CA1069919A - Acid esters of propylene oxide poly-adducts - Google Patents
Acid esters of propylene oxide poly-adductsInfo
- Publication number
- CA1069919A CA1069919A CA253,898A CA253898A CA1069919A CA 1069919 A CA1069919 A CA 1069919A CA 253898 A CA253898 A CA 253898A CA 1069919 A CA1069919 A CA 1069919A
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- Prior art keywords
- acid
- acid ester
- dyeing
- propylene oxide
- salt
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
-
- 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
- D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
- D06P1/6076—Nitrogen-containing polyethers or their quaternary derivatives addition products of amines and alkylene oxides or oxiranes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Abstract
Abstract of the Disclosure Acid esters of propylene oxide poly-adducts and their salts, which are obtained by an addition reaction of (a) propylene oxide with (b) a polyfunctional amine, which contains 2 to 9 carbon atoms and at least a second reactive amino group or at least one hydroxyl group, and esterification of the poly-adduct with (c) an oxy-acid which is at least dibasic or with a functional derivative of this acid and, if appropriate, by conversion of the resulting acid ester into a salt.
These acid esters of propylene oxide poly-adducts are particularly effective as dyeing auxiliaries, especially as dispersing and levelling agents for dyeing synthetic fibres and primarily for dyeing linear polyester fibres.
These acid esters of propylene oxide poly-adducts are particularly effective as dyeing auxiliaries, especially as dispersing and levelling agents for dyeing synthetic fibres and primarily for dyeing linear polyester fibres.
Description
9~
The present invention relates -to new acid esters of propylene oxide poly-adducts, a process for their manufacture and their use as dyeing auxiliaries when dyeing synthetic fibres or materials containing such ~ibres with dyestuffs which are insoluble or sparingly soluble in water.
When textile materials are dyed with dyestuffs which are insoluble or sparingly soluble in water, for example by the so-ca-lled high-temperature circulation dyeing method, dispersion difficulties, which are due to inadequate fine dis-tribution of the dyestuffs in the dye liquors, frequently arise~ As a result, dyeings which are uneven and not fast,above all not fast to rubbing, are obtained. Defects o~ this type are noticeable, inter alia, when synthetic fibres, especially the linear polyester fibres, are dyed with disperse dyestu~fs.
As is known, certain auxiliaries, such as, for example, condensation products obtained from naphthalenesulphonic acid and formaldehyde or their alkali metal salts,ox~thylated ~atty alcohols or ligninsulphonates, can be added to the dye bathsin order to stabilise the dispersions of dyestuffs which are sparingly soluble in water.
However, these products possess either only dispersing properties or only levelling proper-ties. Therefore, the two effects can be achieved simultaneously only by using mix-tures of different auxiliaries. Due to their high tendency to foaming, many dispersing agents àlso impair the dispersion and dyeing process.
,..
. , . : :,, " ,,: . .-- , .. . . :, : . , . ,; , . . . .
~9 New dyeing auxiliaries have now been ~ound which enable level dyeings which are fast to rubbing to be obtained when materials containing synthetic fibres are dyed with dye-stu~fs which are sparingly soluble to insoluble in water.
The new auxiliaries are acid esters o~ propylene oxide poly-adducts and their salts,which have been manufactured by an addition reaction oP (a) propylene oxide with (b) a poly-functional amine, which contains 2 to 9 carbon atoms and at least a second reactive amino group or at least one hydroxyl group, a~d esterification o~ the poly adduct with (c) an oxy-acid which is at least dibasic or with a functional derivative of this acid and,i~ apFn~x~a~ by conversion o~ the resulting acid ester into a salt.
The new products can be present as ~ree acids or as salts, ~or example alkali metal salts or ammonium salts.
Alkali metal salts which may be mentioned are, in particular, the sodium and potassium salts,and ammonium salts which may be mentioned are the ammonium, trimethylammonium, monoethanol-ammonium, diethanolammonium and triethanolammonium salts. ~`
.
The poly-adducts are pre~erably manufactured as ammonium sal-ts.
The new acid esters are derived from poly-adducts which are obtained from the components (a) and (b) and which approp-riately have an average molecular weight of 1,000 to 6,000, preferably 3,000 to 5,0000 Poly-adducts o~ this type can be manufactured, ~or example, by an addition reaction of about 15 to 100 mols, preferably about 50 to 85 mols, of propylene ox~de (a) with one mol o~ the component (b)~ Poly-adducts .
, -,. . .
. ; , "" ..
,,.,~
~, .. , . .. . .
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which have an average molecular weight o~ 2,000 to 4,000 are also preferred.
The new acid esters o~ propylene oxide poly-adducts are manufactured by subjecting (a) propylene oxide to an addition reaction with (b) a polyfunctional amine which con-tains 2 to 9 carbon atoms and at least a second reactive amino group or at least one hydroxyl gro~p and converting the addition product into the acid ester using (c) an oxy-acid which is at least dibasic, or a functional derivative of this acid, and op-tionally converting the resulting acid ester into the abovementioned salts.
Possible amines, which, as starting materials, can be reacted with propyiene oxide, are, in principle, poly~unctional amines which contain either at least two reactive amino groups or at le~st one reactive amino group and one hydroxyl group, it being possible ~or the reactive amino groupsto be primary and/or secondary. Amines which have proved suitable are, above all, alkylene polyamines which contain 2 to 6 carbon atoms and 2 to 4 amino groups~ Polyfunctional alkyleneamines which can be used are, for example, ethylenediamine, propylene-diamine, butylenediamine, pentylenediamine, hexamethylene-diamine, diethylenetriamine, triethylenetetramine, 1,2-propylenediamine, dipropylenetriamine, tripropylenete~ramine and dibutylenetriamine. Preferred polyamines are alkylene-diamines with 2 or 3 carbon atoms, such as propylenediamine and especially ethylenediamine.
Amines which have 2 to 6 carbon atoms and contain at ,.,._.. .. ,. ., . .. . . ..... ., .......... ,.,.. , . - . : . . , . . . . .. ; : ,. , . ., :. .
~L~699~
leàst one hydroxyalkyl group, for example hydroxyalkylamines, such as ~-hydroxyethylamine, ~- or ~-hydroxypropylamine or ~,r-dihydroxypropylamine; bis-hydroxyalkylamines, such as bis~ hydroxyethylamine~, bis-~-hydroxypropylamine or bis-(a-methyl-~-hydroxyethyl)-amine; tris-hydroxyalkylamines9 such as tris-(~-hydroxyethyl)-amine and N-alkyl-N-hydroxy-alkylamines, such as N-methyl- or N-ethyl-N-~-hydroxypropyl-amine, also prove to be particularly valuable. N-Met~yl-N-~-ethanolamine and, especially, tris-~-ethanolamine and ~-ethanolamine are preferred.
Both the propylene oxide addition reaction and the esterification can be carried out according to known methods.
Polybasic oxy-acids which can be used to form the new acid esters are sulphonated organic, preferably aliphatic, mono- or di-carboxylic acids with 3 to 6 carbon atoms, such as, for example, sulphosuccinic acid, or, in particular, polybasic inorganic oxy-acids, such as sulphuric acid. In place of the acids it is also possible to use their functional deriva-tives, such as acid anhydrides, acid halides, acid esters or acid amides. Chlorosulphonic acid and, especially, sulphamic àcid may be mentioned as examples of ~hese functional deriva-tives.
As a rule, the esterification according to the invention is carried out by simply mixing the reactants whilst warming, appropriately to a temperature between 50 and 100C. The ~ree acids which are first formed can then be converted into the corresponding alkali metal or ammonium salts. Conversion ~6~9~C~
into the salts is carried out in the customary manner by adding bases, such as, for example, ammonia, monoethanolamine, triethanolamine or alkali metal hydroxides, for example sodium hydroxide or potassium hydroxide. According to a particularly preferred embodiment, the acid sulphuric acid esters are manufactured direct in the form of their ammonium salts by warming the propylene oxide addition products with sulphamic acid, appropria-tely in the.presence of urea.
A typical representative of the new products is the ammonium salt of the sulphuric acid ester of an addition i product which has been obtained from ethylenediamine and propylene oxide and which appropriately has an average mole-cular weight of 3,000 to 4,000, preferably 3j,600.
A further representative which contains sulpho groups is the sulphosuccinic acid half-ester o~ a poly-adduct obtained by an addition reaction of propylene oxide and ethylenediamine, the poly~adduct advantageously having an average molecular weight o~ 3,000 to 4,000, preferably 3,600.
With the aid of the anionic poly-adducts described above it is now possible to eliminate the disadvantages which were described initially and which arise when organic syn-thetic ~ibres, especially polyes-ter fibres, are dyed with disperse dyestuffs without the addition of an auxiliary or with the additives used hitherto. The technical advance depends, above all, on the excellent dispersion-stabilising action of the poly-adducts on the dyestuff, so that neither an aggrega-tion nor a precipitation of the dyestuff takes place during the . ,...... ,,. :.... :. :.. , ... :. . ... :, .
, ` !
, 69~L9 entire dyeing process.
A further advantage of these compounds, which are employed as levelling and dispersing agents, lies in the low tendency to foaming. Accordingly, there is no danger of froth stains forming on the dyeings and a more rapid pene-tration of the goods and an increase in the rate of flow in the dyeing machines are thus ensured.
The new acid esters of propylene oxide poly-adducts are used as dyeing auxiliaries, especially as dispersing and levelling agents, for dyeing synthetic ~ibres or materials containing such fibres and especially for dyeing linear poly-esters.
The amounts in which the acid esters of the poly-propylene oxide adducts, or their salts, are added to the dye ba-thsvary between 0.1 and 5 g, preferably 0.5 to 2 g, per litre of the aqueous dye liquor.
It is ~requently desirable to incorporate an anti-foaming agent into the aqueous solution o~ the acid ester in order to improve the properties of the dye bath,to which the dispersing agent is added, and sometimes also to increase the migration of the dyestu~f. A satisfactory type of anti-foaming agent is a silicone emulsion, for example a 5 to l~/o strength aqueous silicone emulsion, which can also be employed in combination with higher alcohols with 4 to 22 carbon atoms, .-~
especially with 2-ethyl hexanol. However, the most suitable anti-foaming agents are water-insoluble alkylene oxide adducts of higher alcohols, for example the adduct of 1 mol of " , , ~ .
~ [)6i99~) e-thylene oxide with 1 mol of stearyl alcohol, and also esters of aliphatic dicarboxylic acids and the higher alcohols mentioned, or the higher alcohols on their own, for example n-butyl alcohol or 2-ethylhexanol.
Adipic acid di-2~ethyl-hexyl ester and also poly-siloxanes, such as, for example, methylpolysiloxane, have proved very particularly suitable.
The amount in which the anti-foaming agent is employed can be as low as, for example, 0~5% by weight but is advan-tageously at least 10% by weight and preferably 15 to 60% by weight, based on the weight of the acid ester or its salt.
Water-miscible alcohols can also be added to the solution oP the new acid ester. Alcohols which are suitable for this purpose are, in par-ticular, lower aliphatic alcohols, such as alkanols, for example ethyl alcohol, n- and iso-propyl alcohol and tert.-butyl alcohol, alkylene glycols, for example ethylene glycol and 295-hexanedioi and their lower monoalkyl ethers, as well as mixtures thereof.
Dyestuffs which are insoluble or sparingly soluble in water are to be understood as vat dyestuffs, organic pigments and, above all, disperse dyestuffs which have an affinity for the fibre, that is to say -those which are absorbed on textile synthe-tic fibre materials.
The dyestuffs can belong to ~ery diverse categories, for example acridone dyestuffs, nitro dyestuffs, methine and polymethine dyestuffs, styryl and azos-tyryl dyestuffs, xanthene dyestuffs, oxazine dyestuffs, aminonaphtho~ulnone , ;''; :; ':' :'.; . , .' :,., ::. :: ':,' ~ .
: , . : : ~ . : .' ' ''' :'' :'''' ' ~ 69 ~
dyestuffs 9 coumarin dyestuffs and, in particular, anthraquin-one dyestuffs and azo dyestuffs, such as monoazo dyestuffs and disazo dyestu~fs.
Mixtures of such dyestuffs can also be employed.
The new anionic poly-adduc-ts can also be employed when whitening undyed textile materials with optical brighteners which are sparingly soluble in water.
The latter can belong to any desired categories of brightener. In particular they are stilbene compouinds, coumarins~ benzocoumarins, pyrazines; pyrazolines, oxazines, triazolyl, benzoxazolyl, benzofurane or benzimidazolyl com-pounds and naphthalic acid imides~
The amount of dyestuffs added to the liquor depends on the desired depth of colour; in general~ amounts of 0.01 to 10 per cent by weight, based on the fibre material employed, have proved suitable.
Examples which may be mentioned of fibre materials which can be dyed in the presence of the new adducts are cellulose ester fibres, such as cellulose 2~-acetate fibres and cellulose triacetate fibres, synthetic polyamide fibres, for example those made from ~-caprolactam, from adipic acid and hexamethylenediamine and from ~-aminoundecanoic acid, polyurethane fibres, polyolefine fibres~ for example poly- ~
propylene fibres, polyacrylonitrile fibres, including modified acrylic fibres~ and, above all9 linear polyester fibres.
Linear polyester fibres are to be understood as synthetic fibres which are obtained by a condensation reaction of _ g _ ',. ~ ' ~ ;. :, . .................... ., ,. :........... .
,, , :. ...
~ ~6g9~
terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis-(hydroxymethyl)-cyclohexane, and also copolymers of terephthalic acid and isophthalic acid and ethylene glycol. The fibre materials can also be used as mixed fabrics with one another or with other fibres, ~or example mixtures of polyacrylonitrile/polyester, polyamideJ
polyester, polyester/viscose and polyester/wool~
The fibre material can be in very di~erse stages of processing, for example in the form of flock, piece goods, such as woven fabrics and knitted fabrics, bundles of yarn or wound packages or as non-woven fabrics, a textile floor covering or a tufted carpet.
The dyeings are advantageously carried out from an a~ueous li~uor by the exhaustion process. Linear polyester ~ibres are preferably dyed by the so-called high-temperature process in closed pressure-resistant machines at tempera-tures of above 100C, preferably between 110 and 140C, under pressure.
Examples of suitable closed vessels are circula-ting liquor machines, such as cheese machines or beam dyeing machines, winches, jet dyeing machines or rotary-type dyeing machines, paddles or jiggers. The liquor ratio can accordingly be chosen within a wide range, for example 1:1 to 1:100, preferably 1:10 to 1:50~ The linear polyester fibres can also be dyed at temperatures beiow 100C, ~or examplè in the temperature range from 75 to 98C, in ~he presence of the customary carriers, for example phenylphenols, polychloro-, , . ~, .. , , ' ": : ', , , ' ' ; ' : , .,. . . ' . .
, , ,, . ' ',',, ,'. '. ~ ;. ' ,.
benzenes, xylenes, toluenes, naphthalenes or diphenyl.Cellulose 2~-acetate fibres are preferably dyed at tempera-tures of 80-85C, whilst cellulose triacetate fibres are advantageously dyed at the boiling point (98C) of the aqueous bath.
The use of carriers is superfluous when dyeing cellu-lose 2~-acetate or polyamide fibres.
When preparing the dye liquors it is appropriate to start from aqueous solutions of the acid ester or its salt a~d to add suitable auxiliaries, such as, for example, anti- -~oaming agents and lower alcohols, to these. The liquors can contain mineral acids, such as, for example, sulphuric acid or phosphoric acid, organic acids, appropria-tely lower aliphatic carboxylic acids, such as formic acid, acetic acid or oxalic acid, and/or salts, such as ammonium acetate, ammonium sulphate or sodium acetate. The acids serve, above all, to adjust the pH value of the liquors which can be used according to the invention; as a rule, the pH value is 4 to 8 and pre~erably 4.5 to 5.5.
The textile material is introduced into the liquor, which can have a temperature o~ 40 to 70C, and the material -is treated for 5 to 15 minu-tes at this tempera-ture. The dye-stuff and, where appropriate, the carrier are then added and the temperature of the liquor is raised in order to dye in the indicated temperature range for 50 to 100 minutes.
The dyed material is then rinsed, and dried, in the customary manner. A reductive after-treatment is normally ',.. '.'. ', .', ' ' ' ' ' .:-: . ~.
~69~1~
not necessary.
It is important that a fine dispersion of the dyestuff is not only inltially present but that the degree of dispersion is also maintained during the entire dyeing process. As is known, certain disperse dyestuffs tend, above all under the conditions of high-temperature dyeing, to convert into a less fine form. The result of this is that the dyestu~f settles on the surface of the material to be dyed. Such agglomera-tions and deposits of dyestuff can be avoided particularly well by means of the anionic poly-adducts according to the invention.
The synthetic fibre material can also be dyed con-tinuously, that is to say by impregnating with an aqueous formulation which contains a disperse dyestuff, an anionic poly-adduct according to the invention and, optionally, a thickener and an acid and squeezing off to the desired content of impregnating liquor of 60 to 120% of the weight of fibre and subsequently subjecting to a heat treatment, such as, for example, steaming at temperatures of 98 to 105C with neutral saturated steam or thermofixing at 180 to 210C.
Uniform and deep dyeings~ which additionally are distinguished by good fastness to rubbing and good dye yields, are obtained on syn-thetic organic fibre material, especially on linear polyester fibres, by the dyeing process according to the invention.
In the examples which follow percentages denote per-centages by weight and parts denote parts by weight.
, .... :: . ,; ; ,.
~ '9 Example_l 60 g of an adduct which was obtained from ethylene-diamine and propylene oxide and has an average molecular wei~ht of 3,600 are warmed to 60 - 65C. Subsequently~ 7.2 g of urea are introduced in the course of 15 minutes and 7.2 g of sulphamic acid are introduced in the course of 30 minutes.
The reaction mixture is stirred for a further 30 minutes at 60-65C, then warmed to 95C in the course of 30 minutes and ke~t at 95 - 110C for 6 hours~ A product which is readily soluble in water and contains 90% of the ammonium salt of the acid sulphuric acid ester of the adduct is obtained. The product has a surface tension of 37.0 dyne/cm at 24C.
5.2 g of maleic anhydride are introduced in the course o~ 15 minutes, at 60C, into 46 g of a poly-adduct which was obtained from ethylenediamine ancL propylene oxide and has an average molecular weight o~ 3,600. The reaction mixture is then kept at 100C for 30 minutes and at 125C for 60 minutes, After cooling to 90 - 100C, a solution o~ 7.8 g of sodium sulphite in 54 g of water is added to the reaction product and the mixture is kept at 100C for a further 9 hours. A
solution which contains 50/ of the sodium salt of the sulpho-succinic acid ester of the abovementioned poly-adduct is obtained. The surface tension at 24C is 38.3 dyne/cm.
Example 3 41.8 g of a poly-adduct which was obtained from ethylenediamine and propylene oxide and has an average mole-. I . .' . .
~L~6g~19 cular weight of 1,020 are esterified as described in Example 1, using 18 g of sulphamic acid in the presence of 18 g of urea.
The resul-ting product is readily soluble in water. The surface tension at 24C is 39.1 dyne/cm.
Example 4 5g g of a poly adduct which was obtained from ethylenediamine and propylene oxide and has an average mole-cular weight of 5,920 are esterified as described in Example 1, using 4.5 g of su]phamic acid in the presence of 4.5 g of urea~
whereupon a product which is readily soluble in water is -obtained. The surface tension at 24C is 35.4 dyne/cm.
Example 5 46.6 g of a poly-adduct which was obtained from mono-isopropanolamine and propylene oxide and has an average mole-cular weight of 2,330 are esterified as described in Example 1, using 6.4 g of sulphamic acid in the presence of 6.4 g o~ urea.
A product which is readily soluble in water is obtained.
The surface tension at 24C is 36.0 dyne/cm.
Example 6 r
The present invention relates -to new acid esters of propylene oxide poly-adducts, a process for their manufacture and their use as dyeing auxiliaries when dyeing synthetic fibres or materials containing such ~ibres with dyestuffs which are insoluble or sparingly soluble in water.
When textile materials are dyed with dyestuffs which are insoluble or sparingly soluble in water, for example by the so-ca-lled high-temperature circulation dyeing method, dispersion difficulties, which are due to inadequate fine dis-tribution of the dyestuffs in the dye liquors, frequently arise~ As a result, dyeings which are uneven and not fast,above all not fast to rubbing, are obtained. Defects o~ this type are noticeable, inter alia, when synthetic fibres, especially the linear polyester fibres, are dyed with disperse dyestu~fs.
As is known, certain auxiliaries, such as, for example, condensation products obtained from naphthalenesulphonic acid and formaldehyde or their alkali metal salts,ox~thylated ~atty alcohols or ligninsulphonates, can be added to the dye bathsin order to stabilise the dispersions of dyestuffs which are sparingly soluble in water.
However, these products possess either only dispersing properties or only levelling proper-ties. Therefore, the two effects can be achieved simultaneously only by using mix-tures of different auxiliaries. Due to their high tendency to foaming, many dispersing agents àlso impair the dispersion and dyeing process.
,..
. , . : :,, " ,,: . .-- , .. . . :, : . , . ,; , . . . .
~9 New dyeing auxiliaries have now been ~ound which enable level dyeings which are fast to rubbing to be obtained when materials containing synthetic fibres are dyed with dye-stu~fs which are sparingly soluble to insoluble in water.
The new auxiliaries are acid esters o~ propylene oxide poly-adducts and their salts,which have been manufactured by an addition reaction oP (a) propylene oxide with (b) a poly-functional amine, which contains 2 to 9 carbon atoms and at least a second reactive amino group or at least one hydroxyl group, a~d esterification o~ the poly adduct with (c) an oxy-acid which is at least dibasic or with a functional derivative of this acid and,i~ apFn~x~a~ by conversion o~ the resulting acid ester into a salt.
The new products can be present as ~ree acids or as salts, ~or example alkali metal salts or ammonium salts.
Alkali metal salts which may be mentioned are, in particular, the sodium and potassium salts,and ammonium salts which may be mentioned are the ammonium, trimethylammonium, monoethanol-ammonium, diethanolammonium and triethanolammonium salts. ~`
.
The poly-adducts are pre~erably manufactured as ammonium sal-ts.
The new acid esters are derived from poly-adducts which are obtained from the components (a) and (b) and which approp-riately have an average molecular weight of 1,000 to 6,000, preferably 3,000 to 5,0000 Poly-adducts o~ this type can be manufactured, ~or example, by an addition reaction of about 15 to 100 mols, preferably about 50 to 85 mols, of propylene ox~de (a) with one mol o~ the component (b)~ Poly-adducts .
, -,. . .
. ; , "" ..
,,.,~
~, .. , . .. . .
~699:~
which have an average molecular weight o~ 2,000 to 4,000 are also preferred.
The new acid esters o~ propylene oxide poly-adducts are manufactured by subjecting (a) propylene oxide to an addition reaction with (b) a polyfunctional amine which con-tains 2 to 9 carbon atoms and at least a second reactive amino group or at least one hydroxyl gro~p and converting the addition product into the acid ester using (c) an oxy-acid which is at least dibasic, or a functional derivative of this acid, and op-tionally converting the resulting acid ester into the abovementioned salts.
Possible amines, which, as starting materials, can be reacted with propyiene oxide, are, in principle, poly~unctional amines which contain either at least two reactive amino groups or at le~st one reactive amino group and one hydroxyl group, it being possible ~or the reactive amino groupsto be primary and/or secondary. Amines which have proved suitable are, above all, alkylene polyamines which contain 2 to 6 carbon atoms and 2 to 4 amino groups~ Polyfunctional alkyleneamines which can be used are, for example, ethylenediamine, propylene-diamine, butylenediamine, pentylenediamine, hexamethylene-diamine, diethylenetriamine, triethylenetetramine, 1,2-propylenediamine, dipropylenetriamine, tripropylenete~ramine and dibutylenetriamine. Preferred polyamines are alkylene-diamines with 2 or 3 carbon atoms, such as propylenediamine and especially ethylenediamine.
Amines which have 2 to 6 carbon atoms and contain at ,.,._.. .. ,. ., . .. . . ..... ., .......... ,.,.. , . - . : . . , . . . . .. ; : ,. , . ., :. .
~L~699~
leàst one hydroxyalkyl group, for example hydroxyalkylamines, such as ~-hydroxyethylamine, ~- or ~-hydroxypropylamine or ~,r-dihydroxypropylamine; bis-hydroxyalkylamines, such as bis~ hydroxyethylamine~, bis-~-hydroxypropylamine or bis-(a-methyl-~-hydroxyethyl)-amine; tris-hydroxyalkylamines9 such as tris-(~-hydroxyethyl)-amine and N-alkyl-N-hydroxy-alkylamines, such as N-methyl- or N-ethyl-N-~-hydroxypropyl-amine, also prove to be particularly valuable. N-Met~yl-N-~-ethanolamine and, especially, tris-~-ethanolamine and ~-ethanolamine are preferred.
Both the propylene oxide addition reaction and the esterification can be carried out according to known methods.
Polybasic oxy-acids which can be used to form the new acid esters are sulphonated organic, preferably aliphatic, mono- or di-carboxylic acids with 3 to 6 carbon atoms, such as, for example, sulphosuccinic acid, or, in particular, polybasic inorganic oxy-acids, such as sulphuric acid. In place of the acids it is also possible to use their functional deriva-tives, such as acid anhydrides, acid halides, acid esters or acid amides. Chlorosulphonic acid and, especially, sulphamic àcid may be mentioned as examples of ~hese functional deriva-tives.
As a rule, the esterification according to the invention is carried out by simply mixing the reactants whilst warming, appropriately to a temperature between 50 and 100C. The ~ree acids which are first formed can then be converted into the corresponding alkali metal or ammonium salts. Conversion ~6~9~C~
into the salts is carried out in the customary manner by adding bases, such as, for example, ammonia, monoethanolamine, triethanolamine or alkali metal hydroxides, for example sodium hydroxide or potassium hydroxide. According to a particularly preferred embodiment, the acid sulphuric acid esters are manufactured direct in the form of their ammonium salts by warming the propylene oxide addition products with sulphamic acid, appropria-tely in the.presence of urea.
A typical representative of the new products is the ammonium salt of the sulphuric acid ester of an addition i product which has been obtained from ethylenediamine and propylene oxide and which appropriately has an average mole-cular weight of 3,000 to 4,000, preferably 3j,600.
A further representative which contains sulpho groups is the sulphosuccinic acid half-ester o~ a poly-adduct obtained by an addition reaction of propylene oxide and ethylenediamine, the poly~adduct advantageously having an average molecular weight o~ 3,000 to 4,000, preferably 3,600.
With the aid of the anionic poly-adducts described above it is now possible to eliminate the disadvantages which were described initially and which arise when organic syn-thetic ~ibres, especially polyes-ter fibres, are dyed with disperse dyestuffs without the addition of an auxiliary or with the additives used hitherto. The technical advance depends, above all, on the excellent dispersion-stabilising action of the poly-adducts on the dyestuff, so that neither an aggrega-tion nor a precipitation of the dyestuff takes place during the . ,...... ,,. :.... :. :.. , ... :. . ... :, .
, ` !
, 69~L9 entire dyeing process.
A further advantage of these compounds, which are employed as levelling and dispersing agents, lies in the low tendency to foaming. Accordingly, there is no danger of froth stains forming on the dyeings and a more rapid pene-tration of the goods and an increase in the rate of flow in the dyeing machines are thus ensured.
The new acid esters of propylene oxide poly-adducts are used as dyeing auxiliaries, especially as dispersing and levelling agents, for dyeing synthetic ~ibres or materials containing such fibres and especially for dyeing linear poly-esters.
The amounts in which the acid esters of the poly-propylene oxide adducts, or their salts, are added to the dye ba-thsvary between 0.1 and 5 g, preferably 0.5 to 2 g, per litre of the aqueous dye liquor.
It is ~requently desirable to incorporate an anti-foaming agent into the aqueous solution o~ the acid ester in order to improve the properties of the dye bath,to which the dispersing agent is added, and sometimes also to increase the migration of the dyestu~f. A satisfactory type of anti-foaming agent is a silicone emulsion, for example a 5 to l~/o strength aqueous silicone emulsion, which can also be employed in combination with higher alcohols with 4 to 22 carbon atoms, .-~
especially with 2-ethyl hexanol. However, the most suitable anti-foaming agents are water-insoluble alkylene oxide adducts of higher alcohols, for example the adduct of 1 mol of " , , ~ .
~ [)6i99~) e-thylene oxide with 1 mol of stearyl alcohol, and also esters of aliphatic dicarboxylic acids and the higher alcohols mentioned, or the higher alcohols on their own, for example n-butyl alcohol or 2-ethylhexanol.
Adipic acid di-2~ethyl-hexyl ester and also poly-siloxanes, such as, for example, methylpolysiloxane, have proved very particularly suitable.
The amount in which the anti-foaming agent is employed can be as low as, for example, 0~5% by weight but is advan-tageously at least 10% by weight and preferably 15 to 60% by weight, based on the weight of the acid ester or its salt.
Water-miscible alcohols can also be added to the solution oP the new acid ester. Alcohols which are suitable for this purpose are, in par-ticular, lower aliphatic alcohols, such as alkanols, for example ethyl alcohol, n- and iso-propyl alcohol and tert.-butyl alcohol, alkylene glycols, for example ethylene glycol and 295-hexanedioi and their lower monoalkyl ethers, as well as mixtures thereof.
Dyestuffs which are insoluble or sparingly soluble in water are to be understood as vat dyestuffs, organic pigments and, above all, disperse dyestuffs which have an affinity for the fibre, that is to say -those which are absorbed on textile synthe-tic fibre materials.
The dyestuffs can belong to ~ery diverse categories, for example acridone dyestuffs, nitro dyestuffs, methine and polymethine dyestuffs, styryl and azos-tyryl dyestuffs, xanthene dyestuffs, oxazine dyestuffs, aminonaphtho~ulnone , ;''; :; ':' :'.; . , .' :,., ::. :: ':,' ~ .
: , . : : ~ . : .' ' ''' :'' :'''' ' ~ 69 ~
dyestuffs 9 coumarin dyestuffs and, in particular, anthraquin-one dyestuffs and azo dyestuffs, such as monoazo dyestuffs and disazo dyestu~fs.
Mixtures of such dyestuffs can also be employed.
The new anionic poly-adduc-ts can also be employed when whitening undyed textile materials with optical brighteners which are sparingly soluble in water.
The latter can belong to any desired categories of brightener. In particular they are stilbene compouinds, coumarins~ benzocoumarins, pyrazines; pyrazolines, oxazines, triazolyl, benzoxazolyl, benzofurane or benzimidazolyl com-pounds and naphthalic acid imides~
The amount of dyestuffs added to the liquor depends on the desired depth of colour; in general~ amounts of 0.01 to 10 per cent by weight, based on the fibre material employed, have proved suitable.
Examples which may be mentioned of fibre materials which can be dyed in the presence of the new adducts are cellulose ester fibres, such as cellulose 2~-acetate fibres and cellulose triacetate fibres, synthetic polyamide fibres, for example those made from ~-caprolactam, from adipic acid and hexamethylenediamine and from ~-aminoundecanoic acid, polyurethane fibres, polyolefine fibres~ for example poly- ~
propylene fibres, polyacrylonitrile fibres, including modified acrylic fibres~ and, above all9 linear polyester fibres.
Linear polyester fibres are to be understood as synthetic fibres which are obtained by a condensation reaction of _ g _ ',. ~ ' ~ ;. :, . .................... ., ,. :........... .
,, , :. ...
~ ~6g9~
terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis-(hydroxymethyl)-cyclohexane, and also copolymers of terephthalic acid and isophthalic acid and ethylene glycol. The fibre materials can also be used as mixed fabrics with one another or with other fibres, ~or example mixtures of polyacrylonitrile/polyester, polyamideJ
polyester, polyester/viscose and polyester/wool~
The fibre material can be in very di~erse stages of processing, for example in the form of flock, piece goods, such as woven fabrics and knitted fabrics, bundles of yarn or wound packages or as non-woven fabrics, a textile floor covering or a tufted carpet.
The dyeings are advantageously carried out from an a~ueous li~uor by the exhaustion process. Linear polyester ~ibres are preferably dyed by the so-called high-temperature process in closed pressure-resistant machines at tempera-tures of above 100C, preferably between 110 and 140C, under pressure.
Examples of suitable closed vessels are circula-ting liquor machines, such as cheese machines or beam dyeing machines, winches, jet dyeing machines or rotary-type dyeing machines, paddles or jiggers. The liquor ratio can accordingly be chosen within a wide range, for example 1:1 to 1:100, preferably 1:10 to 1:50~ The linear polyester fibres can also be dyed at temperatures beiow 100C, ~or examplè in the temperature range from 75 to 98C, in ~he presence of the customary carriers, for example phenylphenols, polychloro-, , . ~, .. , , ' ": : ', , , ' ' ; ' : , .,. . . ' . .
, , ,, . ' ',',, ,'. '. ~ ;. ' ,.
benzenes, xylenes, toluenes, naphthalenes or diphenyl.Cellulose 2~-acetate fibres are preferably dyed at tempera-tures of 80-85C, whilst cellulose triacetate fibres are advantageously dyed at the boiling point (98C) of the aqueous bath.
The use of carriers is superfluous when dyeing cellu-lose 2~-acetate or polyamide fibres.
When preparing the dye liquors it is appropriate to start from aqueous solutions of the acid ester or its salt a~d to add suitable auxiliaries, such as, for example, anti- -~oaming agents and lower alcohols, to these. The liquors can contain mineral acids, such as, for example, sulphuric acid or phosphoric acid, organic acids, appropria-tely lower aliphatic carboxylic acids, such as formic acid, acetic acid or oxalic acid, and/or salts, such as ammonium acetate, ammonium sulphate or sodium acetate. The acids serve, above all, to adjust the pH value of the liquors which can be used according to the invention; as a rule, the pH value is 4 to 8 and pre~erably 4.5 to 5.5.
The textile material is introduced into the liquor, which can have a temperature o~ 40 to 70C, and the material -is treated for 5 to 15 minu-tes at this tempera-ture. The dye-stuff and, where appropriate, the carrier are then added and the temperature of the liquor is raised in order to dye in the indicated temperature range for 50 to 100 minutes.
The dyed material is then rinsed, and dried, in the customary manner. A reductive after-treatment is normally ',.. '.'. ', .', ' ' ' ' ' .:-: . ~.
~69~1~
not necessary.
It is important that a fine dispersion of the dyestuff is not only inltially present but that the degree of dispersion is also maintained during the entire dyeing process. As is known, certain disperse dyestuffs tend, above all under the conditions of high-temperature dyeing, to convert into a less fine form. The result of this is that the dyestu~f settles on the surface of the material to be dyed. Such agglomera-tions and deposits of dyestuff can be avoided particularly well by means of the anionic poly-adducts according to the invention.
The synthetic fibre material can also be dyed con-tinuously, that is to say by impregnating with an aqueous formulation which contains a disperse dyestuff, an anionic poly-adduct according to the invention and, optionally, a thickener and an acid and squeezing off to the desired content of impregnating liquor of 60 to 120% of the weight of fibre and subsequently subjecting to a heat treatment, such as, for example, steaming at temperatures of 98 to 105C with neutral saturated steam or thermofixing at 180 to 210C.
Uniform and deep dyeings~ which additionally are distinguished by good fastness to rubbing and good dye yields, are obtained on syn-thetic organic fibre material, especially on linear polyester fibres, by the dyeing process according to the invention.
In the examples which follow percentages denote per-centages by weight and parts denote parts by weight.
, .... :: . ,; ; ,.
~ '9 Example_l 60 g of an adduct which was obtained from ethylene-diamine and propylene oxide and has an average molecular wei~ht of 3,600 are warmed to 60 - 65C. Subsequently~ 7.2 g of urea are introduced in the course of 15 minutes and 7.2 g of sulphamic acid are introduced in the course of 30 minutes.
The reaction mixture is stirred for a further 30 minutes at 60-65C, then warmed to 95C in the course of 30 minutes and ke~t at 95 - 110C for 6 hours~ A product which is readily soluble in water and contains 90% of the ammonium salt of the acid sulphuric acid ester of the adduct is obtained. The product has a surface tension of 37.0 dyne/cm at 24C.
5.2 g of maleic anhydride are introduced in the course o~ 15 minutes, at 60C, into 46 g of a poly-adduct which was obtained from ethylenediamine ancL propylene oxide and has an average molecular weight o~ 3,600. The reaction mixture is then kept at 100C for 30 minutes and at 125C for 60 minutes, After cooling to 90 - 100C, a solution o~ 7.8 g of sodium sulphite in 54 g of water is added to the reaction product and the mixture is kept at 100C for a further 9 hours. A
solution which contains 50/ of the sodium salt of the sulpho-succinic acid ester of the abovementioned poly-adduct is obtained. The surface tension at 24C is 38.3 dyne/cm.
Example 3 41.8 g of a poly-adduct which was obtained from ethylenediamine and propylene oxide and has an average mole-. I . .' . .
~L~6g~19 cular weight of 1,020 are esterified as described in Example 1, using 18 g of sulphamic acid in the presence of 18 g of urea.
The resul-ting product is readily soluble in water. The surface tension at 24C is 39.1 dyne/cm.
Example 4 5g g of a poly adduct which was obtained from ethylenediamine and propylene oxide and has an average mole-cular weight of 5,920 are esterified as described in Example 1, using 4.5 g of su]phamic acid in the presence of 4.5 g of urea~
whereupon a product which is readily soluble in water is -obtained. The surface tension at 24C is 35.4 dyne/cm.
Example 5 46.6 g of a poly-adduct which was obtained from mono-isopropanolamine and propylene oxide and has an average mole-cular weight of 2,330 are esterified as described in Example 1, using 6.4 g of sulphamic acid in the presence of 6.4 g o~ urea.
A product which is readily soluble in water is obtained.
The surface tension at 24C is 36.0 dyne/cm.
Example 6 r
2.8 g of mono~-ethanolamine and 60 g of benzene are added to 44.6 g of the product obtained according to Example 1.
The benzene and ammonia are then driven off in vacuo, whereupon the monoethanolamine salt of the acid sulphuric acid ester of the adduct, of ethylenediamine and propylene oxide, with an average molecular weight of 3,600 is obtainedL The sur~ace tension at 24C is 36~4 dyne/cmO
.
.
- .... . .... --. , ~ - - . ~
~;;06~9~L9 E~y~
29.6 g of the adduct of l mol of mono-~-ethanolamine and 50 mols of propylene oxide (average molecular weight 2,960) are warmed to 60 - 6~C. After stirring vigorously, 6.5 g of urea are introduced in the course of 15 minutes and 6.5 g of sulphamic acid are introduced in the course of 30 minutes.
The mixture is kept at 60 - 65C for a further one hour, warmed to 90C in the course of 30 minutes and kept at 95 -100C for 6 hours. It is then cooled to 70C and 120 g 0~
water are added to the reaction product. A solution which contains 20% Of the ammonium salt Of the acid sulphuric acid ester of the adduct is obtained. The surface tension at 24C is 37 .2 dyne/cm~
Example 8 The procedure is as descr:ibed in Example 7 but 41.3 g of the adduc-t of 1~2-diaminopropane and 70 mols of propylene oxide (average molecular weight 4,130) and also 12.2 g of urea and 12.2 g of sulphamic acid are used. 160 g of water are then added to the reaction product, a 2~/o strength solution of the ammonium salt of the acid sulphuric acid ester being obtained~ The surface tension at 24C is 36.2 dyne/cm.
' .
The procedure of Example 7 is followed but 47.8 g of the adduct o~ triethylenetetramine and 80 mols Of propylene oxide (average molecular weight 4,780) and also 18 g Of urea and 18 g Of sulphamic acid are used. 184 g of water are then added to the reaction product, whereupon a 20/~ strengtb solution ~ 15 -' '"' " ' ' ~ ' " ~ ' ', , ', ' "' ' ' " . ' ' ~ ' ' " ' , ' :
g~
of the ammonium salt of the acid sulphuric acid ester of the adduct is obtained. The surface tension at 24C is 35.7 dyne/cm.
The procedure is as described in Example 7 but 46.3 g of the adduct of tris-~-ethanolamine and propylene oxide (average molecular weight 4,630) and also lOo9 g of urea and 10.9 g of sulphamic acid are used. After carrying out the reaction, 178 g of water are added to the reaction product, whereupon a 20% strength solution of the ammonium salt of the acid sulphuric acid ester of the adduct is obtained. The surface tension at 24C is 36.1 dyne/cm.
Example 11 The reaction is carried out according to the instruc-tions in Example 7 but 48 g of the adduct of N-methyl-N-~-ethanolamine and 81 mols of propylene oxide (average molecular weight 4,800) and also 19 g of urea and 19 g of sulphamic acid are used. When the reaction has ended, 164 g of water are added to the reaction product, whereupon a 20% strength solu-tion of the amrnonium salt of the acid sulphuric acid ester is obtained. The surface tension at 24C is 35.5 dyne/cm.
Example 12 25 g of a knitted fabric of polyethylene glycol tere-- ` phthalate are treated, in a circulating liquor dyeing apparatus, at 60C for 10 minutes with a liquor which contains 0.6 g of ammonium sulphate and 0.3 g of a mixture of auxiliaries, con-sisting of 55 par-ts of the sulphuric acid ester obtainecl .
, ' . ,,' :' , ~ , ~ . !
9~L~
according to Example 1, 10 parts of adipic acid di-2-ethyl-hexyl ester and 35 parts of water and isopropanol (1:1), in 300 ml of water and has been adjusted to a pH of 505 with 85%
strength formic acid. 0.625 g o~ a dyestuff of the formula C1 NH- _ -C2H5 (1) 02N ~ N = N ~ \ ~ NH-2 NH-CH2CH20H--~
.... .. ; . . ... . --: , are then added to the liquor and the dye liquor is heated to 130C in the course of 30 minutes. Dyeing is carried out for 60 minutes at this temperature and the liquor is cooled to 90C.
The resulting dyeing is rinsed and dried. A level, brilliant, red dyeing which is ~ast to rubbing results.
Level dyeings are also obtained with the products according to Examples 2 to 11 when these are used in a corresponding amount in place of the product according to Example 1.
Exam~le 13 If, in Example 12, the mixture of auxiliaries mentioned in that example is replaced by 0~6 g o~ a product which con-tains 50 parts o~ the ammonium salt according to Example 1, 50 parts of water and 0~8 part of methylpolysiloxane in aqueous emulsion and in other respects the procedure is as described in Example 12, a level dyeing is again obtaineds Similarly good results are obtained when, in each case, , .. ....
6~9~9 one` o~ the acid esters obtained according to Examples 2 to 11 is employed in place of the product prepared according to Example 1. Appropriately, preparations which contain about 2~/o of the sulphuric acid estersmentioned and 0.35/0 of methyl-polysiloxane in aqueous emulsion are used and 1.38 g of these preparations are employed.
Example 14 25 g of a knitted fabric of polyethylene glycol tere~
phthalate, wound on a perforated metal support, are treated, in a circulating liquor dyeing apparatus, for 10 minutes at 60C with a liquor which contains 0.6 g of ammonium sulphate9 0.3 g of a mixture of auxiliaries, consisting of 55 parts of the sulphuric acid ester obtained according to Example 1, 10 parts of adipic acid di-2-ethyl-he~yl ester and 35 parts of water and isopropanol (1:1), and 1.5 g of a carrier of the trichlorobenzene/diphenyl type in 300 ml of water and has been ad~usted to a pH of 5.5 with 85% strength formic acid.
0.625 g o~ a dyestuff of the formula (1) are then added to the liquor and the dye liquor is heated to 98C in the course of 30 minutes. Dyeing is carried out for 60 minutes at this temperature and the liquor is then cooled to 90C. The resulting dyeing is rinsed and dried~ A level, brilliant, red dyeing which is fast to rubbing and which shows no deposit of dyestuff on the inside of the support for the wound fabric results.
Example 15 10 g of a textured polyethylene terephthalate fabric .' ' ~D6~ 9 are trea-ted, in a dyeing apparatus, for 10 minutes at 60C
with a liquor which contains 0.2h g of ammonium sulphate and 0~24 g of the auxiliary according to Example 1 in 120 ml of water and has been adjusted to a pH of 5.5 with 85% strength formic acid. Subsequently9 the liquor is hea-ted to 135C in the course o~ 35 minutes and 0.018 g of a dyestuff of the formula -R-02S ~ N ~ N
~ CH
R CH3 and C2H5 ( 1~
00015 g of a dyestuff of the formula 02N ~ N~-N-CH2C~2-0-eH2~t~2C~
C~12CH CN
~1 2 .
and 0.015 g of a dyestuff of the ~ormula - I2 . C~3 (4) ~ 02N ~ ~ N = N ~ NH-C~I2Ci~?OCH2CH2C~`J
Cl NHCOC~2CH3 ,.
- , . . ..
are then added. Dyeing is carried out for 30 minutes at this temperature and the liquor is then cooled to 90C. The ., . ' ~ ~ " , """ " ' '' ' ' `'' ' ' ' , ' '' .
~6~9~L9 resulting dyeing is rinsed and dried. A level grey dyeing is obtained.
Example 16 .
25 g of a knitted fabric of polyethylene glycol tere-phthalate are treated, in a circulating liquor dyeing apparatus, for 10 minutes at 60C with a liquor which contains 0.6 g of ammonium sulphate and 0.3 g of the sulphuric acid ester obtained according to Example 1 in 300 ml of water and has been adjusted to a pH of 5.5 with 85% strength ~ormic acid.
1.35 g of a mixture of dyestuffs consisting of 0.875 g o~ a dyestuff of the formula .. . .. . . .. .. ... .. . . . . .. . .
, ~H~
(5) N02 ~ N-~ ~
R = H and -CH3 (1:2) and 0.475 g of a dyestuff of the ~ormula - - - -- - - - . . .
OH -Br (6) _ ~ C~cO ~ _ .. . -~ - :
are then added to the liquor and the dye liquor is heated to 130C in the course o~ 30 minutes. Dyeing is carried out for 60 minutes at this temperature and the liquor is cooled to 90C. The resulting dyeing is rinsed and dried. A level, ~69~
brilliant, red dyeing which is fast to rubbing results.
Example 17 400 g of a wound package of polyethylene glycol tere-phthalate fibres are treated, in a circulating liquor dyeing apparatus, for 10 minutes at 60C with a liquor which contains 16 g of ammonium sulphate and 4 g of a mixture of auxiliaries, which consists of 50 parts of the sulphuric acid ester obtained according to Example 1, 50 parts of water and 0.8 part of methylpolysiloxane in aqueous emulsion, in 8 litres of water and has been adjusted to a pH of 5.5 with 85% strength formic acid. 1 g of a mixture of dyestuffs consis-ting of 0.4 g of ::
a dyestuff of the formula . ~ . . . . . . . .
NO ~ ~T--N ~ N(CII2CII2C~T)2 .
0.2 g of a dyestuff o~ the formula , . . .. ~
(8) ~T02 ~ ~=~ ~ N(C~I2c~20cOcll3)2 .
CN ~ -and 0~4 g of a dyestuff `of the formula 01~ 0 ~TH
Br ~l~ O OH
is then added to the liquor and the dye liquor is hea-ted to - ~ , , : .
~6~19~
130C in the course of 30 minutes. Dyeing is carried out for 60 minutes at this temperature and the liquor is then cooled to 90C, after which the resulting dyeing is rinsed and dried~ A level grey dyeing is obtained.
Example 18 10 g of a woven ~abric of polyacryloni-trile are treated, in a dyeing apparatus, for lO minutes a-t 60C with a liquor which contains 0.8 g of the sulphuric acid ester obtained according to Example 1 in 400 ml of water and has been adjusted to a pH of 5.5 with 80% strength acetic acid. 0.05 g o~ a dyestuff of -the formula .. . .
NH-CH
(10) ~
O. NH-CH2CH~OH
. . .
are then added to the liquor and the dye liquor is heated to 98C in the course of 30 minutes. Dyeing is carried out for 60 minutes at this temperature and the liquor is cooled to 60C. The resulting dyeing is rinsed and dried. A level, pale blue dyeing which is fast to rubbing resultsO
Example 19 5 g of a woven fabric of -triacetate are introduced, in a high-temperature dyeing apparatus, into a liquor which contains 0.2 g of the sulphosuccinic acid ester obtained according to Example 2 in 200 ml o~ water and has been adjusted to a pH of 5.5 with 80/ s-trength acetic acid and which contains ,:
. , . .,.:
; ~ , , ,, , . , , , ,., ,,.,., :. , :: . : :
~699:~L9 0.05 g of the dyestuff of the formula (10), employed in Example 18. The dye liquor was then heated to 125C in the course of 45 minutes. Dyeing is carried out for 30 minutes at this temperature and the liquor is then cooled to 80C.
The resulting dyeing is rinsed, and dried, in the customary manner. A level, brilliant, blue dyeing which is fast to rubbing results.
.
0.1 g of a disperse dyestuff of the formula NH~ 0 NH2 (11) ~ ~
. B0 0 N~l-C~3 is stirred into 300 ml of water, which contains 0.15 g of the sulphosuccinic acid ester obtained according to Example 2.
As is customary when dyeing, the liquor is then heated to 98C
in the course of 30 minutes and kept a-t this temperature for 10 minutes, After cooling, the dye liquor is withdrawn through a circular filter, in order to detec-t any agglomeration of the dyestuff. The dyestuff dispersion is still flawless after this treatment; no deposits of dyestuff due to agglomeration are ~ound. ~ -Example 21 .
10 g of a wo~en fabric consisting of a (50:50) mixture of polyethylene glycol terephthalate and wool are treated, in a dye bath;wlth a liquor which contains 0.8 g of ammonium .
sulphate and 0.8 g of the sulphuric acid ester obtained according to Example 1 in 400 ml of water as well as 0.2 g of the disperse dyestuff of the ~ormula (12) H0-C~12~CH~-0 - ~ N = N ~ N = ~ OH
and has been adjusted to a pH of 5.5 with 80% strength acetic acid. The dye liquor is then warmed to 98C in the course o~ 30 mi~utes, whilst agitating the fabric continuously, dyeing is carried out at this temperature ~or 60 minutes and the dyeing is then rinsed and dried in the customary manner.
The woven fabric treated in this way displays a deep dyeing of the polyester portion and a distinct reservation o~
the wool portion.
xample 22 Piece goods made of polyacrylonitrile are padded, on a padder, at a liquor pick-up o~ 100 per cent by weight, with an aqueous liquor which is at room temperature and contains, per litre- 5 g Qf the disperse dyestu~f of the ~ormula (10), used in Example 18, 6 g of starch ether and 5 g o~ the sulphuric acid ester obtained according to Example 1 and the pH value o~
which has been adjusted to 5.5 with acetic acid.
The goods treated in this way are then treated, without intermediate drying, in a steamer for 30 minutes at 105C
(saturated steam). The goods are then rinsed, and dried, in , , ~ .. ., . . :......... .
.. . . : ,. ~ .
: : ~
~699~
the`customary manner.
A brilliant9 level, pale blue dyeing which is fast to rubbing is thus obtained.
Example 23 Textured polyethylene terephthalate w~ven fa~ricis imp~g-nated, at 20 to 30C, with an impregnating liquor which con-tains 29 g/l of a dyestuff of the formula (5), 10 g/l of the sulphuric acid ester obtained according to Example 1~ 2 g/l of an alginate thickener, 0.5 g/l of a sodium alkylnaphthalene-sulphonate and 2 g/l of monosodium phosphate and has been ad~usted to a pH of 6.5 with acetic acid. The fabric is then squeezed off to 98%, based on the dry weight of the goods, dried at 120C for 3 minutes and subjected to thermofixing at 190C for 45 seconds. The dyeing is washed with cold water and dried. A level red dyeing is obtained. The customary reductive after-clearing can optionally also be carried out after rinsing.
.
~ ? , ~ ~
.~ , :, :.. ,,:: ;,~ , ::, .: . . :;
: . , . .. .... : . . . . - . .... .... .
The benzene and ammonia are then driven off in vacuo, whereupon the monoethanolamine salt of the acid sulphuric acid ester of the adduct, of ethylenediamine and propylene oxide, with an average molecular weight of 3,600 is obtainedL The sur~ace tension at 24C is 36~4 dyne/cmO
.
.
- .... . .... --. , ~ - - . ~
~;;06~9~L9 E~y~
29.6 g of the adduct of l mol of mono-~-ethanolamine and 50 mols of propylene oxide (average molecular weight 2,960) are warmed to 60 - 6~C. After stirring vigorously, 6.5 g of urea are introduced in the course of 15 minutes and 6.5 g of sulphamic acid are introduced in the course of 30 minutes.
The mixture is kept at 60 - 65C for a further one hour, warmed to 90C in the course of 30 minutes and kept at 95 -100C for 6 hours. It is then cooled to 70C and 120 g 0~
water are added to the reaction product. A solution which contains 20% Of the ammonium salt Of the acid sulphuric acid ester of the adduct is obtained. The surface tension at 24C is 37 .2 dyne/cm~
Example 8 The procedure is as descr:ibed in Example 7 but 41.3 g of the adduc-t of 1~2-diaminopropane and 70 mols of propylene oxide (average molecular weight 4,130) and also 12.2 g of urea and 12.2 g of sulphamic acid are used. 160 g of water are then added to the reaction product, a 2~/o strength solution of the ammonium salt of the acid sulphuric acid ester being obtained~ The surface tension at 24C is 36.2 dyne/cm.
' .
The procedure of Example 7 is followed but 47.8 g of the adduct o~ triethylenetetramine and 80 mols Of propylene oxide (average molecular weight 4,780) and also 18 g Of urea and 18 g Of sulphamic acid are used. 184 g of water are then added to the reaction product, whereupon a 20/~ strengtb solution ~ 15 -' '"' " ' ' ~ ' " ~ ' ', , ', ' "' ' ' " . ' ' ~ ' ' " ' , ' :
g~
of the ammonium salt of the acid sulphuric acid ester of the adduct is obtained. The surface tension at 24C is 35.7 dyne/cm.
The procedure is as described in Example 7 but 46.3 g of the adduct of tris-~-ethanolamine and propylene oxide (average molecular weight 4,630) and also lOo9 g of urea and 10.9 g of sulphamic acid are used. After carrying out the reaction, 178 g of water are added to the reaction product, whereupon a 20% strength solution of the ammonium salt of the acid sulphuric acid ester of the adduct is obtained. The surface tension at 24C is 36.1 dyne/cm.
Example 11 The reaction is carried out according to the instruc-tions in Example 7 but 48 g of the adduct of N-methyl-N-~-ethanolamine and 81 mols of propylene oxide (average molecular weight 4,800) and also 19 g of urea and 19 g of sulphamic acid are used. When the reaction has ended, 164 g of water are added to the reaction product, whereupon a 20% strength solu-tion of the amrnonium salt of the acid sulphuric acid ester is obtained. The surface tension at 24C is 35.5 dyne/cm.
Example 12 25 g of a knitted fabric of polyethylene glycol tere-- ` phthalate are treated, in a circulating liquor dyeing apparatus, at 60C for 10 minutes with a liquor which contains 0.6 g of ammonium sulphate and 0.3 g of a mixture of auxiliaries, con-sisting of 55 par-ts of the sulphuric acid ester obtainecl .
, ' . ,,' :' , ~ , ~ . !
9~L~
according to Example 1, 10 parts of adipic acid di-2-ethyl-hexyl ester and 35 parts of water and isopropanol (1:1), in 300 ml of water and has been adjusted to a pH of 505 with 85%
strength formic acid. 0.625 g o~ a dyestuff of the formula C1 NH- _ -C2H5 (1) 02N ~ N = N ~ \ ~ NH-2 NH-CH2CH20H--~
.... .. ; . . ... . --: , are then added to the liquor and the dye liquor is heated to 130C in the course of 30 minutes. Dyeing is carried out for 60 minutes at this temperature and the liquor is cooled to 90C.
The resulting dyeing is rinsed and dried. A level, brilliant, red dyeing which is ~ast to rubbing results.
Level dyeings are also obtained with the products according to Examples 2 to 11 when these are used in a corresponding amount in place of the product according to Example 1.
Exam~le 13 If, in Example 12, the mixture of auxiliaries mentioned in that example is replaced by 0~6 g o~ a product which con-tains 50 parts o~ the ammonium salt according to Example 1, 50 parts of water and 0~8 part of methylpolysiloxane in aqueous emulsion and in other respects the procedure is as described in Example 12, a level dyeing is again obtaineds Similarly good results are obtained when, in each case, , .. ....
6~9~9 one` o~ the acid esters obtained according to Examples 2 to 11 is employed in place of the product prepared according to Example 1. Appropriately, preparations which contain about 2~/o of the sulphuric acid estersmentioned and 0.35/0 of methyl-polysiloxane in aqueous emulsion are used and 1.38 g of these preparations are employed.
Example 14 25 g of a knitted fabric of polyethylene glycol tere~
phthalate, wound on a perforated metal support, are treated, in a circulating liquor dyeing apparatus, for 10 minutes at 60C with a liquor which contains 0.6 g of ammonium sulphate9 0.3 g of a mixture of auxiliaries, consisting of 55 parts of the sulphuric acid ester obtained according to Example 1, 10 parts of adipic acid di-2-ethyl-he~yl ester and 35 parts of water and isopropanol (1:1), and 1.5 g of a carrier of the trichlorobenzene/diphenyl type in 300 ml of water and has been ad~usted to a pH of 5.5 with 85% strength formic acid.
0.625 g o~ a dyestuff of the formula (1) are then added to the liquor and the dye liquor is heated to 98C in the course of 30 minutes. Dyeing is carried out for 60 minutes at this temperature and the liquor is then cooled to 90C. The resulting dyeing is rinsed and dried~ A level, brilliant, red dyeing which is fast to rubbing and which shows no deposit of dyestuff on the inside of the support for the wound fabric results.
Example 15 10 g of a textured polyethylene terephthalate fabric .' ' ~D6~ 9 are trea-ted, in a dyeing apparatus, for 10 minutes at 60C
with a liquor which contains 0.2h g of ammonium sulphate and 0~24 g of the auxiliary according to Example 1 in 120 ml of water and has been adjusted to a pH of 5.5 with 85% strength formic acid. Subsequently9 the liquor is hea-ted to 135C in the course o~ 35 minutes and 0.018 g of a dyestuff of the formula -R-02S ~ N ~ N
~ CH
R CH3 and C2H5 ( 1~
00015 g of a dyestuff of the formula 02N ~ N~-N-CH2C~2-0-eH2~t~2C~
C~12CH CN
~1 2 .
and 0.015 g of a dyestuff of the ~ormula - I2 . C~3 (4) ~ 02N ~ ~ N = N ~ NH-C~I2Ci~?OCH2CH2C~`J
Cl NHCOC~2CH3 ,.
- , . . ..
are then added. Dyeing is carried out for 30 minutes at this temperature and the liquor is then cooled to 90C. The ., . ' ~ ~ " , """ " ' '' ' ' `'' ' ' ' , ' '' .
~6~9~L9 resulting dyeing is rinsed and dried. A level grey dyeing is obtained.
Example 16 .
25 g of a knitted fabric of polyethylene glycol tere-phthalate are treated, in a circulating liquor dyeing apparatus, for 10 minutes at 60C with a liquor which contains 0.6 g of ammonium sulphate and 0.3 g of the sulphuric acid ester obtained according to Example 1 in 300 ml of water and has been adjusted to a pH of 5.5 with 85% strength ~ormic acid.
1.35 g of a mixture of dyestuffs consisting of 0.875 g o~ a dyestuff of the formula .. . .. . . .. .. ... .. . . . . .. . .
, ~H~
(5) N02 ~ N-~ ~
R = H and -CH3 (1:2) and 0.475 g of a dyestuff of the ~ormula - - - -- - - - . . .
OH -Br (6) _ ~ C~cO ~ _ .. . -~ - :
are then added to the liquor and the dye liquor is heated to 130C in the course o~ 30 minutes. Dyeing is carried out for 60 minutes at this temperature and the liquor is cooled to 90C. The resulting dyeing is rinsed and dried. A level, ~69~
brilliant, red dyeing which is fast to rubbing results.
Example 17 400 g of a wound package of polyethylene glycol tere-phthalate fibres are treated, in a circulating liquor dyeing apparatus, for 10 minutes at 60C with a liquor which contains 16 g of ammonium sulphate and 4 g of a mixture of auxiliaries, which consists of 50 parts of the sulphuric acid ester obtained according to Example 1, 50 parts of water and 0.8 part of methylpolysiloxane in aqueous emulsion, in 8 litres of water and has been adjusted to a pH of 5.5 with 85% strength formic acid. 1 g of a mixture of dyestuffs consis-ting of 0.4 g of ::
a dyestuff of the formula . ~ . . . . . . . .
NO ~ ~T--N ~ N(CII2CII2C~T)2 .
0.2 g of a dyestuff o~ the formula , . . .. ~
(8) ~T02 ~ ~=~ ~ N(C~I2c~20cOcll3)2 .
CN ~ -and 0~4 g of a dyestuff `of the formula 01~ 0 ~TH
Br ~l~ O OH
is then added to the liquor and the dye liquor is hea-ted to - ~ , , : .
~6~19~
130C in the course of 30 minutes. Dyeing is carried out for 60 minutes at this temperature and the liquor is then cooled to 90C, after which the resulting dyeing is rinsed and dried~ A level grey dyeing is obtained.
Example 18 10 g of a woven ~abric of polyacryloni-trile are treated, in a dyeing apparatus, for lO minutes a-t 60C with a liquor which contains 0.8 g of the sulphuric acid ester obtained according to Example 1 in 400 ml of water and has been adjusted to a pH of 5.5 with 80% strength acetic acid. 0.05 g o~ a dyestuff of -the formula .. . .
NH-CH
(10) ~
O. NH-CH2CH~OH
. . .
are then added to the liquor and the dye liquor is heated to 98C in the course of 30 minutes. Dyeing is carried out for 60 minutes at this temperature and the liquor is cooled to 60C. The resulting dyeing is rinsed and dried. A level, pale blue dyeing which is fast to rubbing resultsO
Example 19 5 g of a woven fabric of -triacetate are introduced, in a high-temperature dyeing apparatus, into a liquor which contains 0.2 g of the sulphosuccinic acid ester obtained according to Example 2 in 200 ml o~ water and has been adjusted to a pH of 5.5 with 80/ s-trength acetic acid and which contains ,:
. , . .,.:
; ~ , , ,, , . , , , ,., ,,.,., :. , :: . : :
~699:~L9 0.05 g of the dyestuff of the formula (10), employed in Example 18. The dye liquor was then heated to 125C in the course of 45 minutes. Dyeing is carried out for 30 minutes at this temperature and the liquor is then cooled to 80C.
The resulting dyeing is rinsed, and dried, in the customary manner. A level, brilliant, blue dyeing which is fast to rubbing results.
.
0.1 g of a disperse dyestuff of the formula NH~ 0 NH2 (11) ~ ~
. B0 0 N~l-C~3 is stirred into 300 ml of water, which contains 0.15 g of the sulphosuccinic acid ester obtained according to Example 2.
As is customary when dyeing, the liquor is then heated to 98C
in the course of 30 minutes and kept a-t this temperature for 10 minutes, After cooling, the dye liquor is withdrawn through a circular filter, in order to detec-t any agglomeration of the dyestuff. The dyestuff dispersion is still flawless after this treatment; no deposits of dyestuff due to agglomeration are ~ound. ~ -Example 21 .
10 g of a wo~en fabric consisting of a (50:50) mixture of polyethylene glycol terephthalate and wool are treated, in a dye bath;wlth a liquor which contains 0.8 g of ammonium .
sulphate and 0.8 g of the sulphuric acid ester obtained according to Example 1 in 400 ml of water as well as 0.2 g of the disperse dyestuff of the ~ormula (12) H0-C~12~CH~-0 - ~ N = N ~ N = ~ OH
and has been adjusted to a pH of 5.5 with 80% strength acetic acid. The dye liquor is then warmed to 98C in the course o~ 30 mi~utes, whilst agitating the fabric continuously, dyeing is carried out at this temperature ~or 60 minutes and the dyeing is then rinsed and dried in the customary manner.
The woven fabric treated in this way displays a deep dyeing of the polyester portion and a distinct reservation o~
the wool portion.
xample 22 Piece goods made of polyacrylonitrile are padded, on a padder, at a liquor pick-up o~ 100 per cent by weight, with an aqueous liquor which is at room temperature and contains, per litre- 5 g Qf the disperse dyestu~f of the ~ormula (10), used in Example 18, 6 g of starch ether and 5 g o~ the sulphuric acid ester obtained according to Example 1 and the pH value o~
which has been adjusted to 5.5 with acetic acid.
The goods treated in this way are then treated, without intermediate drying, in a steamer for 30 minutes at 105C
(saturated steam). The goods are then rinsed, and dried, in , , ~ .. ., . . :......... .
.. . . : ,. ~ .
: : ~
~699~
the`customary manner.
A brilliant9 level, pale blue dyeing which is fast to rubbing is thus obtained.
Example 23 Textured polyethylene terephthalate w~ven fa~ricis imp~g-nated, at 20 to 30C, with an impregnating liquor which con-tains 29 g/l of a dyestuff of the formula (5), 10 g/l of the sulphuric acid ester obtained according to Example 1~ 2 g/l of an alginate thickener, 0.5 g/l of a sodium alkylnaphthalene-sulphonate and 2 g/l of monosodium phosphate and has been ad~usted to a pH of 6.5 with acetic acid. The fabric is then squeezed off to 98%, based on the dry weight of the goods, dried at 120C for 3 minutes and subjected to thermofixing at 190C for 45 seconds. The dyeing is washed with cold water and dried. A level red dyeing is obtained. The customary reductive after-clearing can optionally also be carried out after rinsing.
.
~ ? , ~ ~
.~ , :, :.. ,,:: ;,~ , ::, .: . . :;
: . , . .. .... : . . . . - . .... .... .
Claims (22)
1. An acid ester or salt thereof of a poly-propylene oxide adduct of an average moleculare weight of 1000 to 6000, wherein the ester is obtained by addition reaction of (a) propylene oxide with (b) a polyfunctional amine, which contains 2 to 9 carbon atoms and at least a second reactive amino group or at least one hydroxyl group, and esterification of the poly-adduct with (c) an oxy-acid which is at least dibasic or with functional derivative of this acid and.
if appropriate, by conversion of the resulting acid ester
if appropriate, by conversion of the resulting acid ester
2. An acid ester according to Claim 1, wherein the poly-adduct of the components (a) and (b) has an average molecular weight of 3,000 to 5,000.
3. An acid ester according to Claim 1, wherein the component (b) is an alkylenepolyamine with 2 to 6 carbon atoms and 2 to 4 amino groups.
4. An acid ester according to Claim 1, wherein the component (b) is an alkylenediamine with 2 or 3 carbon atoms.
5. An acid ester according to Claim 1, wherein the component (b) is ethylendiamine.
6. An acid ester according to Claim 1, wherein the component (b) is an alkanolamine with 2 to 6 carbon atoms.
7. An acid ester according to Claim 1, wherein the component (b) is .beta.-ethanolamine.
8. An acid ester according to Claim 1, wherein the component (c) is sulphamic acid.
9. An acid ester according to Claim 1, wherein the component (c) is sulphosuccinic acid.
10. A process for the manufacture of an acid ester or a salt thereof, of the composition as defined in Claim 1, which process comprises subjecting (a) propylene oxide to an addition reaction with (b) a polyfunctional amine which contains 2 to 9 carbon atoms and at least a second reactive amino group or at least one hydroxyl group and converting the addition product into an acid ester using (c) an oxy-acid which is at least dibasic or a functional derivative of this acid, and converting the acid ester, if appropriate, into a salt.
11. A process according to Claim 10, which comprises converting the resulting acid ester into an alkali metal salt or an ammonium salt.
12. A process according to Claim 10, which comprises carrying out the esterification with sulphamic acid.
13. A process for dyeing (including brightening) synthetic fibres or materials containing such fibres with dyestuffs which are sparingly soluble to insoluble in water, which process comprises dyeing the fibres in the presence of an acid ester, or its salt, defined in Claim 1.
14. A process according to Claim 13, which comprises carrying out the dyeing in the presence of the ammonium salt of the sulphuric acid ester of an addition product obtained from ethylenediamine and propylene oxide.
15. A process according to Claim 13, which comprises carrying out the dyeing in the presence of the sulpho-succinic acid half-ester of a poly-adduct obtained by an addition reaction of propylene oxide with ethylene-diamine.
16. A process according to Claim 13, which comprises the use of 0.1 to 5 g of the acid ester, or of its salt, per litre of dye liquor.
17. A process according to Claim 13, which comprises the use of the acid ester or a salt thereof in combination with an anti-foaming agent.
18. A process according to Claim 17, which comprises the use of adipic acid di-2-ethyl-hexyl ester or methyl-polysiloxane as the anti-foaming agent.
19. A process according to Claim 13, which comprises carrying out the dyeing by an exhaustion process.
20. A process according to Claim 13, which comprises carrying out the dyeing at a temperature of 110 to 140°C.
21 A process according to Claim 13, which comprises the sue of linear polyester fibres as the synthetic fibres.
22. An aqueous dye liquor for dyeing (including brightening) synthetic fibres or materials containing such fibres, espe-cailly linear polyester fibres, said liquor containing an acid ester, or a salt thereof, as defined in Claim 1 and at least one dyestuff which is sparingly soluble to insoluble in water.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH717375A CH617055GA3 (en) | 1975-06-04 | 1975-06-04 | Process for dyeing or optically brightening man-made fibres or man-made fibre materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1069919A true CA1069919A (en) | 1980-01-15 |
Family
ID=4321040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA253,898A Expired CA1069919A (en) | 1975-06-04 | 1976-06-02 | Acid esters of propylene oxide poly-adducts |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS51148799A (en) |
| BE (1) | BE842530A (en) |
| CA (1) | CA1069919A (en) |
| CH (1) | CH617055GA3 (en) |
| DE (1) | DE2624431A1 (en) |
| FR (1) | FR2313411A1 (en) |
| GB (1) | GB1540640A (en) |
| NL (1) | NL7605789A (en) |
| ZA (1) | ZA763309B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0014689A1 (en) * | 1979-02-13 | 1980-08-20 | Ciba-Geigy Ag | Auxiliary agent and its use in the dyeing or optical bleaching of polyester textile materials |
| US6113656A (en) * | 1995-01-17 | 2000-09-05 | Milliken & Company | Method of dyeing low pill polyester |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1231254A (en) * | 1958-04-30 | 1960-09-28 | Ciba Geigy | Process for the dyeing of nitrogenous fibers and preparations suitable for carrying out this process |
-
1975
- 1975-06-04 CH CH717375A patent/CH617055GA3/en unknown
-
1976
- 1976-05-28 NL NL7605789A patent/NL7605789A/en not_active Application Discontinuation
- 1976-06-01 DE DE19762624431 patent/DE2624431A1/en not_active Withdrawn
- 1976-06-02 FR FR7616642A patent/FR2313411A1/en active Granted
- 1976-06-02 GB GB22784/76A patent/GB1540640A/en not_active Expired
- 1976-06-02 CA CA253,898A patent/CA1069919A/en not_active Expired
- 1976-06-03 BE BE167581A patent/BE842530A/en unknown
- 1976-06-03 ZA ZA00763309A patent/ZA763309B/en unknown
- 1976-06-04 JP JP51064700A patent/JPS51148799A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| BE842530A (en) | 1976-12-03 |
| ZA763309B (en) | 1978-01-25 |
| NL7605789A (en) | 1976-12-07 |
| FR2313411B1 (en) | 1979-04-27 |
| FR2313411A1 (en) | 1976-12-31 |
| JPS51148799A (en) | 1976-12-21 |
| DE2624431A1 (en) | 1976-12-16 |
| GB1540640A (en) | 1979-02-14 |
| CH617055B (en) | |
| CH617055GA3 (en) | 1980-05-14 |
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