CN1106872A - Aqueous textile auxiliary formulations - Google Patents

Aqueous textile auxiliary formulations Download PDF

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Publication number
CN1106872A
CN1106872A CN94109500A CN94109500A CN1106872A CN 1106872 A CN1106872 A CN 1106872A CN 94109500 A CN94109500 A CN 94109500A CN 94109500 A CN94109500 A CN 94109500A CN 1106872 A CN1106872 A CN 1106872A
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Prior art keywords
formula
textile auxiliary
surface active
acid
ionic surface
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Inventor
R·库瑞黎
A·施泰林
W·施赖博
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Novartis AG
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Ciba Geigy AG
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    • 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
    • C11D3/0026—Low foaming or foam regulating 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
    • 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
    • D06M13/10—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 oxygen
    • D06M13/165—Ethers
    • 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
    • D06M13/10—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 oxygen
    • D06M13/165—Ethers
    • D06M13/17—Polyoxyalkyleneglycol ethers
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers

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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)
  • Detergent Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Described are low-foam aqueous textile auxiliaries comprising (a) a nonionic surfactant of the formula (1) (b) a nonionic surfactant of the formula (2) (c) a polymeric compound of an ethylenically unsaturated sulphonic or carboxylic acid or anhydride, (d) a hydrotroping agent and optionally (e) an aliphatic, saturated monoalcohol. The textile auxiliaries are suitable for use as dispersants and for wetting, washing and/or bleaching fibre materials.

Description

Aqueous textile auxiliary formulations
The present invention relates to low foam, non-silicone aqueous textile auxiliary formulations, their preparation and the stabilizing agent of various application thereof as bathing as wetting agent, surfactant, dispersant or peroxide bleaching.
Wetting agent is used for the preliminary treatment of textile fiber material, and its effectiveness comprises, especially promotes the separation of fiber impurity or the carrying out of acceleration bleaching process.This analog assistant must satisfy (Comply
Figure 941095002_IMG7
Meet satisfy) about the different requirements of application facet, must be chemically stable as them under strong alkaline condition usually, also must have short wetting time, be low foaming and can suppress the production process foaming and be easy to biodegradable.
By the fatty pure polyglycol ether of the known wetting agent of prior art and, the end-blocking fatty alcohol polyglycol ether of so-called compound ether particularly.In the aliphatic alkyl chain, contain 8-12 carbon atom and in polyether chain, contain the foam inhibition auxiliary agent of the compound ether of 7-12 ethylene oxide unit(s) as EP-A-0124815 is disclosed as low foaming cleaner.International pct application WO92/15664 discloses textile auxiliary formulations, and this prescription also contains the fatty alcohol polyglycol ether of open chain and/or end-blocking except the homopolymers of olefinic unsaturated sulfonic acid or carboxylic acid or their acid anhydrides.
Unexpectedly find now, the aliphatic alcohol polyglycol ether that contains the special end-blocking of special structural units (as aliphatic alkyl group, propoxylation degree, ethoxylation degree and end-blocking) combination has good low foaming characteristic, wettability, alkali resistance and biological degradability, it is splendid therefore being used for textile auxiliary formulations.
Therefore, the aqueous textile auxiliary formulations that the present invention relates to comprises:
(a) formula (1) non-ionic surface active agent
Figure 941095002_IMG8
In the formula
R 1Be that strictness is 8-10 linear carbon atom alkyl group,
R 2Be the alkyl group of 1-4 carbon atom,
m 1Be the numerical value of 0.5-2,
n 1Be the numerical value of 6-9.
(b) formula (2) non-ionic surface active agent (2)
Figure 941095002_IMG9
In the formula
R 3Be C 8-C 18Alkyl,
R 4Be hydrogen, methyl or ethyl,
n 2Be the numerical value of 1-40,
(c) polymer of olefinic unsaturated sulfonic acid or carboxylic acid or their acid anhydrides,
(d) hydrotropic agent, as optional components,
(e) aliphatic saturated monohydroxy alcohol.
Because they have the inhibition of extremely low foamability and the foaming of good production process, can exempt therefore that the other foam in hibitors of interpolation particularly contains silicone compounds in the fabric auxiliary agent.
Substituent R in the formula (1) 1Be the straight-chain alkyl of 8-10 carbon atom radical of saturated aliphatic monohydric alcohol, i.e. n-octyl, n-nonyl or positive decyl, preferred R 1It is n-octyl.The chain part that " it is linear that strictness is " speech implication in this article can be regarded as alkyl is no more than 0.5%(weight).Therefore obviously containing the side chain homologue usually in 5-25%(weight) compound ether based on oxo alcohol of scope is not suitable for as non-ionic surface active agent (a).
R in the formula (1) 2Be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl or the tert-butyl group, preferred R 2It is normal-butyl.
m 1Preferred value is 1.2-1.7, n 1Preferred value is 6-8, most preferably is 6-7.
About low foaming power, wettability and biological degradability, formula (3) compound ether is a particular importance for being used as component (a),
Figure 941095002_IMG10
The method that obtains this compound ether at first is that the expoxy propane with suitable mol ratio is that oxirane adds in the n-octyl alcohol then, then with the n-butyl chloride end-blocking.
These capped nonionics prepare with known method, common expoxy propane and oxirane and 1mol alcohol R with suitable mol ratio 1-OH reaction, then, gained adduct and alkyl halide R 2-Hal, preferred C 1-C 4Alkyl chloride reacts.
Formula (2) component (b) is (nio-surfactant) non-ionic surface active agent of last end-blocking.R in the formula (2) 3Base is from the saturated C of aliphatic series 8～C 18Monohydric alcohol, from natural alcohols such as laruyl alcohol, myristyl alcohol, cetanol or stearyl alcohol and from synthetic alcohols such as 2-ethylhexanol, 1,1,3,3-tetramethyl butanols, suffering-2-alcohol, isononyl alcohol, trimethyl be alcohol, Exxal 12, Decanol, C usually 9～C 13Oxo alcohol, tridecanol, different tridecanol or contain the linear primary alconol (Alfols) of 8～18 carbon atoms.Some representative of this class Alfols is Alfol(8-10), Alfol(9-11), Alfol(10-14), Alfol(12-13) or Alfol(16-18).(" Alfol " is registration mark).
Be applicable to that the illustrative examples as the non-ionic surface active agent of component (b) is the addition polymer that preferably contains the saturated alcohols of 2-10mol oxirane and 8-18 carbon atom.
The non-ionic surface active agent of formula (4) representative is significant especially,
Figure 941095002_IMG11
In the formula
R 5Be C 11～C 13Alkyl
Component (c) can be homopolymers or copolymer.
The starting monomer that is applicable to preparation component (c) homopolymers is ethylenically unsaturated monomer sulfonic acid or carboxylic acid.Monocarboxylic acid, dicarboxylic acids and their acid anhydrides and sulfonic acid all are suitable for, and each acid contains ethylenically unsaturated aliphatic group and preferred no more than 7 carbon atoms.The monocarboxylic acid that contains 3-5 carbon atom is preferred, generally includes acrylic acid, methacrylic acid, the acid of α propylene halide, 2-ethoxy acrylic acid, α alpha-cyanoacrylate, butenoic acid and vinyl acetic acid.Preferred olefinic unsaturated dicarboxylic acid is fumaric acid, maleic acid or itaconic acid and mesaconic acid, citraconic acid, glutaconate and methylmalonic acid.Particularly preferably be maleic anhydride in these sour acid anhydrides.
The monomer sulfonic acid that is applicable to homopolymerization generally comprises vinyl sulfonic acid or 2-acrylamido-2-methyl propane sulfonic acid.The preferred polymeric carboxylic acid is a polymethylacrylic acid, the polyacrylic acid of more specifically saying so.Polyacrylic molecular weight ranges used in the invention process is from 1000-2, and 000,000, be preferably 3500-800,000.
The homopolymers that is applicable to new formulation component (c) is to prepare with known method, can make by in temperature range 60-100 ℃ that is suiting in the presence of the catalyst monomer that is suitable for being carried out polymerization easily.
Preferably can form the initator of free radical for the catalyst of preparation component (c).For the illustrated example that realizes the initator that this reaction is suitable be symmetrical aliphatic azo-compound such as azobis isobutyronitrile, azo two (2-methyl valeronitrile), 1,1 '-azo two (1-encircles nitrile) and 2,2 '-azo pair isobutyric acid Arrcostabs; Symmetry diacyl peroxide such as acetyl group, propiono or bytyry peroxide, benzoyl peroxide and lauroyl peroxide that benzoyl peroxide, bromine, nitro, methyl or methoxy replace; Peroxidating dicarboxylic ester such as peroxidating diethyl dicarboxylate, diisopropyl ester, two cyclohexyl esters and the dibenzyl ester of symmetry; Cross the sad tert-butyl ester, t-butyl perbenzoate or peracetic acid tert-butyl group phenyl ester and peroxide carbamate such as the tert-butyl group-N-(phenyl peroxide) carbamate or the tert-butyl group-N-(2, the 3-dichloro or-4-chlorphenyl peroxide) carbamate.Other peroxide that is suitable for is that tert-butyl hydroperoxide, di-tert-butyl peroxide, cumene hydroperoxide, dicumyl peroxide and the tert-butyl group are crossed pivalate.Other compounds suitable for use is a potassium peroxydisulfate, and it is optimized in the enforcement of the present invention.
The positive usual amounts of catalyst is the 0.1-10%(weight of raw material), be preferably 0.5-2%(weight).
It is favourable reacting under inert atmosphere, is easily in blanket of nitrogen.
As fruit component (c) is a copolymer, can be prepared on the spot, promptly side by side prepares with new formulation.The embodiment of this method variant is described in down.
The hydrotropic agent of component (c) can be selected from:
-Shi (5) is fragrant and mellow
Figure 941095002_IMG12
In the formula
X 1Be-(CH 2) 1-6,-CH=CH-CH 2-or-O-(CH 2) 2-6,
R 6, R 7And R 8Be hydrogen, hydroxyl, halogen or C independently of one another 1-C 6Alkoxyl generally includes benzylalcohol, 2,4-dybenal, benzyl carbinol, phenoxetol, 1-phenoxy group-2-propyl alcohol (phenoxy group isopropyl alcohol) and cinnamyl alcohol;
The sulfonate of-terpenoid or monokaryon or double-core aromatic compounds is as the sulfonate of camphor, toluene, dimethylbenzene, cumene and naphthols;
-saturated and undersaturated aliphatic C 1-C 11Monocarboxylic acid such as acetate, propionic acid, acid or undecenoic acid;
-saturated or unsaturated C 3-C 12Binary or polybasic carboxylic acid such as malonic acid, succinic acid, glutaric acid, hexanedioic acid, pimelic acid, suberic acid, azelaic acid and decanedioic acid; Hendecanoic acid and dodecane dicarboxylic acid, fumaric acid, maleic acid, tartaric acid and malic acid and citric acid and aconitic acid;
All above-mentioned organic acids can be their water soluble salts also, as alkali metal salt, and particular certain cancers or sylvite or ammonium salt.
The particularly preferred novel hydrotropic agent that is suitable for component (d) is formula (a 6) alkyl sulfate
（6）R 9O-SO 3X 2
In the formula
R 9Be (saturated side chain or the straight chain of aliphatic series contains 4-24 carbon atom) group, and
X 2Be hydrogen, alkali metal or ammonium.
If alkyl sodium sulfate salt is the form of salt, it can be sodium salt, sylvite or ammonium salt qualifiedly so, and sodium salt is preferred.
Very preferably the hydrotropic agent as component (d) is an alkyl sulfate, substituent R in its Chinese style (b) 9It is the alkyl that contains 4-24 carbon atom aliphatic series saturated monohydroxy alcohol.This alkyl can be a straight or branched.
The aliphatic saturated monohydroxy alcohol that is suitable for is a natural alcohol, as laruyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, tetracosanol or tadenan.Substituent R 9It is preferred coming the following compounds of the aliphatic side chain synthol of the preferred 4-8 of a self-contained 4-12 carbon atom carbon atom: as isobutanol, sec-butyl alcohol, the tert-butyl alcohol, isoamyl alcohol, 2-ethyl butanol, 2-methyl anyl alcohol, 5-methyl heptan-3-alcohol, 2-ethylhexanol, 1,1,3,3-tetramethyl butanols, suffering-2-alcohol, isononyl alcohol, trimethyl be alcohol, Exxal 12, decyl alcohol or C 9-C 11Oxo alcohol.
Alkyl sulfate can be also can use separately or use as (technical) mixture with the form of its salt in novel wetting agent.
Most preferred hydrotropic agent is a 2-ethylhexyl sulfate
Formula (6) alkyl sulfate and their alkali metal or amine salt also can with some other compound, as with C 1-C 10Alkyl phosphonic acid or C 1-C 10Alkyl phosphonate is together as hydrotropic agent.
These alkyl sulfates can prepare by inciting somebody to action corresponding alcohol and reacting this known method as sulfuric acid, fuming sulphuric acid, chlorosulfonic acid or sulfur trioxide.
The aliphatic alcohol that is applicable to optional components (e) is straight chain alcohol preferably, this class alcohol or by synthetic method preparation or the fatty alcohol obtained from natural material with known method.The alcohol of natural origin comprises as myristyl alcohol, cetanol, stearyl alcohol or oleyl alcohol.Synthol mainly is meant the alcohols of being derived by branched-chain hydrocarbons, generally include isobutanol, sec-butyl alcohol, the tert-butyl alcohol, isoamyl alcohol, 2-ethyl butanol, 2-methyl anyl alcohol, 5-methyl heptan-3-alcohol, 2-ethylhexanol, 1,1,3,3-tetramethyl butanols, suffering-2-alcohol, isononyl alcohol, trimethyl be alcohol, triethyl group nonyl alcohol, Decanol, C 9-C 11Oxo alcohol or hexadecanol.This class alcohol can certainly be mixture, and specifically such mixture can be from the C of common grease chemical industry 4-C 18The standard technique mixture of straight chain alcohol.
The fabric auxiliary formula of preferentially selecting for use comprises:
(a) formula (1) non-ionic surface active agent,
(b) formula (2) non-ionic surface active agent,
(c) polyacrylic acid,
(d) 2-ethylhexyl sodium sulphate,
(e) 3,5, the 5-trimethyl is pure as optional components.
The textile auxiliary formulations of especially preferentially selecting for use comprises:
(a) formula (3) non-ionic surface active agent,
(b) formula (4) non-ionic surface active agent,
(c) polyacrylic acid and
(d) 2-ethylhexyl sodium sulphate.
The method for preparing the fabric auxiliary formula is added component (a) and (b), (c), (d) and optional (e) in the water to, or these components are mixed, and stirring is also added deionized water up to obtaining uniform solution.This process is mechanical means purely, under elevated temperature, generally carries out easily 30-40 ℃ of scope.Chemical reaction does not take place.
Another embodiment of preparation fabric auxiliary agent comprises at first makes monomer olefinic unsaturated sulfonic acid or carboxylic acid or their acid anhydride at one or more non-ionic surface active agents (a) and/or (b), and catalyst exists down, regulate PH to 4.5 and react, add all the other components then until obtaining uniform solution with preparation component (c).
Its PH of the textile auxiliary formulations for preparing is 3-5, preferred 3.5-4.5.Required PH is with as magnesium hydroxide, potassium hydroxide solution, one, two or triethanolamine, and preferably sodium hydroxide solution is regulated.
Preferred fabric auxiliary formula in whole mixtures (percentage by weight is with solid content meter), comprising:
Component (a) 3-40%(weight), preferred 10-30%(weight),
Component (b) 5-40%(weight), preferred 5-20%(weight),
Component (c) 3-20%(weight), preferred 3-10%(weight),
Component (d) 1-15%(weight), preferred 1-10%(weight),
Component (e) 0-10%(weight), preferred 0-5%(weight), and water is added to 100%.
New formulation is the non-silicone textile auxiliary formulations low foaming, that soil release characteristics is arranged.Because they are liquid form, they can use easily, thereby are specially adapted to modern measuring equipment.They serve many purposes so meet different application requirements.
They also can be used as the stabilizing agent that wetting agent, textile detergent, dispersant or peroxide bleaching are bathed.
They are gone back the utmost point and are suitable for as general purpose house detergent in addition.
Therefore, the present invention also relates to the method for wetting, the washing and/or the bleaching of fibrous material, this method comprises being existed by following textile auxiliary formulations handles described material down in aqueous medium.
(a) formula (1) non-ionic surface active agent
Figure 941095002_IMG13
In the formula
R 1Be that strictness is 8-10 linear carbon atom alkyl group,
R 2Be the alkyl group of 1-4 carbon atom,
m 1Be the numerical value of 0.5-2,
n 1Be the numerical value of 6-9,
(b) formula (2) non-ionic surface active agent (2)
Figure 941095002_IMG14
In the formula
R 3Be C 8-C 18Alkyl,
R 4Be hydrogen, methyl or ethyl,
n 2Be the numerical value of 1-40,
(c) polymer of olefinic unsaturated sulfonic acid or carboxylic acid or their acid anhydrides,
(d) hydrotropic agent,
(e) monohydric alcohol that aliphatic series is saturated is as optional components.
The textile auxiliary formulations that preferably is used for this method comprises:
(a) formula (3) non-ionic surface active agent,
(b) formula (4) non-ionic surface active agent,
(c) polyacrylic acid, and
(d) 2-ethylhexyl sodium sulphate.
Adding the consumption of handling textile auxiliary formulations of the present invention in the bath to is 0.1-60 grams per liter (handle and bathe), is preferably 0.2-10 grams per liter (handle and bathe).These baths also can contain other component such as desizing agent, dyestuff, fluorescent whitening agent, synthetic resin and alkali such as NaOH, hydrogen peroxide and magnesium salts.
The useful fiber material is: native cellulose that cellulose is particularly not pretreated such as hemp, flax, jute, viscose staple fibre, viscose, acetate rayon, native cellulose fibre and preferred raw cotton, wool, polyamide, polyacrylonitrile or polyester fiber and blended fiber such as polyacrylonitrile/cotton or polyester/cotton flower blended fiber.
Its outward appearance of handled fibrous material can be in any form, as cellulosic material can loose raw material, the form of yarn, fabric or knitwear.This material is usually always with the pure cellulose textile fabric or the form of mixing the textile material of formation with cellulosic textile fibre with synthetic textile fibres.Fibrous material can be handled in the bath at the aqueous solution and handle continuously or batch processing.
The aqueous solution handle to be bathed and can be applied to fibrous material with known method, suitable method be in pad bath, flood to pick-up rate be 70-120%(weight).Padding method is used in particular for steam and pads and pad in the technology in batches.
In temperature is 10-60 ℃ of scope, but preferably at room temperature implement dipping.The heat treatment that makes cellulosic material in temperature is 80-140 ℃ of scope, stand to choose wantonly after dipping and the squeezing.Preferably heat-treat with steam, treatment temperature is 95-140 ℃, preferred 100-106 ℃.Heat treatment need with the time from 30 seconds to 60 minutes.The character and the temperature range that depend on firing equipment.At the article that pad in the technology to be flooded in batches is to be rolled not carry out drying, is packaged in room temperature with plastic sheet and deposits 1-24 hour.
The processing of fibrous material also can (be bathed and be generally 1: 3 to 1: 100 with the article ratio in big the bath, preferred 1: 4 to 1: 25) carry out, temperature 10-100 ℃, preferred 60-98 ℃, usual conditions be under the atmospheric pressure in equipment commonly used as impregnating mangle, injector or dye jigger dye vat in about 1/4 to 3 hour of processing.If desired, also can reach under 150 ℃ and handle, preferred 105-140 ℃, under pressure, in elevated temperature equipment, handle in temperature range.
If technological requirement needs, then this fiber is used warm water, the thorough rinse of cold water then with 90-98 ℃ of hot water, and suitably neutralization is dry under elevated temperature then.
Percentage in following explanation embodiment all by weight percentage.
The preparation of prescription
Embodiment 1:
With the 7.2g50% molecular weight is that 4000 the polyacrylic acid aqueous solution adds in the 50.0g deionized water.
Then following component is admixed successively:
8.2g40%2-ethylhexyl metabisulfite solution,
6.4g6mol the addition polymer of the different tridecanol of oxirane and 1mol (containing active material 90%),
25.5g formula (101) capped nonionics (101)
And 2.7g3,3, the 5-trimethyl is alcohol.
Its cloud point of the prescription of resultant thickness slightly is 35.2 ℃
Embodiment 2:
With the 7.2g50% molecular weight is that 4000 the polyacrylic acid aqueous solution adds in the 50.0g deionized water.
Then following component is admixed successively:
8.2g40%2-ethylhexyl metabisulfite solution,
6.4g3mol oxirane and 1molC 10The fatty alcohol addition polymer,
25.5g formula (101) capped nonionics, and
2.7g3,5, the 5-trimethyl is alcohol.
Its cloud point of the prescription of resultant thickness slightly is 28.3 ℃.
Embodiment 3:
With the 7.2g50% molecular weight is that 4000 the polyacrylic acid aqueous solution adds in the 50.0g deionized water.
Then following component is admixed successively:
8.2g40%2-ethylhexyl metabisulfite solution
6.4g1molC 9-C 11The addition polymer of fatty alcohol and 4mol oxirane,
25.5g formula (101) capped nonionics, and
2.7g3,5, the 5-trimethyl is alcohol.
Its cloud point of the prescription of resulting thickness slightly is 33.5 ℃.
Embodiment 4:
With the 7.2g50% molecular weight is that 4000 the polyacrylic acid aqueous solution adds in the 50.1g deionized water.
Then following component is admixed successively:
8.2g40%2-ethylhexyl metabisulfite solution
9.5g1molC 9-C 11Fatty alcohol and 4mol ethylene oxide addition polymer,
22.3g formula (101) capped nonionics, and
2.7g3,5, the 5-trimethyl is alcohol.
Its cloud point of the prescription of resultant thickness slightly is 38.6 ℃.
Embodiment 5:
With the 7.2g50% molecular weight is that 4000 the polyacrylic acid aqueous solution adds in the 50.1g deionized water.
Then following component is admixed successively:
8.2g40%2-ethylhexyl metabisulfite solution,
12.7g1molC 9-C 11The addition polymer of fatty alcohol and 4mol oxirane,
19.1g formula (101) capped nonionics,
2.7g3,3, the 5-trimethyl is alcohol.
Its cloud point of the prescription of resultant thickness slightly is 41.5 ℃.
Embodiment 6:
With the 7.2g50% molecular weight is that 4000 the polyacrylic acid aqueous solution adds to
50.0g in the deionized water.
Then following component is admixed successively:
8.2g40%2-ethylhexyl metabisulfite solution,
6.4g1molC 9-C 11The addition polymer of fatty alcohol and 4mol oxirane,
25.1g formula (102) capped nonionics
Figure 941095002_IMG16
2.7g3,5, the 5-trimethyl is alcohol.
Its cloud point of the prescription of resultant thickness slightly is 37.7 ℃.
Embodiment 7a: the polymerization of acrylic acid (amount of component b) in the presence of the oxo alcohol ethoxylate:
110.0g deionized water and
38.0g1molC 13The product of oxo alcohol and 4mol oxirane places boiling flask and is heated to 88-92 ℃ under 20 °-30 ℃, obtains the white emulsion of emulsus, muddiness.Under 90 ℃, add 38g acrylic acid and 0.2g potassium peroxydisulfate (being dissolved in 0.6g water) initiator solution simultaneously.
Time to acrylic acid note amount is 180 minutes, to time of initator note amount be 195 minutes.
With the polymer solution stir about of gained 15 to 30 minutes, be cooled to 25 ℃ then.Add at cooling stage
4.5g sodium hydroxide solution (30%) is lower than 70 ℃ in temperature and fully stirs.The emulsus polymer emulsion becomes transparent, colourless and uniform then.
Embodiment 7b: the preparation of new formulation
In temperature is to add in the polymer solution of embodiment 7a preparation under 20-30 ℃:
413.3g deionized water,
88.0g cumene sodium sulfonate (40%),
272.0g formula (101) non-ionic surface active agent, and
29.0g trimethyl is alcohol.
The foam volume of gained new formulation is that the 10ml(test method is referring to embodiment 12-16).
Embodiment 8-11: repeat embodiment 7a and the described process of 7b, each used component is listed in table 1.
Table 1
Figure 941095002_IMG17
Application Example
Below among the embodiment 12-16, carry out the foaming power test by 53902 pairs of prescriptions of the present invention of DIN, if under these experimental conditions foam volume≤50ml, then corresponding prescription is low foaming.
Embodiment 12:
Contain the solution (200ml) of 2.5g/l embodiment 1 preparation prescription, regulate PH to 10, press its foaming power of DIN 53902 measurement of test method with NaOH.Foam volume is 20ml under these experimental conditions.
Embodiment 13:
All the other repeat the process of embodiment 12 except the prescription that the prescription with 2.5g embodiment 2 preparations replaces embodiment 1 to prepare.Foam volume is 20ml.
Embodiment 14:
All the other repeat the process of embodiment 12 except the prescription that the prescription with 2.5g embodiment 3 preparations replaces embodiment 1 to prepare.Foam volume is 30ml.
Embodiment 15:
All the other repeat the process of embodiment 12 except the prescription that the prescription with 2.5g embodiment 4 preparations replaces embodiment 1 to prepare.Foam volume is 50ml.
Embodiment 16:
Except the prescription with 2.5g embodiment 6 preparations replaces the prescription of embodiment 1 preparation, all the other repeat the process of embodiment 12.Foam volume is 40ml.

Claims (17)

1, low foaming aqueous textile auxiliary formulations
(a) formula (1) non-ionic surface active agent
Figure 941095002_IMG1
In the formula
R 1Be that strictness is linear 8-10 carbon atom alkyl group,
R 2Be the alkyl group of 1-4 carbon atom,
m 1Be the numerical value of 0.5-2,
n 1Be the numerical value of 6-9.
(b) formula (2) non-ionic surface active agent
Figure 941095002_IMG2
In the formula
R 3Be C 8-C 18Alkyl
R 4Be hydrogen, methyl or ethyl,
n 2Be the numerical value of 1-40.
(c) polymer of olefinic unsaturated sulfonic acid or carboxylic acid or their acid anhydrides,
(d) hydrotropic agent,
(e) aliphatic saturated monohydroxy alcohol is as optional components.
2, according to the textile auxiliary formulations of claim 1, R wherein 1It is n-octyl.
3, according to the textile auxiliary formulations of claim 1 or 2, R wherein 2It is normal-butyl.
4, according to each textile auxiliary formulations of claim 1-3, wherein component (a) is formula (a 3) compound ether
Figure 941095002_IMG3
5, according to each textile auxiliary formulations of claim 1-4, wherein component (b) is formula (a 4) non-ionic surface active agent
Figure 941095002_IMG4
In the formula
R 5Be C 11-C 13Alkyl.
6, according to each textile auxiliary formulations of claim 1-5, wherein component (c) is that molecular weight is 2,000-2,000,000 polyacrylic acid.
7, according to each textile auxiliary formulations of claim 1-6, wherein component (d) is a 2-ethylhexyl sodium sulphate.
8, according to each textile auxiliary formulations of claim 1-7, this prescription comprises
(a) formula (1) non-ionic surface active agent,
(b) formula (2) non-ionic surface active agent,
(c) polyacrylic acid,
(d) 2-ethylhexyl sodium sulphate,
(e) 3,5, the 5-trimethyl is pure as optional components.
9, according to each textile auxiliary formulations of claim 1-7, this prescription comprises
(a) formula (3) non-ionic surface active agent,
(b) formula (4) non-ionic surface active agent,
(c) polyacrylic acid and
(d) 2-ethylhexyl sodium sulphate.
10, according to any one textile auxiliary formulations of claim 1-9, its PH scope is 3-5.
11, according to the textile auxiliary formulations of claim 1, this prescription comprises
3-40%(weight) component (a), 10-30%(weight),
5-40%(weight) component (b),
3-20%(weight) component (c),
1-15%(weight) component (d),
0-10%(weight) component (e), and
Water adds to 100%.
12, any one the preparation method of textile auxiliary formulations of claim 1-11, this method comprises at first makes monomer olefinic unsaturated sulfonic acid or carboxylic acid or their acid anhydride at one or more non-ionic surface active agents (a) and/or (b) and in the presence of the catalyst, regulate PH to 4.5 and react, add all the other components then with preparation component (c).
13, any one textile auxiliary of claim 1-11 is as wetting agent, textile detergent, dispersant or the stabilizing agent of bathing as peroxide bleaching.
14, the method for wetting, washing and/or bleached fiber material, this method have been included in following textile auxiliary formulations and have existed handle described material down in aqueous medium,
(a) formula (1) non-ionic surface active agent (1)
In the formula
R 1Be that strictness is 8-10 linear carbon atom alkyl group,
R 2Be the alkyl group of 1-4 carbon atom,
m 1Be the numerical value of 0.5-2,
n 1Be the numerical value of 6-9,
(b) formula (2) non-ionic surface active agent (2)
Figure 941095002_IMG6
In the formula
R 3Be C 8-C 18Alkyl,
R 4Be hydrogen, methyl or ethyl,
n 2Be the numerical value of 1-40,
(c) polymer of olefinic unsaturated sulfonic acid or carboxylic acid or their acid anhydrides,
(d) hydrotropic agent,
(e) aliphatic saturated monohydroxy alcohol is as optional components.
15, according to the method for claim 14, this method comprises the application of following textile auxiliary formulations:
(a) formula (3) non-ionic surface active agent,
(b) formula (4) non-ionic surface active agent,
(c) polyacrylic acid, and
(d) 2-ethylhexyl sodium sulphate.
16, according to the method for claim 14 or 15, wherein the use amount of textile auxiliary formulations is (every liter of solution) 0.1-60g, preferred (every liter of solution) 0.2-10g.
17, use the fibrous material of handling according to each method of claim 14-16.
CN94109500A 1993-08-12 1994-08-11 Aqueous textile auxiliary formulations Pending CN1106872A (en)

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DE19750455C1 (en) * 1997-11-14 1999-04-29 Henkel Kgaa Aqueous hydrogen peroxide formulation used as bleach for pretreating soiled textile, especially laundry
US6537662B1 (en) 1999-01-11 2003-03-25 3M Innovative Properties Company Soil-resistant spin finish compositions
FR2794476B1 (en) * 1999-06-07 2001-11-16 Rhodia Chimie Sa USE OF TERPENIC POLYALCOXYL DERIVATIVES IN THE TREATMENT OF TEXTILE FIBERS
AU1954101A (en) 1999-12-08 2001-06-18 Procter & Gamble Company, The Compositions including ether-capped poly(oxyalkylated) alcohol wetting agents
US6593287B1 (en) 1999-12-08 2003-07-15 The Procter & Gamble Company Compositions including ether-capped poly(oxyalkylated) alcohol surfactants
AU2079401A (en) 1999-12-08 2001-06-18 Procter & Gamble Company, The Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
US6844309B1 (en) 1999-12-08 2005-01-18 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
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CN104652090A (en) * 2013-11-15 2015-05-27 Lg电子株式会社 Washing machine
CN111910437A (en) * 2020-08-04 2020-11-10 广东湛丰精细化工有限公司 Wetting agent for three-proofing finishing and preparation method thereof
CN111910437B (en) * 2020-08-04 2022-05-27 广东湛丰精细化工有限公司 Wetting agent for three-proofing finishing and preparation method thereof

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