AU608775B2 - Improvements in or relating to textile printing and dying - Google Patents

Description

SS U .vLr THE COMMISSIONER OF PATENTS.

Rdwd. Watks Sons, Melbourne.

I).r f.br COMMONWEALTH OF AUSTRALIA yi|l' PATENTS ACT 1952-69 COMIPLETE SPECIF

(ORIGINAL)

608775 PH 07938 PH 09056 10.09.1986 19.11.1986 Class Application Number: Lodged: FEE STAMP TO VALUE OF V LOc, ATACHE .AlL OFFICER... Complete Specification Lodged: Accepted: Published: Priority: "Related Art 1

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This document contains the am:endments made under Section 49 and is correct for printing.

9 BEP 1987 .Or Y1 0 Name of Applicant: ,Address of Applicant: a BASF AUSTRALIA LTD. and DR. HENRY DONENFELD Chelsea House, 55 Flemington Road, North Melbourne, Victoria, Australia, and 129 Male Street, Brighton, Victoria, Australia.

Actual Inventor: DR. HENRY DONENFELD and EDUARD LEMANIS EDWD. WATERS SONS, 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Address for Service: Complete Specification for the invention entitled: IMPROVEMENTS IN OR RELATING TO TEXTILE PRINTING AND DYEING The following statement is a full description of this invention, including the best method of performing it known to us Edwd. Waters Sons, Melbourne.

2 -2- IMPROVEMENTS IN OR RELATING TO TEXTILE PRINTING AND DYEING This invention relates to textile printing and dyeing (hereinafter sometimes referred tp as 'textile colouring' or 'colouring').

There are currently two common methods of textile printing, viz. direct and transfer paper printing. Of these two methods of printing, direct printing is by far the more prevalent form of printing because transfer paper printing is limited to certain synthetic fibres and their mixtures with cellulosic fibres and the effect of transfer paper printing is different from the character of conventional printing.

Direct colouring may take the form of pigment or soluble dyestuff colouring. As is well known, direct 11.15 colouring with pigments as opposed to soluble dyestuffs, involves physically binding the pigments to the fibre surface using a binder, e.g. acrylic dispersion. Nowadays, pigment printing is preferred because of its ease of application e.g. the pigment preparations are incorporated in a printing emulsion containing water, thickener, 1 o emulsifier and various fixing agents, handle modifiers and, optionally, solvents such as white spirit, the iesultant to .emulsion being printed onto the textiles, dried and heat cured.

The disadvantages of pigment colouring are the handle and the limited fastness to rubbing. Furthermore, o the pigment colouring process when used in dyeing as opposed to printing has the further disadvantage of being limited to pale shades only, because of limitations in build-up and :30 unsatisfactory rub-fastness properties, in depth generally above 2% by weight fabric pigment preparation on the fibre e.g. 20 g/l with 100% liquor pick up by weight of fabric.

Printing of synthetic/cellulosic fibre mixtures with soluble dyestuff mixtures has the disadvantage of high cost and/or poor reproducibility whilst dyeing with soluble ?'1 -3dyes does not have the aforementioned disadvantage of reproducibility to the same extent as printing.

Printing with soluble dyestuffs requires lengthy processing, e.g. after printing and/or dyeing, the goods need to be steamed or heat cured to fix the dyestuffs and subsequently thickeners and unfixed dyestuffs and other unreacted reagents used need to be removed in a separate washing process. Similarly, conventional anti-migration agents and unfixed dyestuff and other unreacted agents need to be removed by washing from fabrics dyed by continuous dyeing processes with soluble dyes by conventional methods.

Furthermore, printing of fibre mixtures, e.g.

synthetic/cellulosic fibre mixtures with soluble dyestuffs requires the application of two or more dyestuff types, specific for each fibre. Because of the different fixing procedures for each dyestuff class, the process normally suffers almost insurmountable disadvantages of high costs S and/or poor reproducibility.

oAccordingly, it is a principal objective of this 50° invention to provide a process for direct colouring of textile fibres which combines substantially all the advantages of both pigment and dyestuff colouring, but substantially avoids the disadvantages of both types of direct colouring.

It is another objective of this invention to CtC* simplify the application, and particularly the selection, of pigments and dyestuffs to suit various textile fibres and mixtures thereof and hence to reduce the costs by reduction of inventory and capital costs.

According to one aspect of the invention, there is provided a process for direct colouring of textile fibres comprising appropriately pre-treating/cleaning said fibres by conventional methods, preparing a solution of a cross-linking agent being a solution of a water insoluble technical hexamethoxymethyl melamine, hereinafter referred to as "melamine" (see also attached Chemical Glossary of 4 Trade Marks), in a C4_ 8 glycol, adding said solution of the cross-linking agent to a dye liquor or printing paste containing a colourant, e.g. pigments or dyestuffs and mixtures thereof (excluding cationic dyestuffs) in the presence of an acid donor, applying the resultant mixture to said fibres and drying and curing said fibres.

The invention is applicable to a wide variety of fibres but the invention is of particular advantage and importance to fabrics consisting of 100% cellulosic fibres and their blends of synthetic fibres, e.g. cotton, cotton/polyester and polyester/rayon blends.

Preferably, the amount of melamine, glycol and acid donor are in the ranges of 5 to 80g/l(g/kg), 5 to 120g/l (g/kg) and 1 to 100g/l(g/kg) respectively based on the dye liquor or print paste. More preferably, the above amounts are 10 to 50g/l and 15 to 50g/l respectively for the melamine and the glycol.

It is essential that the melamine is water insoluble. As is well known, pure hexamethoxymethyl melamine is a water soluble substance at room temperature.

To render the melamine water insoluble, it is slightly self-condensed.

By necessity, polycondensed mixtures of nuclear melamine are obtained, the complicated chemistry of which 4 4.

could be stated in a simplified form as follows: Water insoluble melamine derivatives, such as penta/hexamethoxymethyl melamine (P/H MOMM), by necessity will be a mixture of polycondensed poly-nuclear melamine.

As all N-methylol compounds are in equilibrium with their :30 amines and free formaldehyde, there will always be a possibility for formation of free amino groups which may Al react with another N-methylol group and form a diaminal (uron) N-N'-methylene compound. N-methylol compounds are basically amino-semi-acetals and their methyl derivatives will be amino-acetals.

5 The commercial, at room temperature insoluble, melamine derivatives, described as essential for this invention (such as Luwipal* 066 and Cymel** 303), therefore, will be a mixture of insoluble poly-nuclear polycondensates, free formaldehyde, methanol and P/H MOMM.

In contrast to water soluble melamines (such as Luwipal* 068 and Kaurit* M70), which do not give satisfactory results in this invention, products such as Luwipal 066* are practically totally methylated (penta or hexa). In the presence of aqueous acid (below about pH the methyl group can be split off; the product becomes soluble again and starts to react and condensate.

The production of such a poly condensed compound is well-known and is generally as follows: Melamine is reacted with formaldehyde and acetylated with methanol. In the presence of acid catalysts Colo and in the absence of other functional groups, ii, condenses S. with itself. Such a product is termed "technical" 0. hexamethoxymethyl melamine and is commercially available.

Generally, these mixtures comprise 50 to 70% by weight hexamethoxymethyl melamine and also contain its condensation products of 2 to 3 and up to 6 molecules of precondensed melamine. For instance, a typical mixture may contain about t 60% by weight hexamethoxymethyl melamine, about 13% by weight of the 2 to 4 molecular condensate and about 26% of the 6 molecular condensate Luwipal 066*).

Examples of C 4 8 glycols are 2-methyl-butane-1,4diol, butane-1,2-diol, butane-1,3-diol, butane-1,4-diol and butane-2,3-diol, hexane-2,5-diol, pentane-1,5-diol and neopentyl glycol. Preferably, the glycols used are 2-methyl -pentane-2,4-diol, 2-methylpentane-1,5-diol and hexane-1,6diol.

Regd. Trade Mark of BASF AKTIENGESELLSCHAFT Trade Mark of AMERICAN CYANAMID COMPANY 6 For the dyeing of fibres, the acid donor is preferably one or more saturated aliphatic C_ 6 dicarboxylic acids and these are used in an amount of 1 to 5 g/l by volume of dyebath. Examples of these acids are succinic, glutamic and adipic acids, or commercially available mixtures thereof Eulysin*S). Alternatively, an acrylic acid polymer or a heat saponifiable organic ester such as Eulysin* WP, can be used as acid donor.

For the preparation of print pastes, the acid donor is preferably a preparation of a high molecular weight acrylic acid homopolymer or copolymer with acrlyamide and is used preferably in an amount of 10 to 100 g/kg., more preferably 10-50 g/kg by weight print paste. Its primary function is however as a conventional thickener in the print pastes.

The process according to the invention, can be applied using dyestuffs or pigments, however, pigments, anionic dyes, vat dyes and disperse dyes are preferred (cationic dyestuffs generally do not work because of their S" 20 ionic nature). It may be advantageous to use blends of different types of colourants, e.g. pigments with similar colour dyestuffs, to obtain improved y__ld and fastness S properties.

Drying can be done separately from curing or preferably in one operation. The curing reaction is very fast provided the fibres can be dried very quickly.

Generally, curing is in the temperature range to 220 0 C for a period of 5 seconds to 4 minutes, preferably in the temperature range 1800 to 210°C for a period of fifteen to :30 sixty seconds.

The dye liquor may contain further conventional additives, such as anti-foam agents Leophen dispersion agent Setamol* WS), wetting agents (LEOPHEN and anti-migration agents Primasol* AMK). Often level dyeings are obtained particularly in the case of pigments, without addition of conventional anti-migration Regd. Trade Mark of BASF AKTIENGESELLSCHAFT ic L. 7 7 agents; therefore a separate drying process in most cases is not necessary and the fabrics can be dried at curing temperatures. In fact, this is the preferred method.

The print pastes may, in addition, also contain conventional thickening agents. In the process of this invention, the thickening agents, e.g. polyacrylates, may act as the acid donor. Furthermore, agents may be added to the paste to improve the printing properties thereof e.g.

diethylene glycol. Optionally, emulsifiers Luprintol PE*) and solvents with low or no aromatic content may also be added.

Advantageously, silicone oils and vegetable oils, optionally in the presence of urea, may also be added to the print paste to enhance further the rub fastness and soft handle.

It is preferred to use silicone oil which should be, preferably, between 1,000 to 15,000 cps (centipoise) S° and, more preferably, between 5,000 and 12,500 cps.

"The preferred vegetable oil is castor oil (first 20 pressing).

Preferably, the amount of silicone oil (optionally with urea) added is 1-100g/kg print paste (each), but more preferably 10-60g/kg print paste (each), and more preferably 20-35g/kg print paste of silicone oil and 30-70g/kg urea.

'25 According to a further aspect of the invention, additions of small amounts of pigment binders are preferred 44 4 and have a beneficial effect on the resultant fastness properties, particularly rub- and wash-fastness. The use of a binder is particularly beneficial for 100% cotton goods or their mixture, if they have not been sufficiently pretreated. Binders are also sometimes beneficially added for the purpose of preventing anionic dyestuffs staining white polyamide fibres during the first washing process.

Accordingly, the use 10 to 100 g/kg by weight print paste or dye liquor) of dispersions of cross-linked copolymers of acrylic acid ester, acrylonitrile, acrylic Regd. Trade Mark of BASF AKTIENGESELLSCHAFT _i -L L v 8 acid and N-methylol methyl acrylamide (Helizarin Binder* TW) were found to be beneficial.

In deep shades, 10 to 100 g/kg, by weight print paste or dye liquor, of binder was used, this having three further benefits: increase in rub fastness; and assistance in fixation of the colourants on 100% cotton, especially if it is not well pretreated (purified); and preventing staining of accompanying polyamide fibres during washing.

Interesting and very elegant, pleasing and useful print effects can be obtained by addition of silicate particles Iriodin**) to the print paste. This effect can be further enhanced by curing the prints by heat calendering under 2 to 5 tons pressure plus heat), S, instead of heat curing only.

o According to another aspect of the invention, there is provided an improved dye liquor or print paste comprising '20 a colourant (excluding cationic dyestuffs), an acid donor and a cross-linking agent being a solution of a water insoluble technical hexamethoxymethyl melamine in a C 4 8 glycol.

According to a further aspect of the invention, there is provided a cross-linking agent for use in 0 0O combination with a dye liquor or print paste being a o* solution of a water insoluble technical hexamethoxymethyl melamine in a C4- glycol.

According to yet a further aspect of the invention, 30 in the case of the use of a high sublimation fast Red disperse dyestuff Celestren* Red 2G, CI Disperse Red 346) the cross-linking agent may simply be a C4_, glycol In this situation, similar advantages and effects are obtainable to those in connection with the aforementioned cross-linking agent.

Regd. Trade Mark of BASF AKTIENGESELLSCHAFT Regd. Trade Mark of MERCK DARMSTADT i. 1 1. ,i r According to another aspect of the invention, there is provided an improved print paste comprising a colourant (excluding cationic dyestuffs), one or more synthetic thickening agents, a cross-linking agent being a solution of a water insoluble technical hexamethoxymethyl melamine in a

C

4 glycol and a silicone or vegetable oil, optionally in the presence of urea.

According to a further aspect of the invention, there is provided a composition for enhancing the handle, the rub resistance and water absorption of print pastes comprising a mixture of silicone oil and urea.

According to yet a further aspect of the invention, the improved print paste and resultant print properties can be obtained by dispersing the water insoluble technical hexamethoxymethyl melamine into the print paste (described above) without previously dissolving it in a C 4 8 glycol.

In this case, the print paste composition is limited to S containing, as a colourant, pigments or predominantly pigments. Thus, according to this aspect of the invention, there is provided a composition for enhancing the handle, S. the rub resistance and wet fastener properties of print pastes containing, as the colourant, pigments or predominantly pigments, and a mixture of silicone or vegetable oil and hexamethoxymethyl melamine (technical,

S(

t 25 water insoluble) e.g. Luwipal 066*.

The C4- 8 glycols appear to have several functions: 1I) They dissolve and keep the melamine resin in solution.

2) They provide hydroxyl groups for cross-linking with functional groups inthe colourants, the melamine resin and the fibres.

3) They can cross-link with the melamine forming the melamine acetal, which in turn can cross-link via the hydroxy groups in the cellulose with similar groups in the pigments or dyestuffs, depressing the swelling of the fibre.

Regd. Trade Mark of BASF AKTIENGESELLSCHAFT 1 cl 10 4) They improve the wet fastness, presumably by forming insoluble complexes with the dyestuffs and probably condensing with the hydroxyl groups in cotton, The resultant dyestuff particles seem to be present in highly crystallised form since quite goods yields and brillance are obtained.

Similarly, the melamine, resin reacts with various functional groups, e.g. hydroxyl, carboxyl, amide, sulpho, etc., commonly found in natural fibres, such as cotton, and various dyestuffs, e.g. anionic dyestuffs.

It will be clear from the above .that the invention has the following advantages to offer to the user: 1. No wash-off necessary to remove unfixed dye bath impurities (saving of energy and capital), compared to conventional processes of dyeing and printing 100% cellulose or blends thereof with synthetic fibres by using conventional (non-pigment) dyestuff systems.

For example: Disperse/Vat dyestuffs applied to PE/Cotton ;o fabric PALANIL/INDANTHREN* Disperse/Reactive dyestuffs applied to PE/Cotton fabric; PALANIL/BASILEN* S- Reactant dyestuffs applied to PE/Cotton 25 fabric; CELLESTREN* 2. No causticizing pretreatment for the textile fabric *t needed compared to some other dyestuff classes, in other processes. Faster processing, e.g. curing times which translates into capital saving.

3. Improved wet, light and rub fastness properties, compared to some other dyestuff classes and processes, e.g. compared to some direct dyestuffs, acid dyestuffs and pigments in deep shades, etc.

Also the resistance to dry cleaning solvents is improved.

Regd. Trade Mark of BASF AKTIENGESELLSCHAFT .U gn 11 4. Handle of fabric is at least comparable or improved relative to conventional pigment prints or dyeing.

Good definition of prints.

6. Applicable to wide variety of fabrics, i.e. quite non-fibre specific. Fibre reactive groups cross-link whilst fibres without such groups e.g.

polyester, are bound by adhesion with the melamine derivative resin on the one hand and the insoluble dye complex on the other, e.g. salt formation with the melamine and cross-linking between dye, C 4 8 diols and melamine.

7. Non-staining or very little staining of polyamide or wool fabric during washing.

8. Faster curing at 180-210 0 C for as quick as 15 to seconds.

9. Shorter fixation time in dry heat. This makes fixation by dry heat, e.g. stenter/hot flue, very economical.

Compared to pigment printing, the invention has the 20 following advantages: Improved fastness to rubbing in deep shades; Depending on the chemical nature of the dyestuff used, no binder or considerably smaller amounts of binder and acid donor are necessary.

It will further be appreciated from the above that the present invention provides a process which is more economical (Table I) than the prior art processes and which provides improved reproducibility. Furthermore, the S 30 colourants are most easily applied because only one colour type can be used on the fibre mixtures. Moreover, there are advantages for 100% cotton fabrics, namely more economical dyestuffs can be used as there can be freer selection of dyestuffs for their various properties, i.e. light fastness, dry cleaning properties etc., irrespective of what the intended original use for the dye was, i.e. dyes originally If tt t 40 1 4t 04 01 0*44 12 intended for completely other applications can now be used, to obtain highly desirable results, e.g. anionic dyestuffs originally intended to be used for the dyeing of leather can be used for dyeing and printing of 100% cotton.

From the above, it follows that: Elegant combination of dyeing, printing, and finishing processes are possible (Table II and Example 12).

Deep shades can be dyed rub- and wash-fast utilizing the invention with most pigments; basically most organic pigments are suitable.

Carbon black and iron oxide mixtures work also for production of dark brown shades. Carbon black works on its own for production of blacks.

Most colour depths can be obtained, wherein conventional pigment dyeing the depth is limited to approximately 2% pigment preparation by weight of fabric dyed.

High sublimation disperse dyes, e.g. Cellestren* when used in the invention, can be completely fixed, with heat, making further processing, such as washing rinsing and drying unnecessary.

Similarly, disperse and vat dye mixtures, e.g.

Cottetren* can be fixed with heat alone by utilising the invention.

Anionic dyestuffs offer cost advantages in dark shades, particularly Eukesolar* liquid/ Vialon*.

In light shades pigments are used preferably for light fastness.

The wash fastness of direct dyes are improved.

By using, in addition, the optional components of silicone or vegetable oil, optionally in the presence of urea, the following additional advantages are obtained: i. The soft handle and the rub fastness is further improved.

Regd. Trade Mark of BASF AKTIENGESELLSCHAFT s-' 13 13 2. The prints have improved absorbency.

3. Compared to conventional pigment prints, apart from the softer handle and superior rub fastness, also lesser amounts of binder dispersion are necessary. For example, in the invention, never more tham 100 g/kg print paste is necessary, whilst in conventional print paste up to 200 g/kg are being necessarily used, Even so, by conventional methods, one cannot obtain the same exceptionally high rub fastness properties, compared to the invention. Binders with low glass transition temperature can be used to advantage, resulting in particularly soft handles. These binders could not be used in conventional pigment printing in deep shades as the high amounts needed would result in "sticky" handle and poor rub fastness.

4. The invention is ideal for terry goods and delicate jersey knit goods, as well as for fibre blends such as Sacetate/cotton and Polyester/Rayon, however, it is of course applicable and shows advantages on all kinds of textile fibres.

5. The prints generally withstand 1000 rubs by the AASC crockmeter method, whilst the standard test method is 10 rubs.

The invention will now be described and illustrated in the following Examples which have been carried out, unless otherwise indicated, by the following general methods.

GENERAL METHODS** Method I Pretreatment I for 100% cotton.

The loomstate cloths are saturated at 20-300 with a liquor containing: Regd. Trade Mark of BASF AKTIENGESELLSCHAFT The general methods of pre-treatment are by no means mandatory, as any soundly practised conventional pre-treatment method will suffice for the purpose of this invention.

-z I

'+I

14 a detergent stable to alkalis e.g. Kieralon OL* 6.6 g/l a wetting agent eg. Leophen M* 1.5 g/l a Peroxide stabiliser and extraction. agent Prestogen EB 21 g/l Caustic Soda (46% solution) Hydrogen Peroxide 50% After saturation, the fabrics are squeezed to a pick up of approx. 80% rolled up into a batch, covered wityh polyethylene film and kept rolled for 16 hours. The fabric roll is then transferred to a jig machine and treated with the following chemicals: Caustic soda oxidative starch degrading agent eg. Lufibrol 0* 3 g/l S' Kieralon OL 2 g/l i start running at 40 0 C, raise ovei one end to 95 0 C, run two Sends at 95 0 C, rinse with water for two ends at 95 0 C, rinse with fresh water for two ends at 40 0 C, neutralise with cold water containing dicarboxylic or carboxylic acids eg.

Eulysin S to pH 6-8.

After this treatmemt, the fabrics should be o0 reasonably free of sizing agents and impurities and should .o0 have a neutral to slightly acid pH value.

Method II Pretreatment for 50/50 Polyester Cotton.

Loomstate cloth, containing sizes, sighting colour and other impurities, is saturated with the following O* chemicals, liquor: Alkali stable wetting agent eg. Leophen FK-1* 7 g/l Detergent, stable to alkali eg. Kieralon OL 3 g/l Peroxide stabiliser eg. Prestogen K* 10 g/l Caustic soda Sodium silicate 8 g/1 Oxidative starch degrading agent eg. Lufibrol 0 9 g/1 Hydrogen Peroxide 50% 44ml/l Regd. Trade Mark of BASF AKTIENGESELLSCHAFT 15 After saturation, the fabric is squeezed to a pick up of 90% by weight fabric and steamed for 6 mins at 103-105 0 C in saturated steam, eg. Arioli steamer.

After steaming, the fabric is washed off in open width, through an open-width washing machine as follows: 1st Tank containing: Sodium hydroxide flakes 15 g/l Kieralon OL 6 g/l Reductive extraction agent eg. Lufibrol KB* 4 g/1 Bath temperature 98 0

C

2nd Tank containing: Sodium hydroxide flakes 10 g/l t Kieralon OL 3 g/l Lufibrol KB 4 g/1 Bath temperature 98 0

C

3rd Tank containing: 3 g/l Kieralon OL Bath temperature 98 0

C

Regd. Trade Mark of BASF AKTIENGESELLSCHAFT 4 4 I 4 t ti t 430 I I

I

I; 16 4th Tank containing: Water at 980C if b0 o .jy o ~t o 0 0 0D 04 44 0 80 6I Tank containing: Water, set with Eulysin S to pH 6th Tank containing overflowing cold water.

Method III Pretreatment for nylon/cotton/acetate.

The loomstate fabric is desized on a jig machine with 1% solution of starch degrading enzyme at 600C; pH 5-6.

After 8 hours reaction, the fabric is washed in a winch machine with Kieralon OL 2g/l at 800C for 30 mins. followed by one rinse with water at 450C, one rinse at room temperature.

The fabric is now ready for colouring according to invention.

Method IV Preparation of cross linking agent solution The indicated amount of tech. hexamethoxymethyl melamine is dissolved, by stirring at room temperature, into the indicated amount of a suitable diol (see This solution is now ready for use.

S I 17 Method V Preparation of typical print paste Into the prescribed amount of water (usually 600 to 800 g/kg) print paste emulsion is added by stirring at room temperature the prescribed amounts of: Antifoam and/or wetting agent, plus optionally urea Thickening agents 0A Handle modifying agents, e.g. silicone and l vegetable oils and cross linking agent solution o This mixture is homogenised by stirring at high speeds, e.g.

2,800 to 3,000 RPM, with a suitable mixing machine.

Finally, the prescribed amount of binder dispersion is added by slow stirring say 500 RPM.

B

9 To this mixture the prescribed amounts of colours are added o by slow stirring. The paste is made ready for printing, by a final adjustment to constant printing viscosity, either by addition of electrolyte solution or additional thickening b agent; and by straining through a mesh at least as fine as the finest screen used for printing.

Method VI Preparation of conventional print paste for pigment printing I on screen printing machines.

To the prescribed amount of water (usually 600-750 g/kg print paste) at room temperature, is added by stirring, the prescribed amounts of following ingredients: It 18 Ammonia (32%) Antifoam Thickeners Handle modifiers and emulsifying emulsion Yield improving agents 1/2 of the prescribed amount of binder dispersion.

Into this mixture is emulsified at high speed 2800-3000 RPM, the prescribed amount of solvent eg. white spirit.

Finally, the second half of binder dispersion is added under slow stirring.

To this preparation the prescribed amounts of colours are added by slow stirring; the printpaste is ready for printing after adjusting to a crnstant printing viscosity, either r 'by addition of electrolyte solution or additional thickening agents, and after straining through a mesh at least as fine as the finest screen used in printing.

tl Method VII

I

Preparation of padding liquor.

2 To a smaller than prescribed amount of water, at room temperature 25-30 C, are added by stirring the prescribed amounts of following ingredients: .i El 19 Wetting Agent (non foaming) Cross linking agent solution Acid donor Binder dispersion Colour The mixture is adjusted to the prescribed volume with water 4' f and stirred until homogeneous. It is strained into a padding Si,, trough, through a fine sieve or cloth.

0 4 o o oo0 0 o0 0 0 0 e o o opr o o o 0 6 0 0 0 04 o «0 0 9 0 ~1

'I-

20 EXAMPLE 1 A. Printing with 1:2 metal complex anionic disperse dyestuff (Method I, II respectively 'for preparation; IV and V for print paste preparation) 1,000 g of dyestuff printing paste was first prepared by mixing the following materials: Water (variable) r 44 i t 4 I 20 20 Mixture of Acid Violet CI 12196 and Acid Blue CI 12195 (EUKESOLAR** Navy R conc. liquid) Tech. Hexamethoxymethyl Melamine (CYMEL 303*) 2-methyl pentane-2,4-diol Polyacrylic Printing Binde.r (Helizarin Binder TW) Dicarboxylix acids (EULYSIN S) Polyacrylic thickener (LUTEXAL HP**) 2g Yg (variable) i 4 *4 64* I 4I I I I I t 44 4 4 4 lOo0g The above print paste composition was then applied to 100% cotton and to 50/50 polyester cotton fabric through a flat screen of 50 mesh using a magnetic roller squeegee on a J. Zimmer flat bed printing machine, dried at 60 0 C and then cured for 3-4 minutes at 170 0 C or, alternatively, 15-60 seconds at 190 0 C, no wash-off being necessary.

Trade Mark of AMERICAN CYANAMID COMPANY Regd. Trade Mark of BASF AKTIENGESELLSCHAFT r 21 21 B. Dyeing with 1:2 metal complex anionic disperse dyestuff The same process as described for printing was used except that the following composition (1,000g) was first prepared as a padding liquor: (Method VII) Water 749g Mixture of Acid Violet CI 12196 and Acid Blue CI 12195 (EUKESOLAR Navy R o.o: cone. liquid) i 10 Non-foaming wetting agent (LEOPHEN M) Ig 0o Polyacrylic Printing Binder (Helizarin TW) o oc Tech. Hexamethoxymethyl Melamine (CYMEL 303) 2-methyl pentane-2,4-diol 4 0 g o 0 0" dicarboxilic acids (EULYSIN S) 2g 1000g o oo B 0 I S The above padding liquor was applied at 250C on a cotton and o°e0" polyester cotton fabric, 70% pick up; dried and cured like the print (see above).

Good to very good fastness properties to light, washing and 0o 0 rubbing (wet and dry) were obtained.

S22 EXAMPLE 2 The following print paste was prepared as in Example 1 (Methods I.

IV, V): Water 731g Ammonia 3g Anti foaming agent (DEFOAMER TP*) 3g LUTEXAL HP 63g 2-methyl pentane-2,4-diol Tech. Hexamethoxymethyl Melamine 10 (CYMEL 303) Helizarin Binder TW 100g Acid Black CI63 (EUKESOLAR Black EE A R conc. liquid) 24g EUKESOLAR Navy Blue R conc. liq. 36g 15 Acid Red CI226 (EUKESOLAR Red G) EUKESOLAR Yellow G 1000g I t T 20 metres of Cotton sheeting cloth was printed with the above formulation on a flat bed BUSER printing machine, using a mesh screen, dried at 110 0 C and crease resist finished by foam T application of a crease resist glyoxal urea formaldehyde resin e.g. FIXAPRET TX 205* and cured on a stenter for 11 seconds at 190 0 C; running speed 76m/min.

23 The following composition was used for the foam resin application, through a Stork rotary screen applicator: Water 761g Acetic acid 90% 2g Polyethylene emulsion, e.g. Perapret PE 240* Fixapret TX 205 165g Nekanil* TC 129 (non-ionic surface active, foaming agent) Lutensit* TC KD (anionic surface active, foaming agent) 2g 1000g application b.w.f.

Regd. Trade Mark of BASF AKTIENGESELLSCHAFT 4e 4 It ii 44t I ZI 44I 4 4 i I I 4 1 1414 I 1 I I 4 I- 24- EXAMPLE 3 Blue and Black prints were produced with a print paste prepared as in Example 1, as follows: Water Xg(variable) Lutexal HP Diethylene Glycol lOg (to improve running properties) 2-methyl Pentane-2,4-diol r* Tech. Hexamethoxymethyl Melamine (CYMEL 303) lOg S.o Eukesolar cone. liquid (variable) 1000g -a Blue: 5g/kg Eukesolar Navy R conc. liquid, 15g/kg Luconyl Blue 679 (Aqueous dispersion of Pigment Blue a ad S" Black: 70g/kg Eukesolar Black R cone. liquid.

o.0 The above compositions were printed, dried, heat fixed S* at 1900C, 76m/min. (crease resist foam finished as in Example 11 sec. dwell time. Various other dark S 20 prints were produced in this way, e.g. royal blue, dark blue, dark brown, black on 100% cotton and 50/50 PE/cotton fabric.

Ii 25 EXAMPLE 4 Brown Print with 1:2 metal complex anionic disperse dyestuff Paste prepared as in Example 1: Water 699.4g Defoamer* TP 10% solution Diethylene glycol Ammonia 32% (10% solu.) Lutexal HP Helizarin Binder TW 100g 2-methyl pentane-2,4-diol Tech. Hexamethoxymethyl M-lamine S(CYMEL 303) Eukesolar Red G' cone. liquid 17g Eukesolar Yellow RL liquid (Acid Yellow CI119) 4g Eukesolar Black RL conc. liquid 18g Eukesolar Navy Blue RL conc. liquid 1.6g 1000g Printed and dried as in Example 1 on 100% cotton and 50/50 polyester cotton fabric and cured for 60 seconds at 1900C.

I I'I I S Regd. Trade Mark of BASF AKTIENGESELLSCHAFT 26 EXAMPLE Printing with 1:2 metal complex; water soluble anionic dyestuffs 0OOg print paste was prepared with the following composition: I t Water 1:2 metal complex dyestuff (Ortolar? Black RL (Acid Black CI 63) or Ortolan*Brown 3R (Acid Brown) 2-methyl pentane-2,4-diol Tech. Hexamethoxymethyl Melamine (Luvipal 066) Polyacrylic Thickeners (Lutexal HP) and Lutexal l-VW) Polyacrylic Dispersion Printing Binder Helizarin Binder TW 7 3 0g 3 Og 3 0g 8 0g log lOOg looog The composition was printed, dried and cured as in Example 1.

Regd. Trade Mark of BASF AKTIENGESELLSCHAFT 27 EXAMPLE 6 Print on 100% and 50/50__pclyester/cotton fabric with 1:2 metal complex disulphonate dyestuff Print paste was prepared and pLInted as 1, but with the following composition: Water Lutexal HP Helizarin Binder TW 2-methyl pentane-2,4-diol Tech. Hexamethoxymethyl Melamine Silicone oil** 200/12500 Liquid paraffin 1:2 metal complex disulphonate-Acid Red C1357 (Acidol Scarlet M-IL*) in Example 700g bOog 1000g 4 4 4t44 It I 4 64 4 44 4 4 4 *4 4 4 4 4 4 4 44 44 #4 4 #44 V 444 4 1 II 46 44 4 4 4 4 444440 4 0 Regd. Trade Mark of BASF AKTIENGESELLSCHAFT Also known as "Siloxane 200/12500"1 manufactured by DOW CORNING 28.- EXAMPLE 7 Printing and Dyeing with Disperse Dyestuff on 100% cotton and 50/50 polyester cotton fabric.

A. Printing was effected as in Example 1, wiith the following print paste composition: Water 715g Lutexal HP Helizarin Binder TW 150g Diethylene Glycol 2 0g 2-methyl pentane-2,4-diol Tech. Hexamethoxymethyl Melamine lOg Disperse yellow CI 213 (Cellestren Yellow 5G) 4 4 1000g Printing and curing was carried out for 60 seconds at 190 0 C (no predrying).

B. Dyeing The following padding liquor was prepared (Method VII):- Water 8 34g Leophen M Ig 2-methyl pentane-2,4-diol Tech. Hexamethoxymethyl melamine Helizarin Binder TW 2 0g Eulysin WP 1Og Cellestren Yellow 5G' 3 0g 1000g 29 EXAMPLE 7 B. continued: The above liquor composition was applied to produce a pick-up by weight of fabric on 100% cotton and 50/50 polyester/ cotton fabric; curing for 60 seconds at 190 0

C.

EXAMPLE 8 Dyeing on 100% cotton and 50/50 polyester/cotton fabric with a red disperse dye A pad dyeing was carried out as in Example 7B, with the following pad liquor: S 10 Water 699g Leophen M Ig 2-methyl pentane-2,4-diol 120g Tech. Hexamethoxymethyl Melamine I Eulysin WP S 15 Secondary Dispersion of Polyethylene Wax (PERAPRET PE 240*) 3 0g Cellestren Red 2G' 44. 1000g Regd Trade Mark of BASF Aktiengesellschaft EXAMPLE 9 Printing and dyeing with aqueous pigment dispersions A. A print paste was prepared and printed on 100% cotton sheeting; 50/50 polyester/cotton and 65/35 polyester cotton; as in Example 1 with the following print paste: Water 805g Lutexal HP Silicone oil 200/12500 Helizarin Binder TW Tech. Hexamethoxymethyl melamine Aqueous Dispersion of Pigment Red (Helizarin Red GR) l/ 1000g

C

B. Dyeing with an aqueous pigment dispersion The following pad liquor was prepared: Water 8 Leophen M ig 2-methyl pentane-2,4-diol Tech. Hexamethoxymethyl melamine Anti-migration agent e.g. Vitexal PFA* 2g Eulysin S 2g Helizarin Red GR 1000g Padded at 25 0 C and 65% pick-up; curing for 60 seconds at 190 0

C.

Regd Trade Mark of BASF Aktiengesellschaft ~I 31 EXAMPLE Print on 50/50 Polyester/Cotton with 1:2 metal complex sulphonamide dyestuff, combined with 1:2 metal complex disperse dyestuff A print paste was prepared and printed as set General Methods with the following composition: Water Lutexal HP Diethylene glycol 2-methyl pentane-2,4-diol Tech. hexamethoxymethyl melamine Eulysin WP Acid Red CI 226 (Eukesolar Red G conc.) Acid yellow CI 119 (Eukesolar Yellow R) Acid Blue/Violet Mix (Ortolan N.Blue BR) out in the 805g

I.

4 C 1 C

C..

I

1000g Printed on Zimmer magnetic table with 50 mesh flat cured 60 seconds at 1900C.

screen and then I I -32 EXAMPLE 11 Print with aqueous pigment dispersion, combined with disperse dye (General Methods I, II, III respectively, IV and V).

Print on 100% cotton, 50/50 polyester cotton and 50/50 acetate/cotton fabric were prepared, printed and cured as in Example 10 with the following composition: @0 0 0 a p 000 o 00 0 00 O 0 a 0 0 0, o 000 o P Water Lutexal HVW Lutexal HP Helizarin Binder TW Diethylene glycol 2-methyl pentane-2,4-diol Tech. Hexamethoxymethyl melamine Eulysin WP Aqueous dispersion of pigment green CI 36 (Luconyl green 915*) Disperse Yellow CI 213 (Gellestren yellow 5C) 765g 1log 1log log loQOg

I

33 EXAMPLE 12 (General Methods I, II, IV, VI and VII) Combined dyeing/printing and finishing process technique, on 100% cotton and 50/50 polyester cotton light weight sheeting fabrics.

A "TAUPE" and a "COCOA" shade was produced.

A. A padding liquor was prepared as in Example 9B, with the following composition: Water 9 11.5g Leophen M Ig 2-methyl pentane-2,4-diol 10 Tech. Hexamethoxymethyl Melamine lOg Eulysin S Vitexal PFA Helizarin Binder TW t.

It 0

I

Oret 0 00 0 0 0 0 0 o 0* 0 0 D c* 0 ti t t 15 To two lots of 100 litres, each of this padding following colour composition was added:- Aqueous Dispersions of: Taupe Pigment Red (cf. Table III) (Helizarin Pink BT) 0.16g Pigment Yellow 83 (Helizarin brilliant yellow RRT) 0.

3 6 g Helizarin Dk. Brown TT 1.

36 g (mixture of carbon black iron oxide) Padding Liquor 1000g 1000g liquor, the Cocoa 0.

8 7g 0.

6 2g 7. 1000g I ji 34 2 lots of fabric were padded with each formulation respectively, to 60% pick up, through a Kuesters pad mangle; the pad dyeings were pre-dried to 12% residual moisture, by infra red radiation.

Both fabrics were overprinted with the following pigment print pastes: Water 630g/kg 803g/kg Ammonia 32% 2g/kg 2g/kg Anti foam B (1:1 water) 2g/kg 2g/kg Lutexal HP 26g/kg 24g/kg Emulsion FK 8520* 50g/kg :o LuprimoPl CW(colour intensifier) 30g/kg 24g/kg White spirit 100g/kg 0 00 On. Helizarin Binder TW 150g/kg S 15 Alginate thickener 5% solution 10g/kg 00 0 a o Two designs, Gallery and Heathcote respectively, were printed with 7 and 3 colourways respectively containiTn various amounts ooo (from 100g/kg to 1.5g/kg), of combinations selected from two or more aqueous pigment dispersions, from the following range: 20 HELIZARIN Black HDT, Blue RT, Red BBT, Violet RFKI, Yellow RRT, °o 0 green BT, scarlet B, Blue BT, Dark Brown TT.

A Buser flat bed machine using 60 and 80 mesh screens at running speed was used, The prints were dried at 110 0 C 20 seconds; they were then coated with a crease resist foam containing a standard glyoxal urea formaldehyde resin formulation (Fixapret TX205*) (Method VII) through a Stork rotary screen and cured through a stenter at 190 0

C

for 11 seconds, running speed 76 m/min. Thus, the ground dyed shade, the print and the crease resistant finish was cured in one operation.

Manufactured by BASF AUSTRALIA LTD.

Regd. trade mark of BASF AKTIENGESELLSCHAIT L I- 1 f

I

rr~aUI- j. LL~-i-ri The following fastness properties were obtained: COCOA**/GALLERY** TAUPE**/HEATHCOTE** poly/cotton cotton poly/cotton cotton Light Rub Dry Wet 7 4 3/4 6 4 3(print) 7 4/5 4/5 6 dyeing/print dyeing/print dyeing/print dyeing/print 4 9c I 14 Machine Wash 10 Domestic Detergent 1 x wash 4/5 x wash 4, Industrial 15 Detergent Kieralon OL plus soda ash x washes 4/5 4/5 4/5 3 4 4/5 4/5 4/5 4/5 4/5 4/5 4/5 3 4/5 4/5 Trade/brand names of Sheridan Textiles (formerly Division of Pacific Dunlop Limited).

These fastness properties were considered above average for domestic sheeting fabrics widely sold in Australia.

Wa~N-- II 36 EXAMPLE 13 A print was produced, as in Example 10, using the following composition: Water 71'. g Ammonia 5 g Antifoam* B 29 g Lutexal HD 24 g Luvipal 066 10 g 2 methyl Pentane-1,5 diol 80 g Silicone Oil 200/12500 40 g Helizarin Binder TW 45 g Cellestren Red 2G 35 g Helizarin Red GR 15 g 1000 g EXAMPLE 14 The following standard formulation was used to check behaviour of a variety of colourants, when applied to 100% cotton, by padding to 60% pick up and curing for seconds at 200 0

C.

Colourant Xg(variable) Tech. Hexamethoxymethyl melamine 30 g (Luvipal 066) 2-methyl pentane-1,5 diol 45 g alternatively 2-methyl pentane-2,4 diol 45 g alternatively Hexane-1,6-diol 45 g Leophen M 1.2 g Eulysin S' 2.5 g Helizarin Binder TW 20 g 1000 g Marketed by BASF AUSTRALIA DOW CORNING AUSTRALIA

I

I- 'i

I

37 The dyeings were soaped with an industrial detergent e.g. 2g/l Kieralon B* for 10 min at 100 0

C,

Rinsed and dried and tested for fastness properties.

The following properties were found (unless otherwise indicated, the glycol used was 2-methyl-1,5-diol):

I

S Regd. trade mark of BASF AKTIENGESELLSCHAFT

~I

Il c j;;iiiliiliil-:ili:li- ai iii-- i-I 38 Light Xenotest Wash Test ISO 3 a) b) Solvent perchlor Rubbing dry wet c) a) b) c) 5 g/l Helizarin Brilliant Pink BT >6 soaped >6 g/l Helizarin Brilliant Yellow RRT>6 f4 soaped g/l Helizarin 0Dark Brown TT soaped g/l Helizarin Dark Brown TT soaped (2,4-diol) g/l Helizarin Dark Brown TT soaped (1,6-diol) g/l Cellestren Blue GG soaped g/l Indanthren Blue GCD soaped 75 g/l Eukesolar Black R liquid soaped >6 4-5 5 4 4-5 4-5 5 4-5 5 4-5 4-5 4-5 5 4-5 5 4-5 4-5 4-5 5 4-5 5 4-5 4-5 4-5 5 3-4 4-5 4-5 4 4-5 5 4 4-5 4-5 4-5 4-5 5 4 4-5 4-5 4 4-5 5 4 4-5 4-5 4-5 4-5 5 4 4-5 4-5 4 4-5 5 4-5 4-5 4-5 4-5 4-5 5 3-4 3-4 3-4 3-4 3-4 3-4 3-4 3-4 4 3-4 4 3-4 3-4 3 44 4( 444 4 44 4 44 tel' 5 4-5 4-5 4-5 2 4 5-6 4-5 4-5 4-5 2-3 4 4-5 2-3 2-3 4-5 2-3 2-3 4 4-5 4-5 4 4-5 4-5 4-5 4 4-5 5 3 4-5 5 3 4-5 2 4-5 3-4 4-5 4 4-5 1-2 4 3 4-5 4 3 2-3 Notes: Light fastness is measured on scale 1-8 (8 being the best) 25 a) b) c) change of shade on scale 1-5 (5 being the best) staining of cotton on scale 1-5 (5 being the best) staining of wool on scale 1-5 (5 being the best) means greater than 39 EXAMPLE Dyeing with disperse dyestuff (as per Example 1B but with no hexamethylene melamine) on 100% cotton and 50/50 polyester cotton.

Water Leophen M Primasol AMK Perapret PE 2/40 2-methyl pentane 2,4-diol Cellestren Red 2G 669g i g 200g i0O~g Pad 65% pick up; dry 601C; cure 60 seconds at 2 00 0

C.

it 6*Q 4.

4.

*s* 4 16 I I 6 It 6666 t 44 I. I 4666 4 64 64 6 EXAMPLE 16 Printing with solvent dyes A print paste was prepareJ according to the general method V; except that the solvent dyes were always predissolved in cyclohexane.

Water 72 8 g Lutexal HP Helizarin Binder TW lOOg 1" 2-methyl pentane-2,4 -diol S,~0 Tech. Hexamethoxymethyl melamine (CYMEL 303) Solvent Blue CI 21 1.25g (Oracet Blue*) Solvent Black CI 6 7g o 0 15 (Savinyl Black BN**) Solvent Brown CI 28 0.

6 g (Savinyl Brown GLS**) Solvent Red CI 122 0.6g S. (Neozapon Red Cyclohaxanone 100g 1000g flOOOg Printed, dried and cured as in Example 1.

S Reg Trade Mark of Ciba/Geigy Reg Trade Mark of Sandoz.

Reg Trade Mark of BASF Aktiengesellschaft.

-41- EXA~MPLE 17 As Example 16 except that for the colourants the following composition was used Aqueous Dispersion of Figment Yellow CI (Luconyl yellow O98***) 2.5g/kg print/paste Solvent Blue CI 38 (Savinyl Blue 3GLS'**) 2.5g/kg I I I 4 4 42 EXAMPLE 18 An improved colourant range is produced by mixing various selected colourants together (e.g.

450g CI Pigment Red 112 preparation plus 50g Disperse Yellow 213) at room temperature; Mixing separately, at room temperature, 475g silicone oil 200/12500** and 25g hexamethoxymethyl melamine (technical water insoluble'), resulting in a very smooth paste, which is then added to mixture and the components are then mixed together at room temperature resulting in colour Varying amounts of colour are then added to a print paste containing g/kg urea x g/kg thickener e.g. Lutexal HP* (variable) 20-100 g/kg Acrylic Binder dispersion Helizarin Binder TW*) S, 9 g/kg Hexamethoxymethyl melamine (technical insoluble) Luwipal 066*) 1-35 g/kg Silicone oil 12/12,500 "y g/kg water (variable) Total 1000g EXAMPLE 19 Preparation of a typical colourant, provisionally termed "Donanthren Yellow GC" Pigment Yellow 16 4000g Disperse Yellow 213 1000g Silicone oil 200/12500 4750g Hexamethoxymethyl melamine 250g (technical, water insoluble) (Luwipal 066) Total 10000g The above ingredients were mixed together by simple stirring at room temperature until a homogeneous product was obtained. This composition is now ready for use in print pastes as the "colourant".

Regd. Trade Mark of BASF AKTIENGESELLSCHAFT Made by DOW CORNING t i, II 43 EXAMPLE A product, provisionally termed Product XPG, is prepared by stirring together at room temperature, until homogeneous, 9800g of hexamethoxymethyl melamine (technical, water insoluble) (Luwipal 066) and 200g of silicone oil 200/12500 Total 100009 This composition can be used as an additive to print paste to enhance the softness of handle, the rub resistance and wet fastness properties of said print paste.

EXAMPLE 21 1kg yellow print paste was produced by blending together at room temperature with a variable speed stirrer (0-3000 RPM) the following ingredients: Water 750g Polyacrylic thickner (Lutexal HP) Urea Helizarin Binder TW 100g Product XPG (Example 20) Yellow colourant as in Example 19

I

C(

It

CC.

C C1 Cs:

I

L

t 25 Total i000g This paste was printed on 100% cotton fine woven fabric, 65/35 polyester/rayon, 50/50 polyester/cotton, nonchlorinated wool, polyester/cotton/lycra knitted fabric and 100% cotton towelling, through an 80 mesh flat bed screen, on a Zimmer magnetic squeegee table, dried at 1000C and cured at 1900C for 60 seconds. ISO wash test 3 gave a rating of 4-5 and standard rub test by crock meter 10 rubs was EXAMPLE 22 1 kg Black Print Paste The following composition was blended together at room temperature, by stirring, until a homogenous paste was I ;i 1 I I-L- i- I 44 obtained: Water Polyacrylic Thickener (Lutexal HP) Urea Helizarin Binder TW Silicone 200/12,500 Hexamethoxymethyl melamine (technical, water insoluble) (Luwipal 066) Helizarin Black HDT Helizarin Blue RT Helizarin br.Red BBT Cellestren* Yellow 5G 717g 100g 9g 4g lO1000g t *t 9 o e This paste was printed on 100% cotton, and 65/35 polyester/rayon fabrics, through a 80 mesh flatbed screen, on a Zimmer magnetic squeegee table, dried at 100 0 C and cure-1 at 190 0 C for 60 seconds.

EXAMPLE 23 a 00 o0 o qo* o using

A)

The same procedure was used as in Example 21 but the following colours: 45g/kg Aqueous preparation of Pigment Yellow 16 Disperse Yellow 213 23 g/kg Aqueous preparation of Pigment Orange 34 2 gm/kg Disperse Yellow 213 S6 0 lOg/kg Aqueous preparation of Aqueous preparation of Disperse Yellow 213 Aqueous preparation of Aqueous preparation of Aqueous preparation of Aqueous preparation of Aqueous preparation of Aqueous preparation of Aqueous preparation of Pigment Pigment Pigment Pigment Pigment Pigment Pigment Pigment Pigment Red 146 Yellow 83 Blue 15:3 Blue 15:1 Violet 23 Blue 15:3 Green 36 Green 36 Green 7 Regd. Trade Mark of BASF AKTIENGESELLSCHAFT L G) 45g/kg Aqueous preparation of Pigment Violet 23 Cellestren Red 2G* H) 10g/kg Aqueous preparation of CI Pigment Yellow 83 12.5g/kg Aqueous preparation of CI Pigment Black 1 18.8g/kg Aqueous preparation of CI Pigment Blue 15:1 lOg/kg Aqueous preparation of CI Pigment Red 146 All gave the same good fastness properties as in Example 21.

EXAMPLE 24 1kg matt white print paste, suitable to be printed on coloured ground shades, was prepared by blending together the following ingredients: Water 555g Polyacrylic thickener (Lutexal HP) Acrylic Binder Dispersion (Helizarin Binder TW) 150g Silicone oil Siloxane DC 200/12500 Hexamethoxymethyl melamine (Luwipal 066) Aqueous preparation of rutile Titanium Dioxide eg. Helizarin white RFK1 200g Total 100lO This paste was printed dried and cured as in Example 21, but on 50/50 polyester/cotton sheeting fabric.

The same good fastness properties were obtained.

4 4 EXAMPLE The same procedure was used as in Example 21 but using the following formulation:

I

46 Water Urea Thickener (Lutexal HP) Hexamethoxymethyl melamine (technical, water insoluble) (Luwipal 066) Hexylene glycol Silicone oil 200/12500 Helizarin Binder TW Disperse Yellow 213 Pigment Red 146 685g lOOg lOg 0 a 04« o o 0 0 00 0 0 00 O 0 0 4 o oo, 0 *0 o0 0 0 o0 0 a 0@ Total Q000g The same good fastness properties as in Example 21 were obtained.

Very soft prints with very good fastness properties were obtained.

All the materials produced in the above examples (for which detailed fastness figures are not provided) were tested, with emphasis on light, rubbing and wash fastness and assessed visually.

The following methods, issued by the Standards Association of Australia, were used to test all the samples (except No. 14): light fastness AS 2001.4.21 (MVTF lamp) rub fastness AS 2001.4.3 (lOx and 100 x washing also extended rubbing) AS 2001.4.15 ISO 3 (International Standards Organization) dry cleaning AS2001.4.16 The materials produced in Example 14 were tested according to the International Standards Organization specifications. (It is to be noted that the AS standards are based on the ISO specifications but adapted to the more stringent climatic conditions prevailing in Australia and required particularly for meeting Government contracts requirements).

Regd. Trade Mark of BASF AKTIENGESELLSCHAFT -46a In all cases the materials tested at least met and often surpasses commercial standard requirements as practised in Australia, Europe, U.S.A. and other developed markets.

0t 0 *0 Manufactured by BASF AUSTRALIA LTD.

Regd. trade mark of BASF AKTIENGESELLSCHAFT 47 EXAMPLE 26 COMPARATIVE EXAMPLE Illustrating Processing Advantages Dyeing or printing of PE/Cotton with disperse and VAT dyes compared to Invention Typical Process: Pre-Treatment: Desizing Caustic Extraction (optional) Bleaching Washing Drying Dyeing Pad Vat and Disperse Dyes Dry Heatfix, say 60 sec. 210 0

C

Invention Desizing Not required Bleaching Washing Drying Pad dyestuff and cross linking agents, etc.

*Dry Heatfix, say 3-4 '4 4r 4 s 4 I I( I I I

II

20 minutes, 170 0 C, or 5-60 sec., 190 0 C-210 0

C

or HT-steam, say, 10-15 min. 185 0

C

Pad with NaOH and Hydrosulphite 25 Steam, say 60 seconds. 102 0

C

Rinse, oxidize, soap, rinse Dry *Optional, but precautions should be that excess liquor is removed and does not cause migration/sagging.

Printing by conventional process Similar to dyeing, but specialised steamer (Flash Ager) required not available or not installed in Australia at present. With the invention, however, no such specialised machinery is needed.

-i L- (r c; IPJEI1LIOLLIII 48 EXAMPLE 27 Dyeing or printing of PE/Cotton with disperse and Reactive Dyestuffs compared to Invention 0 0 Q 4 0 0O o 40 0 4 9 0 a a 00

S**

04 0 0 0 0004 o 0b 04 0 Typical Process Pretreatment Desizing Caustic Extraction Bleaching Washing i0 Drying Dyeing Pad Disperse eyes Dry 15 Heatfix, say 60sec. 2150C Reduction clear (hydro- 20 sulphite/caustic) Wash Dry Repad with Reactives Fix Wash Dry Printing Not practical generally non reproduceable results Invention Desizing Not required Bleaching Washing Drying Pad dyestuffs and cross-linking agent, etc.

Dry Heatfix, say 3-4 min.

1700C or 5-60 sec. 1900C-210°C or HT steam gay 10-15 mins. at 185 C Not required Not required Not required Not required Not required Not required Not required Highly practical reproduceable results, since both fibres coloured with same colourant 1 I Ipc~PPO1L"D"errn4+ i~ u^~il- 49 TABLE II EXAMPLE OF ELEGANT PROCESS SEQUENCES For dyeing a ground shade on P/C 50/50 light-weight bed sheeting, followed by printing and resin finishing: A. 1. Pad ground shade with invention and dry (e.g.

infra red pre-dry followed in one operation by cylinder or hot flue drying).

2. Print with invention or pigments; dry in one operation.

3. Apply crease-resist resin by foam and fix ground shade, prints, and resin in one operation, say at 190 0 C, 15-17 seconds.

B. 1. Prepad colour/invention plus crease resist resin, e.g. Fixapret COC from the same bath, idry.

2. Print with invention or conventional pigment paste.

r 3. Heat fix ground shade, resin and print in one stenter pass.

I i -I 0 000 0 0 0 000 00 0 00 0 0 0 0 0 0 0 0 *0 0 0 0 0 00 000 00 0 00 000 000 C @00 0 0 o 0000 00 00 00 0 00 00 00 +6

PRE-TREATMENT

Resizing Caustic Extraction Bleaching Washing Drying Dyeing: Pad Dyestuffs Dry

CONTINUOUS

CONVENTIONAL

PIGMENTS SYSTEM yes optional yes yes yes Helizarin yes ±ABLE, DYEING OR PRINTING CELLETRENf very necessary very necessary yes yes yes Cellestren yes OF PE/COTTON

DISPERSE/VAT

yes desirable yes yes yes Palanil Indanthren yes

INVENTION

yes no advantage known yes yes yes wide selection, except cationic Optional. Can be combined with heat fixation 0, 000 0 0 0 020 a o0o o o o0 0 c a o o a o o a o a c O oc o aoo e a D o 0 0 0 0 0 o 0 0 0 0 0 0 0 o 0000 00 0 TABLE 1(Continued) DYEING OR PRINTING OF PE/COTTON CONTINUOUS

PRE-TREATMENT

Fix Dyestuffs Repad Chemicals e.g. Hydro Caustic Pad Steam Fix say 60 min. 102°C Rinse, oxidise, soap, rinse

CONVENTIONAL

PIGMENTS SYSTEM Dry heat 150 C, min. or HT-steam, 175 0

C,

min.

CELLESTREN

Dry heat: 215°C 30 seconds HT steam 180 0

C

15 minutes

DISPERSE/VAT

Dry heat: 215°C 30-45 seconds

INVENTION

Dry heat, 1900C 5-7 seconds No No Yes Yes Remove Glyecin* (fixing agent) CD and unfixed residues by washing Yes Similar Glyezin CD can be added to Yes Dry Yes Printing Similar Similar, but Flash Ager necessary Similar 51 TABLE III Chemical Glossary of Trade Marks Product Cas* No.

Description 1. Lutexal HP 26100-47-0 6 47 42-9 6-7 104376-61-6 2. Acrisint 311 I II 6t *4* 64 a *06 4 II I 4 4 4 (4 3. Eulysin WP 4. Primasol AMI( 37295-87-1 9 00 3-0 1-4 3002-18-4 2 508 5-0 2-3 2 59 87-3 0-8 8247 1-4 2-9 1047-16-1 22 094-9 3-5 63 58-3 0-1 ammonium acrylate, polymer with acrylamide (C 3 H NO)X solentN)ph (petroleum) heavy aliphatic (mf not specified) 1,2, 3-propanetriol, polymer with (chloromethyl) oxirane and oxirane ,momo-9-octadecenyl ether, (Z is ononylpheno 1, ethoxylated (water) (0 2H4 0 nC 1 5 H 2 4 0 acrylic acid, homopolymer

C

3 H 4 0 2 triethanolamine triacetate C 12 H2 1 NO 6 acrylamide, polymer with sodium acrylate

C

3 H NO. C3 HO 2 .Na)x acrylic aci polymer with acrylamide, sodium salt (C3HN.0 3 H4 0 2 poly(o,%cy-1,2-ethanediyl), phenoxy)-1-( 2, 4-dimethylphenoxy)=methyl ethyl-, w-hydroxy- (mf not specified) pigment violet 19 0.1. pigment yellow 081 0.1. pigment violet 23 It.,

I,

Luprintol PE 6. Helizarin Brill.Pink BT Aqueous preparation based on: Chemical Abstracts System.

Colour index as published by: Society of Dyers and Colourists U.K. and American Association of Textile chemists and Colourists.

52 7. Siloxane 200/12500 to 200/1000 8. Luwi~pal 066 6314 8-6 2-9 3 08 9-11-0 Cymel 303 Setamo. WS Siloxanes and silicones, di-Me 1,3,5-triamine, N,N,N', Nf,Nr',N'F hexamethoxymethyl melamine hexakis (methoxymethyl C 15 H 30 napthalenesulfonic acid, polymer with formaldehyde sodium salt (C 10

H

8 0 3 S.CH 2 0),.XNa 9 08 4-06-4 Ortolan B Brown 3R Cellestren Yellow Liquid Helizarin Red GR C.I. acid brown 33 64 611-9 2-3 6 53 5-4 6-2 Butanamide 2,4dimethoxyphenyl.)-3-oxo-2- [2-(3-phenyl-1,2-4- )phenyl C.I. pigment red 112 (aqueous preparation of)

II

It t 4' 4O It 14 tI Ii,' 4 It tilt I I I I, I

Claims (49)

1. A process for direct colouring of textile fibres comprising appropriately pre-treating said fibres, preparing a solution of a cross-linking agent being a solution of a water insoluble technical hexamethoxymethyl melamine in a C 4 8 glycol, adding said solution of the cross-linking agent to a dye liquor or printing paste containing a colourant (excluding cationic dyestuffs) in the presence of an acid donor, applying the resultant mixture to said fibres and drying and curing said fibres.

2. A process for dyeing textile fibres comprising appropriately pre-',eating said fibres, preparing a solution of a cross-linking agent being a solution of a water 0 :o insoluble technical hexamethoxymethyl melamine in a C 4 o glycol, adding said solution of the cross-linking agent to a o dye liquor containing a colourant (excluding cationic o dyestuffs/ in the presence of an acid donor selected from 0 the group consisting of one or more saturated aliphatic C 4 6 ooo,' dicarboxylic acids, or commercially available mixtures thereof, acrylic acid polymers, and heat saponifiable organic esters, applying the resultant mixture to said fibres and drying and curing said fibres.

3. A process as claimed in claim 2 wherein said textile fibres are 100% cellulosic fibres and their blends with synthetic fibres. 04o0oo 0

4. A process as claimed in either of the preceding claims 2 and 3 wherein the amount of melamine and glycol are °o in the ranges 5 to 80 g/l (g/kg) and 5 to 120 g/l (g/kg) o respectively based on the dye liquor. 0 i J j -ili i 1 54 A process as claimed in claim 4 wherein said melamine and glycol are used in an amount of 10 to 50 g/l and 15 to 50 g/l (g/kg) respectively based on the dye liquor.

6. A process as claimed in any one of the preceding claims 2 to 5 wherein said acid donor is used in an amount of 1 to 5 g/l based on the dye liquor.

7. A process as claimed in any one of the preceding claims 2 to 6 wherein said C 4 8 is selected from the group consisting of 2-methyl-butane-1,4-diol; butane -1,2-diol; butane-1,3-diol; butane-1,4-diol; butane-2,3-diol; pentane-1,5-diol; neopentyl glycol; 2-methyl-pentane-2,4-diol; 2-methylpentane-1,5-diol and hexane-1,6-diol. o° 8. A process as claimed in any one of the preceding claims 2 to 7 wherein said colourant is selected from SO pigments, anionic dyes, vat dyes, disperse dyes and suitable 0 blends thereof. 4 0 4 9. A process as claimed in any one of the preceding claims 2 to 8 wherein said drying and curing are effected in one operation.

10. A process as claimed in claim 9 wherein said drying/curing is effected in the temperature range 150-210 0 C ,onl for a period of 5 seconds to 4 minutes.

11. A process as claimed in claim 10 wherein said drying/curing is effected in the temperature range 180-210 0 C S for a period of 15 to 60 seconds. 4 4

12. A process as claimed in any one of the preceding claims 2 to 11 wherein there is also added to the dye liquor a pigment binder in an amount of 10 to 100 g/l. IA Ij LA "autL' 1"cL A UL OkIOV' rll~r~r; LCHrI 55

13. A process for printing textile fibres comprising appropriately pre-treating said fibres, preparing a solution of a cross-linking agent being a solution of a water insoluble technical hexamethoxymethyl melamine in a C 4 _g glycol, adding said solution of a cross-linking agent to a printing paste containing a colourant (excluding cationic dyestuffs) in the presence of an acid donor selected from acrylic acid polymers, applying the resultant mixture to said fibres and drying and curing said fibres.

14. A process as claimed in claim 13 wherein said textile fibres are 100% cellulosic fibres and their blends with synthetic fibres. A process as claimed in either of the preceding claims 13 and 14 wherein the amount of melamine and glycol are in the ranges 5 to 80 g/kg and 5 to 120 g/kg respectively based on the print paste. oo So 16. A process as claimed in claim 15 wherein said melamine and glycol are used in an amount of 10 to 50 g/kg and 15 to 50 g/kg respectively based on the print paste.

17. A process as claimed in any one of the preceding claims 13 to 16 wherein the acrylic acid polymer is used in J an amount of 10 to 100 g/kg based on the print paste. Sa o

18. A process as claimed in claim 17 wherein the on. acrylic acid polymers used in "n amount of 10 to 50 g/kg based on the print paste.

19. A process as claimed in any one of the preceding 84: claims 12 to 18 wherein said C4_ glycol is selected from the group consisting of 2-methyl-butane-1,4-diol; butane -1,2-diol; butane-1,3-diol; butane-1,4-diol; butane-2,3-diol; _i I 56 pentane-1,5-diol; neopentyl glycol; 2-methyl-pentane-2,4-diol; 2-methylpentane-1,5-diol and hexane-1,6-diol. A process as claimed in any one of the preceding claims 13 to 19 wherein said colourant is selected from pigments, anionic dyes, vat dyes, disperse dyes and suitable blends thereof.

21. A process as claimed in any one of claims 13 to wherein a silicone or vegetable oil, and, optionally, urea are added to the print paste.

22. A process as claimed in claim 21 wherein said silicone oil is in the range between 1000 to 15,000 cps. 0900 .o 23. A process as claimed in claim 22 wherein said o .silicone oil is in the range between 5000 to 12,500 cps.

24. A process as claimed in either of claims 21 and 22 O0 wherein said silicone oil (optionally with urea) is used in 9, an amount of between 1 to 100 g/kg print paste (each). A process as claimed in claim 24 wherein said silicone oil (optional with urea) is used in an amount of o6ooo between 10 to 60 g/kg print paste (each). 0 VC 0 26. A process as claimed in claim 24 or claim ooo, S wherein said silicone oil is used in an amount of 25 to g/kg and the urea is used in an amount of 30 to 70 g/kg.

27. A process as claimed in any one of claims 13 to 26 o wherein said silicate particles are added to the print paste. Craa~p i 57

28. A process as claimed in any one of preceding claims 13 to 27 wherein said drying and curing are effected in one operation.

29. A process as claimed in claim 28 wherein said drying/curing is effected in the temperature range 150-210°C for a period of 5 seconds to 4 minutes. A process as claimed in claim 29 wherein said drying/curing is effected in the temperature range 180-210 0 C for a period of 15 to 60 seconds.

31. A process as claimed in any one of claims 13 to wherein the printed fibres are also subjected to heat calendering.

32. A process as claimed in any one of the preceding ,,44 claims 13 to 31 wherein there is also added to the print S paste a pigment binder in an amount of 10 to 100 g/kg. I A process for direct colouring of textile fibres ;c .comprising appropriately pre-treating said fibres, dispersing a cross-linking agent being a water insoluble technical hexamethoxymethyl melamine in a printing paste containing a colourant consisting of a pigment or predominantly a pigment in the presence of an acid donor and, optionally, in the presence of silicone or vegetable oil, applying the resultant mixture to said fibres and drying and curing said fibres.

34. A dye liquor or print paste comprising a colourant (excluding cationic dyestuffs), an acid donor and a o cross-linking agent being a solution of a water insoluble technical hexamethoxymethyl melamine in a C 4 8 glycol. -z -e i I 58 A dye liquor comprising a colourant (excluding cationic dyestuffs), an acid donor selected from the group consisting of one or more saturated aliphatic C 4 6 dicarboxylic acids or commercially available mixtures thereof, acrylic acid polymers and/or copolymers, and heat saponifiable organic esters and a cross-linking agent being a solution of a water insoluble technical hexamethoxymethyl melamine in a C4- 8 glycol.

36. A dye liquor as claimed in claim 35 wherein the amount of melamine and glycol are in the range of 5 to g/l and 5 to 120 g/l based on the dye liquor.

37. A dye liquor as claimed in claim 36 wherein said melamine and glycol are used in an amount of 10 to 50 g/l and 15 to 50 g/l respectively based on the dye liquor.

38. A dye liquor as claimed in any one of claims 3E to 37 wherein said acid donor is used in an amount of 1 to g/l based on the dye liquor.

39. A dye liquor as claimed in any one of claims 35 to 38 wherein said C 8 glycol is selected from the group consisting of 2-methyl-butane-l,4-diol; butane-1,2-diol; butane-1, 3-diol; butane-l,4-diol; butane-2,3-diol; t diol; pentane-l,5-diol; neopentyl glycol; 2-methyl-pentane -2,4-diol; 2-methylpentane-l,5-diol and hexane-1,6-diol. i 9 A dye liquor as claimed in any one of claims 35 to 39 wherein said colourant is selected from pigments, anionic dyes, vat dyes, disperse dyes and suitable blends thereof. 440

41. A dye liquor as claimed in any one of claims 35 to also containing a pigment binder in an amount of 10 to 100 g/1. L 'fc- 59

42. A print paste comprising a colourant (excluding cationic dyestuffs), an acid donor selected from acrylic acid polymers and/or copolymers, and a cross-linking agent being a solution of a water insoluble technical hexamethoxymethyl melamine in a C 4 glycol.

43. A print paste as claimed in claim 42 wherein the amount of melamine and glycol are in the ranges 5 to 80 g/kg and 5 to 120 g/kg respectively based on the print paste.

44. A print paste as claimed in claim 43 wherein said melamine and glycol are used in an amount of 10 to 50 g/kg and 15 to 50 g/kg respectively based on the print paste. A print paste as claimed in any one of preceding claims 42 to 44 wherein the acrylic acid polymer is used in an amount of 10 to 100 g/kg. i

46. A print paste as claimed in claim 45 wherein the acrylic acid polymer is used in an amount of 10 to 50 g/kg.

47. A print paste as claimed in any one of preceding claims 42 to 46 wherein said C 4 8 glycol is selected from the group consisting of 2-methyl-butane-1,4-diol; butane -1,2-diol; butane-l,3-diol; butane-1,4-diol; butane-2, 3-diol; hexane-2,5-diol; pentane-1,5-diol neopentyl glycol; 2-methyl-pentane-2,4-diol; 2-methylpentane-1,5-diol and hexane-1,6-diol. 4

48. A print paste as claimed in any one of preceding claims 42 to 47 wherein said colourant is selected from pigments, anionic dyes, vat dyes, disperse dyes and suitable blends thereof. 60

49. A print paste as claimed in any one of preceding claims 42 to 48 also comprising a silicone or vegetable oil and, optionally, urea. A print paste as claimed in claim 49 wherein said silicone oil is in the range between 1000 to 15,000 cps.

51. A print paste as claimed in claim 50 wherein said silicone oil is in the range between 5000 to 12,500 cps.

52. A print paste as claimed in any one of claims 49 to 51 wherein said silicone oil (optionally with urea) is in an amount of between 1 to 100 g/kg print paste (each).

53. A print paste as claimed in claim 52 wherein said silicone oil (optionally with urea) is in an amount of between 10 to 60 g/kg print paste (each).

54. A print paste as claimed in either of claims 52 and 53 wherein said silicone oil is in an amount of 25 to g/kg and said urea is in an amount of 30 to 70 g/kg. A print paste as claimed in any one of the preceding claims 42 to 54 also including silicate particles.

56. A print paste as claimed in any o..a of the preceding claims 42 to 55 also including a pigment binder in an amount of 10 to 100 g/l. *4jt i 9

57. A print paste comprising as the colourant, pigments or predominantly pigments, and a water insoluble technical hexamethoxymethyl melamine dispersed therein, optionally in o* the presence of silicone or vegetable oil. 944 .8 61

58. A cross-linking agent for use in combination with a dye liquor or print paste being a solution of a water insoluble technical hexamethoxymethyl melamine in a C 4 8 glycol.

59. A cross-linking agent as claimed in claim 58 wherein the amount of melamine and glycol are in the ranges to 80 g/l (g/kg) and 5 to 120 g/l (g/kg) respectively based on the dye liquor or print paste. A cross-linking agent as claimed in claim 59 wherein said melamine and glycol are used in an amount of to 50 g/l (g/kg) and 15 to 50 g/l (g/kg) respectively based on the dye liquor or print paste.

61. A cross-linking agent as claimed in any one of the oo preceding claims 58 to 60 wherein said C4_- is selected from ooS the group consisting of 2-methyl-butane-l,4-diol; butane o" I -1,2-diol; butane-l,3-diol; butane-1,4-diol; butane-2, 3-diol; hexane-2,5-diol; pentane-1,5-diol; neopentyl glycol; o o 2-methyl-pentane-2,4-diol; 2-methylpentane-l,5-diol and r hexane-1,6-diol. 0

62. A cross-linking agent for use in combination with a print paste being a solution of a water insoluble technical hexamethoxymethyl melamine in a C. 8 glycol, and a silicone on or vegetable oil and, optionally, urea. o°oosv 63. A cross-linking agent as claimed in claim 62 wherein said silicone oil is in the range between 1000 to 15,000 cps. 0u

64. A cross-linking agent as claimed 63 wherein said Ssilicone coil is in the range between 5000 to 12,500 cps. 1r". .,4 P 1 3 a) E >1 Q) >1 C a) (a 4 (a ^i P4 U 62 A cross-linking agent as claimed in any one of the preceding claims 62 to 64 wherein said silicone oil (optionally with urea) is in an amount of between 1 to 100 g/kg print paste (each).

66. A cross-linking agent as claimed in claim wherein said silicone oil (optional with urea) is in an amount of between 10 to 60 g/kg print paste (each).

67. A cross-linking agent as claimed in either of claims 65 and 66 wherein said silicone oil is in an amount of 25 to 35 g/kg and wherein said urea is in an amount of to 70 g/kg.

68. A cross-linking agent as claimed in any one of preceding claims 62 to 67 also including silicate particles. DATED this 14th day of January, 1991. BASF AUSTRALIA LTD. DR. HENRY DONENFELD WATERMARK PATENT TRADEMARK ATTORNEYS 2nd Floor "The Atrium" 290 Burwood Road HAWTHORN VICTORIA 3122 AUSTRALIA 4 4 4444 44 4444