounds 2-bromo-2-nitro-propanediol-1,3, l-bromo-l-nitro- 3,3,3-trichloropropanol-2, 2-brorno-2-nitro-butanol-1.
• Example 1 7% by weight of the acrylic acid ester of [2-hydroxy-3- (di-hexadecyl-methyl-ammonium)propyl] chloride; 2% by weight of the adduct of nonylphenol with 9 to 10 mols of ethylene oxide;
• Residue water.
• the softening agent For the preparation of the softening rinsing agent, the softening agent together with the nonionic dispersing agent and the organic solvent were converted to a homogeneous melt at 50 to 60 C. At the same time the glycolic acid and the optical brightener were dissolved in water, and this aqueous solution added the above-named melt with vigorous agitation. The thus-obtained preparation is distinguished by good pourability and distributability in water. Perfumes and dyes may be added to the finished preparation.
• the textile softener the acrylic acid ester of [2-hydroxy-3-(dihexadecyl methylammonium)-propyl] chloide, used according to Example 1, can be prepared by the following procedure, according to US. Pat. 3,397,227.
• Example 2 6% by weight of the acrylic acid ester of [2-hydroxy- 3-(di-tallowalkyl-methyl-ammonium)-propyl] chloride;
• Residue water.
• the textile softening agent composition was compounded as in Example 1.
• Example 3 10% by weight of the acrylic acid ester of [2-hydroxy-3- (dicocoalkyl-methyl-ammonium)-propyl] chloride;
• Residue water.
• the textile softening agent composition was compounded as in Example 1.
• Example 4 terry cloth were rinsed with an aqueous dispersion which contained 0.5 gm./l. or 1.0 gm./l. of active substances, compounded generally as in Example 4, in the last rinse of a drum-washing machine (duration: 5 minutes; liquor ratio 1:25). The samples were then centrifuged and dried by hanging. Subsequently, the hand was judged independently by 4 persons. The evaluation of the hand was expressed in numbers between 1 and 6,
• Fabric type A Samples of new cotton terry cloth were treated for 240 hours in a washing machine under boiling washing conditions with 2.0 gm./l. of sodium tripolyphosphate solution. After drying, the hand number 6 was assigned to this thus pre-hardened fabric.
• Fabric type B Samples of new cotton terry cloth were treated 15 times with a commercial coarse washing agent under boiling washing conditions. After drying, such prehardened fabrics Were assigned the hand number 4. The hand number 1 was assigned to samples of new cotton terry cloth where the sizing was removed and they were treated with a solution of 0.5 gm./l. of ditallowalkyl-dimethyl-ammonium chloride. The softness of new, unlaundered cotton terry cloth corresponds generally to the hand numbers 1.5 to 2.
• Residue water.
• the textile softening agent composition was compounded as in Example 1.
• Example 6 7% by weight of the crotonic acid ester of [2-hydroxy-3- (di-tallow-alkyl-methyl-ammonium)-propyl] chloride; 2% by weight of the adduct of oleyl/cetyl alcohol with about 10 mols of ethylene oxide;
• citric acid 1% by weight of citric acid
• Residue water.
• the textile softening agent composition was compounded as in Example 1.
• the softening rinsing of laundered textiles are treated with a rinsing liquor which contains the softening rinsing agent for laundry of the invention in such an amount that the concentration of the softening agent in the bath liquor is 0.1 to 2.0, preferably 0.2 to 1.0 gm./l.
• a cotton test fabric previously extracted with methanol and dichloromethane served as test material.
• This test fabric was agitated with a dispersion of 0.5 gm./l. of the test preparation (compounded as in Example 4) for 30 minutes, subsequently centrifuged, dried and air-conditioned.
• a fabric treated analogously with water was used.
• the ascending height of water of the softening rinsed strip at the time 1' with the preparation of the invention i is designated as d
• the ascending height of the strip 1 l rinsed with water at the time j is designated as d for the absorptivity value 8; at the time i, that is the percentual residual absorptivity based on water 12
• the absorption time is, according to the true dimension (sec./cm.), a reciprocial speed. An increase, there fore, corresponds a decrease in the absorptivity of the fabric.
• R and R are selected from the group consisting of alkyl and alkenyl having from 10 to 24 carbon atoms, R is alkyl having 1 to 4 carbon atoms,
• A is selected from the group consisting of alkenyl and alkenylene having from 2 to 5 carbon atoms, X is halide and n is an integer of 1 or 2,
• (C) from 0.2% to 30% by Weight of at least one Watersoluble organic solvent having from 1 to 6 carbon atoms selected from the group consisting of watersoluble alkanols, water-soluble alkanediols, Watersoluble alkoxyalkanediols, and water-soluble alkanones, and
• component A is present in an amount of from 2% to 10% by Weight
• component B is present in an amount of from 0.2% to 3% by weight
• component C is present in an amount of from 0.2% to 10% by weight.
• composition of claim 1 containing at least one of the following ingredients in the amount specified:
• a process for the softening of washed textiles which consists of rinsing said Washed textiles with water containing from 0.1 to 2.0 gm./1. of an unsaturated carboxylic acid ester of the formula l I nX- R2 11 References Cited UNITED STATES PATENTS Sobolev 260485 X Sobolev 260486 Eckert et a1. 2528.8 Buck 2528.8 Krause et a1 2528.8 X Carl 117139.5 Balle et al 2528.8 X

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Textile Engineering (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Detergent Compositions (AREA)

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Cited By (11)

• 1970
  • 1970-05-27 DE DE19702025945 patent/DE2025945A1/de active Pending
• 1971
  • 1971-04-29 NL NL7105920A patent/NL7105920A/xx unknown
  • 1971-05-24 BE BE767547A patent/BE767547A/xx unknown
  • 1971-05-24 US US00146515A patent/US3729416A/en not_active Expired - Lifetime
  • 1971-05-25 BR BR3178/71A patent/BR7103178D0/pt unknown
  • 1971-05-26 ES ES391583A patent/ES391583A1/es not_active Expired
  • 1971-05-26 AT AT454671A patent/AT331761B/de not_active IP Right Cessation
  • 1971-05-27 FR FR717119251A patent/FR2100691B1/fr not_active Expired
  • 1971-05-27 ZA ZA713427A patent/ZA713427B/xx unknown

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