CA1051614A - Process for dyeing materials which contain synthetic fibres - Google Patents
Process for dyeing materials which contain synthetic fibresInfo
- Publication number
- CA1051614A CA1051614A CA226,971A CA226971A CA1051614A CA 1051614 A CA1051614 A CA 1051614A CA 226971 A CA226971 A CA 226971A CA 1051614 A CA1051614 A CA 1051614A
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- Prior art keywords
- dye
- adduct
- dyeing
- process according
- acid
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
- C09B67/0086—Non common dispersing agents anionic dispersing agents
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/651—Compounds without nitrogen
- D06P1/65106—Oxygen-containing compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/40—Cellulose acetate
- D06P3/46—Cellulose triacetate
- D06P3/48—Cellulose triacetate using dispersed dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/54—Polyesters using dispersed dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/70—Material containing nitrile groups
- D06P3/72—Material containing nitrile groups using dispersed dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8214—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester and amide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
PROCESS FOR DYEING MATERIALS WHICH CONTAIN SYNTHETIC FIBRES
Abstract of the Disclosure Process for dyeing materials which contain synthetic fibres with dyes that are sparingly soluble to insoluble in water, in the presence of dyeing auxiliaries which are polyadducts of propylene oxide and a polyhydric aliphatic alcohol of at least 2 carbon atoms, wherein said adducts are soluble in water and contain sulphonic acid groups.
The process of present invention is especially suitable for dyeing linear polyester fibres wherein level and strong dyeings are obtained which are in addition characterised by good fastness to rubbing.
Abstract of the Disclosure Process for dyeing materials which contain synthetic fibres with dyes that are sparingly soluble to insoluble in water, in the presence of dyeing auxiliaries which are polyadducts of propylene oxide and a polyhydric aliphatic alcohol of at least 2 carbon atoms, wherein said adducts are soluble in water and contain sulphonic acid groups.
The process of present invention is especially suitable for dyeing linear polyester fibres wherein level and strong dyeings are obtained which are in addition characterised by good fastness to rubbing.
Description
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The present invention provides a novel process for dyeing materials which contain synthetic fibres, the dye liquor suitable for carrying out this process, and the fibrous materials which are dyed according to the novel process.
- When dyeing textile materials with dyes which are - insoluble or sparingly soluble in water, for example by t~e high temperature circulation process, dispersion problems often occur which are due to an inadequate dispersion of the dyes in the dye liquors. Unlevel dyeings of poor fastness, above all poor fastness to rubbing, are consequently obtained.
Such deficiencies also become apparent inter alia in the dyeing of synthetic fibres, especially the linear poly-ester fibres, with disperse dyes.
In order to stabilise dispersions of dyes which are sparingly soluble in water, it is generally known to add certain assistants to the dyebaths, e.g. condensation products of naphthalenesulphonic acid and formaldehyde or the alkali salts thereof, oxethylated fatty alcohols or lignin sulphonates.
However, these products have either only dispersing or levelling properties. It is therefore well-nigh only possible to attain both effects simultaneously by using mixtures of different assistants. Also many dispersants ad-
The present invention provides a novel process for dyeing materials which contain synthetic fibres, the dye liquor suitable for carrying out this process, and the fibrous materials which are dyed according to the novel process.
- When dyeing textile materials with dyes which are - insoluble or sparingly soluble in water, for example by t~e high temperature circulation process, dispersion problems often occur which are due to an inadequate dispersion of the dyes in the dye liquors. Unlevel dyeings of poor fastness, above all poor fastness to rubbing, are consequently obtained.
Such deficiencies also become apparent inter alia in the dyeing of synthetic fibres, especially the linear poly-ester fibres, with disperse dyes.
In order to stabilise dispersions of dyes which are sparingly soluble in water, it is generally known to add certain assistants to the dyebaths, e.g. condensation products of naphthalenesulphonic acid and formaldehyde or the alkali salts thereof, oxethylated fatty alcohols or lignin sulphonates.
However, these products have either only dispersing or levelling properties. It is therefore well-nigh only possible to attain both effects simultaneously by using mixtures of different assistants. Also many dispersants ad-
- 2 - ~
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versely affect the dispersing and dyeing procedure on account of their pronounced tendency to foam.
The novel process makes it possible to obtain level dyeings which are fast to rubbing when dyeing materials which contain synthetic fibres with dyes which are sparingly soluble to insolubl0 in water.
According to the present invention, there is provided a process for dyeing ~including brightening) fibrous materials which contain synthetic fibres selected from cellulose ester, linear polyester, synthetic polyamide, polyurethane, polyolefine and polyacrylonitrile fibres, with a dye that is sparingly soluble to insoluble in water selected from a vat dye, a pigment dye, a disperse dye and a fluorescent brightener, comprising the step of applying to the fibrous material an aqueous liquor having a pH of 4 to 8 and containing 0.01 to 10 percent by weight, based on the weight of the fibrous material, of the dye and 0.1 to 5 grams per litre of dye liquor of a water-soluble acid ester or salt thereof of a polypropyleneoxide adduct of an average moleculare weight of 1000 to 6000 wherein the polypropylene-oxide adduct is an adduct of a homopolymer of propyleneoxide and a poly-hydric aliphatic alcohol of 2 to 6 carbon atoms and wherein the acid ester of the polypropyleneoxide adduct is derived from said adduct and an acid containing a sulphonic acid group.
With the aid of these polyadducts it is now possible to eliminate the disadvantages described hereinbefore which occur when dyeing organic ~ -synthetic fibres, especially polyester fibres, with disperse dyes without addition of assistants or with the previous additives. The advance in the art attained according to the invention resides primarily in the excellent stabilising action of the polyaddicts on the dyestuff dispersion, so that during the entire dyeing procedure there occurs neither an aggregation nor a precipitation of the dye.
A further advantage of these compounds used as levelling agents and dispersants resides in their negligible foaming tendency. There is consequen-tly no danger of foam
. ~ .
~os~
versely affect the dispersing and dyeing procedure on account of their pronounced tendency to foam.
The novel process makes it possible to obtain level dyeings which are fast to rubbing when dyeing materials which contain synthetic fibres with dyes which are sparingly soluble to insolubl0 in water.
According to the present invention, there is provided a process for dyeing ~including brightening) fibrous materials which contain synthetic fibres selected from cellulose ester, linear polyester, synthetic polyamide, polyurethane, polyolefine and polyacrylonitrile fibres, with a dye that is sparingly soluble to insoluble in water selected from a vat dye, a pigment dye, a disperse dye and a fluorescent brightener, comprising the step of applying to the fibrous material an aqueous liquor having a pH of 4 to 8 and containing 0.01 to 10 percent by weight, based on the weight of the fibrous material, of the dye and 0.1 to 5 grams per litre of dye liquor of a water-soluble acid ester or salt thereof of a polypropyleneoxide adduct of an average moleculare weight of 1000 to 6000 wherein the polypropylene-oxide adduct is an adduct of a homopolymer of propyleneoxide and a poly-hydric aliphatic alcohol of 2 to 6 carbon atoms and wherein the acid ester of the polypropyleneoxide adduct is derived from said adduct and an acid containing a sulphonic acid group.
With the aid of these polyadducts it is now possible to eliminate the disadvantages described hereinbefore which occur when dyeing organic ~ -synthetic fibres, especially polyester fibres, with disperse dyes without addition of assistants or with the previous additives. The advance in the art attained according to the invention resides primarily in the excellent stabilising action of the polyaddicts on the dyestuff dispersion, so that during the entire dyeing procedure there occurs neither an aggregation nor a precipitation of the dye.
A further advantage of these compounds used as levelling agents and dispersants resides in their negligible foaming tendency. There is consequen-tly no danger of foam
- 3 ~S~
specks forming on the dyeings and a more rapid penetration of the goods and an increase in the flow velocity in the dyeing machinery are thereby ensured.
The polyadducts used according to the invention are, for example, adducts of propylene oxide and polyhydric ali-phatic alcohols of at least 2, preferably 3 to 6, carbon atoms, whi h are converted into an acid ester with a sulph-onated organic, preferably aliphatic, mono- or dicarboxylic acid of 3 to 6 carbon atoms, e.g. propionic acid or succinic acid, but preferably with an inorganic sulphation agent, especially sulphuric acid or sulphaminic acid.
Suitable polyhydric alcohols as defined herein are those containing at least 2 hydroxy groups, for example alkylene diols with an alkylene radical of 2 to 6 carbon atoms, e.g. ethylene glycol, 1,3- or 1,2-propylene glycol or 1,5-pentane diol, glycerol or trimethylol propane. It is pre-ferred to use aliphatic alcohols which contain 3 carbon atoms and 2 or 3 hydroxy groups.
Sulphated adducts as defined herein with an average molecular weight o 1000 to 6000, preferably 2000 to 3500, have for example proved particularly effective for the use according to the present invention. Of these, adducts which are derived from propylene glycol or glycerol are especially suitable~
, . ~. .. : . . , , , ~
.. : . , . ~;, ;; , ~
05~ 1 4 ` The polyadducts containing sulpho groups to be used according to the invention can be used as free acid or preferably in the form of their alkali metal or ammonium salts. Alkali metal salts are in particular the sodium and potassium salts, and ammonium salts are the ammonium, tri-methylammonium, monoethanolammonium, diethanolammonium and triethanolammonium salts. Preferably the polyadducts are used as ammonium sulphate salts.
Typical examples of the polyadducts which contain sulphonic acid groups used according to the invention are the reaction product obtained by reaction of polypropylene glycol and sulphamic acid 9 the polypropylene glycol having an average molecular weight of 1000 to 3500, preferably 2000, and the sulphated adducts obtained from gl~cerol or trimethylol propane and propylene oxide, the polyadducts having an average molecular weight of 2000 to 6000, prefe-rably 3000 or 2500.
~ further example of a polyadduct which contains sulphonic acid groups is the sulpho-succinic acid half 2Q ester of a polyadduct obtained by addition of propylene oxide to glycerol, said half ester having an average mole-cular weight of about 4000.
The amount of polypropyleneoxy adducts which con-tain sulphonic acid groups used varies according to the . . , . , , ~ .
., , ~ , . , :
.. : . . . , . . . . ~
~5~
present invention between 0.1 and 5 g, preferably 0.5 to g, per litre of aqueous dye liquor.
It is often desirable to incorporate an anti-foaming agent into the aqueous solution of the polyadduct in order to improve the properties of the dyebath to which the dispersant is added and sometimes also to increase the migration of the dye. A satisfactory type of antifoaming agent is a silicone emulsion, for example a 5 to 10% aqueous silicone emulsion, which can also be used in combination with higher alcohols of 4 to 22 carbon atoms, especially with 2-ethyl hexanol. The most suitable antifoaming agents, however, are water-insoluble alkyleneoxy adducts of higher alcohols, for example the adduct of stearyl alcohol and 1 mole of ethylene oxide, as well as esters of aliphatic di-carboxylic acids and higher alcohols or the higher alcohols alone, e.g. butyl alcohol or 2-ethylhexanol. Adipic acid di-2-ethylhexyl ester and methyl polysiloxanes have proved to be the most suitable antifoaming agents.
The amount of antifoaming agent used can be e.g.
0.5 percent by weight, advantageously however at least lO
percent by weight, pre~erably 15 to 60 percent by weight, based on the weight o~ the polyadduct.
It is also possible to add water-miscible alcohols to the solution of the polyadduct. Particularly suitable ; j ,~, ; , , ~ :
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for this purpose are lower aliphatic alcohols, like alkanols, e~g. ethyl alcohol, n-propyl alnd isopropyl alcohol, tert.
butyl alcohol, alkylene glycols, e.g~ ethylene glycol and 2,5-hexane diol and the lower monoalkyl ethers thereof, as well as mixtures thereof.
By dyes which are insoluble or sparingly soluble in water are meant in the context of the invention vat dyes, pigment dyes, and, above all, disperse dyes which have affinity for fibres, i.e. those which exhaust onto textile synthetic fibres.
These dyes can belong to the most widely varying classes, e.g. acridone, nitro, methine and polymethine dyes, styryl and azostyryl dyes, xanthene dyes, oxazine dyes, aminonaphthoquinone dyesg cumarin dyes and especially anthra-quinone dyes and azo dyes, such as monoazo and disazo dyes.
According to the invention, it is also possible to use mixtures of such dyes.
The process according to the invention is also æuitable for whitening undyed textile materials with fluor-escent brighteners which are sparingly soluble in water.
These can belong to any class of fluorescent brightener.
In particular they are stilbene compounds, cumarins, benæo-cumarins, pyrazines, pyrazolines, oxazines, triazolyl, benzo-xazolyl, benzofuran or benzimidazolyl compounds and naphthalic ... . . .. ~.. ..... . .. ., .. .~
"
. ' ~ ' :
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l~Sl~
amides.
The amount of dye which is added to the liquor in the process according to the invention depends on the desired colour strengthi amounts of 0.01 to lO percent by weight, based on the weight of the fibrous material, have proved effective as a rule.
Fibrous materials which can be dyed according to the invention are cellulose ester fibres, such as cellulose 2 1/2-acetate and cellulose triacetate fibres, synthetic polyamide fibres, e.g. those from ~-caprolactam, from adipic acid and hexamethylene diamine9 from w-aminounde-canoic acid, polyurethane, polyolefin fibres, e.g. poly-propylene fibres~ polyacrylonitrile fibres, including moda-cryl fibres, and, above all, linear polyester fibres. By linear polyester fibres are meant synthetic fibres which are obtained by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis-(hydroxymethyl)-cyclohexane, as well as copolymers of terephthalic and isophthalic acid and ethylene glycol. The fibrous materials can also be used as blends of polyacrylonitrile/polyester, polyamide/polyester, poly-ester/viscose and polyester/wool.
The fibrous material can moreover be in the most widely different stages of processing, e.g. in the form of - - . - , . : - , - ~ .
, ' ' ' ~ . ' ' , , :
`: . ` , I ~ . . ` ' ' `
, .,: '. ` ' ` ' ' ` ' : ' -~05~4 flocks, piece goods, such as wovens and knitted fabrics, hanks, wound packages, nonwovens, textile floor coverings or tufted carpets.
Dyeing is effected advantageously from an aqueous liquor by the exhaustion process. Linear polyester fibres are dyed preferably by the high temperature process in sealed and desirably also pressure-resistant apparatus at temperatures of over 100C, preferably between 110 and 140C, and optionally under pressure. Examples of suitable sealed vessels are circulation machines like cheese dyeing and beam dyeing machines, winch becks, jet or drum dyeing machines, paddles or jiggers. The liquor ratio can accor-dingly be chosen within a wide range, e.g. 1:1 to 1:100, preferably 1:10 to 1:50. The dyeing of the linear poly-ester fibres can also be carried out at temperatures below 100C, e.g. ;n the temperature range of 75 to 98C, in the presence of the customary carriers, for example phenyl-phenols, polychlorobenzenes, xylenes, toluenes, naphthalenes or diphenyl. Cellulose 2 1/2-acetate fibres are dyed prefer-ably at temperatures of 80-85C, while cellulose triacetate fibres are dyed with advantage at the boiling point (98G) of the aqueous bath.
The use of carriers is superfluous when dyeing cellulose 2 1/2-acetate or polyamide fibres.
_ 9 _ ~(~5~
When manufacturing the dye liquors, it is desirable to start ~rom the aqueous solutions of the polyadduct and to add to these the appropriate assistants 9 such as anti-foaming agents and lower alcohols. The liquors can contain mineral acids, such as sulphuric acid or preferably phos-phoric acid, organic acids, desirably lower aliphatic car-boxylic acids, e.g. formic, acetic or oxalic acid and/or salts, such as ammonium aceta~e, ammonium sulphate or sod-ium acetate. The acids are used primarily for adjusting the pH of the liquors according to the invention. The pH is normally 4 to 8, preferably 4.5 to 6.5.
The textile material is put into the liquor, which can have a temperature of 40 to 70C, and is treated for 5 to 15 minutes at this temperature. Afterwards the dye and optionally the carrier is added and the temperature of the liquor is raised in order to dye for 50 to 100 minutes in the given temperature range.
The dyed material is subsequently rinsed and dried in the usual way. A reductive aftertreatment is normally not necessary. As a rule the goods remain stationary in the dyeing apparatus and the liquor circulates through them.
It is important that there is not only a fine dispersion of the dye initially, but also that the degree of disper~ion is maintained during the entire dyeing procedure. It is , .. . . ; . .
: -.......... .. ,, - : , .. . .
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; common knowledge that certain disperse dyes, above all under the conditions of high temperature dyeing, tend to become converted into a less fine form. The consequence of this is that the dye no longer exhausts onto the fibre and settles on the surface of the good. Such dyestuff agglomerations and precipitations can be avoided especially well with the anionic -~ polyadducts to be used according to the invention.
According to the invention, the synthetic fibrous material can also be dyed continuously, i.e. by impregna-tion with an aqueous preparation which contains a disperse dye, an anionic polyaddict as defined herein and optionally a thickener and acid, and squeezing it out to the desired content of impregnating liquor of 60 to 120% o the weight of the fibre with subsequent heat treatment, e.g. steaming at temperatures of 98 to 105C with neutral saturated steam or thermofixation at 18V to 210C.
Level and strong dyeings which are characterised in addition by good fastness to rubbing and dye yields are obtained on synthetic organic fibrous material, especially on linear polyester fibres, according to the process of the invention.
In the following manufacturing directions and Examples, which illustrate the invention in more detail, the parts and percentages are by weight.
- ` : :: . . ' . ': ': , : . : : ::. :` `: ~ ! . . . ' ' ' : ~' ' ' ~ 6 Manufacturing Directions . _ _ A. 100 g of pure polypropylene glycol with an average molecular weight of 2000 are heated to 60C. Then 20 g of urea and 20 g of sulphamic acid are added with stirring over the course of 30 minutes. Stirring is continued for 30 minutes at 60-65C, the batch is then heated to 95C
and kept for 10 hours at 95 to 100C. A viscous, yellowish product is obtained which dissolved to give a clear solu-tion in water and contains 80% of the ammonium salt of the disulphuric acid ester.
B. 62 g of the condensation product of glycerol and propylene oxide with an average molecular weight of 3100 are treated as described in A with 6~4 g of urea and 6.4 g of sulphamic acid. A viscous product is obtained which is readily soluble in water and contains 92% of the ammonium salt of the sulphuric acid est~r.
C. 75 g of the adduct of trimethylol propane and propylene oxide with an average molecular weight of 2540 are reacted as described in A with 9.6 g of sulphamic acid in the presence of 9.6 g of urea. A viscous, sulphated pro-duct is obtained which is readily soluble in water.
.. . . . . . .. . . . .
.. . . . . ...
. ~. - ' .~ .: , ,. : .
. . .
... . . . . . . , .: . . i D. 100 g of a maleic acid half ester of the formula CH~ - O ~ ~h - C~l2 - 0~ COCh = COCOGH
CH - O ~ ~H - C~2 _ O ~ COCH = CH - COOH
~H2 - o CIH - CH2 - O COCH c CH ~ COOH
_C~3 _ n3 nl + n2 + n3 = c, 63, molecular weight c. 4000, with the addition of 7.12 g of sodium metabisulphite in 400 ml of water are stirred for 9 hours under reflux, in the course of which the pH of the reaction mixture is kept between 505 and 6.5 with 7.5 ml of a 10% aqueous sodium hydroxide solution. A slightly yellowish, opaque solution is formed which has a degree of addition of 100%, ascertained from the non-reacted amount of ~ulphite.
After evaporation at 40-50C there are obtained 109 g of the sodium salt of the sulphosuccinic acid half ester in the form of a highly hygroscopic, tacky substance.
E. 100 g o the condensation product with an average molecular weight of 4000 obtained from glycerol and propy-: : . : : . . , - .: . ... . . : . . . .
~ Q~
lene oxide are heated to 60C. Then 10 g of urea and 10 g of sulphamic acid are added in 15 and in 30 minutes respect-ively. After further stirring at 60-65C for 30 minutes, the batch is heated to 100C and kept for one hour at 100C
and for a further 4 hours at 105C. The resultant sulpha-tion product dissolved to give a clear solution in water.
F. The procedure of Direction E is carried out, ex-cept that 100 g of a condensation product with an average molecular weight of 6000 obtained from glycerol and pro-pylene oxide are used.
G. 100 g of polypropylene glycol (average molecular weight 10003 are esterified in the same way as in Direction E with 40 g of sulphamic acid in the presence of 40 g of urea. The resultant reaction product contains 66% of the ammonium salt of the acid sulphuric acid ester and dissolves to give a clear solution in water.
H. 47.6 g of the adduct of 1 mole of ethylene glycol and 40 moles of propylene oxide (average molecular weight 2380) are esterified in the same way as in Direction E
in the presence of 8 g of urea with 8 g of sulpham;c acid.
. .: . ~ . : . , ,. , : . -, . , .. , .. :. .. .. : , :. : - . : : ..
. ~ . . .. .
.~ .. . . . :
~ 5 ~
I. 40 g of the product obtained according to Direction B are mixed at 60C with 10 g of adipic acid di-2-ethyl-hexyl ester and then with 0.5 g of the adduct of 1 mole of castor oil and 40 moles of ethylene oxide, 3 g of water and 2.5 g of isopropanol. A liquid, homogeneous product is obtained. A fine emulsion of the adipic acid ester results after the product has been dissolved in water.
K. 37 g of the product obtained according to Direction B are mixed with 3 g of monoethanolamine and then with 50 g of benzene~ Benzene and ammonia are driven off in vacuo, whereupon the monoethanolamine salt of the acid sulphuric acid ester of the condensate of glycerol and propylene oxide of average molecular weight 3100 is obtained.
L. The procedure of Direction K is carried out, ex~ept that 5 g of triethanolamine are used instead of monoethanol-amine. The corresponding triethanolamine salt is obtained.
M. 50 g of the product obtained according to Direction B are treated with 50 g of water and 0.8 g of an aqueous emulsion of methylpolysiloxane is added to the resultant clear solution.
Example 1 25 g of a polyethylene glycol terephthalate knitted fabric are treated for 10 minutes at 60C in a circulation dyeing apparatus with a liquo.r which contains 0.6 g of ammonium sulphate and 0.3 g o:E an assistant mixture consist-ing of 55 parts of the sulphuric acid ester obtained accor-ding to Manufacturing Direction B, 10 parts of adipic acid di-2-ethylhexyl ester and 35 parts of water and isopropanol (1:1) in 300 ml of water, and which is adjusted to pH 5.5 with 85% formic acid. Subsequently 1.35 g of a dyestuff mixture consisting of 0.875 g of a dye of the formula ....
N02 ~ N=~
Cl ~ S02~Cll3 and 0.475 g of a dye of the formula (2) L N \C0 are added to the liquor and the dyebath is heated over the course of 30 minutes to 130C. Dyeing is ?erformed for 60 minutes at this temperature and the liquor is cooled to \
~516 ~ ~
90C. The resultant dyeing is rinsed and dried. A level, brilliant, red dyeing is obtained.
Example 2 400 g of a wound package of polyethylene glycol terephthalate fibres are treated for 10 minutes at 60C in a circulation dyeing apparatus with a liquor which contains 16 g of ammonium sulphate and 8 g of the disulphuric acid ester obtained according to Manufacturing Direction A, dissolved in 8 litres of water, and which is adjusted to pH 5.5 with 85% formic acid, Then 1 g of a dyestuff mixture consisting of 0.4 g of a dye of the formula (3) N02 ~ N=N ~ (CH2CH2C~)2 ~: ' 0.2 g of a dye of the formula
specks forming on the dyeings and a more rapid penetration of the goods and an increase in the flow velocity in the dyeing machinery are thereby ensured.
The polyadducts used according to the invention are, for example, adducts of propylene oxide and polyhydric ali-phatic alcohols of at least 2, preferably 3 to 6, carbon atoms, whi h are converted into an acid ester with a sulph-onated organic, preferably aliphatic, mono- or dicarboxylic acid of 3 to 6 carbon atoms, e.g. propionic acid or succinic acid, but preferably with an inorganic sulphation agent, especially sulphuric acid or sulphaminic acid.
Suitable polyhydric alcohols as defined herein are those containing at least 2 hydroxy groups, for example alkylene diols with an alkylene radical of 2 to 6 carbon atoms, e.g. ethylene glycol, 1,3- or 1,2-propylene glycol or 1,5-pentane diol, glycerol or trimethylol propane. It is pre-ferred to use aliphatic alcohols which contain 3 carbon atoms and 2 or 3 hydroxy groups.
Sulphated adducts as defined herein with an average molecular weight o 1000 to 6000, preferably 2000 to 3500, have for example proved particularly effective for the use according to the present invention. Of these, adducts which are derived from propylene glycol or glycerol are especially suitable~
, . ~. .. : . . , , , ~
.. : . , . ~;, ;; , ~
05~ 1 4 ` The polyadducts containing sulpho groups to be used according to the invention can be used as free acid or preferably in the form of their alkali metal or ammonium salts. Alkali metal salts are in particular the sodium and potassium salts, and ammonium salts are the ammonium, tri-methylammonium, monoethanolammonium, diethanolammonium and triethanolammonium salts. Preferably the polyadducts are used as ammonium sulphate salts.
Typical examples of the polyadducts which contain sulphonic acid groups used according to the invention are the reaction product obtained by reaction of polypropylene glycol and sulphamic acid 9 the polypropylene glycol having an average molecular weight of 1000 to 3500, preferably 2000, and the sulphated adducts obtained from gl~cerol or trimethylol propane and propylene oxide, the polyadducts having an average molecular weight of 2000 to 6000, prefe-rably 3000 or 2500.
~ further example of a polyadduct which contains sulphonic acid groups is the sulpho-succinic acid half 2Q ester of a polyadduct obtained by addition of propylene oxide to glycerol, said half ester having an average mole-cular weight of about 4000.
The amount of polypropyleneoxy adducts which con-tain sulphonic acid groups used varies according to the . . , . , , ~ .
., , ~ , . , :
.. : . . . , . . . . ~
~5~
present invention between 0.1 and 5 g, preferably 0.5 to g, per litre of aqueous dye liquor.
It is often desirable to incorporate an anti-foaming agent into the aqueous solution of the polyadduct in order to improve the properties of the dyebath to which the dispersant is added and sometimes also to increase the migration of the dye. A satisfactory type of antifoaming agent is a silicone emulsion, for example a 5 to 10% aqueous silicone emulsion, which can also be used in combination with higher alcohols of 4 to 22 carbon atoms, especially with 2-ethyl hexanol. The most suitable antifoaming agents, however, are water-insoluble alkyleneoxy adducts of higher alcohols, for example the adduct of stearyl alcohol and 1 mole of ethylene oxide, as well as esters of aliphatic di-carboxylic acids and higher alcohols or the higher alcohols alone, e.g. butyl alcohol or 2-ethylhexanol. Adipic acid di-2-ethylhexyl ester and methyl polysiloxanes have proved to be the most suitable antifoaming agents.
The amount of antifoaming agent used can be e.g.
0.5 percent by weight, advantageously however at least lO
percent by weight, pre~erably 15 to 60 percent by weight, based on the weight o~ the polyadduct.
It is also possible to add water-miscible alcohols to the solution of the polyadduct. Particularly suitable ; j ,~, ; , , ~ :
.. . . - , .: .. . . . .
~. , ,, ~
~o~
for this purpose are lower aliphatic alcohols, like alkanols, e~g. ethyl alcohol, n-propyl alnd isopropyl alcohol, tert.
butyl alcohol, alkylene glycols, e.g~ ethylene glycol and 2,5-hexane diol and the lower monoalkyl ethers thereof, as well as mixtures thereof.
By dyes which are insoluble or sparingly soluble in water are meant in the context of the invention vat dyes, pigment dyes, and, above all, disperse dyes which have affinity for fibres, i.e. those which exhaust onto textile synthetic fibres.
These dyes can belong to the most widely varying classes, e.g. acridone, nitro, methine and polymethine dyes, styryl and azostyryl dyes, xanthene dyes, oxazine dyes, aminonaphthoquinone dyesg cumarin dyes and especially anthra-quinone dyes and azo dyes, such as monoazo and disazo dyes.
According to the invention, it is also possible to use mixtures of such dyes.
The process according to the invention is also æuitable for whitening undyed textile materials with fluor-escent brighteners which are sparingly soluble in water.
These can belong to any class of fluorescent brightener.
In particular they are stilbene compounds, cumarins, benæo-cumarins, pyrazines, pyrazolines, oxazines, triazolyl, benzo-xazolyl, benzofuran or benzimidazolyl compounds and naphthalic ... . . .. ~.. ..... . .. ., .. .~
"
. ' ~ ' :
. : ` ' ', ; . ' ' ` ':
l~Sl~
amides.
The amount of dye which is added to the liquor in the process according to the invention depends on the desired colour strengthi amounts of 0.01 to lO percent by weight, based on the weight of the fibrous material, have proved effective as a rule.
Fibrous materials which can be dyed according to the invention are cellulose ester fibres, such as cellulose 2 1/2-acetate and cellulose triacetate fibres, synthetic polyamide fibres, e.g. those from ~-caprolactam, from adipic acid and hexamethylene diamine9 from w-aminounde-canoic acid, polyurethane, polyolefin fibres, e.g. poly-propylene fibres~ polyacrylonitrile fibres, including moda-cryl fibres, and, above all, linear polyester fibres. By linear polyester fibres are meant synthetic fibres which are obtained by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis-(hydroxymethyl)-cyclohexane, as well as copolymers of terephthalic and isophthalic acid and ethylene glycol. The fibrous materials can also be used as blends of polyacrylonitrile/polyester, polyamide/polyester, poly-ester/viscose and polyester/wool.
The fibrous material can moreover be in the most widely different stages of processing, e.g. in the form of - - . - , . : - , - ~ .
, ' ' ' ~ . ' ' , , :
`: . ` , I ~ . . ` ' ' `
, .,: '. ` ' ` ' ' ` ' : ' -~05~4 flocks, piece goods, such as wovens and knitted fabrics, hanks, wound packages, nonwovens, textile floor coverings or tufted carpets.
Dyeing is effected advantageously from an aqueous liquor by the exhaustion process. Linear polyester fibres are dyed preferably by the high temperature process in sealed and desirably also pressure-resistant apparatus at temperatures of over 100C, preferably between 110 and 140C, and optionally under pressure. Examples of suitable sealed vessels are circulation machines like cheese dyeing and beam dyeing machines, winch becks, jet or drum dyeing machines, paddles or jiggers. The liquor ratio can accor-dingly be chosen within a wide range, e.g. 1:1 to 1:100, preferably 1:10 to 1:50. The dyeing of the linear poly-ester fibres can also be carried out at temperatures below 100C, e.g. ;n the temperature range of 75 to 98C, in the presence of the customary carriers, for example phenyl-phenols, polychlorobenzenes, xylenes, toluenes, naphthalenes or diphenyl. Cellulose 2 1/2-acetate fibres are dyed prefer-ably at temperatures of 80-85C, while cellulose triacetate fibres are dyed with advantage at the boiling point (98G) of the aqueous bath.
The use of carriers is superfluous when dyeing cellulose 2 1/2-acetate or polyamide fibres.
_ 9 _ ~(~5~
When manufacturing the dye liquors, it is desirable to start ~rom the aqueous solutions of the polyadduct and to add to these the appropriate assistants 9 such as anti-foaming agents and lower alcohols. The liquors can contain mineral acids, such as sulphuric acid or preferably phos-phoric acid, organic acids, desirably lower aliphatic car-boxylic acids, e.g. formic, acetic or oxalic acid and/or salts, such as ammonium aceta~e, ammonium sulphate or sod-ium acetate. The acids are used primarily for adjusting the pH of the liquors according to the invention. The pH is normally 4 to 8, preferably 4.5 to 6.5.
The textile material is put into the liquor, which can have a temperature of 40 to 70C, and is treated for 5 to 15 minutes at this temperature. Afterwards the dye and optionally the carrier is added and the temperature of the liquor is raised in order to dye for 50 to 100 minutes in the given temperature range.
The dyed material is subsequently rinsed and dried in the usual way. A reductive aftertreatment is normally not necessary. As a rule the goods remain stationary in the dyeing apparatus and the liquor circulates through them.
It is important that there is not only a fine dispersion of the dye initially, but also that the degree of disper~ion is maintained during the entire dyeing procedure. It is , .. . . ; . .
: -.......... .. ,, - : , .. . .
~5~
; common knowledge that certain disperse dyes, above all under the conditions of high temperature dyeing, tend to become converted into a less fine form. The consequence of this is that the dye no longer exhausts onto the fibre and settles on the surface of the good. Such dyestuff agglomerations and precipitations can be avoided especially well with the anionic -~ polyadducts to be used according to the invention.
According to the invention, the synthetic fibrous material can also be dyed continuously, i.e. by impregna-tion with an aqueous preparation which contains a disperse dye, an anionic polyaddict as defined herein and optionally a thickener and acid, and squeezing it out to the desired content of impregnating liquor of 60 to 120% o the weight of the fibre with subsequent heat treatment, e.g. steaming at temperatures of 98 to 105C with neutral saturated steam or thermofixation at 18V to 210C.
Level and strong dyeings which are characterised in addition by good fastness to rubbing and dye yields are obtained on synthetic organic fibrous material, especially on linear polyester fibres, according to the process of the invention.
In the following manufacturing directions and Examples, which illustrate the invention in more detail, the parts and percentages are by weight.
- ` : :: . . ' . ': ': , : . : : ::. :` `: ~ ! . . . ' ' ' : ~' ' ' ~ 6 Manufacturing Directions . _ _ A. 100 g of pure polypropylene glycol with an average molecular weight of 2000 are heated to 60C. Then 20 g of urea and 20 g of sulphamic acid are added with stirring over the course of 30 minutes. Stirring is continued for 30 minutes at 60-65C, the batch is then heated to 95C
and kept for 10 hours at 95 to 100C. A viscous, yellowish product is obtained which dissolved to give a clear solu-tion in water and contains 80% of the ammonium salt of the disulphuric acid ester.
B. 62 g of the condensation product of glycerol and propylene oxide with an average molecular weight of 3100 are treated as described in A with 6~4 g of urea and 6.4 g of sulphamic acid. A viscous product is obtained which is readily soluble in water and contains 92% of the ammonium salt of the sulphuric acid est~r.
C. 75 g of the adduct of trimethylol propane and propylene oxide with an average molecular weight of 2540 are reacted as described in A with 9.6 g of sulphamic acid in the presence of 9.6 g of urea. A viscous, sulphated pro-duct is obtained which is readily soluble in water.
.. . . . . . .. . . . .
.. . . . . ...
. ~. - ' .~ .: , ,. : .
. . .
... . . . . . . , .: . . i D. 100 g of a maleic acid half ester of the formula CH~ - O ~ ~h - C~l2 - 0~ COCh = COCOGH
CH - O ~ ~H - C~2 _ O ~ COCH = CH - COOH
~H2 - o CIH - CH2 - O COCH c CH ~ COOH
_C~3 _ n3 nl + n2 + n3 = c, 63, molecular weight c. 4000, with the addition of 7.12 g of sodium metabisulphite in 400 ml of water are stirred for 9 hours under reflux, in the course of which the pH of the reaction mixture is kept between 505 and 6.5 with 7.5 ml of a 10% aqueous sodium hydroxide solution. A slightly yellowish, opaque solution is formed which has a degree of addition of 100%, ascertained from the non-reacted amount of ~ulphite.
After evaporation at 40-50C there are obtained 109 g of the sodium salt of the sulphosuccinic acid half ester in the form of a highly hygroscopic, tacky substance.
E. 100 g o the condensation product with an average molecular weight of 4000 obtained from glycerol and propy-: : . : : . . , - .: . ... . . : . . . .
~ Q~
lene oxide are heated to 60C. Then 10 g of urea and 10 g of sulphamic acid are added in 15 and in 30 minutes respect-ively. After further stirring at 60-65C for 30 minutes, the batch is heated to 100C and kept for one hour at 100C
and for a further 4 hours at 105C. The resultant sulpha-tion product dissolved to give a clear solution in water.
F. The procedure of Direction E is carried out, ex-cept that 100 g of a condensation product with an average molecular weight of 6000 obtained from glycerol and pro-pylene oxide are used.
G. 100 g of polypropylene glycol (average molecular weight 10003 are esterified in the same way as in Direction E with 40 g of sulphamic acid in the presence of 40 g of urea. The resultant reaction product contains 66% of the ammonium salt of the acid sulphuric acid ester and dissolves to give a clear solution in water.
H. 47.6 g of the adduct of 1 mole of ethylene glycol and 40 moles of propylene oxide (average molecular weight 2380) are esterified in the same way as in Direction E
in the presence of 8 g of urea with 8 g of sulpham;c acid.
. .: . ~ . : . , ,. , : . -, . , .. , .. :. .. .. : , :. : - . : : ..
. ~ . . .. .
.~ .. . . . :
~ 5 ~
I. 40 g of the product obtained according to Direction B are mixed at 60C with 10 g of adipic acid di-2-ethyl-hexyl ester and then with 0.5 g of the adduct of 1 mole of castor oil and 40 moles of ethylene oxide, 3 g of water and 2.5 g of isopropanol. A liquid, homogeneous product is obtained. A fine emulsion of the adipic acid ester results after the product has been dissolved in water.
K. 37 g of the product obtained according to Direction B are mixed with 3 g of monoethanolamine and then with 50 g of benzene~ Benzene and ammonia are driven off in vacuo, whereupon the monoethanolamine salt of the acid sulphuric acid ester of the condensate of glycerol and propylene oxide of average molecular weight 3100 is obtained.
L. The procedure of Direction K is carried out, ex~ept that 5 g of triethanolamine are used instead of monoethanol-amine. The corresponding triethanolamine salt is obtained.
M. 50 g of the product obtained according to Direction B are treated with 50 g of water and 0.8 g of an aqueous emulsion of methylpolysiloxane is added to the resultant clear solution.
Example 1 25 g of a polyethylene glycol terephthalate knitted fabric are treated for 10 minutes at 60C in a circulation dyeing apparatus with a liquo.r which contains 0.6 g of ammonium sulphate and 0.3 g o:E an assistant mixture consist-ing of 55 parts of the sulphuric acid ester obtained accor-ding to Manufacturing Direction B, 10 parts of adipic acid di-2-ethylhexyl ester and 35 parts of water and isopropanol (1:1) in 300 ml of water, and which is adjusted to pH 5.5 with 85% formic acid. Subsequently 1.35 g of a dyestuff mixture consisting of 0.875 g of a dye of the formula ....
N02 ~ N=~
Cl ~ S02~Cll3 and 0.475 g of a dye of the formula (2) L N \C0 are added to the liquor and the dyebath is heated over the course of 30 minutes to 130C. Dyeing is ?erformed for 60 minutes at this temperature and the liquor is cooled to \
~516 ~ ~
90C. The resultant dyeing is rinsed and dried. A level, brilliant, red dyeing is obtained.
Example 2 400 g of a wound package of polyethylene glycol terephthalate fibres are treated for 10 minutes at 60C in a circulation dyeing apparatus with a liquor which contains 16 g of ammonium sulphate and 8 g of the disulphuric acid ester obtained according to Manufacturing Direction A, dissolved in 8 litres of water, and which is adjusted to pH 5.5 with 85% formic acid, Then 1 g of a dyestuff mixture consisting of 0.4 g of a dye of the formula (3) N02 ~ N=N ~ (CH2CH2C~)2 ~: ' 0.2 g of a dye of the formula
(4) N02 ~ --N ~ N(CH2CH20cOc~3)2 ~ -- . CN
, .. . , . .: .. . . , , ~
105~
and 0.4 g of a dye of the formula .
-Br is added and the dyebath is heated over the course of 30 minutes to 130C. Dyeing is performed for 60 minutes at this temperature and the bath is then cooled to 90C and the resultant dyeing is subsequently rinsed and dried.
A level grey dyeing is obtained.
Exa~le 3 Level dyeings are also obtained by substituting for the assistants used in Examples 1 or 2 equal amounts of a further assistant consisting of 80 parts of the sulphuric acid ester obtained according to Manufacturing Direction B and 20 parts of the condensation product obtained from stearyl alcohol and 1 mole of ethylene oxide and otherwise carrying out the procedure as described therein.
Example 4 Level dyeings are also obtained by substituting for the ~ : . . , ~ ~ ; : , l(~S~
assistants used in Examples 1 or 2 equal amounts of a further assistant consisting ~f 60 parts of the sulphuric acid ester obtained according to Manufacturing Direction B and 40 parts of butyl alcohol and otherwise carrying out the procedure as described therein.
Example 5 Level dyeings are also obtained by substituting or the assistants used in Examples 1 or 2 equal amounts of an assistant consisting of 80 parts of the sulphuric acid ester obtained according to Manufacturing Direction B and 20 parts of a mixture of 5% silicone oil and 95% 2-ethyl-hexanol and otherwise carrying out the procedure as des-cribed therein. ~
Example_6 :
,:
A level dyeing is also obtained by substituting 2.2 g of the sulphuric acid ester obtained according to Manufacturing Direction C and 0.13 g of adipic acid 2-ethyl-hexyl ester for the assistant mixture used in Example l and otherwise carrying out the procedure as described therein, ~ ~5~
Similar results are obtained by using the sulpho-suceinic acid half ester obtained according to Manufacturing Direc-tion D instead of the assistant obtained according to Manufacturing Direction C.
Example 7 Level dyeings which are fast to rubbing are also obtained by substituting 8 g of the product according to Manufactu-ring Direction I or 16 g of the product according to Manufacturing Direction M for the product obtained ac-eording to Manufaeturing Direction A and used in Example 2, or by substitu~ing 0,3 g of the product according to Manufacturing Direction I or 0.6 g of the product aceording to Manufacturing Direction M for the assistant mixture used in Example 1. .
Example 8 Level dyeings are also obtained with the products obtained aeeording to Manufacuring Directions E, F, G, H, K, L, by using these in corresponding amounts instead of the product of Manufaeturing Direction B according to Example l.
- 2~ -- .
, .. ..
0~6 ~ ~
Example 9 40 g of a polyethylene terepht:halate staple fibre woven-fabric are dyed in a dyeing apparatus for 16 minutes at 130C by agitating the goods in a liquor (liquor ratio 1:9) which contains 0.5% (based on the weight of the fabric) of a 20% aqueous dispersion of the fluorescent ~rightener of the formula (6) ~ CH = CH ~ C
- . , :
and 5 g per litre of the preparation according to Manufac-turing Direction I. The bath is drawn off at 130C. The fabric, which is rinsed and dried in the ~ustomary manner, has a very pronounced, brilliant white effect with neutral shade of complete levelness. A dyeing in which there used 4.0 g of a 25% aqueous solution of the levelling agent of the formula C17H35CH20 - (CH2 CH2)35 per litre instead of 0.5 g of the preparation according to Manufacturing Direction I yields under otherwise similar - .~, . . .
, .:
conditions a substantially poorer whitening of insufficient levelness. In places even green discolourations caused by undeveloped brightener are observed on the treated fabric.
Exam~ 10 A polyethylene terephthalate staple fibre fabric is padded in a liquor which contains per litre 5 g of a 20% aqueous dispersion of the fluorescent brightener of the formula C(CH3)3 (7) ~ CH = CH ~ C ~
and 2,5 g o~ the preparation according to Manuacturing Direction I. (Pick-up 50%). The dyeing is subsequently dried at 60C and then fixed for 30 seconds at 190C. A
brilliant, very pronounced white effect is obtained.
A similar dyeing without addition of the preparation according to Manufacturing Direction I yields a fabric which is only insufficiently whitened and of a greenish colour on account of incompletely developed brightener.
The fluorescent brightener is fully developed only at a temperature of 210C but without attaining the effect of .
, ., . - -, . ~ ~
:, ~, , : ., , , ::: , . ~.
,~ .
~ 5~ ~4 a fluorescent whitening carried out with the product according to Manufacturing Direction I and also fixed at 210C. In the same way, it is possible to lower the fixation temperature of a combination of the fluorescent brighteners of the formulae .
(8) Cl ~ ~ CH =CU ~ N
and (9) CN3- C ~
from 190 to 170C by the use of the product according to Manufacturing Direction I.
Example 11 25 g of a polyethylene glycol terephthalate knitted fabric, .
wound on a perforated metal carrier, are treated for 10 minutes at 60C in a circulation apparatus with a liquor which contains 0.6 g of ammonium sulphate and 0.3 g of an , ~ 6 ~ ~
assistant mixture consisting of 55 parts of the sulphuric acid ester obtained according to Manufacturing Direction B, 10 parts of adipic acid di-2-ethyl-hexyl es~er and 35 parts of water and isopropanol (1:1) and 1.5 g of a ~arrier of the type trichlorobenzene/diphenyl in 300 ml of water, and whi~h is ad]usted to pH 5.5 with 85% formic acid, Then 0.625 g of a dye of the formula Cl NH- -(10) ~ ~ ~ N
I N0~ NH-CH2CH2 _ is added to this liquor and the dyebath is heated to 98C
over the course of 30 minutes. Dye;ng is performed for 60 minutes at this temperature and the liquor is after-wards cooled to 90C. The resultant dyeing is rinsed and dried. A level brilliant, red dyeing is obtained with no precipitation of dye on the inside of the carrier.
. . . ,. , -. . ~ . .
.
Example 12 1~ g of polyacrylonitrile fabric are treated for 10 minutes at 60C in a dyeing apparatus with a liquor which contains 0.8 g of an assistant mixture consisting of 55 parts of the sulphuric acid ester according to Manufacturing Direc-tion B, 10 parts of adipic acid di-~-ethyl-hexyl ester and 35 parts of water and isopropanol (1:1) in 400 ml of water, and which is adjusted to pH 5.5 with 80% acetic acid. Then 0.05 g of a dye of the formula NH-CH
O NH-GH2C~20H
is added and the dyebath is heated to 98C over the course of 30 minutes. Dyeing is carried out for 60 minutes at this temperature and the bath is cooled to 60C. The re-sultant dyeing is rinsed and dried. A level light blue dyeing which is fast to rubbing is obtained.
Example 13 In a high temperature dyeîng apparatus, 5 g of a triacetate . - 25 -fabric are put into a liquor which contains 0.2 g of an assistant mixture consisting of 55 parts of the sulphuric acid ester obtained according to Manufacturing Direction B, 10 parts of adipic acid di-2-ethyl-hexyl ester and 35 parts of water and isopropanol (1:1) in 200 ml of water, as well as 0.05 g of the dye of the formula ~11) used in Example 12, and which is adjusted to pH 5.5 with 80% acetic acid. The dyebath is then heated to 125C over the course of 45 minutes. Dyeing is carried out for 30 minutes at this temperature and the bath is subsequently cooled to 80C, The resultant dyeing is rinsed and dried in the usual way.
A level, brilliant, blue dyeing which is fast to rubbing is obtained.
Example 14 0,1 g of a disperse dye of the formula (12) ~
, . .
, - .: ;
~ ~5~ ~ 4 is stirred into 300 ml of water which contains 0015 g of an assistant mixture consisting of 55 parts of the sulphu-ric acid ester obtained according to Manufacturing Direction B, 10 parts of adipic acid di-2-ethyl-hexyl ester, and 35 parts of water and isopropanol (1:1). The dyebath is then, i as is customary in dyeing, heated to 98C over the course of 30 minutes and held for 10 minutes at this temperature.
After it had been cooled, the dyebath was drawn off through a round filter in order to ascertain any dyestuff agglome-ration. Even after this treatment the dyestuff dispersion was still intact and no deposits caused by agglomeration was observed.
Example lS
. :
10 g of a polyethylene glycol terephthalate/wool blended fabric (50:50) are treated in a dyebath with a liquor which contains O.g g of ammonium sulphate and 0,8 g of an assistant mixture consisting of 55 parts of the sul-phuric acid ester obtained according to Manufacturing Direction B, 10 parts of adipic acid di-2-ethyl-hexyl ester and 35 parts ofi water and isopropanol (1:1) in 400 ml of water, as well as 0.2 g of the disperse dye of the formula OCH
~13) HO-CH2-cH2_o ~ N =i~ ~ N =N ~ OH
~H3 and which is adjusted with 80% acetic acid to a pH of 5.5.
The dyebath is heated to 98C over the course of 30 minutes while constantly agitating the fabric, Dyeing is effected for 60 minutes at this temperature and the fabric is sub-sequently rinsed and dried as usual.
A strong dyeing is obtained on the polyester portion of the treated fabric and a distinct reserve on the wool portion.
Example_16 Polyacrylonitrile piece goods are slop padded to 100 per-cent by weight liquor pick-up with an aqueous liquor which contains per litre:
, .. . , . .: .. . . , , ~
105~
and 0.4 g of a dye of the formula .
-Br is added and the dyebath is heated over the course of 30 minutes to 130C. Dyeing is performed for 60 minutes at this temperature and the bath is then cooled to 90C and the resultant dyeing is subsequently rinsed and dried.
A level grey dyeing is obtained.
Exa~le 3 Level dyeings are also obtained by substituting for the assistants used in Examples 1 or 2 equal amounts of a further assistant consisting of 80 parts of the sulphuric acid ester obtained according to Manufacturing Direction B and 20 parts of the condensation product obtained from stearyl alcohol and 1 mole of ethylene oxide and otherwise carrying out the procedure as described therein.
Example 4 Level dyeings are also obtained by substituting for the ~ : . . , ~ ~ ; : , l(~S~
assistants used in Examples 1 or 2 equal amounts of a further assistant consisting ~f 60 parts of the sulphuric acid ester obtained according to Manufacturing Direction B and 40 parts of butyl alcohol and otherwise carrying out the procedure as described therein.
Example 5 Level dyeings are also obtained by substituting or the assistants used in Examples 1 or 2 equal amounts of an assistant consisting of 80 parts of the sulphuric acid ester obtained according to Manufacturing Direction B and 20 parts of a mixture of 5% silicone oil and 95% 2-ethyl-hexanol and otherwise carrying out the procedure as des-cribed therein. ~
Example_6 :
,:
A level dyeing is also obtained by substituting 2.2 g of the sulphuric acid ester obtained according to Manufacturing Direction C and 0.13 g of adipic acid 2-ethyl-hexyl ester for the assistant mixture used in Example l and otherwise carrying out the procedure as described therein, ~ ~5~
Similar results are obtained by using the sulpho-suceinic acid half ester obtained according to Manufacturing Direc-tion D instead of the assistant obtained according to Manufacturing Direction C.
Example 7 Level dyeings which are fast to rubbing are also obtained by substituting 8 g of the product according to Manufactu-ring Direction I or 16 g of the product according to Manufacturing Direction M for the product obtained ac-eording to Manufaeturing Direction A and used in Example 2, or by substitu~ing 0,3 g of the product according to Manufacturing Direction I or 0.6 g of the product aceording to Manufacturing Direction M for the assistant mixture used in Example 1. .
Example 8 Level dyeings are also obtained with the products obtained aeeording to Manufacuring Directions E, F, G, H, K, L, by using these in corresponding amounts instead of the product of Manufaeturing Direction B according to Example l.
- 2~ -- .
, .. ..
0~6 ~ ~
Example 9 40 g of a polyethylene terepht:halate staple fibre woven-fabric are dyed in a dyeing apparatus for 16 minutes at 130C by agitating the goods in a liquor (liquor ratio 1:9) which contains 0.5% (based on the weight of the fabric) of a 20% aqueous dispersion of the fluorescent ~rightener of the formula (6) ~ CH = CH ~ C
- . , :
and 5 g per litre of the preparation according to Manufac-turing Direction I. The bath is drawn off at 130C. The fabric, which is rinsed and dried in the ~ustomary manner, has a very pronounced, brilliant white effect with neutral shade of complete levelness. A dyeing in which there used 4.0 g of a 25% aqueous solution of the levelling agent of the formula C17H35CH20 - (CH2 CH2)35 per litre instead of 0.5 g of the preparation according to Manufacturing Direction I yields under otherwise similar - .~, . . .
, .:
conditions a substantially poorer whitening of insufficient levelness. In places even green discolourations caused by undeveloped brightener are observed on the treated fabric.
Exam~ 10 A polyethylene terephthalate staple fibre fabric is padded in a liquor which contains per litre 5 g of a 20% aqueous dispersion of the fluorescent brightener of the formula C(CH3)3 (7) ~ CH = CH ~ C ~
and 2,5 g o~ the preparation according to Manuacturing Direction I. (Pick-up 50%). The dyeing is subsequently dried at 60C and then fixed for 30 seconds at 190C. A
brilliant, very pronounced white effect is obtained.
A similar dyeing without addition of the preparation according to Manufacturing Direction I yields a fabric which is only insufficiently whitened and of a greenish colour on account of incompletely developed brightener.
The fluorescent brightener is fully developed only at a temperature of 210C but without attaining the effect of .
, ., . - -, . ~ ~
:, ~, , : ., , , ::: , . ~.
,~ .
~ 5~ ~4 a fluorescent whitening carried out with the product according to Manufacturing Direction I and also fixed at 210C. In the same way, it is possible to lower the fixation temperature of a combination of the fluorescent brighteners of the formulae .
(8) Cl ~ ~ CH =CU ~ N
and (9) CN3- C ~
from 190 to 170C by the use of the product according to Manufacturing Direction I.
Example 11 25 g of a polyethylene glycol terephthalate knitted fabric, .
wound on a perforated metal carrier, are treated for 10 minutes at 60C in a circulation apparatus with a liquor which contains 0.6 g of ammonium sulphate and 0.3 g of an , ~ 6 ~ ~
assistant mixture consisting of 55 parts of the sulphuric acid ester obtained according to Manufacturing Direction B, 10 parts of adipic acid di-2-ethyl-hexyl es~er and 35 parts of water and isopropanol (1:1) and 1.5 g of a ~arrier of the type trichlorobenzene/diphenyl in 300 ml of water, and whi~h is ad]usted to pH 5.5 with 85% formic acid, Then 0.625 g of a dye of the formula Cl NH- -(10) ~ ~ ~ N
I N0~ NH-CH2CH2 _ is added to this liquor and the dyebath is heated to 98C
over the course of 30 minutes. Dye;ng is performed for 60 minutes at this temperature and the liquor is after-wards cooled to 90C. The resultant dyeing is rinsed and dried. A level brilliant, red dyeing is obtained with no precipitation of dye on the inside of the carrier.
. . . ,. , -. . ~ . .
.
Example 12 1~ g of polyacrylonitrile fabric are treated for 10 minutes at 60C in a dyeing apparatus with a liquor which contains 0.8 g of an assistant mixture consisting of 55 parts of the sulphuric acid ester according to Manufacturing Direc-tion B, 10 parts of adipic acid di-~-ethyl-hexyl ester and 35 parts of water and isopropanol (1:1) in 400 ml of water, and which is adjusted to pH 5.5 with 80% acetic acid. Then 0.05 g of a dye of the formula NH-CH
O NH-GH2C~20H
is added and the dyebath is heated to 98C over the course of 30 minutes. Dyeing is carried out for 60 minutes at this temperature and the bath is cooled to 60C. The re-sultant dyeing is rinsed and dried. A level light blue dyeing which is fast to rubbing is obtained.
Example 13 In a high temperature dyeîng apparatus, 5 g of a triacetate . - 25 -fabric are put into a liquor which contains 0.2 g of an assistant mixture consisting of 55 parts of the sulphuric acid ester obtained according to Manufacturing Direction B, 10 parts of adipic acid di-2-ethyl-hexyl ester and 35 parts of water and isopropanol (1:1) in 200 ml of water, as well as 0.05 g of the dye of the formula ~11) used in Example 12, and which is adjusted to pH 5.5 with 80% acetic acid. The dyebath is then heated to 125C over the course of 45 minutes. Dyeing is carried out for 30 minutes at this temperature and the bath is subsequently cooled to 80C, The resultant dyeing is rinsed and dried in the usual way.
A level, brilliant, blue dyeing which is fast to rubbing is obtained.
Example 14 0,1 g of a disperse dye of the formula (12) ~
, . .
, - .: ;
~ ~5~ ~ 4 is stirred into 300 ml of water which contains 0015 g of an assistant mixture consisting of 55 parts of the sulphu-ric acid ester obtained according to Manufacturing Direction B, 10 parts of adipic acid di-2-ethyl-hexyl ester, and 35 parts of water and isopropanol (1:1). The dyebath is then, i as is customary in dyeing, heated to 98C over the course of 30 minutes and held for 10 minutes at this temperature.
After it had been cooled, the dyebath was drawn off through a round filter in order to ascertain any dyestuff agglome-ration. Even after this treatment the dyestuff dispersion was still intact and no deposits caused by agglomeration was observed.
Example lS
. :
10 g of a polyethylene glycol terephthalate/wool blended fabric (50:50) are treated in a dyebath with a liquor which contains O.g g of ammonium sulphate and 0,8 g of an assistant mixture consisting of 55 parts of the sul-phuric acid ester obtained according to Manufacturing Direction B, 10 parts of adipic acid di-2-ethyl-hexyl ester and 35 parts ofi water and isopropanol (1:1) in 400 ml of water, as well as 0.2 g of the disperse dye of the formula OCH
~13) HO-CH2-cH2_o ~ N =i~ ~ N =N ~ OH
~H3 and which is adjusted with 80% acetic acid to a pH of 5.5.
The dyebath is heated to 98C over the course of 30 minutes while constantly agitating the fabric, Dyeing is effected for 60 minutes at this temperature and the fabric is sub-sequently rinsed and dried as usual.
A strong dyeing is obtained on the polyester portion of the treated fabric and a distinct reserve on the wool portion.
Example_16 Polyacrylonitrile piece goods are slop padded to 100 per-cent by weight liquor pick-up with an aqueous liquor which contains per litre:
5 g of the disperse dye us~d in Example 12 of the formula (11)
6 g of starch ether 5 g of the assistant mixture consisting of 55 parts of the sulphuric acid ester obtained according to Manufacturing Direction B, 10 parts of adipic acid di-2-ethyl-hexyl ester and 35 parts of water and isopropanol (1:1) and the pH of - 2$ -.
. , , - . , , .-... : ,., , ~ . , , i . : . ~. .. ., . : j ~ 5~
which is adjusted to 5.5 with acetic acid.
Without first drying them, the treated goods are then treated in a steamer for 30 minutes at 105C (saturated steam) and afterwards rinsed and dried in the usual way.
A brilliant, level, light blue dyeing which is fast to rubbing is obtained~
, . -Example 17 10 g of a texturised polyethylene glycol tereph~halate fabric are treated for 10 minutes at 60C in a dyeing apparatus with a liquor which contains 0. 24 g of ammonium sulphate and 0.24 g of an assistant accord ing to Manufac t -uring Instruction I in 120 ml of water and which is adjusted to a pH of 5.5 wi$h 85% formic acid. The liquor is then heated to 135C over the course of 3S minutes and then 0.018 g of a dye of the formula NH
(14) R-02S ~ N = N ~
N2 3 ;.
R = CH3 and C2H5 (1~
:-. ;- ; . . ; ; ~ . .
.. . ~ . ; ~: .
:. : . . ., ~ , . . ". . , ` -0.015 g of a dye of the formula (15) 02N ~ N = N ~ N-cH~cH2-o-cH2cH2cN
Cl CH2CH2CN
and 0.015 g of a dye of the formula (16) 02N ~ N DN ~ NH-CH2CH20CH2CH2CN
Cl NHCOCH2CH3 are added. Dyeing is carried out for 30 minutes at this temperature and the bath is then cooled to 90C. The re-sultant dyeing is rinsed and dried. A level, grey dyeing is obtained.
Example 18 Texturised polyethylene terephthalate fabric is impregnated at 20 to 30C with an impregnating liquor which contains 29 g/l of a dye of the formula .
- , . i................. :.. . - :, ... . ... . ..
: ~ '' -'" : .' '. ~
N~ .
~ 2 (17) 1~02~ ~=N~
Cl So2NH-c:H3 10 g/l of an assistant according to Manufacturing Direction I
2 g/l of alginate thickener 0.5 g/l of sodium alkylnaphthalenesulphonate and 2 g/l of monosodium phosphate and which is adjusted to a pH of 6.5 with acetic acid. The fabric is subsequently squeezed out to 98% liquor pick-up, based on the dry weight of the goods, dried at 120C for 3 minutes and thermofixed at 190C for 45 seconds. The dyeing is washed with cold water and dried~ A level, red dyeing is obtained. If appropriate, it is also possible to carry out the customary reducti~e aftertreatment after ~ -rinsing.
. , , - . , , .-... : ,., , ~ . , , i . : . ~. .. ., . : j ~ 5~
which is adjusted to 5.5 with acetic acid.
Without first drying them, the treated goods are then treated in a steamer for 30 minutes at 105C (saturated steam) and afterwards rinsed and dried in the usual way.
A brilliant, level, light blue dyeing which is fast to rubbing is obtained~
, . -Example 17 10 g of a texturised polyethylene glycol tereph~halate fabric are treated for 10 minutes at 60C in a dyeing apparatus with a liquor which contains 0. 24 g of ammonium sulphate and 0.24 g of an assistant accord ing to Manufac t -uring Instruction I in 120 ml of water and which is adjusted to a pH of 5.5 wi$h 85% formic acid. The liquor is then heated to 135C over the course of 3S minutes and then 0.018 g of a dye of the formula NH
(14) R-02S ~ N = N ~
N2 3 ;.
R = CH3 and C2H5 (1~
:-. ;- ; . . ; ; ~ . .
.. . ~ . ; ~: .
:. : . . ., ~ , . . ". . , ` -0.015 g of a dye of the formula (15) 02N ~ N = N ~ N-cH~cH2-o-cH2cH2cN
Cl CH2CH2CN
and 0.015 g of a dye of the formula (16) 02N ~ N DN ~ NH-CH2CH20CH2CH2CN
Cl NHCOCH2CH3 are added. Dyeing is carried out for 30 minutes at this temperature and the bath is then cooled to 90C. The re-sultant dyeing is rinsed and dried. A level, grey dyeing is obtained.
Example 18 Texturised polyethylene terephthalate fabric is impregnated at 20 to 30C with an impregnating liquor which contains 29 g/l of a dye of the formula .
- , . i................. :.. . - :, ... . ... . ..
: ~ '' -'" : .' '. ~
N~ .
~ 2 (17) 1~02~ ~=N~
Cl So2NH-c:H3 10 g/l of an assistant according to Manufacturing Direction I
2 g/l of alginate thickener 0.5 g/l of sodium alkylnaphthalenesulphonate and 2 g/l of monosodium phosphate and which is adjusted to a pH of 6.5 with acetic acid. The fabric is subsequently squeezed out to 98% liquor pick-up, based on the dry weight of the goods, dried at 120C for 3 minutes and thermofixed at 190C for 45 seconds. The dyeing is washed with cold water and dried~ A level, red dyeing is obtained. If appropriate, it is also possible to carry out the customary reducti~e aftertreatment after ~ -rinsing.
Claims (12)
1. A process for dyeing (including brightening) fibrous materials which contain synthetic fibres selected from cellulose ester, linear polyester, synthetic polyamide, poly-urethane, polyolefine and polyacrylonitrile fibres, with a dye that is sparingly soluble to insoluble in water selected from a vat dye, a pigment dye, a disperse dye and a fluores-cent brightener, comprising the step of applying to the fibrous material an aqueous liquor having a pH of 4 to 8 and containing 0.01 to 10 percent by weight, based on the weight of the fibrous material, of the dye and 0.1 of 5 grams per litre of dye liquor of a water-soluble acid ester or salt thereof of a polypropyleneoxide adduct of an average moleculare weight of 1000 to 6000 wherein the poly-propyleneoxide adduct is an adduct of a homopolymer of propyleneoxide and a polyhydric aliphatic alcohol of 2 to 6 carbon atoms and wherein the acid ester of the polypropylene-oxide adduct is derived from said adduct and an acid con-taining a sulphonic acid group.
2. A process according to claim 1 wherein the polypropylene-oxide adduct is derived from a polyhydric aliphatic alco-hol of 3 to 6 carbon atoms.
3. A process according to either of claims 1 or 2, wherein the acid ester is a sulphur acid ester of a poly-propylene oxide adduct derived from a polyhydric aliphatic alcohol of 3 to 6 carbon atoms.
4. A process according to claim 1, wherein the polypro-pyleneoxide adduct has an average molecular weight of 2000 to 3500.
5. A process according to claim 1, wherein the polyhydric aliphatic alcohol is propylene glycol or glycerol.
6. A process according to claim 1, wherein the aqueous liquor contains 0.5 to 2 g of acid ester of the polypro-pyleneoxide adduct per litre of aqueous liquor.
7. A process according to claim 1, wherein the aqueous liquor further contains an antifoaming agent.
8. A process according to claim 7, wherein the antifoam-ing agent is adipic acid di-2-ethyl-hexyl ester.
9. A process according to claim 1 which comprises carry-ing out the dyeing by an exhaustion process.
10. A process according to claim 1, wherein the synthetic fibres are linear polyester fibres.
11. A process according to claim 1, which comprises carrying out the dyeing at a temperature of 110° to 140°C.
12. An aqueous dye liquor for dyeing (including brightening) fibrous materials which contain synthetic fibres, selected from cellulose ester, linear polyester, synthetic polyamide, polyurethane, polyolefine and polyacrylonitrile fibres, said liquor having a pH of 4 to 8 and containing 0.01 to 10 percent,based on the weight of the fibrous material of a dye that is sparingly soluble to insoluble in water selected from a vat dye, a pigment dye, a disperse dye and a fluorescent brightener and 0.01 to 5 grams per litre of the dye liquor of a water-soluble acid ester or salt thereof of a polypropylene-oxide adduct of an average molecular weight of 1000 to 6000 wherein the polypropyleneoxide adduct is an adduct of a homopolymer of propyleneoxide and a polyhydric aliphatic alcohol of 2 to 6 carbon atoms and wherein the acid ester of the polyproyleneoxide adduct is derived from said adduct and an acid containing a sulphonic acid group.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH672274A CH578081B5 (en) | 1974-05-16 | 1974-05-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1051614A true CA1051614A (en) | 1979-04-03 |
Family
ID=4314021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA226,971A Expired CA1051614A (en) | 1974-05-16 | 1975-05-14 | Process for dyeing materials which contain synthetic fibres |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS5930830B2 (en) |
| AR (1) | AR208315A1 (en) |
| AT (1) | AT372124B (en) |
| BE (1) | BE829109A (en) |
| BR (1) | BR7503024A (en) |
| CA (1) | CA1051614A (en) |
| CH (2) | CH672274A4 (en) |
| DK (1) | DK144803C (en) |
| ES (1) | ES437669A1 (en) |
| FR (1) | FR2271330B1 (en) |
| GB (1) | GB1510331A (en) |
| IL (1) | IL47296A (en) |
| NL (1) | NL7505750A (en) |
| SE (1) | SE403307B (en) |
| SU (1) | SU1077578A3 (en) |
| ZA (1) | ZA753135B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898870B (en) * | 2012-10-20 | 2013-11-20 | 山西青山化工有限公司 | Fluorescent whitening agent composition for cotton cloth |
-
1974
- 1974-05-16 CH CH672274D patent/CH672274A4/xx unknown
- 1974-05-16 CH CH672274A patent/CH578081B5/xx not_active IP Right Cessation
-
1975
- 1975-01-01 AR AR258773A patent/AR208315A1/en active
- 1975-04-29 SE SE7505000A patent/SE403307B/en not_active IP Right Cessation
- 1975-05-14 CA CA226,971A patent/CA1051614A/en not_active Expired
- 1975-05-14 IL IL47296A patent/IL47296A/en unknown
- 1975-05-14 ES ES437669A patent/ES437669A1/en not_active Expired
- 1975-05-15 DK DK212775A patent/DK144803C/en not_active IP Right Cessation
- 1975-05-15 GB GB20680/75A patent/GB1510331A/en not_active Expired
- 1975-05-15 NL NL7505750A patent/NL7505750A/en not_active Application Discontinuation
- 1975-05-15 AT AT0371175A patent/AT372124B/en not_active IP Right Cessation
- 1975-05-15 BR BR3855/75D patent/BR7503024A/en unknown
- 1975-05-15 SU SU752134134A patent/SU1077578A3/en active
- 1975-05-15 FR FR7515196A patent/FR2271330B1/fr not_active Expired
- 1975-05-15 ZA ZA00753135A patent/ZA753135B/en unknown
- 1975-05-15 BE BE156377A patent/BE829109A/en not_active IP Right Cessation
- 1975-05-16 JP JP50057525A patent/JPS5930830B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5930830B2 (en) | 1984-07-28 |
| FR2271330B1 (en) | 1977-04-15 |
| SE7505000L (en) | 1975-11-17 |
| DK144803B (en) | 1982-06-07 |
| SE403307B (en) | 1978-08-07 |
| IL47296A0 (en) | 1975-07-28 |
| FR2271330A1 (en) | 1975-12-12 |
| SU1077578A3 (en) | 1984-02-29 |
| DK212775A (en) | 1975-11-17 |
| GB1510331A (en) | 1978-05-10 |
| JPS50160576A (en) | 1975-12-25 |
| BE829109A (en) | 1975-11-17 |
| DE2521106B2 (en) | 1976-06-16 |
| BR7503024A (en) | 1976-03-23 |
| ZA753135B (en) | 1976-04-28 |
| IL47296A (en) | 1978-04-30 |
| AR208315A1 (en) | 1976-12-20 |
| ATA371175A (en) | 1983-01-15 |
| CH578081B5 (en) | 1976-07-30 |
| NL7505750A (en) | 1975-11-18 |
| CH672274A4 (en) | 1976-02-13 |
| ES437669A1 (en) | 1977-01-16 |
| AT372124B (en) | 1983-09-12 |
| DE2521106A1 (en) | 1975-11-20 |
| DK144803C (en) | 1982-11-01 |
| AU8121375A (en) | 1976-11-18 |
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