Auxiliary agent formulation for pretreating cellulosic fibre materials
The present invention relates to an aqueous auxiliary agent formulation which is used for pretreating cellulosic fibre materials prior to the dyeing process or during the dyeing process of these fibre materials.
It has long been known in the dyeing industry to pretreat cellulosic fibre materials prior to the dyeing process to obtain a dimensionally stable and readily dyeable form. US-A-4,629,470, for example, discloses a process in which a mixture consisting of a crosslinking resin, a crosslinking catalyst and choline is used in the pretreatment process of fibre materials consisting of cellulose.
The processes used to date require the mixtures to be prepared either directly in the pretreatment baths from the individual components or else immediately before use, which is labour-intensive and promotes variations in the composition of the baths.
There is thus a need for a storage-stable auxiliary agent formulation which can be produced in invariable composition for being laid in stock.
It has now been found that this criterion can be met with the aqueous auxiliary agent formulation of this invention. In addition, the novel auxiliary agent formulations are, surprisingly, distinguished by good thermal stability.
Accordingly, this invention relates to an aqueous auxiliary agent formulation, wherein component (A) is a compound of formula
wherein A
' is an anion, and component (B) is a crosslinking resin.
Anion A
" in formula (1) is, for example, a halide, sulfate, CrC
2alkylsulfate, thiosulfate, sulfo- nate, phosphate, acetate, tartrate or carboxylate anion. A
' is preferably the chloride, sulfate, methylsulfate or phosphate anion and, particularly preferably, the chloride anion.
The compound of formula (1) is known under the trivial name choline.
Suitable components (B) of the novel aqueous auxiliary agent formulation are all agents conventionally used for improving the creasing and shrinking behaviour, such as those known, inter alia, from Textilhilfsmittelkatalog 1991 , Konradin Verlag R. Kohlhammer, Leinfelden- Echterdingen 1991.
Suitable components (B) are in particular water-soluble crosslinking resins. Suitable water-soluble crosslinking resins used as component (B) are, for example, water- soluble melamine resins, formaldehyde/melamine resins and formaldehyde/urea resins or precondensates, such as trimethylolmelamine, hexamethylolmelamine or dimethylol urea, or water-soluble formaldehyde (pre)condensates with formamide, thiourea, guanidine, cyan- amide, dicyandiamide and/or with water-soluble organic sulfonates, such as the sodium salt of naphthalenesulfonic acid, or glyoxal urea derivatives, such as the compound of formula
CH., \ 3
'N"CH OH
0=C I N-CH OH
/ CH3
and, in particular, N-methylol derivatives of nitrogen-containing compounds, such as mela- mine/formaldehyde condensates which may be partially or completely etherified, or N-methylol urea compounds.
The melamine/formaldehyde condensates which may be partially or completely etherified can correspond, for example, to formula
wherein Rt, R2, R3, R , R5 and R6 are each independently of one another hydrogen, -CH2-OH or -CH2-OCH3, with the proviso that at least one of R1t R2, R3, R , R5 and R6 has a meaning other than hydrogen.
Examples of the melamine/formaldehyde condensates which may be partially or completely etherified are the compounds of formula
The N-methylol urea compounds which may be etherified are, for example, reaction products of formaldehyde with urea or urea derivatives, which reaction products may be subsequently etherified, and the urea derivatives may suitably be, for example, cyclic ethylene ureas or propylene ureas which can also contain substituents in the alkylene groups, such as hydroxyl groups, or may be urones or unsubstituted or substituted triazone resins.
Examples of corresponding N-methylol urea compounds are unmodified or modified N-me- thylolhydroxyethylene urea products, for example the compounds of formula
H2OH CHpOH CH2OCH„
^ \ 2 \ 2 3
N- CH— OH N- "CH— OCH, N CH— OCH
0=C I 0=C I
N' CH— OH N- -CH— OCH, o=< N .CH- OCH3
CH2OH C /H2OH CH2OCH3
Or
CH,
I
H3COH2C - NHCO - N - CH2- C - CH(OH) - NHCONH - CH2OCH3 , or methylolation products CH2OH CH3
based on propylene urea or ethylene urea/melamine.
Preferred components (B) are unmodified or modified N-methylolhydroxyethylene urea compounds, methylolation products based on propylene urea or ethylene urea/melamine and, in particular, optionally etherified melamine/formaldehyde condensates and glyoxal crosslinking resins. It is also possible to use mixtures of two or more different crosslinking agents as component (B), typically a mixture consisting of one melamine/formaldehyde condensate which is unetherified and of another which is only partially etherified.
The novel aqueous auxiliary agent formulation comprises 10 to 85 % by weight, preferably 20 to 80 % by weight, more preferably 40 to 80 % by weight, of the sum of the components (A) and (B), based on the total weight of the auxiliary agent formulation.
The ratio of components (A) and (B) can vary within a wide range. Preferred formulations are those, wherein the ratio of component (A) to component (B) is from 1 :2 to 3:1 , preferably from 1 :1 to 3:1.
Particularly preferred novel aqueous auxiliary agent formulations contain, besides water, only choline and a crosslinking resin.
If desired, the novel aqueous auxiliary agent formulation can contain besides the components (A) and (B) other components, but no crosslinking catalyst. Suitable components are for example preservatives, dispersants, water-soluble or water-miscible solvents, buffer systems or deaerators.
Suitable preservatives are mainly formaldehyde-donating agents, such as paraformaldehyde and trioxane, preferably aqueous about 30 to 40 % by weight formaldehyde solutions; suitable dispersants are preferably nonionic dispersants; suitable water-soluble or water-miscible solvents are preferably glycols, such as ethylene glycol, diethylene glycol or polyethylene glycols having a molecular weight of 200 to 20000; suitable buffer systems are all customary buffers having an activity range over 4 to 7 pH-values, for example a phosphate buffer, and suitable deaerators are, for example, high-boiling solvents, especially turpentine oils, higher alcohols, preferably C8- to C10alcohols, terpene alcohols, or deaerators based on mineral oils and or silicone oils, preferably commercial formulations consisting of about 15 to 25 % by weight of a mixture of mineral oil and silicone oil and of about 75 to 85 % by weight of a C8alcohol, such as 2-ethyl-n-hexanol.
Suitable nonionic dispersants are in particular those compounds which are listed in EP-A-0468921 under "Component (c)B.
The novel aqueous auxiliary agent formulations are prepared, for example, by placing a preferably aqueous formulation of a crosslinking resin in a vessel and adding, with thorough stirring and preferably at elevated temperature, choline and optional further components, subsequently adjusting the mixture to the desired concentration, if required.
This invention also relates to the use of the novel aqueous auxiliary agent formulation during the pretreatment of cellulosic fibre materials.
The novel aqueous auxiliary agent formulation is present in the pretreatment liquor advantageously in amounts of 15 to 400 g/l, preferably of 60 to 300 g/l, more preferably of 100 to 250 g/l, of dye liquor.
In addition to the novel aqueous auxiliary agent formulation, the pretreatment liquor expediently comprises as component (C) a crosslinking catalyst.
Suitable crosslinking catalysts are, for example, all catalysts customarily used for an anti- crease and antishrink finish, such as those known from Textilhilfsmittelkatalog 1991 , Konradin Verlag R. Kohlhammer, Leinfelden-Echterdingen 1991. Examples of suitable crosslinking catalysts are inorganic acids, such as phosphoric acid, Lewis acids, such as zinc chloride (ZnCI2), zirconoxychloride, NaBF4, AICI3, MgCI2, ammonium salts, such as ammonium sulfate, ammonium chloride (NH4CI) or hydrohalides, preferably hydrochlorides, of organic amines, such as CH3(CH2)2NHCH3» HCI.
Preferred crosslinking catalysts are ammonium salts, in particular ammonium chloride. The crosslinking catalyst is preferably present in the pretreatment liquor in an amount of 0.1 to 40 g/l, more preferably of 1 to 30 g/l, most preferably of 5 to 20 g/l, of dye liquor.
In addition to the components (A), (B) and (C), the pretreatment liquor can contain other customary additives, for example acid donors, such as aliphatic amine chlorides or magnesium chloride, aqueous solutions of inorganic salts, e.g. of alkali chlorides or alkali sulfates, alkali hydroxides, urea, thickeners, such as alginate thickeners, water-soluble cellulose alkyl ethers as well as levelling agents, antifoams and/or deaerators, penetration accelerators, migration inhibitors and wetting agents.
The pretreatment liquor is preferably applied to the cellulosic fibre material by the pad dyeing process by the customary methods of pad dyeing; the pretreatment liquor is applied, for example, at room temperature or at moderately elevated temperature, e.g. in the range from 15 to 40° C. If required, the treated fibre material can be pinched-off to remove superfluous liquid.
After the pretreatment, the fibre material is briefly dried at temperatures of up to 150° C, preferably in the range from 80° to 120° C and is fixed, usually by dry heat (thermofixation), over 1 to 6 minutes at 140 to 200° C.
The pretreated fibre material can then be further processed, for example dyed.
Compared to untreated fibre material, the cellulosic fibre material pretreated with the novel aqueous formulation is distinguished in particular by improved dyeability, especially when dyeing is carried out by the exhaust process using reactive, direct or acid dyes.
ln another of its aspects, this invention also relates to the use of the novel aqueous formulation as dyeing auxiliary when cellulosic fibre materials are being dyed by a pad dyeing process.
Suitable dyes are the reactive, direct or acid dyes conventionally used for dyeing cellulosic materials such as those described, inter alia, in Colour Index, 3rd edition 1971 as well as in the supplements under the sections "Reactive Dyes", "Acid Dyes" or "Direct Dyes". Examples are sulfo group-containing monoazo, disazo, polyazo, metal complexazo, anthraqui- none, phthalocyanine, formazane or dioxazine dyes.
The amount of dye in the dye liquor can vary within wide limits depending on the desired tinctorial strength and is, for example, 1 to 100 g/l, preferably 2 to 70 g/l and, particularly preferably, 5 to 50 g/l, of dye liquor.
The novel aqueous auxiliary agent formulation is present in the dye liquor usefully in an amount of 15 to 400 g/l, preferably of 60 to 300 g/l, more preferably of 100 to 250 g l, of dye liquor.
In addition to the dyes and the novel aqueous auxiliary agent formulation, the dye liquor conveniently contains a crosslinking catalyst as component (C).
Suitable crosslinking catalysts are e.g. all agents conventionally used as catalysts for an anticrease and antishrink finish, such as those known from Textilhilfsmittelkatalog 1991 , Konradin Verlag R. Kohlhammer, Leinfelden-Echterdingen 1991. Examples of suitable crosslinking catalysts are inorganic acids, such as phosphoric acid, Lewis acids, such as zinc chloride (ZnCI2), zirconoxychloride, NaBF4l AICI3, MgCI2, ammonium salts, such as ammonium sulfate, ammonium chloride (NH CI) or hydrohalides, preferably hydrochlorides, of organic amines, such as CH3(CH2)2NHCH3. HCI.
The preferred crosslinking catalysts are ammonium salts, in particular ammonium chloride. The crosslinking catalyst is advantageously present in the dye liquor in an amount of 0.1 to 40 g/l, preferably of 1 to 30 g/l, more preferably of 5 to 20 g/l, of dye liquor.
ln addition to the components (A), (B) and (C), the dye liquor can contain other conventional additives, for example acid donors, such as aliphatic amine chlorides or magnesium chloride, aqueous solutions of inorganic salts, e.g. of alkali chlorides or alkali sulfates, alkali hydroxides, urea, thickeners, such as alginate thickeners, water-soluble cellulose alkyl ethers and also levelling agents, antifoams and/or deaerators, penetration accelerators, migration inhibitors and wetting agents.
The dye liquor is preferably applied to the cellulosic fibre material by the pad dyeing process by the customary methods of pad dyeing; the dye liquor is applied, for example, at room temperature or at moderately elevated temperature, e.g. in the range from 15 to 40° C, and, where required, the fibre material can be subjected to intermediate drying. The subsequent dye fixation on the fibre material is usually carried out by dry heat (thermofixation) for 1 to 6 minutes at 140 to 200° C.
Suitable cellulosic fibre materials are those materials which consist completely or partially of cellulose. Examples are natural fibre materials, such as cotton, linen or hemp, regenerated fibre materials, such as viscose, polynosic or cupprammonium silk, or cellulosic blended fibres, such as cotton/polyester materials. The materials used are mainly wovens, knits or webs of these fibres.
The dyeings obtainable on cellulosic fibre materials using the novel aqueous formulation have good allround fastness properties. They have, for example, high fibre-dye bond stability both in the acid and in the alkaline range, good fastness to light as well as good wetfastness properties, such as fastness to washing, water, seawater, cross-dyeing and perspiration, good fastness to chlorine, rubbing, ironing and pleating, and they are particularly distinguished by high tinctorial strength.
The invention is illustrated by the following Examples. Temperatures are in degrees Celsius and parts and percentages are by weight, unless otherwise stated. The ratio of parts by weight to parts by volume is the same as that between the kilogramme and the litre.
Example 1 :
50 g of an aqueous formulation, comprising 67 % by weight of the compound of formula
CH.OCH,
N CH- ■ OCH, o=< i
N -CH OCHg (50),
CH2OCH3 are charged at 35° C, with vigorous stirring, with 40 g of the compound of formula
in portions, giving a viscous, clear and storage-stable formulation.
Example 2:
50 g of an aqueous formulation, comprising 33 % by weight of the compound of formula
(50), are charged at 35° C, with vigorous stirring, with
50 g of the compound of formula (1a) in portions, giving a viscous, clear and storage-stable formulation.
Example 3:
A cotton fabric is padded with a liquor comprising
160 g/l of the aqueous auxiliary agent formulation of Example 2, and
20 g/l of magnesium chloride hexahydrate, which liquor is adjusted to pH 5.5 with acetic acid. The treated cotton fabric is then dried for
90 seconds at 120° C and fixed for another 90 seconds at 180° C dry heat.
This gives a cationised cotton fabric having a good angle of crease recovery and which can be dyed in deep shades by the exhaust dyeing process using reactive, direct or acid dyes and little or no neutral salt.
The pretreated cotton fabric can also be dyed by a continuous process.
Example 4:
A cotton satin fabric is padded on a pad to a pinch-off effect of about 70% liquor pick-up with a padding liquor comprising
30 g/l of the dye of formula
156 g/l of an aqueous auxiliary agent formulation comprising 44 g of the compound of formula
NfCHjOCHj),
N N)— N(CH,OCH,)2 (51 ),
N(CH2OCH3)2
14 g of the compound of formula
100 g of the compound of formula (1a), 30 g/l of polyethylene emulsion (fabric softener, e.g. Turpex® ACN), 0.8 g/l of 80% acetic acid, and 2.0 g/l of ammonium chloride.
The padded cotton satin fabric is dried for about 2 minutes at 130° C and is then thermofixed for about 5 minutes at 155° C. The dyeing so obtained is then rinsed cold and hot, soaped to the boil twice with 2 g/l of Na2CO3 and 2 g/l of a nonionic surfactant, rinsed and dried. This gives a tinctorially strong red dyeing having good allround fastness properties.