GB1561330A - Materials for the decoration of fabrics - Google Patents

Description

(54) MATERIALS FOR THE DECORATION OF FABRICS (71) We, FABPRINT LIMITED, a British Company of, Helm Mills, Rastrick, Brighouse, West Yorkshire, England, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to materials for the decoration of fabrics used as textile materials and ink compositions for making the same.

Our copending application 7100/74, 9653/74, 27778/74 and 33618/74 cognate (Serial No. 1,496,891) describes and claims a method of decorating textile fabrics which comprises taking a flexible substrate having a removable layer thereon containing a dye and/or pigment and a film forming polymeric base which on heating becomes sufficiently adhesive to adhere under the effect of pressure to the textile fabric more strongly than the layer adheres to the flexible substrate, pressing the layer onto a textile fabric while heating, removing the flexible substrate to leave the layer adhering to the textile fabric and subjecting the fabric to a fixation process which fixes the dye or the pigment to give a fast result and causes a thermal breakdown of the film so that the presence of its residues does not affect the textile properties of the fabric or the fastness of the coloured result.

As indicated in our copending application, within that general process a wide variety of materials may be used for the layer which is applied to the textile to be decorated.

According to the present invention there is provided a decoration material primarily for use in decorating textile fabrics which has the advantage of giving an efficient transfer of the removable layer with very short contact times and which comprises a flexible substrate having a removable layer thereon comprising a base of thermoplastic film forming polymer material together with pigment, a cross linking agent capable of cross linking the thermoplastic polymer, a thermally activated catalyst promoting the cross linking reaction, a high temperature plasticiser and optionally other materials assisting the application of the removable layer to the flexible substrate in the first instance, the polymeric material being chosen and the removable layer being formulated so that when the layer is transferred to a material to be decorated and subjected to heat and pressure in the transfer operation, and any necessary heat fixation treatment, the layer breaks down to provide a discontinuous, non-superficial residual matrix which does not significantly modify the properties of the material after decoration.

The removable layer may contain more than one pigment and the pigment(s) may be inert or capable of reacting with the polymer and/or the cross linking agent.

Such a material is used by bringing it into contact under heat and pressure with the material to be decorated, usually a textile fabric, in order to adhere together the removable pigment-containing layer and the material to be decorated and thereafter subjecting the material to a fixation treatment which fixes the pigment to the material and normally breaks down the transferred layer so that the properties of the material are not significantly modified by the presence of its residues. The use of a thermally activated catalyst makes it possible, using the techniques described in more detail below, to use heat and pressure sufficient to initiate the fixing which can then be allowed to go to completion in time, e.g. a few days, while the material to be decorated is simply stored. The flexible substrate may be removed prior to the fixing treatment or afterwards.Generally if it is to be removed after the fixing treatment a higher combination of temperature and pressure is required in the initial contacting treatment than if the flexible substrate is removed prior to the fixing treatment. In certain circumstances it is advantageous to remove the flexible substrate after the fixing treatment to minimise the risk of contamination of parts of the machinery by pigment and removable layer materials. The initial heat and pressure contacting may be of a very short duration making it possible to achieve transfer and optionally fixation also by a single passage through heated nip rollers i.e. an application of heat and pressure of the order of 10-2 or 10-3 seconds.

Polymers which are preferred as forming the basis of the removable layer are the polyvinylacetals such as polyvinylbutyrals and polyvinylformals. They may be used alone or in mixture with other polymers including acrylic polymers, polyamides, polyvinylacetate or polyvinyl alcohol.

Suitable cross linking agents which can be used include dialdehydes e.g.

glyoxal, epoxy resin monomers and aminoplasts. Of particular value are the methylolated aminoplast monomers e.g. dimethylolurea, dimethyloldihydroxy ethylene urea, dimethylolcyclic ethylene urea or methylolated melamine and their methyl esters such as trimethoxy methyl melamine.

As noted above, the catalysts used to promote the cross linking action are thermally activated. This means that they are ineffective at normal ambient temperature, and so do not tend to cross-link the polymer compound of the decoration material during its manufacture or storage, giving that material a good shelf-life. The temperature at which the catalyst may be activated may vary, but is preferably greater than 100"C. Activation may take place by a heating treatment subsequent to transfer of the removable layer to the material to be decorated or simultaneously therewith.

Preferred temperature activated catalysts are so-called "blocked" catalysts such as the amine or ammonium salts of strong acids, e.g. the ethanolamine or diethanolamine salts of mineral acids, and ammonium salts such as ammonium chloride, nitrate, phosphate and sulphate. The activity of the amine or ammonium salts depends upon the dissociation of the salt. Until a critical temperature is reached the catalyst has no significant effect in the removable film. The catalysts suggested in our copending application referred to above show initiation at quite low temperatures e.g. 50--600C or even lower. By using thermally activated catalysts the threshold temperature is raised.The amine salts of p-toluene sulphonic acid are of especial value in this connection enabling the critical initiating temperature to be raised to as high as 1200C with corresponding advantages in the heat stability of the releasable layer, the flow of the layer during transfer and the extent of thermal breakdown of the removable film during transfer and heat fixation. Suitable amine compounds for combination with p-toluene sulphonic acid include S-carbazide, mono- and di-ethanolamine.

It is particularly desirable to utilise a catalyst/cross linking agent combination that gives a precise temperature threshold for cross linking. Since during the course of forming the removable layer on the flexible substrate by coating or printing, for example, it may be necessary to heat the paper in order to remove solvents; it is important that no cross linking reactions are initiated by such heating. During the transfer process, when heat and pressure are applied, they should initially be sufficient only to ensure that the materials of the removable layer flow readily without the development of the viscosity which is characteristic of the onset of cross linking; however, at the end of the transfer process, the heat and pressure may rise to activate the catalyst.

High temperature plasticisers constitute a special sub-group of plasticisers and have the property of lowering the temperature of the rubber/melt transition. They may or may not also possess the property of normal plasticisers i.e. lower the temperature of the glass/rubber transition to give a softer more pliable film. Since the process of decoration requires that the continuous nature of the transferred film does not survive the fixation process normal plasticisers have no significant role to play. However high temperature plasticisation improves the extent of penetration of the releasable film into the receiving substrate during transfer and the continuation of that process during the subsequent fixation treatment. Suitable materials for use as high temperature plasticisers include fatty acids such as palmitic or stearic acid, esters of stearic acid or palmitic acid with polyethylene glycol or glycerol, paraffin was, stearamide or finely dispersed polyethylene.

The removable layer may be a continuous layer of one colour or may be a discrete layer in the form of a decorative pattern or the like. Such a discrete layer is conveniently produced by printing and in a further aspect the present invention provides printing inks comprising the ingredients of the layer as set forth above dissolved or dispersed in an appropriate solvent.

Specifically the inks according to the present invention comprise an ink vehicle of a thermoplastic polymeric film forming material capable of being cross linked, a cross linking agent capable of cross linking the polymeric film forming material, a pigment or pigments, a catalyst promoting the cross linking reaction and a high temperature plasticiser as outlined above.

Such inks can be formulated according to normal ink making practice and can be adjusted in their consistency to the particular method of application required. It is important to avoid excessive heat during ink formulation so that no initiation of cross !inking occurs and also to avoid the use of acidic materials as additives for the same reason.

The removable layer may be a simple single layer or may be made up of a plurality of sub-layers. The essential feature of the removable layer is that it should contain, either throughout or in at least one of its sub-layers or in the combination of such sub-layers, the components previously described as necessary components of the removable layer. The use of a plurality of sub-layers may in certain circumstances offer particular advantages when it is desired to use particular printing methods. For example printing by lithography requires inks to possess particular properties in relation to their physical reactions with the lithographic plate. To achieve a satisfactory balance of such properties is not easy when the inks also require to possess properties and contain substances such as have been discussed.However by coating or printing the flexible substrate using any appropriate means with a releasable film comprising all of the ingredients necessary to the present invention, drying the coated substrate and then printing the decoration using a normal lithographic ink, a suitable decoration material can be built up. It may be advantageous with some lithographic inks to apply over the printed decoration a further coating similar in composition to the first in order to achieve the best transfer properties and fastness. It is particularly advantageous when lithographic inks are printed to use a thermoplastic base material such as is provided by ultra violet cured inks based on glycidyl methacrylate.Similarly in gravure printing good image production is dependent upon the acceptance of the ink receiving surface of the ink in the engraved cells and the ability of printed dots to flow together to give overall coverage. To assist in this process with the removable layer system of the present invention it may be advantageous previously to coat the flexible support with an overall removable coating of similar composition.

In the production of the decoration materials by any conventional mode of printing, the formation of a plurality of layers is in any case inevitable in multicolour printing processes since the coloured decoration is built up by successive printing with different colours, mixture shades being produced by laying one printed coat on another.

It is important in printing by any method and particularly when a plurality of layers is involved to avoid the use of drying temperatures which may initiate the cross linking reaction or cause the high temperature plasticiser to become operative. The first will give papers of poor storage stability as cross linking may proceed for a period of time after heating ceases and the second will give rise to a tacky paper which cannot be stacked without adherence of separate sheets or layers in a roll of printed paper.

The flexible substrate may be chosen from a wide variety of materials the surface of which is either such that it inherently possesses the necessary release properties between it and the removable layer or which surface may have been treated to give the desired effect. Self-supporting films of cellulose acetate and nitrocellulose or aluminium and other metal foils may be used as such as or paper may be used, e.g. coated with a surface having appropriate release properties such as wax, nitrocellulose, silicone or a rubbery coating e.g. comprising polybutadiene.

Silicone release coated paper, wax coated paper or paper coated with a thermoplastic coating such as are provided by unsaturated esters of acrylic or methacrylic acid cross-linked by ultraviolet irradiation in the presence of appropriate catalysts are the preferred flexible substrates. Certain paper types are usable as such, i.e. without the provision of an applied release coating.

When the decoration materials of the present invention are used, the removable layer should first be transferred to the fabric to be decorated. This is done using the thermoplastic properties of that removable layer, whereafter the layer is subjected to an appropriate fixing treatment which serves to cross link the thermoplastic material to form a discontinuous matrix firmly holding the pigments to the material to be decorated.

Clearly if the removable layer remained during such processing as a layer, it would severely affect adversely the handle and appearance of the fabric after decoration. It is accordingly essential to use a removable layer formulation which will break up on heating to give a discontinuous non-superficial layer and to emplov transfer conditions which enable this process to occur. Accordingly the preferred transfer conditions are such that the high temperature plasticiser in the removable layer becomes operative and the pressure employed promotes adequate flow of the fluid layer into the fabric to be decorated.The temperature to which the removable layer is raised during the transfer process may be such that the cross linking reaction is initiated by activating the catalyst, and if this is done, there is no need for any subsequent heat treatment to fix the pigment, fixing to full fastness taking place automatically over a period e.g. of 10 to 200 hours.

We have found that by choosing appropriate pressures and temperatures for the initial application of the decoration materials according to the present invention onto the fabric to be decorated, sufficient assimilation of the removable layer into the material of the fabric can be achieved so that little or no adhesion remains between the fabric and the flexible substrate. In these circumstances it may be advantageous when using certain machine types for the fixation treatment to leave the composite unseparated during fixation thus protecting parts of the machine from contamination. Normally satisfactory transfer of the removable layer to the fabric to be decorated is obtained using a callender with one or both rollers heated.We have found temperatures from 80 to 1020C and pressures between 40 and 200 Ibs per linear inch of the roller width to give satisfactory results. The best results are obtained when the transfer paper reaches a temperature in the nip such that the high temperature plasticiser becomes operative. Normally such plasticisers are selected so that operating roller temperatures lie between 80"C and 1200C.

Running speeds can be slow e.g. 5-10 meters per minute or faster consistent with the fact that contact times will be of the order of 10-2 seconds or less and it is desirable to achieve an appropriate transfer paper temperature in that short time. If higher pressures are used the degree of transfer into the interstices of the fabric is very high so that the considerations discussed above apply. The conditions cannot be strictly defined since the properties of the material to be decorated affect the transfer conditions since the thickness, density, compressibility etc. of the fabric all affect the extent of heat film transfer into the fabric under the hot high pressure conditions.

Although transfer using a very short duration heat/pressure treatment for example, in a callender, is preferred it is possible to use a static press. Normally this will involve the application of high pressures e.g. 800 psi to achieve satisfactory results and although the duration of the transfer treatment will be longer than when a callender is used it will be much shorter than is normally the case when static presses are used to produce transferred decorations. Normally a static pressure of 58 seconds will be requiredwhenthe materials of the present invention are used.

This may be contrasted with periods of 60 seconds used in, for example, sublimation transfer printing c.f. Defago et al U.S. Patent Specification 3782896.

The fabrics which may be decorated using the materials of the present invention may be cellulosic e.g. cotton, viscose rayon, polynosic rayon, cuprammonium rayon, polyamide e.g. Nylon 66 or Nylon 6, polyester, mixtures of fibres e.g. polyester/cotton or wool/cotton blends, coated fabrics e.g.

polyvinylchloride coated cotton fabrics, aluminium coated fabrics.

The following Examples will serve to illustrate the invention: EXAMPLE 1 A paper coated with a silicone release layer is printed to a dry film thickness of 3 microns with an ink containing in each 100 gms 2 gms of a copper phthalocyanine pigment 15 gms of polyvinyl butyral (Butvar 98-Monsanto Co.) 6 gms of stearylalcohol-ethylene oxide condensate 3 gms of a 20% aqueous solution of dimethylol dihydroxv cyclic ethylene area.

1 gm of ammonium nitrate 73 gms of 64 O.P. ethanol.

The printed paper is brought into contact with a mercerised cotton fabric and passed between two rollers set so as to give a pressure of 100 Ibs per linear inch of nip. The upper roller is made of steel and heated to 1 100C and the fabric paper composite is passed through the nip at 6 yards per minute. The composite is then passed over an oil heated drum at 1650C under a felt blanket used to assist contact.

The fabric is in contact with the heated surface and the contact time is 30 seconds.

After the heat treatment the paper is removed and the fabric is printed with a brilliant blue design of the high fastness to washing and light. Its appearance and handle are substantially those of the unprinted fabric.

If the nip pressure is reduced to 10 Ibs per linear inch of nip and the same procedure adopted then the transferred design is clearly present on the fabric surface. Similarly if the paper is removed before passage around the oil heated drum, then the transferred film is observed to mark the blanket during fixation although the design is no longer fixed in a superficial way.

EXAMPLE 2 A paper coated with a silicone release layer is printed to a dry film thickness of 6 microns by screen printing with an ink containing in each 100 gms, 2 gms of Colour Index Pigment Yellow 1 15 gms of polyvinyl butyral (Butvar 98-Monsanto Co.) 8 gms of stearyl alcohol-ethylene oxide condensate 2 gms of a 20% solution in water of trimethylol melamine 1 gm of ammonium sulphate 40 gms of ethyl cellosolve 33 gms of 64 O.P. ethanol.

The printed paper is brought into contact with cotton interlock fabric and passed between two rollers set so as to give a pressure of 150 Ibs per linear inch of nip. The upper (steel) roller is heated to 125"C and the fabric/paper composite is passed through the nip at 5 yards/minute. The composite is then pressed in a garment press set at a temperature of 165"C for 30 seconds and the paper subsequently removed.

The fabric is printed to a well penetrated yellow shade of high fastness to washing and to light. The handle of the fabric is excellent and the textile characteristics unimpaired.

EXAMPLE 3 The paper of Example I was used to print fabrics made of 67/33 polyestercotton blends, 50/50 cotton-polyamide blends and viscose fabrics: similar results were obtained.

EXAMPLE 4 A paper coated with a silicone release layer is given a second overall coating to a dry layer thickness of 6 microns using a solution which contains in each 100 gms, 16 gms polyvinyl butyral (Butvar 98-Monsanto Co.) 8 gms stearyl alchol-ethylene oxide condensate 3 gms of a 20% aqueous solution of dimethylol dihydroxy cyclic ethylene urea 1 gm ammonium nitrate 72 gms 64 O.P. ethanol.

To the doubly coated paper is applied a design with for example a brush or felt pad using an ink containing in each 100 gms, 5 gms Colour Index Pigment Red 6 10 gms polyvinyl alcohol 85 gms water.

After drying the paper is contacted with a 50/50 cotton/polyester blended fabric and subsequently treated as in Example 2.

The design is found to be transferred completely to the fabric to give a red decoration of excellent fastness to wet treatments and to light.

EXAMPLE 5 An ink is prepared containing in each 100 parts, 5 parts of a pigment selected from the list given below 10 parts of stearyl alcohol-ethylene oxide condensate 2 parts of trimethoxy methyl melamine (40"it aqueous solution) 1.5 parts of ammonium sulphate 1.5 parts of polyvinyl butyral 33.5 parts of 64 OP ethanol 33.0 parts of toluene.

The ink is printed onto silicone release paper or wax release paper by screen printing and dried.

The design may be transferred to a cotton-polyester or cotton fabric by contacting the printed side of the paper with the cloth and heating the composite under pressure (400 Ibs per square inch) at 1250C for 0.03 seconds. The composite may then be heated under light or no pressure for 30 seconds at 1650C. The paper may then be removed leaving the printed design on the fabric providing a decoration which is fast to washing.

Alternatively the paper may be removed from the fabric after the first and before the second heat treatment.

Some pigments which may be used in the ink in this example are listed below, Copper phthalocyanine (blue shade) Carbon black (grey shade)

(red shade)

yellow shade)

(violet shade) EXAMPLE 6 2 gms of a finely divided carbon black pigment 15 gms of polyvinyl butyral (Butvar 98-Monsanto Co.) 10 gms of stearyl alcohol--ethllene oxide condensate 2 gms of trimethoxy methylmelamine 1 gm of the monoethanolamine salt of p4oluene sulphonic acid 2 gms of Bentonite are dispersed in a mixture of 50 parts of polyethylene glycol 200 with 18 parts of diacetone alcohol to form a screen printing ink.A silicone coated paper as used in Example 1 is printed with the ink by screen printing and dried at 75"C. The printed paper is then used to decorate a cotton fabric by passing the paper in contact with the fabric through heated callender rollers operating at a pressure of 70 Ibs per linear inch of nip with one roller heated to a temperature of 95"C. The speed of passage is 20 metres per minute. The paper is then peeled from the cotton fabric leaving the printed design thereon. The fabric is then heated for 30 seconds in an oven at 140"C. After the heat treatment the fabric is decorated with a fast black design. The fastness is found to improve on standing to an even higher standard giving excellent fastness to the I.S.O. No. 4 washing test.

EXAMPLE 7 If in Example 6, the carbon black pigment is replaced by a red pigment (C.I.

Pigment Red 6) and the design is printed by screen printing onto a wax coated paper. An excellent transfer of the design onto a rayon fabric is achieved by increasing the callender pressure to 115 Ibs per linear inch and the temperature of the heated roller to 1100C. The fastness of the decoration after heat treatment as described in Example 6 is excellent.

EXAMPLE 8 An ink made up as shown in Example 6 is applied by screen printing to a wax coated paper which is then used to decorate a cotton fabric by passing the paper in contact with the fabric between heated calender rollers at a pressure of 100 lbs per linear inch of nip with one roller heated to a temperature of 190"C and with a running speed of I yard per minute. The paper is then peeled from the fabric. After storage for 7 days the fastness of the decoration is greately improved over that which may be observed immediately after the paper is peeled and is equal to that observed of the pattern is produced by the transfer and fixation conditions employed in Example 5.

EXAMPLE 9 A coating solution of 15 parts of polyvinylbutyral dissolved in 85 parts of npropanol is applied to a paper coated with an ultraviolet radiation cured butylmethacrylate composition containing a suitable photochemical initiator and dried. The polyvinylbutyral coating is applied at a wet thickness of 6 ,u.

The coated paper is printed with a conventional lithographic ink containing a copper phthalocyamine pigment using normal procedures and then coated again with a solution containing 15 parts of polyvinyl butyral 10 parts of stearyl alcohol 2 parts of trimethoxy methyl melamine 1 part of the diethanolamine salt of p. toluene sulphonic acid dissolved 72 parts of n-propanol and dried at 500 C. The wet thickness of the second coating is 6 ,.

The printed paper is then used to decorate a cottdn/polyester blended shirting fabric by bringing it into contact with the fabric and passing the composite through a heated callender set at a pressure of 70 Ibs per linear inch and the temperature of the heated roller at 1000 C. After passage through the callender the paper is removed leaving the decorating design on the fabric. The latter is then heated for 45 seconds at 1350C to give a blue decoration of very high fastness to severe washing and to light.

EXAMPLE 10 8 parts of a copper phthalocyanine pigment 15 parts of polyvinyl butyral 12 parts of stearyl alcohol-ethylene oxide condensate 2 parts of trimethylolmelamine 2 parts of ammonium nitrate are dispersed in 61 parts of 64 O.P ethanol to form a gravure printing ink. A design is then applied to an ultraviolet radiation cured butylmethacrylate coated paper as used in Example 8 by gravure printing using a force of 9 Kg cm-' and a running speed of 20 cm sec-'.

The printed paper is then used to decorate a cotton fabric by the procedure described in Example 6. The fabric is thus decorated with a blue design of very high washing and dry cleaning fastness.

The words Butvar and Cellosolve used herein are Registered Trade Marks.

WHAT WE CLAIM IS: 1. A decoration material comprising a flexible substrate having a removable layer thereon, the layer comprising a base of thermoplastic film-forming polymeric material, a pigment, a cross-linking agent capable of cross-linking the thermoplastic polymer, a thermally activated catalyst promoting the cross-linking reaction, and a high temperature plasticiser, the polymeric material being chosen and the removable layer being formulated so that when the layer is transferred to a material to be decorated and subjected to heat and pressure in the transfer operation, and any necessary heat fixation treatment, the layer breaks down to provide a discontinuous, non-superficial residual matrix which does not significantly modify the properties of the material after decoration.

2. A decoration material according to claim 1 wherein the removable layer contains one or more pigments at least some of which are capable of reacting with the polymer and/or of reacting with the cross-linking agent.

3. A decoration material according to claim 1 or 2 wherein the thermoplastic film-formillg polymer material is a polyvinylbutyral.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (27)

**WARNING** start of CLMS field may overlap end of DESC **. EXAMPLE 8 An ink made up as shown in Example 6 is applied by screen printing to a wax coated paper which is then used to decorate a cotton fabric by passing the paper in contact with the fabric between heated calender rollers at a pressure of 100 lbs per linear inch of nip with one roller heated to a temperature of 190"C and with a running speed of I yard per minute. The paper is then peeled from the fabric. After storage for 7 days the fastness of the decoration is greately improved over that which may be observed immediately after the paper is peeled and is equal to that observed of the pattern is produced by the transfer and fixation conditions employed in Example 5. EXAMPLE 9 A coating solution of 15 parts of polyvinylbutyral dissolved in 85 parts of npropanol is applied to a paper coated with an ultraviolet radiation cured butylmethacrylate composition containing a suitable photochemical initiator and dried. The polyvinylbutyral coating is applied at a wet thickness of 6 ,u. The coated paper is printed with a conventional lithographic ink containing a copper phthalocyamine pigment using normal procedures and then coated again with a solution containing 15 parts of polyvinyl butyral 10 parts of stearyl alcohol 2 parts of trimethoxy methyl melamine

1 part of the diethanolamine salt of p. toluene sulphonic acid dissolved 72 parts of n-propanol and dried at 500 C. The wet thickness of the second coating is 6 ,.

The printed paper is then used to decorate a cottdn/polyester blended shirting fabric by bringing it into contact with the fabric and passing the composite through a heated callender set at a pressure of 70 Ibs per linear inch and the temperature of the heated roller at 1000 C. After passage through the callender the paper is removed leaving the decorating design on the fabric. The latter is then heated for 45 seconds at 1350C to give a blue decoration of very high fastness to severe washing and to light.

EXAMPLE 10

8 parts of a copper phthalocyanine pigment

15 parts of polyvinyl butyral

12 parts of stearyl alcohol-ethylene oxide condensate

2 parts of trimethylolmelamine

2 parts of ammonium nitrate are dispersed in 61 parts of 64 O.P ethanol to form a gravure printing ink. A design is then applied to an ultraviolet radiation cured butylmethacrylate coated paper as used in Example 8 by gravure printing using a force of 9 Kg cm-' and a running speed of 20 cm sec-'.

The printed paper is then used to decorate a cotton fabric by the procedure described in Example 6. The fabric is thus decorated with a blue design of very high washing and dry cleaning fastness.

The words Butvar and Cellosolve used herein are Registered Trade Marks.

WHAT WE CLAIM IS: 1. A decoration material comprising a flexible substrate having a removable layer thereon, the layer comprising a base of thermoplastic film-forming polymeric material, a pigment, a cross-linking agent capable of cross-linking the thermoplastic polymer, a thermally activated catalyst promoting the cross-linking reaction, and a high temperature plasticiser, the polymeric material being chosen and the removable layer being formulated so that when the layer is transferred to a material to be decorated and subjected to heat and pressure in the transfer operation, and any necessary heat fixation treatment, the layer breaks down to provide a discontinuous, non-superficial residual matrix which does not significantly modify the properties of the material after decoration.

2. A decoration material according to claim 1 wherein the removable layer contains one or more pigments at least some of which are capable of reacting with the polymer and/or of reacting with the cross-linking agent.

3. A decoration material according to claim 1 or 2 wherein the thermoplastic film-formillg polymer material is a polyvinylbutyral.

4. A decoration material according to any of claims I to 3 wherein the

thermoplastics film-forming polymer material comprises a mixture of a polyvinylacetal and one or more of acrylic polymers, polyamides, polyvinyl acetate and polyvinyl alcohol.

5. A decoration material according to any preceding claim wherein the crosslinking agent is one or more dialdehydes.

6. A decoration material according to any of claims 1 to 4 wherein the crosslinking agent is a methylolated aminoplast monomer.

7. A decoration material according to claim 6 wherein the cross-linking agent is selected from dimethylolurea, dimethyloldihydroxy ethylene urea, dimethylolcyclic ethylene urea, methylolated melamine and trimethoxy methyl melamine.

8. A decoration material according to any preceding claim wherein the catalyst is selected from amine and ammonium salts of strong mineral acids.

9. A decoration material according to any of claims 1 to 7 wherein the catalyst is an amine salt of p-toluene sulphonic acid.

10. A decoration material according to any of claims 1 to 9 wherein the high temperature plasticiser is selected from high molecular weight fatty acids, esters of high molecular weight fatty acids with polyethylene glycol or glycerol, paraffin wax, stearamide and polyethylene.

11. A decoration material according to any of claims 1 to 10 wherein the removable layer is present on the flexible substrate as a number of discrete areas.

12. A decoration material according to any of claims 1 to 10 wherein the removable layer is present as a continuous coating over the whole of the flexible substrate.

13. A decoration material according to any of claims I to 12 wherein the removable layer is made up of a plurality of sublayers.

14. A decoration material according to any of claims 1 to 12 wherein the removable layer is made up of a first sublayer containing the components listed in claim I with the exception of the pigment, a lithographic image printed thereon in one or more colours and printed from pigment containing inks and a second sublayer over the lithographic image and of composition similar to the first sublayer.

15. A decoration material according to any of claims 1 to 14 wherein the flexible substrate is a cellulose acetate or nitrocellose film, an aluminium foil, or a surface treated paper.

16. A decoration material according to any of claims I to 14 wherein the flexible substrate is a silicone release coated paper.

17. A decoration material according to any of claims 1 to 14 wherein the flexible substrate is a wax coated paper.

18. A decoration material according to any of claims 1 to 14 wherein the flexible substrate is a paper coated with a thermoplastic coating formed of a mixture of unsaturated esters of acrylic or methacrylic acid cross-linked by ultraviolet irradiation.

19. A decoration material substantially as hereinbefore described with reference to any one of the foregoing specific Examples 1 to 10.

20. A method of decorating a substrate which comprises applying a decoration material according to any preceding claim thereto under the action of heat and pressure, and subjecting the removable layer of such decoration material on the substrate to treatment to fix the decoration on the substrate.

21. A method of decorating a substrate according to claim 20 wherein the substrate is a textile fabric.

22. A method of decorating a substrate according to claim 20 or 21 wherein the flexible substrate is removed from the substrate prior to the fixing treatment.

23. A method according to any of claims 20 to 22 wherein the decoration material and substrate to be decorated are brought together between heated calender rolls under a line pressure of 40 to 200 Ibs/linear inch of roller width.

24. A method according to any of claims 20 to 23 wherein the substrate to be decorated is a textile fabric and the fabric and decoration material are passed through heated calender rolls at a speed of at least 5 m/minute.

25. A method according to any of claims 20 to 24 wherein the heat and pressure are sufficient to activate the catalyst and initiate the fixation reaction.

26. A method of decorating a substrate substantially as hereinbefore described with reference to any one of the foregoing specific Examples 1 to 10.

27. A decorated substrate produced by the method of any of claims 20 to 26.